Effect of nanoclay dispersion on the processing of polyester nanocomposites

By: Muhammad Ali Bashir August 2008

Department of Mechanical Engineering McGill University, Montreal, QC, Canada, H3A 2K6

A thesis submitted to McGill University In partial fulfillment of the requirements for the degree of Master of Engineering

RSUM
Le procd dinjection sur renfort (RTM) est de plus en plus utilis en industrie automobile pour produire de grands volumes de carrosseries faible cot. Cependant, les paramtres du procd peuvent avoir un effet ngatif sur les proprits mcaniques et le fini de surface de la pice produite. Une rsine polyester insatur (UP) mixe des nanocharges organiques confre de meilleurs paramtres de production, ce qui est une proccupation majeure pour le fini de surface des pices RTM. Les nano-charges sont des particules faites de couches de silicate traites pour assurer leur compatibilit avec diffrentes rsines. Plusieurs techniques pour synthtiser les nanocomposites sont possibles avec les systmes UP. Trois techniques de mixage ont t tudies : mixage squentiel, mixage avec solvant et mixage simultan. La mthode la plus efficace a ensuite t slectionne et utilise pour fabriquer des chantillons. Deux types de mixage, un moulin trois cylindres et lultrasonification, ont t introduits pour mixer un systme UP/agent anti-retrait (LPA)/styrne avec nano-charges. Leffet de ces deux approches sur la dispersion des nano-charges a t observ par la diffraction rayons X. Suite ces rsultats et des mesures de viscosit, lultrasonification a t choisie comme tant la mthode optimale de mixage (OMM) pour le systme tudi. Un des principaux facteurs qui a influenc ce choix tait lvaporation non-contrle de styrne durant la mthode TRM. 0% 5% de nano-charges a ensuite t ajout la rsine en utilisant la mthode OMM. Leffet de lajout des charges sur la viscosit, la cintique de raction, le module de conservation et la temprature de transition vitreuse (Tg) a t investigu. Il a t observ que lajout des nano-charges augmente le module de conservation et la viscosit, mais diminue lgrement la temprature de transition vitreuse et lactivit de polymrisation. Des tests de rtrcissement de la rsine ont montr une faible rduction du retrait compar au systme sans nano-charges, mais le typique mcanisme de contrle du retrait na pas t observ.

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ABSTRACT
The automotive industry is increasingly using resin transfer moulding (RTM) to produce composite body panels at high volumes and low costs. However, the processing parameters affect the physical and mechanical properties of the final finished part, which may have negative impact on the desired mechanical properties and surface finish. Unsaturated polyester (UP) mixed with organo nanoclay provides improved processing parameters which is a major concern for surface finish in RTM parts. Organo clays are silicate layers treated suitable to make them organophilic in order to be compatible with resin systems. UP systems give rise to numerous possible approaches in synthesizing nanocomposites. Three different techniques to synthesize nanocomposite systems, sequential mixing, solvent mixing and simultaneous mixing were studied and a suitable synthesizing technique was selected and used to make the nanocomposite systems. Two mixing approaches, three roll mill (TRM) machine and ultrasonication, were introduced to mix a pre-promoted UP resin/Low Profile Additive (LPA)/St system with organoclay. The effect of using these two approaches on the dispersion of the clays within the resin mix was studied using X-ray diffraction. Based on the results obtained from the X-ray analysis and viscosity measurements, ultrasonication was chosen as the optimum mixing method (OMM) for this system. One of the factors that influenced these results was the uncontrolled evaporation of styrene during the application of TRM. 0-5 wt% of Cloisite 20A was then added to the resin and mixed using optimum mixing method (OMM). The effect of adding clays on the viscosity, cure kinetics, storage modulus and glass transition temperature (Tg) was investigated. It was seen that the addition of clays increased the storage modulus of the resin samples, increased the viscosity, reduced the glass transition temperature very slightly and reduced the cure activity of the resin-clay system. Shrinkage tests on these resin-clay systems showed some reduction in shrinkage, however the typical shrinkage control mechanism was not observed.

ACKNOWLEDGEMENTS
I would like to acknowledge Professor Pascal Hubert who accepted me as a member of the Composite Materials and Structures Laboratory. His help and support throughout my research were greatly appreciated and guided me towards a challenging career within the same field. Auto21, Network of Centers of Excellence, and Ford Motor Company are acknowledged as well for their financial support. The following people are also sincerely thanked for various reasons (in no particular order): Everybody from the Composite Materials Lab for their help and a wonderful time during my masters program. Jonathan Lalibert for his endless patience and technical help/input. Genevieve Palardy and Lole Khoun for their support throughout the understanding of their previous work. Catherine Billotte and Isabelle Ortega for their valuable support in using the equipments at cole Polytechnique. AOC chemicals and Southern clay products for their generous supply of material samples.

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TABLE OF CONTENTS
RSUM ............................................................................................................................ ii ABSTRACT......................................................................................................................... i ACKNOWLEDGEMENTS................................................................................................ ii TABLE OF CONTENTS................................................................................................... iii LIST OF FIGURES ........................................................................................................... vi LIST OF TABLES.............................................................................................................. x LIST OF SYMBOLS AND ACRYNOMS........................................................................ xi 1. Introduction................................................................................................................. 1 1.1. 1.2. 1.3. 1.4. 2. 2.1. 2.2. Composites in the Auto Industry ........................................................................ 1 Resin Transfer Moulding (RTM)........................................................................ 2 Motivation........................................................................................................... 5 Objectives and Thesis Outline ............................................................................ 6 Nanocomposites.................................................................................................. 8 Processing of nanoclays.................................................................................... 10 Characterization methods for dispersion of clays..................................... 11 Synthesizes of nanocomposites................................................................. 13 Mixing methods ........................................................................................ 17 Parameters effecting dispersion ................................................................ 19 Morphology............................................................................................... 20 Rheological properties .............................................................................. 23 Material strength ....................................................................................... 25 Glass transition temperature ..................................................................... 27 Volumetric shrinkage................................................................................ 29 Cure Kinetics ............................................................................................ 32

Literature Review........................................................................................................ 8

2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.2.5. 2.3. 2.3.1. 2.3.2. 2.3.3. 2.3.4. 2.3.5. 2.4. 2.5. 3.

Physical and mechanical properties .................................................................. 23

Literature review summary ............................................................................... 34 Research Objectives and Approach .................................................................. 35

Experimental Procedures .......................................................................................... 38 iii

3.1. 3.2.

Materials Used .................................................................................................. 38 Resin Characterization ...................................................................................... 39 Sample Preparation to develop optimum mixing method (OMM)........... 39 X-ray diffraction ....................................................................................... 42 Sample preparation for to characterize the effects of nanoclays .............. 43 Cure kinetics ............................................................................................. 43 Rheology and volumetric shrinkage measurements ................................. 44 Dynamic mechanical analyzer (DMA) ..................................................... 46

3.2.1. 3.2.2. 3.2.3. 3.2.4. 3.2.5. 3.2.6. 4. 4.1.

Results and discussions............................................................................................. 48 X-ray diffraction ............................................................................................... 48 Effect of TRM roller distance ................................................................... 49 Effect of mixing time ................................................................................ 50 4.1.1. 4.1.2. 4.2. 4.3.

Rheological behaviour during mixing process ................................................. 53 Rheological behaviour on addition of nanoclays.............................................. 56 Rheological characterization of pre-promoted unsaturated polyester ...... 56 Effect of adding nanoclays on viscosity ................................................... 57 Effect of nanoclays on the gel point ......................................................... 59 Determining the LVR (linear viscoelastic region).................................... 60 Effect of post cure..................................................................................... 61 Effect of nanoclays on storage and loss modulus ..................................... 63 Establishing evaluation criteria for the glass transition temperature (Tg). 66 Effect of nanoclays ................................................................................... 69

4.3.1. 4.3.2. 4.3.3. 4.4. 4.4.1. 4.4.2. 4.4.3. 4.5. 4.5.1. 4.5.2. 4.6. 4.7.

Storage modulus................................................................................................ 60

Glass transition temperature ............................................................................. 66

Cure Kinetics .................................................................................................... 71 Volumetric Shrinkage ....................................................................................... 75 Effect of nanoclays on pre-formulated and pre-promoted resin ............... 75 Effect of LPA and styrene on shrinkage control of the base resin............ 76

4.7.1. 4.7.2. 5. 6. 5.1.

Conclusion ................................................................................................................ 79 Future Work ...................................................................................................... 80 References................................................................................................................. 82

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APPENDIX A................................................................................................................... 93 APPENDIX B ................................................................................................................... 98

LIST OF FIGURES
Figure 1-1: The Kaiser-Darrin made its apparition in 1952, but only got into production in 1954 [8]-[10]................................................................................................................... 2 Figure 1-2: The Resin Transfer Moulding (RTM) process................................................. 3 Figure 2-1: Scheme of composite structures arising from the interaction of layered silicates and polymers [17]. ................................................................................................ 9 Figure 2-2 2 deviation, the phase shift causes constructive (left figure) or destructive (right figure) interferences ................................................................................................ 12 Figure 2-3: XRD of 4 wt% Cloisite 10A dispersed in unsaturated polyester at varying shear mixing speeds [17]. ................................................................................................. 13 Figure 2-4: Curing mechanism of UP: (a) styrene-UP solution before curing; and (b) after curing [41]. Long curves represents long polymer chains; short solid lines represent styrene and solid dots represent free radicals. .................................................................. 16 Figure 2-5: High magnification TEM micrographs revealing different morphologies for DER................................................................................................................................... 23 Figure 2-6 : Viscosity of alkyd/24 wt% I.28MC organo-clay nanocomposite, prepared by mechanical mixing at high shear levels/high temperature for several durations. Samples tested at 80C [33]. ........................................................................................................... 25 Figure 2-7: Storage modulus as a function of temperature; (a) pure epoxy resin; (b) nanocomposite with 5 wt% of silica; (c) nanocomposite with 10 wt% silica [ 56].......... 26 Figure 2-8: Glass transition temperature of Cloisite 10A and CaCO3 for loadings between 0 and 10 wt% [17]. ............................................................................................. 28 Figure 2-9: LPA mechanism initiation reaction, (2) micro-gelling, (3) intra and interparticle reactions experienced during the polymerisation process, (4) the role of the micro-void formation ........................................................................................................ 30 Figure 2-10: Volume change profile of UP/St/LPA system with different Cloisite 20A content cured at 35 8C (0.5% cobalt octoate, 1.5% MEKP, 300 ppm BQ, and 3.5% LPA) [43].................................................................................................................................... 32 Figure 2-11: Heat flow for various nanoclay content as obtained from DSC runs by Hussain [69] ...................................................................................................................... 33

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Figure 3-1: The three roll milling machine with all its major features and components [93].................................................................................................................................... 40 Figure 3-2: The mould used to cure samples used for X-ray analysis and DMA testing. 42 Figure 3-3: Parallel plate setup on the rheometer ............................................................. 45 Figure 4-1: Effect of the roller spacing on dispersion of the resin with 4 wt% Cloisite 20A ........................................................................................................................................... 50 Figure 4-2: XRD patterns showing the effect of time (ultrasonication) and number of passes (TRM) for 4 wt% Cloisite 20 A............................................................................. 52 Figure 4-3: XRD Pattern comparing ultrasonication and TRM methods 4 wt% Cloisite 20A.................................................................................................................................... 53 Figure 4-4: Viscosity as a function of shear rate for different mixing techniques at 25C ........................................................................................................................................... 54 Figure 4-5: Schematic of the variration in viscosity as a result of the mixing process. This schematic summarizes the different effects that changes the viscosities. Green line is neat resin; pink is ultrasonication for 60 minutes; blue is TRM 1 pass; black is TRM 3 pass. 54 Figure 4-6: Characteristic Newtonian behaviour of the as received R580-ZPE-14 resin system. Tests were carried out at 25C............................................................................. 57 Figure 4-7: Viscosity as a function of shear rate for different clay content at 25C using ultrasonication for 60 minutes at 50C. ............................................................................ 58 Figure 4-8: Viscosity as a function of curing time until the gel point. Tests were carried out under oscillation mode at 40C................................................................................... 60 Figure 4-9: Storage modulus as function of amplitude at 25C. The sample contains 3 w% of Cloisite 20A prepared using ultrasonication for 60 minutes at 50C........................... 61 Figure 4-10: Effect of post curing on storage modulus and loss modulus for samples made with 3 wt% Cloisite 20A. The tests were carried out at 25C................................. 62 Figure 4-11: Storage modulus as a function of temperature with the addition of Cloisite 20A. Samples were prepared by using ultrasonication for 60 minutes at 50C. .............. 64 Figure 4-12: Loss modulus as a function of temperature with the addition of Cloisite 20A. Samples were prepared by using ultrasonication for 60 minutes at 50C. ....................... 64 Figure 4-13: Increasing trend of the storage modulus with increase in clay content measured at 30C .............................................................................................................. 65

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Figure 4-14: Evaluation of glass transition temperature using storage modulus and loss modulus. The sample contains 0 wt% Cloisite 20A prepared using ultrasonication for 60 minutes at 50C................................................................................................................. 67 Figure 4-15: Tan delta curve for 0 wt% Cloisite 20A prepared using Ultrasonication for 60 minutes at 50C............................................................................................................ 68 Figure 4-16: Glass transition temperature as a function of clay content at 30C. The onset of loss in storage modulus is used as the evaluation criteria ............................................ 71 Figure 4-17: Total heat of reaction as a function of clay content when using ultrasonication for 60 minutes at 50C. ............................................................................ 73 Figure 4-18: Cure rate as a function of degree of cure for various clay content mixed using ultrasonication for 60 minutes at 50C.................................................................... 74 Figure 4-19: Heat flow curves for nanocomposites synthesized using ultrasonication for 60 minutes at 50C............................................................................................................ 74 Figure 4-20: Volumetric shrinkage (shown as positive) for the R580 resin system and modified R580 system with 4 wt% Cloisite 20A at 40C ................................................ 77 Figure 4-21: Effect of LPA on shrinkage control of T580-63 (base resin for R580-ZPE14) at 80C ........................................................................................................................ 78 Figure 4-22: Effect of styrene on shrinkage of T580-63 (base resin for R580-ZPE-14) at 80C .................................................................................................................................. 78

Figure B 1: Dynamic DSC scan at 10C/min for T580-63 with 3% cobalt 1% and MEKP catalyst .............................................................................................................................. 99 Figure B 2: Dynamic DSC scan at 3C/min for T580-63 with 3% cobalt 1% and MEKP catalyst ............................................................................................................................ 100 Figure B 3: Dynamic DSC scan at 3C/min for T580-63 with 1.5% cobalt 1% and MEKP catalyst ............................................................................................................................ 102 Figure B 4: Dynamic DSC scan at 3C/min for T580-63 with 1.5% cobalt 1% and MIBKP catalyst..................................................................Error! Bookmark not defined. Figure B 5: Isothermal scan at 75C for T580-63 resin + 1.5% cobalt 3% + 1.5% MIBKP ......................................................................................................................................... 103

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Figure B 6: Volumetric Shrinkage results as a function of DOC for T580-63 resin with 1.5% Coblat 3% and MIBKP at 75C,............................................................................ 104

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LIST OF TABLES
Table 3-1: Materials used for research.............................................................................. 38 Table 3-2: Summary of mixing techniques and parameters tested on resin mix with 4 wt% of Cloisite 20A.......................................................................................................... 41 Table 4-1: XRD analysis showing the d-spacing for different samples ........................... 52 Table 4-2: Percentage increase in the storage modulus at 30C with addition of Cloisite 20A.................................................................................................................................... 65 Table 4-3: Glass transition temperature as measured from three different criteria .......... 70 Table 4-4: Glass transition values measured using the half length criteria of the storage modulus............................................................................................................................. 71

LIST OF SYMBOLS AND ACRYNOMS

Acronyms CTE DMA DSC LPA PE PMMA PS PU PVAc RTM SMC TMA UP OMM MMT O-MMT TRM Coefficient of thermal expansion Dynamic mechanical analyzer Differential scanning calorimetry Low profile additive Polyethylene Poly(methylmetacrylate) Polystyrene Polyurethane Poly(vinyl acetate) Resin transfer moulding Sheet moulding compound Thermo-mechanical analyzer Unsaturated polyester Optical mixing method montmorillonite Organic montmorillonite Three roll milling

Latin Symbols CTE Fz h h0 HR H n Coefficient of thermal expansion Normal force Gap between the parallel plates of the rheometer at a given time Initial gap between the parallel plates of the rheometer Total heat of reaction of a resin sample Heat of reaction generated during the first TMA cycle Number of panels

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|* n| t T Tg T V0 V V dV/dt dT/dt

Norm of the viscosity Time Temperature or thermocouple (if followed by a number) Glass transition temperature Temperature difference Initial volume of a resin sample Volume of a resin sample at any time Volume shrinkage Rate of volume change Rate of temperature change

Greek symbols 0 C Thermal Total v Degree of cure Initial degree of cure of the samples Cure dimensional changes Thermal dimensional changes Total dimensional changes Volumetric cure shrinkage Poissons ratio

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1. Introduction
The automotive industry is well known to consistently look for methods to improve design by reducing weight and costs. Today, these costs include the environmental concerns as well as the consumer satisfaction. Lightweight materials, such as composites, are well-suited to reduce the total mass of cars. A lower mass implies lower fuel consumption and therefore, an improvement in fuel efficiency. A brief overview of the composites and processes used in the car industry will be presented in section 1.1. A description of the resin transfer moulding (RTM) process as well as its problems and solutions will be given in sections 1.2 and the motivation behind this research will be presented in section 1.3. The general work objectives and thesis outline will be discussed in section 1.4.

1.1. Composites in the Auto Industry

The automotive sector is one of the major consumers of plastics and consumes over 8% of total domestic/engineering plastics manufactured in the world. The first true step toward the use of fibre-reinforced materials was in 1953 with the famous Corvette from General Motors. Practically at the same time, Kaiser-Frazer introduced a sports car, the Kaiser-Darrin, with a body made of polyester/fibreglass (Figure 1-1). Composite materials showed promises for the car industry. They were light, strong, resistant to rust, ideal for low production runs and could be moulded into different shapes more easily than metals. In the automobile industry today, composite materials are used in applications as varied as car body panels (doors, roofs) [87], semi-structural parts (front bumpers) [88], and engine parts (cylinder-head covers) [87, 88]. The use of thermoplastic composite materials in the automotive industry, already used for under-thehood components (radiator-tanks, heater-fan housings, cooling fans) [89], has recently witnessed a strong growth, with new applications such as intake manifolds, rocker covers, and engine thermostat parts [89]. Structural parts for front-ends and tailgate frames, mainly molded through the injection compression or other injection technology,

have also benefited from the advantages provided by composites. Most of the composites used for these applications are based on polyamide or polypropylene.

Figure 1-1: The Kaiser-Darrin made its apparition in 1952, but only got into production in 1954 [8][10].

More recent examples of composite uses in the automotive industry include front ends (Peugeot 405, Audi A4, Volkswagen Golf/Polo, Ford Focus), front fenders (Lincoln Continental, GM Camaro/Firebird/Thunderbird), tail doors (Citroen, Fiat, Renault, Mercedes A Class), side doors (GM Corvette, Mazda, Saturn) and even transmission mounts and clutch for the Porsche Carrera [89]. However, most of those parts are made by sheet moulding compound (SMC) and few developments were made with resin transfer moulding (RTM). A notable exception is the most recent Aston Martin DB9, which exhibits UP/fibreglass body panels manufactured by RTM [90].

1.2. Resin Transfer Moulding (RTM)

The Resin Transfer Molding Process has been in use for decades. It is one of the best methods for making composite parts with thermoset materials, and is uniquely capable of satisfying the low-cost/high-volume parts per year of the automotive industry as well as the higher performance/lower volume parts per year of the aerospace industry. In short: Resin Transfer Molding is excellent for producing complex composite parts with short cycle times.

The automotive industry has used resin transfer molding (RTM) for decades. The resin transfer molding process is fairly simple and is described in Figure 1-2 below: A twopart, matched-metal mold (or tool) is made. A preform is placed into the mould (step 1), and the mold is closed (step 2). The resin is then pumped under pressure through injection ports into the mould (step 3) and follows predesigned paths through the preform. When the mould is completely filled, the excess resin flows through the vent port. Both the mould and resin can be heated as needed for the application (step 4). Heat is applied to the resin system in accordance to the cure cycle in order to cure the resin. At the end of the cure cycle the mould is opened and the composite part is de-moulded (step 5). A more detailed description of the process is explained in the following paragraph.

Figure 1-2: The Resin Transfer Moulding (RTM) process

The above is a simplified model of the RTM production machine. The first step in the Resin Transfer Molding technique is creating the preform. The preform is the matrix, already in the shape of the finished product, which the resin will be injected into. There are a few steps in making a preform. These are:

 Selecting the type of fibre. There are several different types of fibre available for use with composites. Random Mats. Two Dimensional Woven Fabrics Unidirectional Fabric Other fibre forms: Knit fibres, other 2 dimensional weaves and 3 dimensional weaves After selecting the fibre type, the fibre must be preformed into the shape of the finished product. There are several methods of performing. Some of these are listed below: Cut and place preforming: In this method, nearly any 2 dimensional woven fabric and some 3 dimensional ones may be used. Individual layers of the preform are separately cut, placed into the female mold cavity by hand, and then contact preformed within the tool. Directed fibre preforming: This method uses a 'sprayer' to fire chopped fibres at a perforated screen shaped like the finished product. The mould is then closed and heated up to the appropriate cure temperature The resin is injected into the cavity through an injection port. positioned at the other end. There are several benefits to using the resin transfer molding process over the alternative processes available. One of the most prominent benefits is the separation of the actual molding process from the design of the fibre shape. Having the fibre preform stage occur at a different time than the injection and curing stages allows the manufacturer a much greater amount of flexibility and precision when designing a piece. The advantages can be summarized below: The cost of the equipment is low; It is a closed-mould process, so the volatile emissions are limited and it is easier the control the part thickness;

When the mould is completely filled, the excess resin flows through the vent port

 Components have a good surface finish on all sides (For instance, in SMC, the surface of the parts can suffer from small defects such as pinholes. Rework is often needed to obtain a Class A surface finish); Parts with complex, large and/or hollow shapes can be moulded; The fibre volume fraction can reach 60%; the parts produced therefore have superior mechanical properties.

1.3. Motivation
Many factors are to be considered in the manufacturing of composite automotive parts. Cost remains a major obstacle to a wider usage of composites for automotive applications. Car companies that developed a worldwide market throughout all social classes require a large volume of production. Moreover, the manufactured parts also need to satisfy a surface quality standard, commonly referred to as Class A in the automotive industry. There is no precise definition for this standard, but mathematically-speaking, a Class A surface should possess curvature continuity between surfaces sharing the same boundary [92]. The surface should be flat, smooth, and exempt of undesirable waviness and have an optical appearance identical to an adjacent steel panel [91, 92]. The automotive industry has increasingly used RTM to produce composite parts. It possesses interesting advantages over the other processes, but so far, only companies with a low volume of production, such as Aston Martin, have successfully developed it according to Class A surface finish. The main issue is related to the control of the surface quality, which is influenced by the resin volumetric changes, the fibres orientation/distribution, the flow distribution, the painting process (glass transition temperature might be play a role here) and the surface finish of the mould. The volumetric changes however have the strongest effect on the surface quality as they include two phenomena: cure shrinkage and thermal expansion/contraction. The cure shrinkage of the resin, being more significant than its thermal expansion, leads to surface defects such as ripples, sink marks, fabric print through, and dimensional inaccuracy. Previously [44, 45], it was found that adding Low Profile Additives (LPA) resulted in

improved surface finish. Recently, it is seen that adding silica nanoclays to the resin/LPA system shows further improvement in shrinkage control and has an effect on the glass transition temperature. The glass transition temperature is important to ensure greater thermal stability in post cure painting process in order to ensure that there is no degradation in the surface finish. Therefore, synthesises of these nanocomposites is becoming of large interest to researchers and industries alike. Thus, in order to completely understand the physical and mechanical behaviour of the nanocomposites, it is necessary to develop a good understanding of the different techniques available to synthesis a nanocomposite, as well as the constraints, advantages and disadvantages of these techniques. Furthermore, there is a need to study the compatibility of the materials, different mixing methods available to disperse the clays and the various parameters that are involved with these mixing methods as they have a significant effect on the crystallographic structure of the nanocomposite which is known to be crucial towards the final performance of the composite. Ultimately, an understanding of these parameters and constraints will help us develop processes and techniques to manufacture nanocomposite systems that will achieve the desired properties in terms of strength, volumetric shrinkage and glass transition temperature.

1.4. Objectives and Thesis Outline

The general goal of this work is to understand the various parameters involved in the synthesis and processing of a nanoclay modified unsaturated polyester resin. The idea is to understand the relationship between the processing parameters and the final physical and mechanical properties. In this research, two most common mixing method, shear mixing and ultrasonication will be studied using a pre-formulated unsaturated polyester resin. Chapter 2 contains the literature review where the nanocomposites are described. The different synthesizing methods and mixing techniques are reviewed and their effect of the dispersion is also included. Chapter 2 also tries to correlate the various properties to the synthesizing and mixing techniques and compare the effects of these different mixing techniques. Chapter 3 describes the materials and experimental procedures used in this

research: x-ray diffraction, differential scanning calorimetry, rheology and dynamic mechanical analysis. The results of dispersion, viscosity, volumetric cure shrinkage, glass transition and storage modulus are shown in Chapter 4. Finally, the conclusion as well as appropriate future work related to this topic, is given in Chapter 5.

2. Literature Review
The literature review contains topics that were judged to be the most pertinent for this research. LPA and their expansion mechanism are described extensively. The various synthesizing methods for nanocomposites (section 2.2.2), mixing processes (section 2.2.3) and influence of various operational parameters like speed, time and temperature (section 2.2.4) are reviewed. The influence of adding nanoclay to epoxy and unsaturated polyester on rheological properties (section 2.3.1), the mechanical properties (section 2.3.2) the glass transition temperature (section 2.3.3), most importantly the volumetric shrinkage (section 2.3.4) and cure kinetic (section 2.3.5),and has been reviewed in this chapter. A particular attention is given to the synthesizing and mixing techniques as they are known to affect the nanocomposite performance.

2.1. Nanocomposites
Nanocomposites systems, in which the filler has a dimension in the nano meter range in at least one spatial direction, may be divided into two categories: intercalated systems and exfoliated systems. Intercalated nanocomposites are formed when the polymer penetrates into the silicate layers resulting in their finite expansion. Exfoliated systems consist of individual nano meter-thick silicate layers distributed in the polymer matrix (see Figure 2-1 ). In more details, immiscible, mica-type silicate tactoids exist in their original aggregated state with no intercalation of the polymer matrix into the galleries. For this case, the particles act as micro-scale fillers. Intercalated nanocomposites have the polymer matrix intercalated between the silicate layers and the expanded silicate layers are still in order. Exfoliated nanocomposites, in which the individual 1 nm thick silicate layers are completely dispersed in a polymer matrix and the gallery structures, are completely destroyed [17]. Both intercalated and exfoliated nanocomposites exhibit significantly enhanced properties when compared to the neat polymers or conventional composites. The formation of nanocomposites is dependent upon the matrix and its ability to penetrate the silicate layers. Nanocomposites developed from thermoset polymers can be 8

prepared via in situ, intercalative polymerization [9, 16] with phenol, epoxy and polyester resins all included in this category. Many nanocomposite systems have been investigated to date utilizing variety of inorganic silicates or other nano-elements and a number of thermoplastic and thermosetting resins. This involves swelling the organophilic clay with a compatible monomer followed by a cross-linking reaction. During swelling, the monomer diffuses from the bulk monomer into the galleries between the silicate layers. The final morphology depends on the degree of penetration of the monomer into the organo layered silicate structure [9]. More on different synthesizing methods will be discussed in section 2.2.2. It is believed that the high aspect ratio (102000) of the nano-scaled layered silicate and their dispersion in the resin plays a key role in the improvement of the properties of nanocomposites [11]. Improvements in mechanical properties [12, 13], thermal stability [14] and dielectic properties [15] have been widely documented. Notably, low concentrations of silicate (15 wt%) result in the aforementioned improvements.

Figure 2-1: Scheme of composite structures arising from the interaction of layered silicates and polymers [17].

Most common thermoset polymers that are studied are epoxies and styrenated unsaturated polyesters (UP). However, whereas epoxy based nanocomposites have been

extensively investigated [25, 26, 27, 28] there are only a few studies on UP based ones. UP resins are bi-component systems comprising of an UP pre-polymer (alkyd) that is usually dissolved in styrene monomer. In the presence of a peroxide catalyst, the system cures to an insoluble, infusible, cross-linked matrix resin. A large portion of nanocomposite research utilizes minerals of the 2:1 layered silicates, very often smectite and specifically montmorillonite. Smectites are noted in the literature as being unique in their ability to expand or contract while maintaining their 2-D crystallographic structure and for their high cation exchange capabilities [75]. These properties are key elements that attribute to their selection as a nanoclay especially when the goal is to achieve exfoliation of individual silica layers within a polymer (known to improve mechanical properties). Interestingly, it is seen in the literature that when different clays are mixed under identical conditions, different results are observed for dispersion. This is due to the fact that the organic treatments performed on the naturally hydrophilic minerals make them organophilic (to be able to be compatible with polymers to assist inter-gallery absorption) and introduce cations which also play an essential role in the resulting morphology, as the size of initial gallery spacing of the silicates is affected by the size of cations used as well as the cation exchange capability of the silicate. In the same way, when different resin systems are used different results are obtained as the compatibility is affected. Therefore, it is widely agreed upon that the dispersion of nanoclays depend heavily on the resin-clay interactions. This in turn means that the mechanical properties and shrinkage control of the nanocomposite is controlled by these interactions.

2.2. Processing of nanoclays

This section will look into the dispersion characterization and various parameters involved in preparing the samples involving the nanocomposites. As seen from the previous sections, these parameters play an important role in determining the level of intercalation and hence the property changes of the sample.

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2.2.1.

Characterization methods for dispersion of clays

It is well known that dispersion of nanoclays in the resin is a pre-requisite to the required improvement in properties [9-37]. Therefore, it is important to be able to characterize the dispersion of these cays. Most researches have used X-ray diffraction as means to characterize dispersion. However, it is essential that the clay particles have a distinct reflection and the samples are thin. For this purpose, some researchers have suggested to progressively remove layers of a sample and carry out the diffraction tests to check for dispersion through the thickness [17,29]. X-ray scattering techniques are a family of non-destructive analytical techniques which reveal information about the crystallographic structure, chemical composition, and physical properties of various materials. These techniques are based on observing the scattered intensity of an x-ray beam hitting a sample as a function of incident and scattered angle, polarization, and wavelength or energy. Braggs law is then used to compute the crystallographic spacing. Braggs law is as follows:
n = 2d sin

(Eq. 2-1)

n is an integer determined by the order given, is the wavelength of x-rays d is the spacing between the planes in the atomic lattice, and is the angle between the incident ray and the scattering planes

11

Figure 2-2 2 deviation, the phase shift causes constructive (left figure) or destructive (right figure) interferences

Two main types of scattering techniques have been found in the literature [13-25, 134042]. Small angle X-ray scattering (SAXS) probes structure in the nanometer to micrometer range by measuring scattering intensity at scattering angles 2 close to 0. Wide angle X-ray diffraction (WAXD) is a technique concentrating on scattering angles 2 larger than 5. The type of scattering technique used depends on the typical properties of clays that are being studied. Most clay under consideration had typical peaks anywhere between 2 equal to 3 and 2 equal to 5. Hence most of the studies conducted for the dispersion of these nanoclays consisted of small angle X-ray scattering. Although some papers [69] can be found making use of the WAXD methodology due to availability of the technique or a larger reflection angle of the clays. Typical range for scanning samples is between 2 equal to 2 and 2 equal to 10. Figure 2-3 represents a typical result obtained from several XRD tests on samples with different mixing speed (one of the parameters involved in the mechanical mixing method used by the Rudd [17]). The results obtained are analyzed using Braggs law (Eq. 2-1) to calculate the d-spacing. As seen above a reflection peak is a clay property. As these clays are dispersed into the resin, the reflection peak typically shifts to a lower angle and reduces in intensity. The lower the angle and the intensity peak, the greater the d-spacing and hence greater inter-gallery spacing of the silicates. As discussed earlier, the improvement in thermal, mechanical and shrinkage properties is dependent on the amount of intercalation and exfoliation reached. The increase gallery spacing is a direct indication of an increase in intercalation or exfoliation. 12

Figure 2-3: XRD of 4 wt% Cloisite 10A dispersed in unsaturated polyester at varying shear mixing speeds [17].

Although many researchers observe the shift in peak relative to the initial peak there are some that have quantified exfoliation and intercalation [8]. The extreme limit or idealized state of exfoliation is defined by individual silicate layers separated as fully as geometrically possible based on their volume fraction within the polymer. Although Tolle [8] has defined exfoliation as spacing between the silicate layers greater than 10 nm, there are no details found as to the process of assigning specific spacing as a starting point of exfoliation. However, as seen in most other papers, relative analysis of the peak and their intensity gives sufficient information to the degree of dispersion of these nanoclays within the resin.

2.2.2.

Synthesizes of nanocomposites

There are essentially three different approaches to synthesise polymerclay nanocomposites: melt intercalation, solution and in situ polymerisation. The melt intercalation process was invented relatively recently by Vaia et al. [80]. A thermoplastic

13

polymer is mechanically mixed with organophilic clay at elevated temperature. The polymer chains are then intercalated between the individual silicate layers of the clay. The proposed driving force of this mechanism is the enthalpic contribution of the polymer/organoclay interactions. This method is becoming increasingly popular since the resulting thermoplastic nanocomposites may be processed by conventional methods such as extrusion and injection moulding. In the solution method, the organoclay, as well as the polymer, are dissolved in a polar organic solvent [79]. The entropy gained by the desorption of solvent molecules allows the polymer chains to diffuse between the clay layers, compensating for their decrease in conformational entropy [79]. After evaporation of the solvent, an intercalated nanocomposite was obtained. This strategy can be used to synthesise epoxyclay nanocomposites [82] but the large amount of solvent required is a major disadvantage. The in situ polymerization approach was the first strategy used to synthesise polymer clay nanocomposites and is a convenient method for thermoset-clay nanocomposites [83]. It is similar to the solution method except that the role of the solvent is replaced by a polar monomer solution. Once the organoclay has been swollen in the monomer, the curing agent is added and complete exfoliation occurs in favourable cases. According to a previous study [84], the polymerisation is believed to be the indirect driving force of the exfoliation. The clay, due to its high surface energy, attracts polar monomer molecules in the clay galleries until equilibrium is reached. The polymerisation reactions occurring between the layers lower the polarity of the intercalated molecules and displace the equilibrium. This allows new polar species to diffuse between the layers and progressively exfoliate the clay. Therefore, the nature of the curing agent as well as the curing conditions is expected to play a role in the exfoliation process. Phenol resins, epoxy resins and UP resins can all be prepared using this method. Preparation ways involved with epoxy resin and UP resin can differ depending on the curing mechanism and the constraints involved with the synthesizing techniques. Where as the constraints and parameters involved with various mixing techniques will be

14

discussed in the following section, this section will look into more details on using the in situ and melt intercalation for unsaturated polyester (UP) resin. Unsaturated polyesters (UP) can be dissolved in a polymerizable monomer such as styrene. A UP is a long-chain linear polymer containing a number of reactive double bonds. The styrene monomer, which also contains C and C reactive double bonds, acts as a curing agent by bridging adjacent polyester molecules at their unsaturation points. During the styreneunsaturated polyester cross linking copolymerization, the initiator decomposes and creates free radicals in the system. The free radicals grow and form long-chain molecules by connecting styrene monomers and unsaturated polyester molecules by both inter- and intra-molecular reactions. A schematic of the growth of free radicals is shown in Figure 2-4 [41]. Due to the typical curing mechanism of unsaturated polyester, the styrene monomer, unsaturated polyester linear chain and organophilictreated MMT exist together in the nanocomposite formation system. Consequently, the behaviours of each component in the nanocomposite formation system are very important. Such multi-component UP systems gives rise to the possibility of numerous approaches in synthesizing UP nanocomposites. As seen before the nanocomposites of thermoset polymer can be prepared by the in situ intercalative polymerization method (simultaneous) and melt intercalation (sequential mixing). During the simultaneous mixing method these thermosetting nanocomposite materials are prepared by first swelling the various organo-modified montmorillonite (MMT) with the proper polymerizable monomers (like styrene), followed by crosslinking reactions. During swelling, the monomer diffuses from the bulk monomer into the galleries between the silicate layers. Depending on the degree of penetration of the monomer into the organolayered silicate (OLS) structure, different types of nanocomposites can be obtained ranging from intercalated to exfoliated or delaminated. This first method, simultaneous mixing, is similar to the method used for preparing conventional UP/filler composites, which was also used by others [30, 31, 32]. The second method is the sequential mixing. In the first step, pre-intercalates of the unsaturated polyester (UP) resin and montmorillonite (MMT) clay are generated, i.e., mixtures of the resin and the organophilic treated MMT are prepared. The second step is the addition of styrene to the

15

resin/MMT pre-intercalates. The addition of styrene after adding the clays creates yet another parameter in synthesis and performance evaluation of the nanocomposites. Many studies have already been conducted on the effects of styrene on UP/LPA composites [46]. It can be seen from these studies that styrene play a critical role in UP/St/LPA polyester systems during the phase separation and micro cracking process, which is considered the driving mechanism for shrinkage control. This second step is then followed by curing of the system by adding the appropriate catalyst.

Figure 2-4: Curing mechanism of UP: (a) styrene-UP solution before curing; and (b) after curing [41]. Long curves represent long polymer chains; short solid lines represent styrene and solid dots represent free radicals.

Suh et al. [29] compared the two different ways of mixing organically modified clay with UP. They suggest that a more homogeneous network (i.e., homogeneous cross linking reaction inside and outside of the silicate layers) was obtained for nanocomposites prepared via sequential mixing. The reason being UP chains, styrene monomers and organic organophilic MMTs (O-MMTs) coexist in the mixing medium. The styrene monomers diffuse into the gallery of the O-MMTs much faster than the UP chains (because of the size and the functionality of the UP polymer chains). If the curing reaction starts in these conditions, the styrene homo-polymer is produced primarily in the interlayer of the O-MMT and the crosslinking density decreases inside and outside of the O-MMT, because the styrene monomers are concentrated on the interlayer and styrene monomers are insufficient for the crosslinking the reactive double bonds of the unsaturated polyester. Therefore, by taking advantage of the multi component UP

16

systems, the silicate layers can initially be penetrated by UP polymer chain and then by styrene in additional steps as defined by the sequential mixing techniques.

2.2.3.

Mixing methods

Methodological approach to study the effects of various mixing processes, applied shearing levels, organo-clay contents and mixing temperatures were developed in various literature [29, 30, 31, 32]. These methodological approaches provides basis for understanding the structuring processes involved in the formation of resin/organo-clay nanocomposites and establishing materials-processing-structure interrelations. The three main categories for mixing techniques are: ultrasonication, mechanical or shear mixing and static mixing Ultrasonication generates alternating low-pressure and high-pressure waves in liquids, leading to the formation and violent collapse of small vacuum bubbles. This phenomenon is termed cavitation and causes high speed impinging liquid jets and strong hydrodynamic shear-forces. These effects are used for the deagglomeration of nanometre-size materials. In this aspect, ultrasonication is an alternative to high-speed mixers and agitator bead mills. Ultrasonic provides more energy to the polymer chains and the silicate layers, so that the polymer chains would enter more easily into the galleries between the silicate layers. Also, an ultrasonic bath promotes exfoliation and prevents formation of agglomerates. Mechanical mixing or shear mixing is a very broad term that can be applied to mechanical blades, rollers or manual hand mixing used for mixing clays with the resin. This technique involves the use of a mechanical device to disperse the nano-particles into the resin. Different techniques and a wide range of parameter are seen in the literature when it comes to the applying mechanical or shear fixing [9-33, 70-72] The mixing processes either mechanical or ultrasonication illustrates the increase in the different clay basal spacing (characterized by X-ray diffraction, TEM or SEM). All organo-clays show some increase in the gallery spacing when mixed using the techniques 17

described above. Narkis [37] studied the intercalation of various organo-clays and showed different clays had different intercalation. This has been attributed to the amount of organophilic treatment of the clay [33-37]. Interestingly, the lower amount of organophilic treatment gives rise to higher degrees of intercalation, resulting in higher increase in basal spacing [37]. However, Suh and Park [38] observed opposite trends for poly99-vinyle carbazole (PVK)/stearlamine treated MMT system, where lower amounts of treatment have led to lower intercalation levels. Therefore, the relation between amount of organophilic treatment and intercalation levels depends on the characterization technique and initial basal spacing as supplied by the manufacturer. Narkis [37] reported that although the basal spacing varies with the amount of treatment, the end d-spacing for the organo-clay remains the same. Three different mixing techniques were investigated by researchers to determine the effect on basal spacing and intercalation levels: static heating (annealing), mechanical mixing and ultrasonication. However, no conclusive information or results are available to impose superiority of one method over the other. Results seen in the literature suggests that no direct correlation can be established between mixing technique and the intercalation levels as these results are influenced by other parameters like type of resin used and the types of clay and their treatment, as well as the resin-clay interaction. For example, Yasmin et all [70] suggested that nanocomposites with higher clay content could not be mixed using ultrasonication process due to increased viscosity of the mixture. In the same way, as indicated by several researchers regarding polymer/clay system [36-41], intercalation maybe achieved just by static heating. None the less, these intercalation processes maybe facilitated by dynamic processes such as mechanical mixing and ultrasonication. It is interesting to mention here that shear mixing has been reported to reduce the aspect ratio of clay particles [70] especially when using the milling process. This is because the milling process breaks the clay platelet during mixing as observed in microscopic imaging used. The high aspect ratio of the clays is known to play an important role in improvement of the mechanical properties and therefore the mixing process may have an influence on the nanocomposite properties.

18

2.2.4.

Parameters effecting dispersion

Mixing time in the preparation of resin/clay mixtures is one of the parameters that need to be determined for optimal results. Most researchers [29-33] agreed that a one hour period of mixing using ultrasonication and mechanical mixing shows sufficient intercalation for both epoxies and polyesters. Nevertheless, further mixing may lead to better dispersion of the already intercalated clay or to delamination [38]. X-ray analysis of the samples (Figure 2-3) clearly indicated that extent of intercalation increased due to increase in mixing speed using the shear mixing technique (and in case of a three-roll mill with a decrease in roller spacing [70]). Samples with varying clay content and varying shear speed have been tested. Results from these samples clearly supported the suggestion that the extent of intercalation increased with mixing speed and decrease in clay content. Although not many studies have been found that evaluate the effect of the amplitude applied during the ultrasonication process, it is believed that an increase in the amplitude will have similar effect as to increasing the speed in shear mixing. Others have also shown that high shear promotes the exfoliation of the silicate layers [43]. Adversely, large amounts of clay may also result in aggregation of clay in the polymer matrix [43], which may inhibit further intercalation and exfoliation, resulting in the observed two coexisting intercalated-clay populations. Moreover, it is also possible that the amount of polymer in a system containing very high clay content (more than 10% wt) is insufficient to intercalate all the clay to the larger extent (a starved condition), resulting in the two intercalated-clay populations structure. In other studies [21] resin was mixed between different rpm ranges by an air driven shear mixer, subsequently polymerised and then analysed using X-ray diffraction (XRD). Generally, the results found in the literature agree when reporting the affect of shear and amount of nanoclays on the intercalation level. Generally, increasing the mixing temperature results in reducing the polymer viscosity, affecting both the shear level exerted during the mixing process and the mobility of the polymer chains and segments. Low matrix viscosity imparts low shear stresses on the clay agglomerates, which may skew the stack of platelets rather than separate them [44],

19

and might also facilitate the aggregation of clay, hindering the penetration process of polymer chains and segments into the clay layers. At the same time, increases polymer mobility is expected to facilitate intercalation of clay at shorter times. Narkis [37] and Huang et al [45] studied the effect of mixing temperature by preparing the nanocomposites at higher temperatures. Narkis [37] found that mixing at higher temperature (130C as compared to 180C) does not result in a large intercalation extent. These results are contrary to the ones reported by Huang [42] who found that meltmixing, static melt-intercalation and solution intercalation of low viscosity polymer appear to be advantageous in achieving disruption of the silicate structures or high level of intercalation at short processing times. However, the reason for reduced or no effect of temperature [33] could be due to the fact the lowered matrix viscosity, causing decreased shearing during mixing, hinders the intercalation and exfoliation processes and has a stronger effect on structuring than the increased chain mobility. Mixing time is yet another important parameter during the preparation of nanocomposites. Many researchers [83-88, 24-33, 38-41] have studied the effect of varying the time using different mixing method (mechanical mixing, ultrasonication and three-roll mill). In case of a three roll mill, the number of passes have been set equivalent to the time during which the shearing is applied. All results in the literature agree that increasing the time has increased intercalation (measured by XRD) as more and more layered silicates are penetrated by the resin.

2.2.5.

Morphology

Understanding of the development of morphology for various nanocomposites has been under investigation over the past decade. Morphological studies have been used in the past to establish an understanding of how curing [8, 10-13] and processing [17-33, 70-74] of these nanocomposites effect the morphology and dispersion and as a result effect the over all performance of the nanocomposites. Although this understanding is certainly necessary to enable effective material development, it is of critical importance for tailoring morphology-sensitive properties such as toughness and permeability. This is of specific importance for thermosetting resins like epoxies and polyesters, for these 20

properties provide the limitations for their use in automotive and aerospace industries. Furthermore, the sensitivity of morphological development to the processing conditions has been well documented in polymer literature and also proposed in nanocomposite literature [73(a)-74]. Most of the researchers use microscopic imaging techniques to verify and confirm results that are obtained by the x-ray scattering method. Microscopic imaging provides a visual interpretation of the XRD results and allows us to understand and confirm these results. The three most common types of imaging techniques found in the literature are discussed here. The scanning electron microscope (SEM) is a type of electron microscope that images the sample surface by scanning it with a high-energy beam of electrons. The electrons interact with the atoms that make up the sample producing signals that contain information about the sample's surface topography, composition and other properties such as electrical conductivity. SEM micrographs have a very large depth of focus yielding a characteristic three-dimensional appearance useful for understanding the surface structure of a sample. This great depth of field and the wide range of magnifications (commonly from about 25 times to 250,000 times) are available in the most common imaging mode for specimens in the SEM, This particular type of microscope is exceedingly useful and is seen in the literature the most. Transmission electron microscopy (TEM) is a microscopy technique whereby a beam of electrons is transmitted through an ultra thin specimen, interacting with the specimen as it passes through it. An image is formed from the electrons transmitted through the specimen, magnified and focused by an objective lens and appears on an imaging screen. There are a number of drawbacks to the TEM technique. Many materials require extensive sample preparation to produce a sample thin enough to be electron transparent, which makes TEM analysis a relatively time consuming process with a low throughput of samples. The structure of the sample may also be changed during the preparation process. Also the field of view is relatively small, raising the possibility that the region analysed

21

may not be characteristic of the whole sample. There is potential that the sample may be damaged by the electron beam. The optical microscope, often referred to as the "light microscope", is a type of microscope which uses visible light and a system of lenses to magnify images of small samples. Optical microscopes are the oldest and simplest of the microscopes. The objective lens is a cylinder containing one or more lenses to collect light from the sample. At the lower end of the microscope tube one or more objective lenses are screwed into a circular nose piece which may be rotated to select the required objective lens. Typical magnification values of objective lenses are 4x, 5x, 10x, 20x, 40x, 80x and 100x. Some high performance objective lenses may require matched eyepieces to deliver the best optical performance. However, other non-optical microscopes like scanning electron microscope (SEM) and transmission electron microscope (TEM) can magnify exponentially greater than the optical microscope. The choice of the methodology to capture images is dependent on the particle size and type. It is generally seen that optical microscopy does not give a very accurate picture of the nanocomposite structure as the particles involved are nano-sized therefore requiring much higher magnification. Therefore many researchers prefer either SEM or TEM in order to observe morphological development in nanocomposites.

22

Figure 2-5: High magnification TEM micrographs revealing different morphologies for DER 331 epoxy (Dow Chemical) and 5 wt% of Cloisite 30B [60].

2.3. Physical and mechanical properties

2.3.1. Rheological properties

The rheological properties of particulate suspensions are sensitive to their structure, particle size and shape, and surface characteristics of the dispersed phase. Thus rheology potentially offers a means to asses the state of dispersion in nanocomposites while still in the melt state, and may offer a tool complimentary to traditional methods of material characterization such as X-ray scattering etc.[42].

The viscosity of all nano clay composites (based both on epoxies and on polyester) increases due to addition of the clays [29-33, 42]. The increase of viscosity was in agreement to the amount of intercalation achieved in the mixture. Higher intercalation of a particular clay in the mixture displayed larger increase in viscosity [17, 33, 42]. The viscosity measurements were done mostly by using a conventional rheometer [42- 45] or

23

Rheometrics dynamic analyzer (RDA) [17, 59] using parallel plate arrangements. Viscosity was measured under an isothermal condition where the gel point was defined as the point where the reduced viscosity r = / 0 ( is the instantaneous viscosity and 0 is the initial viscosity) reaches 103.

For all nanocomposites higher mixing time and dynamic processes like mechanical mixing resulted in larger increase in viscosity [33]. It was also seen that these nanocomposite system showed shear thinning which has been linked to the reorientation of silicate layers in the direction of the flow (Figure 2-6). As shown by Huang et al. [42], relative to static annealing, the application of shear appears to be advantageous in achieving disruption of the silicate structure and dispersion of the resulting particles. It was previously suggested by Ishida et al. [46] that increasing the mixing time allows the formation of both intercalated and exfoliated nanocomposites. The increased viscosity may be attributed to three simultaneous processes. First, a higher intercalation level that resulted in higher effective clay content and less polymer segments and chain participating in the bulk flow process [42, 47]. Second, exfoliation, which results in a higher exposed clay surface and thus higher interaction levels between the polymer and clay that may partially arrest segmental movements [35]. Third, higher viscosity values are also obtained due to better dispersion of the particles [48]. Generally, the interaction of polymer chains with filler particles can alter the chain kinetics in the region immediately surrounding the particle. The interaction, physical or chemical, between the polymer chains and the filler surface restricts the molecular mobility of the affected chains, changes the packing density of polymer chains, and modifies the conformation and orientation of chain segments in the neighbourhood of the surface. Due to the clays extremely high specific surface area, even low filler contents that are well dispersed in a system provide an enormous amount of interfacial area through which the bulk properties of the polymer can be altered [49, 50].

24

Figure 2-6 : Viscosity of alkyd/24 wt% I.28MC organo-clay nanocomposite, prepared by mechanical mixing at high shear levels/high temperature for several durations. Samples tested at 80C [33].

2.3.2.

Material strength

Many variations of the measure of material strength can be found in the literature. Researchers have tried to use tensile tests [17, 50, 56, 58] (using tensile testing equipments like Instron testing systems) to determine the Youngs modulus (also known as tensile modulus), as well as three point bending tests and cantilever beam tests using a dynamic mechanical analyzer (DMA) to measure the flexural strength and storage modulus [17, 29, 30, 40, 76]. The youngs modulus is measure of the stiffness of a material. It is also known as the youngs modulus, modulus of elasticity, elastic modulus or tensile modulus. The storage and loss modulus in viscoelastic solids measure the stored energy, representing the elastic portion, and the energy dissipated as heat, representing the viscous portion (loss modulus).

25

Figure 2-7: Storage modulus as a function of temperature; (a) pure epoxy resin; (b) nanocomposite with 5 wt% of silica; (c) nanocomposite with 10 wt% silica [ 56].

It is largely reported in the literature that the incorporation of nanoclays into epoxy or UP [17, 29, 30, 56, 58] resins and of carbon nanotubes into the resin system [60] have increased the mechanical properties like tensile strength and storage modulus. The general trend seen is large initial increase of strength with approaching plateau as the clay content increases. The initial increase in stiffness is linked to the large aspect ratio of the clay particles that contribute to the reinforcement of the resin as well as increased clayresin interaction related to the degree of intercalation and exfoliation [29, 40, 58, 76]. The decrease in the strength of these nanocomposites with increasing clay content is due to reduced exfoliation that causes weak adhesion of clays to the resin and therefore a reduction in the stiffness. Hence, it can be seen that the stiffness of nanocomposites depends on the mixing method, the compatibility (therefore the treatment) of the nanoclays with the resin system and the overall curing mechanism of the system under consideration. Since the increase in stiffness is largely related to the clay-particle adhesion and interaction, there are some papers that show opposite trends in regards to the stiffness of nanocomposites. It has been seen that a reduced intercalation and 26

exfoliation has been linked to the reduction of storage modulus [77] and of tensile modulus [56] of the nanocomposites as the clay-resin adhesion tends to become weaker with reduced exfoliation. It is seen that there some discrepancies in observation of the stiffness and tensile strength of the nanocomposites. However, most researchers agree on slight increase in the storage modulus of the nanocomposites for very low (generally less than 5 wt%) clay content.

2.3.3.

Glass transition temperature

The glass transition temperature, Tg is the reversible passage between the rubbery and solid/glassy states for thermoset resins. For neat UP resins, Tg varies significantly depending on their composition. It can go from 85C to almost 200C for fully cured samples [50-53]. Tg can be measured by thermo-mechanical analysis (DTMA) [60], dynamic mechanical analysis (DMA) [29] (the inflection of the storage modulus curve), differential scanning calorimetry and dielectrometry [17, 69] as found in the literature. Differential scanning calorimetry measures a change in heat capacity; DMA measures the change in the mechanical properties of storage or loss modulus (where the Tg is the point of inflection of the storage modulus or peak of loss modulus or peak of tan ) and the dielectrometry measures a change in the permittivity (increase around Tg) and loss factor. It should be mentioned that the Tg obtained from the dielectric measurement lacked of consistency. Results in the literature showed that if the frequency of the field is increased, the glass transition occurs at a higher temperature [69]. The effect of nano clays on the glass transition temperature is an area of debate amongst researchers. Results shown in Figure 2-8 show an increase in the Tg, but opposite trends are also observed. As for the effect of LPA, most studies tend to agree: the addition LPA causes a slight decrease in Tg [53- 55]. Huang and Horng [53] studied the effect of various LPA on the glass transition temperature.

27

Figure 2-8: Glass transition temperature of Cloisite 10A and CaCO3 for loadings between 0 and 10 wt% [17].

Rudd [17] showed using DSC (Differential scanning calorimeter) by non-isothermal analysis of the polymerised samples that the glass transition temperature increased (up to 11 C for 4 wt% clay, see Figure 2-8). However, other related studies [56, 57] have shown clay to decrease the curing reactivity, which generally results in lower cross-link density and longer polymer chains among the cross-linking points. This would tend to decrease the glass transition temperature. As mentioned in section 2.3.5, unsaturated polyesters containing styrene may show reduced reactivity. This is because the styrene monomers are concentrated on the interlayer and styrene monomers are insufficient for the crosslinking the reactive double bonds of the unsaturated polyester. More so, it would be expected that increased exfoliation levels would result in reduced reactivity due to the suggested consumption of free radicals by clay particles [58]. On the other hand Suh [29] tried using the sequential mixing technique to show that the homogenous dispersion of styrene monomer (which act as a curing agent) with increase in time results in the Tg

28

reaching up to the value of pure UP resin. This supported the hypothesis that an increase in the crosslink density within the UP resin, causes an increase in the glass transition temperature. Miyagawa [60] reported that the Tg increased linearly for epoxy resins with the amount of carbon nanotubes (CNT). Alternatively, Narkis [33] tried to correlate the intercalation results to understand the effect on the glass transition temperature. He found that the glass transition temperature decreased after 0.5 hours of mixing followed by an increase upon further mixing. It is suggested that the decrease was due to the mechanical degradation. The Tg increase may be the result of slight cross linking reactions or due to evaporation of degraded low molecular weight fractions. XRD results showed that due to intercalation of more polymer chains into the organo-clay galleries and exfoliation of more clay platelets, there was increased interaction between the polymer chains and clay surfaces. Thus the Tg increases with mixing time. It can be concluded that the changes in Tg are the result of complicated balance between the alterations exhibited by the polymer itself and the polymer-clay interactions, affected by amount of clay, mixing temperature and time. Different characterization techniques (DMA or DSC) resulted in different results as well. Therefore, it is important to realise the possibility of difference in the data represented by various researchers.

2.3.4.

Volumetric shrinkage

Varied methods to measure the cure shrinkage of resins, without taking the effect of any additives into consideration, were developed over the past years [60-64]. While some of those techniques were elaborated for epoxy resins, they are valid nonetheless for all types of thermoset resins. The most common instrument to measure volumetric shrinkage remains the dilatometer [61-62], [63, 64]. Being generally slightly modified in most studies, the principle is always the same: the sample is placed in a cavity of known dimensions and its thickness variation is monitored at constant temperature. The sample is sometimes submerged in a different fluid, in which volume variation is recorded during cure. It is then possible to calculate the final volume of the sample and obtain its volumetric shrinkage

29

V =

(V0 V )
V0

(Eq. 2-2)

Where V0 is the initial volume of the sample of the resin and V is the volume at any given time. An efficient way to eliminate or reduce the shrinkage is to employ a small amount of thermoplastic materials, often called low profile additives (LPAs), into the resin system [17, 33, 43]. LPAs have been found to be very effective in volume shrinkage control of UP resins cured in high-temperature processes, such as compression moulding of sheet moulding compounds (SMCs) and injection moulding of bulk moulding compounds (BMCs). The shrinkage control mechanism has been studied extensively and it is generally believed that thermal expansion during heating and microvoid formation during cooling contributes to the shrinkage control [4-6, 44-46]
Precipitated thermoplastic

UP, styrene and thermoplastic

Free radical

Micro-gel

Inter-particle reaction Intra-particle reaction

microvoid

Figure 2-9: LPA mechanism initiation reaction, (2) micro-gelling, (3) intra and inter-particle reactions experienced during the polymerisation process, (4) the role of the micro-void formation

In the UP/St/LPA system, a reaction-induced phase separation occurs during curing, resulting in a UP-rich phase and an LPA-rich phase. If microvoids can form in the LPArich phase or at the interface of the two phases, polymerization shrinkage can be reduced or eliminated without any thermal effect [65-67]. Recently, researchers have found that 30

adding silica based nanoclays to resin systems tend to improve the shrinkage control for these systems. It was found that the reaction rate of the LPA rich phase is much lower than that of the UP-rich phase because of the high St/UP ratio (i.e. the StSt reaction is much slower than the StUP copolymerization) and the low cobalt promoter level in the LPA-rich phase (i.e. the cobalt promoter has a higher solubility in the UP-rich phase during partitioning). Since a liquid LPA phase can release stresses resulting from polymerization shrinkage of the UP rich phase, the stress-induced local cracking in the LPA-rich phase or at the interface of the two phases will not occur until after the gelation of the LPA-rich phase. This local cracking leads to volume expansion of the curing system, thereby compensating some of the polymerization shrinkage [67]. It has been suggested that increasing the reaction rate in the LPA-rich phase could result in an earlier microvoid formation/volume expansion in the system for better shrinkage control [67]. An acid-modified LPA [67] was shown to have the ability to attract more cobalt promoter to the LPA-rich phase, resulting in a higher reaction rate in the LPA-rich phase. The dilatometry results demonstrated that acid-modified LPA provided earlier volume expansion and better shrinkage control. Cao et al. [68] found that the addition of a secondary monomer such as methyl methacrylate or a co-promoter such as 2,4pentanedione can also improve the shrinkage control of the UP/St/LPA systems because the presence of the co-promoter and co monomer has a more pronounced effect on increasing the reaction rate in the LPA-rich phase than in the UP-rich phase. Rudd [17] and Xu [43] showed that addition of nano clays to the resin matrix improves the volumetric shrinkage control when compared to UP/St/LPA resin systems.

31

Figure 2-10: Volume change profile of UP/St/LPA system with different Cloisite 20A content cured at 35 8C (0.5% cobalt octoate, 1.5% MEKP, 300 ppm BQ, and 3.5% LPA) [43].

Xu and Lee [43] have tried to study the effect of partition of nanoclays on the reaction kinetics and chemorheology of the LPA rich and UP rich phases. They implemented temperature induced phase separation method as a qualitative assessment for the nanoclays selectivity and behaviour of the two important phases. It was observed that almost all the nanoclay chose the LPA-rich phase during temperature-induced phase separation and that the conversion of the UP-rich phase when the LPA-rich phase reaches gelation was lower in samples with nanoclays. In the UP/St/LPA system with nanoclays, the UP-rich phase was seen as continuing to react after the gelation of the LPA-rich phase. This polymerization shrinkage may lead to micro-cracking in the system to compensate some of the volume shrinkage.

2.3.5.

Cure Kinetics

32

In this section, the effect of nanoclays on five different characteristics related to the cure kinetics of UP resins will be discussed: onset of reaction, peak temperature of the exotherm during cure, total heat of reaction, reaction rate and final degree of cure. A considerable amount of research was done on each of those subjects. However, results vary, as will be seen in the following paragraphs. A differential scanning calorimeter (DSC) is commonly used to characterize the cure kinetics of resin systems. This technique measures the heat generated during the polymerization reaction, which is highly exothermal. Before cure, the system contains styrene, UP molecules and curing agents (i.e. a catalyst and an accelerator). As the polymerization reaction progresses, UP molecules form polymer chains by linking the styrene monomers.

Figure 2-11: Heat flow for various nanoclay content as obtained from DSC runs by Hussain [69]

Most researchers agree that with the addition of the organoclay to the resin system, the nanocomposites showed lower curing onset temperature. Moreover, the temperatures in

33

the exothermal heat peak for nanocomposites are shifted to lower temperatures. This demonstrates the catalytic effect of nanoclay on the cross-linking reaction of the resin with curing agent [43, 69, 78]. The filled Org-MMT reduces the gelation time and increases the rate of the curing reaction while reducing the total heat of reaction (Figure 2-11). This is believed mainly due to the fact that montmorillonite acts as a free radical scavenger, adversely affecting the crosslinking process and decreasing the cross-link density. Therefore, researchers have linked the reduction in total heat of reaction and the cure activity to increase in the intercalation of the cure particles into the silicate galleries.

2.4. Literature review summary

The literature review reported effects of various synthesizing methodology, compatibility of different clays to different resin systems (based on their organic treatment), mixing techniques on the dispersion of clays in resin systems. Almost all researchers employed X-ray diffraction analysis to characterize dispersion and study these effects. Three synthesizing methodologies were seen in the literature. While most researchers emphasized the compatibility of the materials as a prime factor in the choosing the method, there were some who were able to show that the sequential mixing techniques are more suited to styrenated polyester systems when compared to the simultaneous mixing method. It was seen that mixing techniques (like ultrasonication, shear mixing and static mixing) involve many parameters like time, temperature, amplitude and shearing levels that affected the dispersion of the clays. It was seen that increasing the time and shearing levels generally increased the intercalation levels resulting better dispersion. However, no direct correlation could be found between the effects of temperature on the intercalation levels. There was a considerable amount of discrepancies seen in the literature in regards to the physical and mechanical properties of the synthesized nanocomposites. Most researchers reported an increase in viscosity on addition of nanoclays and tried to correlate X-ray diffraction results (intercalation) to increase in viscosity. Some work was also done to measure the shrinkage of UP/ St/LPA based nanocomposites and it has been reported that the addition of clays enhance the shrinkage control of UP. However, when measuring the

34

glass transition temperature, opposite trends were seen amongst various reports. The increase of glass transition temperature due to incorporation of nanoparticles was explained by a strong adhesion between polymer and particles. This strong adhesion restricted the motion near the organic-inorganic interface, which shortened the polymer chain (increase in thermal stability). In the same way a decrease in Tg was linked to the weak adhesion between the clay particles, which generally resulted in lower cross-link density and longer polymer chains which caused a decrease in the Tg. This lower cross link density was due to the consumption of the free radicals by the clays which tend to reduce the total heat of reaction during the cure kinetic analysis of nanocomposites which has been seen by the lower peak of the heat flow curves. Papers have generally agreed that the addition of clays have a catalytic affect on the cure kinetics of the resin, resulting in early curing onset temperature and the exothermal peak has been shifted to a lower temperature. It has been seen that the storage modulus increased with the addition of nanoclays due to the high aspect ratio and high elastic modulus of the clays. Other mechanical properties like the youngs modulus and the ultimate tensile strength are a topic of debate amongst the researchers. However, it can be said with certainty that the degree of dispersion (degree of intercalation or exfoliation) of clays and the clay-resin interaction has been linked directly to the behaviour of mechanical properties. To improve this clay-particle interaction and the dispersion of the clays various parameters have been studied by researchers. As mentioned earlier, shearing level and applied amplitude, mixing time and temperature has been in the focus for researchers. These studies have been conducted on epoxy systems quite extensively. However, the mixing of UP-clay resin systems cannot be found extensively within the literature. Also the relatively new sequential mixing method has been said to have great potential for polyester resin systems and it provides a good potential for some future work.

2.5. Research Objectives and Approach

The long term objective of the research is to obtain better shrinkage control and improved glass transition temperature by using nano-modified resins or nanocomposites. However, due to various possibility of synthesizing the nanocomposites, it is necessary to study the synthesis and mixing techniques involved with making nanocomposite systems.

35

Therefore, this thesis will study the effects and various parameters involved in mixing UP resin with silicate nanoclays. This will help establish a good understanding of the various synthesizing technique first and then choose the suitable technique for the pre-formulated polyester resin. The next step will be to compare different mixing techniques like ultrasonication and three-roll mill for this polyester resin and study the effect on the clay dispersion. This will be done using X-ray diffraction and then some basic rheological tests. These techniques have various parameters that will be needed to be studied. These parameters are discussed here in brief. Ultrasonication parameters to be considered: Frequency type: Frequency to be used is has to be established. Degassing (sinusoidal) frequency applies sinusoidal frequency to the sample while ultrasound (constant frequency) applies constant frequency to the samples in order to disperse the clays. Power (amplitude): The ultrasonication machine available for this research has fixed amplitude. Hence, variations in amplitude will not be possible. Temperature: temperature will be fixed at 50C to ensure temperature rise due to ultrasonication does not interact with the results. No variation in the temperature will be made as research time was a constraint. Time: the effects of the sonication time will be studied by in order to establish an optimum mixing time that would be useful to then compare the dispersion with the three Roll Mill (TRM) Amount of nanoclays: 4 wt% clay will be used to make sure the effects of clays are clearly visible when comparing it with three roll mill (TRM) The three roll mill (TRM) parameters to be considered are: Speed: speed of rotation is fixed on the TRM available for this research Amount of nanoclays: 4 wt% clay will be used to make sure the effects of clays are clearly visible when comparing it with three roll mill (TRM) Distance: the distance between the front roller and the center roll and the back roller and center roll will be adjusted for various samples. These samples shall be studied 36

Temperature: temperature control is not installed on the TRM right now. However, if the time and the resources permit, it will be installed and the temperature will be set at 50C.

Number of cycle: different number of cycles shall be used to see the effect on dispersion.

These parameters are going to be adjusted and studied to establish an optimum mixing method (OMM) using the synthesizing technique chosen earlier. Once the OMM is established for this particular nanocomposite system, resin characterization tests will used to study the effects of the clay content. These tests will reveal the cure kinetics, rheological behaviour, modulus, glass transition temperature and volumetric shrinkage of nanocomposite system and help us understand the relationship between synthesizing techniques, material compatibility and material properties.

37

3. Experimental Procedures
In this chapter the materials used in this research will be described (Section 3.1). The experiments carried out to characterize the resin after the application of mixing technique as well the addition of nanoclays are also discussed in section 3.2.

3.1. Materials Used

Table 3-1: Materials used for research

Material Type Resin Clay

Name R580-ZPE-14 Cloisite 20 A

Description UP Resin Molecular weight: 800 900 g/mol Pre-promoted with LPA and promoter Modified with quaternary ammonium salt ~ 65 wt% C18, ~30 wt% C16, and ~5 wt% C14 Methyl Isobutyl Ketone Peroxide (MIBKP)

Vendor AOC Southern Clay Products Syrgis

Initiator

NOROX PULCAT AW

In this study, the polyester resin was reinforced with montmorillonite (MMT) clay particles to fabricate UP/LPA/St/Clay composite. The unsaturated polyester system was obtained from AOC Resin. The system chosen for this study was the R580-ZPE-14. R580-ZPE-14 is a unique low profile polyester resin system for use in resin transfer moulding (RTM) and other liquid moulding processes. R580-ZPE-14 offers (as claimed by the manufacturer) Class A smoothness for low volume application. R580-ZPE-14 is pre-promoted with cobalt for convenience. The base resin for this pre-formulated, premixed system is the T580-63 by AOC. Unfortunately, due to proprietary issues, the exact quantities of the LPA and promoter added to the R580 system are unknown. Organically treated MMT clay was obtained from Southern Clay Products Inc. Cloisite 20A (basal spacing 24.9 ) was used for this study. It consisted of natural MMT modified with a dimethyl, dehydrogenated tallow (containing ~ 65 wt% C18, ~30 wt% C16, and ~5 wt%

38

C14) quaternary ammonium salt. Cloisite 20A contains about 38 wt% of organic modifier. The organic treatment modifies the clay surface from hydrophilic to hydrophobic which could make them compatible to the resin system to assist inter-gallery absorption (that would enhance properties). To initiate polymerization (curing), 1.5 wt% of a free radical initiator, MIBKP was added.

3.2. Resin Characterization

3.2.1. Sample Preparation to develop optimum mixing method (OMM)

The sample preparation for section 3.2.2 will be discussed here. The samples are prepared by adding 4 %wt of Cloisite 20A to the pre-formulated resin R580 in a plastic container and mixed manually using a metal rod until a homogenous mixture is achieved. The synthesizing technique used for this type of the resin is only limited to the in situ (simultaneous mixing method) since the resin is already pre-formulated (i.e. the styrene and the thermoplastic LPA are already added in quantities not disclosed due to propriety issues). The reason to use 4%wt is to ensure any effects of adding clays in terms of the dispersion could be seen. Also, it can be seen that typical quantity of clays used are between 1 wt% and 10 wt% with majority of the systems showing optimum improvements around 4wt % or 5 wt% nanoclay [17]. Two mixing methods were used to disperse the nanoclays into the resin system via the simultaneous synthesizing method. The three roll mill (TRM) used (Figure 3-1) for this study was obtained from Torrey Hills Technologies, LLC (The model is S2.5). At the beginning of the processing, the feed (slow) and the apron (fast) roll were set manually. One of the parameters involved in this study was the effect of the roller distance on dispersion. Hence, using the adjustment screws the distances between the apron (fast) roller and the mid roller and the feed (slow) roller and mid roller were adjusted according to the requirement. The speed of the rolls was fixed in this model and no temperature control had been installed. The speed of the feed (slow) roller was 31 rpm, the center roller 84 rpm and the apron (fast) roller was 174 rpm with each roller diameter of 6.35 cm. The distances between the rollers were chosen in accordance to the manufacturers 39

recommendation for efficient and safe operation. The eccentricity of the roller was roughly 10m, which was a major constraint for adjusting the distance between the rollers (the minimum distance used was 40m as suggested by the laboratory technician). Material was transferred from the center roll to the apron roll by adhesion and removed from the apron roll by a wooden stick that runs against the roll. The dispersion is achieved by the shear forces generated between adjacent rolls. The parameters that were adjusted between different samples were the number of passes and the distances between the rollers. Table 1 summarizes the parameters used for mixing.

Figure 3-1: The three roll milling machine with all its major features and components [93].

40

Table 3-2: Summary of mixing techniques and parameters tested on resin mix with 4 wt% of Cloisite 20A.

Sample Name Ultra_60 Ultra_30 TRM_F40_B100 TRM_F60_B150 TRM_F80_B200 3Pass_F40_B100 1Pass_F40_B100

Mixing Technique Temperature (C) Ultrasonication 50 Ultrasonication TRM TRM TRM TRM TRM 50 25 25 25 25 25

Parameter Tested Mixing time (60 minutes) Mixing time (30 minutes) Roller distance (F= 40 m; B = 100 m) Roller distance (F= 60 m; B = 150 m) Roller distance (F = 80 m; B = 200 m) Number of passes (3 passes) Number of passes (1 pass)

Ultrasonication method used in this study, generates alternating low-pressure and high pressure waves in liquids, leading to the formation and violent collapse of small vacuum bubbles. This phenomenon is termed cavitation and causes high speed impinging liquid jets and strong hydrodynamic shear-forces. These effects are used for the deagglomeration and milling nano-size clays as required for better dispersion of these clays in to the resin system. Ultrasonication was applied for 30 minutes and 60 minutes, and the organo-clay content was 4 wt% of the final composite composition. The ultrasonication used in this study was a D-78224 Singen/Htw by ELMA. A sinusoidal frequency was applied during this process at a temperature of about 50C to avoid any localized heating effects. The mixing process involves the mixture in a closed container, thereby minimizing any possibility of styrene evaporation. The mass of the samples were measured before and after ultrasonication process confirmed that less than 0.1% of mass loss was caused by this mixing process.

41

Figure 3-2: The mould used to cure samples used for X-ray analysis and DMA testing.

The samples described in Table 3-2 were cured by adding 1.5% of the MIBKP catalyst and pouring the sample into a mould (see Figure 3-2). The mould consisted of a Teflon insert which had 12 openings, each of which was 50mm x 4mm x 2mm (L x W x D). A Thermal Product Solutions (TPS) oven (model PRO 750) was used to cure the samples using the following cure cycle. The mould has an opening for pressure inlet. This opening was connected to the air pressure supply through a pressure regulator. The regulator was set to provide a pressure of 551.58 kPa (80 psi). The samples were cured with a ramp from 25C to 80C in one hour followed by a hold at 80C for one hour and then cooled down to 25C in one hour. During this entire curing process, the pressure was kept constant at 80psi. After cool down the samples were removed from the Teflon inserts and stored away in zip lock bags to be used later for x-ray analysis and DMA tests.

3.2.2.

X-ray diffraction

As seen in literature commonly, X-ray diffraction has been used to study the dispersion on nanoclays with in the system. The X-ray diffraction (XRD) was performed at McGill University on a Max 3100 X-ray generator with Cu radiation (40KV, 20mA) in the small angle X-ray scattering mode (SAXS). Diffraction was performed from 2 to 10 at a scan rate of 1/min with a step size of 0.05. The diffraction beam was monochromated before 42

detection. The clay powder and clay-UP samples were placed on a sample holder using clay. The sample (17mm x 12mm x 2mm) was made by using a mould that consisted of a Teflon insert. The Teflon insert had 12 openings, each of which was 50mm x 4mm x 2mm. Three samples were then cut to length (17mm) using a blade and placed together on the sample holder to achieve an equivalent width of about 12mm.

3.2.3.

Sample preparation for to characterize the effects of nanoclays

Once the optimum mixing method (OMM) has been established, the next step was to characterize the resin and study the effects of adding Cloisite 20A nanoclays to the R580 pre-formulated resin using the OMM. For the following sections, the resin sample was prepared by adding the 0wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt% and 5 wt% of Cloisite 20A nanoclays into the resin and mixing it manually until a homogenous mixture was obtained. Once this homogenous mixture was obtained, the optimum mixing method (OMM) that was developed in section 4.1 was applied to each sample in order to uniformly disperse the clays into the mixture and characterized the system using cure kinetics, viscosity measurements, dynamic mechanical analysis (DMA), glass transition Tg measurements and volumetric shrinkage measurements. These techniques are discussed in the following sections.

3.2.4.

Cure kinetics

A TA Instruments Q100 differential scanning calorimeter was used to determine the heat of reaction and cure kinetics of UP/LPA/St/clay resin samples. This task was assisted by the Universal Analysis software provided by TA Instruments. A two-step calibration was performed before the series of tests. The cell resistance and capacitance calibration was carried out using two equal weight sapphire discs. Cell constant and temperature calibration was then conducted using pure indium. The resin scans were performed on samples having a mass between 5 mg and 15 mg, with an average of 12.96 1.98 mg, sealed in hermetic aluminum pans withstand 2 atm internal pressure before being sealed and placed in the DSC. Dynamic scans from room temperature to 220C at a rate of

43

3C/min were used in nitrogen atmosphere to determine the resin total heat of reaction. The total reaction exotherms were calculated from the area under the scanning DSC heat flow curves (Eq. 3-1). The exotherms data can be converted to reaction rate and degree of cure as a function of time by assuming that the total reaction exotherm corresponds to a fully cured resin or a degree of cure of one. The dynamic scans were performed on resin with 0 wt%, 2 wt%, 3wt%, 4 wt% and 5 wt% of nanoclays. Two samples were prepared according to the procedure described in Section 3.2.3 and polymerization was initiated by adding 1.5% of MIBKP , for a total of ten DSC samples.

H (t )dt H (t )dt
0

H (t ) Hr

(Eq. 3-1)

3.2.5.

Rheology and volumetric shrinkage measurements

The AR 2000 Series rheometer from TA Instruments was used in association with the Rheology Advantage Data Analysis software to measure the viscosity and volumetric cure shrinkage of the resin through a modified procedure. The viscosity tests were performed first to study the effects of the two mixing methods discussed in Section 3.2.1 on the resin system by using a flow test and then later study the effects of adding nanoclays on the viscosity (sample prepared as discussed in Section 3.2.3). The viscosity () of a liquid is then defined as the stress divided by the rate of change of strain (d/dt). Newtons original postulate can then be phrased as that the viscosity of a material is constant: the stress is proportional to the flow rate. The more easily a liquid flows, the lower the viscosity. Parallel plate arrangement (25mm in diameter) was used at 25C to study the effect of viscosity with shear rate. Figure 3-3 shows the 25 mm diameter parallel plate setup. Calibration procedure including rotational mapping, inertia of the plates (1.17 0.04 N.m.s2) and zero gap was performed before each test. The shear rate was varied from 44

0.1 s-1 to 10 s-1 in flow test and the variations of viscosity were studied. Steady state flow mode was used, which applies successive shear values and data is sampled at equilibrium conditions of 25C. The rheological tests were conducted on uncured resin samples. The main features of such curves are most easily seen if the data are plotted on logarithmic axes (i.e. with 0.1, 1, 10 etc. equally spaced). For parallel plate geometry, the shear rate and the shear stress experienced by the sample vary with radial position, and the viscosity calculated is Newtonian equivalent i.e. the assumption is made that viscosity is independent of the shear rate. The exact viscosity is then obtained by using the stress correction transformation in the rheology advantage data.
Normal force Fz

Rotating plate Gap

Fixed plate

Figure 3-3: Parallel plate setup on the rheometer

The volumetric shrinkage tests were carried out at 40C for the pre-formulated R580ZPE-14 resin system in accordance to the resin manufacturers guidance. However, some tests were also required for the base resin. These tests were conducted at 80C as guided by the technicians. When the temperature reached a steady state, the resin was injected between the plates in order to obtain in initial gap of approximately 1000 m. Due to the viscous resin, the volume of each sample was hard to control precisely. Before gelation, the rheometer was set to oscillation mode at the desired isothermal temperature of 40C with a maximum angular strain of 15% at 0.2 Hz. When the viscosity | *| reached 1000 Pa.s (this where G and G cross over), the second step was initiated, which set the

45

normal force applied on the sample to 0.1 N. This procedure was designed to measure the shrinkage based on the gap change between the parallel plates. A constant force was applied on the resin sample throughout its shrinkage after gelation. The volumetric shrinkage was calculated using Eq. 3-2, based on the assumption that the resin was incompressible with a constant Poissons ratio of 0.5 [44]:
3

1 h h0 v = 1 + 3 h0 time and h0 (m) is the initial gap.

(Eq. 3-2)

where v is the volumetric strain or shrinkage, h (m) is the gap between the plates at any

3.2.6.

Dynamic mechanical analyzer (DMA)

The storage modulus and the loss modulus of the UP/LPA/St/Clay mixture were measured as a function of temperature using the DMA in flexion mode. The DMA used was a Q800 from TA Instruments. Dynamic mechanical analysis of the sample beam in single cantilever bending mode was performed and the elastic modulus values were obtained as a function of the test temperature. Material was heated at a constant rate. While heating, the material is deformed (oscillated) at a constant displacement (amplitude) over a range of frequencies and the mechanical properties measured. The temperature range over which these results were analyzed were between 30C and 140C. The compliance of the apparatus was less than 0.6 m N1 which was determined by a prior calibration of DMA in single cantilever mode. The moment applied to the sample was set at 0.9Nm with average sample size of 17.6mm x 3.85mm x 2mm.The samples were cured with a ramp from 25C to 80C in one hour followed by a hold at 80C for one hour and then cooled down to 25C in one hour. The amplitude for these studies was determined by studying the linear viscoelastic region using with a frequency of 1 Hz. The linear region can be measured for a material using a strain sweep test. In a strain sweep test, the frequency of the test is fixed and the amplitude is incrementally increased. Once the storage modulus and the loss modulus were obtained for samples with clay content

46

0%, 2%, 3%, 4% and 5%, the glass transition temperatures for these samples were defined as the onset temperature for decrease in the storage modulus.

47

4. Results and discussions

This section will look at the results obtained as per the experimental plan in appendix A. Section 4.2 discusses the results obtained from the two mixing techniques, ultrasonication and shear mixing using the three roll mill. Section 4.2 discusses the rheological properties as a result of applying these mixing techniques and identifying the optimum mixing method (OMM). Section 4.3 discusses the rheological properties of nanocomposites as a function of nanoclay content, section 4.4 discuses the volumetric shrinkage, section 4.5 displays the mechanical properties and section 4.6 shows the cure kinetics.

4.1. X-ray diffraction

In this section, X-ray diffraction was used to study the crystallographic spacing of the silicate layers as they are dispersed into the R580-ZPE-14 resin system using the ultrasonication and three-roll milling machine. The first part of this section consists of identifying the best dispersion results from each of the mixing techniques (ultrasonication and three-roll mill) and then comparing them to each other. Two set of samples were prepared as discussed in section 3.2.2. Both results obtained were identical; therefore, one was selected to be displayed here. The incorporation of nanoscale-layered silicates within thermosetting resins presented unique challenges. Curing of thermosetting involves the interaction of chemical kinetics (as explained in section 2.2.2) and the changing physical and mechanical properties. Near vitrification, the kinetics is affected by the local viscosity. The viscosity, in turn, is a function of the temperature and the extent of reaction. In thermal cures of nanocomposites, the level of exfoliation or intercalation of the silicate layers maybe impacted by the competition between the growing network formation, which tend to impede the ability of silicate layers to separate, and the lower viscosity, which will tend to ease physical separation of silicate sheets. Once cross-linking proceeds, the molecular weight of the resin and the viscosity increase, both of which will impede silicate mobility, and hence exfoliation.

48

The position of the initial peak provides information on the size of the developing structure through the relationship between basal plane separation, d and the wavelength (Braggs law, Eq. 2-1). The relative intensity provides information on the number of scattering structures, regardless of whether they are oriented aggregates or individual sheets and the peak breadth provides information on the scattering domains. Broader peaks correspond to smaller scattering domains, sharper peaks to larger domains.

4.1.1.

Effect of TRM roller distance

The first sets of mixing procedures were carried out by adjusting the roller distances on the three-roll milling machine. Cloisite 20A nanoclay was mixed at room temperature with clay content of 4 wt% of R580-ZPE-14 as described in section 3.2.1. The ratio of distance between back roll and center roll to the distance between front roll and center roll was always kept constant at 2.5:1. This was to make sure to eliminate any inconsistencies that may result if this ratio is altered. During the application of the TRM, we have experienced some difficulties. The major concern was the styrene evaporation from the polyester resin during the processes, which caused a dramatic increase of the viscosity. Styrene evaporation was accelerated due to heat occurred on the rolling mills due to higher shear effect. The polyester resin with high viscosity stacked on the rolls and it caused some difficulties for the collection of the resin, due to the uncontrolled styrene evaporation, and thus the final styrene compositions with in the resin blends were unknown. Similar problems may have occurred while applying the sonication technique, but less than 0.1% change in mass was observed for this technique, indicating negligible styrene evaporation. Figure 4-1 shows the X-ray diffraction spectra for Cloisite 20A composite with clay loading of 4 wt%. A prominent peak corresponding to the basal spacing of pure Cloisite 20A occurs at a d spacing (interlayer spacing) of 2.4 nm (3.32 2) is clearly seen (calculated using Eq. 2-1). As seen from Figure 4-1 the distances between the rollers have a significant effect on the level of exfoliation. The shift in the peak and the broadened peak with less intensity are characteristic of increasingly disordered intercalated structures (i.e. a decrease in the degree of coherent layer stacking). As the distance between the rollers decreases, the peak intensity decreases and

49

shifts slightly to lower angles, indicating increased d-spacing which has been linked to intercalated/ exfoliated structures. However, as mentioned earlier, the increased shearing effect due to smaller roller distances have caused styrene evaporation leading to rapid increase in viscosity. This rapid increase in viscosity will hinder exfoliation (as discussed in the next section).

TRM F=80 B=200 TRM F=60 B=150 TRM F=40 B=100

Intensity (a.u.)

Cloisite 20A

6 7 2 (Degrees)

10

Figure 4-1: Effect of the roller spacing on dispersion of the resin with 4 wt% Cloisite 20A

4.1.2.

Effect of mixing time

The following set of experiments was performed to evaluate the effect of time (or number of passes for the TRM) on the dispersion of the nanoclays. As seen in section 2.2.4 the mixing time has a significant influence on the dispersion of nanoclays in the resin system. Figure 4-2 shows the effect of number of passes when using the TRM and the different mixing times when using the ultrasonication. As expected, the peak intensity decreases with the increase in number of passes while the roller distance is kept constant leading to a better intercalated system. With each additional pass the nanoclay resin system is subjected to additional shearing resulting in increased penetration of the resin into the silicate layers. A more detailed insight suggests that stress induces the break up of large

50

clay particles into dispersed stacks of silicate tactoid, followed by additional shearing of tactoid into smaller stacks of silicate platelets. Similar results are seen for the TRM and shear mixing techniques [14, 33, 40, 85]. Figure 4-2 also shows the XRD pattern for different sonication times. There is a reduction in the intensity for increased sonication time. This again reflects that increasing the sonication time leads to increased intercalated mixtures which can be seen from the broadening of the peak (which reflects smaller scattering domain), shift of the intensity peak to lower angles (increased interlayer spacing) and slight increase in viscosity. Finally, the two mixing techniques are compared in Figure 4-3. The results clearly favour the sample from ultrasonication as it shows better dispersion. One of the factors for this result could also be the increased viscosity of the mixture during the TRM process due to styrene evaporation. It is believed that an increase in viscosity will impede the ability of silicate layers to separate and form exfoliated structures. However, it would be interesting to see the effect of using sequential mixing (styrene and LPA added post mixing) on the dispersion of clays in polyester resin. Table 4-1 displays the d-spacing of the various samples under consideration. Although the d-spacing remains the same for ultrasonication sample (Ultra_60) and TRM sample (TRM F=40 B=100), the reduced intensity and broadened peak for the Ultra_60 sample confirms better dispersion.

51

Intensity (a.u.)

Ultra_30min Ultra_60min TRM 3 passes TRM 1 pass Cloisite 20A

6 7 2 (Degrees)

10

Figure 4-2: XRD patterns showing the effect of time (ultrasonication) and number of passes (TRM) for 4 wt% Cloisite 20 A. Table 4-1: XRD analysis showing the d-spacing for different samples

Sample name Cloisite 20A Ultra_60 Ultra_30 TRM F=40 B=100 TRM F=60 B=150 TRM F=80 B=200 TRM F=40 B=100 3 Pass TRM F=40 B=100 1 Pass

Mixing technique Ultrasonication Ultrasonication TRM TRM TRM TRM TRM

Parameter tested d spacing (nm) 2.4 Mixing time 3.89 (60 minutes) Mixing time 3.63 (30 minutes) Roller distance 3.89 (F= 40 m; B = 100 m) Roller distance 3.63 (F= 60 m; B = 150 m) Roller distance 3.47 (F = 80 m; B = 200 m) Number of passes 3.47 (3 passes) Number of passes 3.39 (1 pass)

52

TRM F=40 B=100 - 3 Pass Ultra_60min Cloisite 20A

Intensity (a.u.) 2

6 2 (Degrees)

10

Figure 4-3: XRD Pattern comparing ultrasonication and TRM methods 4 wt% Cloisite 20A

4.2. Rheological behaviour during mixing process

This section discusses the results showing the viscosity variation due to the application of the different mixing techniques and compliments the discussions in previous section. It is well known that the level of exfoliation affects the viscosity. Hence this section will be used as another tool in identifying the technique which results in greater level of exfoliation.

53

100

10 Viscosity (Pa.s)
TRM - 1 Pass Ultrasonication 60 min TRM - 3 Pass Neat Resin

0.1

0.01 0.1 1 Shear Rate (1/s) 10

Figure 4-4: Viscosity as a function of shear rate for different mixing techniques at 25C

Viscosity (Pa.s)

``

Shear Rate (1/s)

Figure 4-5: Schematic of the variation in viscosity as a result of the mixing process. This schematic summarizes the different effects that change the viscosities. Solid line is neat resin; round dots is ultrasonication for 60 minutes; long dash dots is TRM 1 pass; square dots is TRM 3 pass.

Exfoliation

Exfoliation + styrene evapouration

54

As seen in Figure 4-4, mixing techniques clearly have an effect on the viscosity. While samples from all different mixing techniques showed a significant increase in the viscosity, the change for each sample was different. The samples from the TRM process showed the most increase in viscosity when compared to the ultrasonication samples. As discussed previously (section 4.1), the increase in viscosity can be linked to a combination of increased exfoliation of the clay particles into the resin system and styrene evaporation. When we consider the results discussed in section 4.1 (where the Xray diffraction results showed better dispersion for the sonication samples (Figure 4-3)) it can be concluded that styrene evaporation was the dominant factor for the increase in viscosity in TRM samples. Since, the change in mass for the sonication samples was less 0.1%, the viscosity increase of these samples when compared to the neat as received resin system can be related to increased levels of exfoliation (also confirmed by X-ray diffraction results in section 4.1). Similarly, when we compare the TRM viscosities only, it can be seen that increasing the number of passes increases the viscosity. At the same time, Figure 4-2 confirms better dispersion with the increase in number of passes. So it can be said about the TRM that styrene evaporation along with exfoliation affects the viscosity. Figure 4-5 shows a schematic of the effects that causes the increase in viscosity. As discussed earlier, for ultrasonication technique, there is no styrene evaporation. However, there needs to be more work done that will establish the quantity of styrene evaporation. Sequential mixing method that involves addition of styrene and LPA after the mixing process is one such method. A base resin can be mixed with the clays and the change in viscosity can be measured. This change in viscosity can then be directly associated with exfoliation only. Therefore, with the simultaneous mixing method TRM does not provide conclusive and satisfactory dispersion. These results are significant, indicating the potential of the sequential synthesizing technique for UP based nanocomposites, where process such as TRM can be tested and utilized. In such cases, the increase in viscosity can be used as an alternative tool (or as a verification process) to measure the dispersion of clays in UP-clay systems.

55

4.3. Rheological behaviour on addition of nanoclays

In order to quantify the performance of the liquid resin mix tested for this work, the viscosity increase due to the presence of nanoclays has been characterized using a parallel plate rheometer. In liquid composite moulding, the viscosity of the resin is very important in order to ensure proper impregnation of the fibrous reinforcements. A large increase in viscosity induces slower impregnation of the reinforcements that results in longer cycle time or improper impregnation which could cause a decrease in mechanical properties.

4.3.1.

Rheological characterization of pre-promoted unsaturated polyester

This section determines the behaviour of the resin as received from manufacturer. It is important to see if Newtonian behaviour is observed for this resin. The test was carried out by studying the viscosity as a function of the shear rate. The shear rate was varied between 0 10 s-1. The result of the change in viscosity as a function of shear rate is shown in Figure 4-6. As seen in Figure 4-6 the viscosity tends stay constant with increase in the shear rate. This is typical of a Newtonian fluid, which states that the stress is proportional to flow rate.

56

1
R580-ZPE-14

Viscosity (Pa.s)

0.1

0.01 0.1 1 Shear Rate (1/s)

Figure 4-6: Characteristic Newtonian behaviour of the as received R580-ZPE-14 resin system. Tests were carried out at 25C

10

4.3.2.

Effect of adding nanoclays on viscosity

Figure 4-7 displays the viscosity of the resin system with clay content 1 4 wt% as a function of the shear rate. The scattered data and initial high values are due to instability of the flow at these frequencies. It is important to mention here that the rheometer used in this experiment makes an assumption of Newtonian behaviour in regards to the liquid. Therefore the results should only be interpreted in relative terms and not in absolute terms.

57

100

10 Viscosity (Pa.s)

1 wt% 2 wt% 3 wt% 4 wt% Neat resin

0.1

0.01 0.1 1 Shear Rate (1/s) 10

Figure 4-7: Viscosity as a function of shear rate for different clay content at 25C using ultrasonication for 60 minutes at 50C.

As expected, there is an increase in resin viscosity with the increase in nanoclay content. This viscosity increase is related to the increase of the contact surface between the clay and the polymer molecules, which induces higher resistance during the shear stress. As the clay particles increase so does the clay-resin interactions, which cause an increase in resistance to flow, therefore increasing the viscosity. Further more, the change from Newtonian to pseudo plastic behaviour may also be attributed to the strong interaction between layered silicates and the polymer. The decrease in viscosity (shear thinning) with increased shear rate may be attributed to the orientation of the layered silicate particles parallel to the direction of flow. This reorientation of the clay particles causes the resistance to flow to decrease and hence cause a reduction in the viscosity. The increase of viscosity when compared to the original resin system also signifies the intercalation of the clay particles into the resin mix. However, other factors like styrene evaporation due to localized heating (which maybe hard to control with sealed mold or other practical methods) may also influence the viscosity.

58

4.3.3.

Effect of nanoclays on the gel point

It was seen in section 2.3.5 that addition of nanoclays changed the cure kinetics of the resin system. One way to establish the effect on the rate of cure reaction is to study the variation in viscosity with curing time. It is known that as the polymerization reaction occurs, the viscosity of the system increases as the polymer chains cross link and increases the density. Rheological tests carried out to study the shrinkage effects were used to study the change in viscosity. Before gelation, the tests were carried out in oscillation mode at isothermal temperature of 40C. The gel time was defined as the time when the viscosity, *, reaches a value of 1000 Pa.s. As seen from Figure 4-8, there is a significant difference in the rheological behaviour of the neat resin system and nano-modified resin system. One important observation made was that the viscosity had increased for both systems (when compared to its value at 25C, before the addition of the initiator) before the tests were initiated. This indicates that the system is unstable at room temperature and starts the polymerization reaction as soon as the initiator is added. This sort of behaviour prevents the observation of very initial stages of reaction. Hence, it should be taken into consideration for any future work that maybe carried out using this system. From Figure 4-8, it can also be observed that the increase is viscosity is much quicker for the nano-modified resin system as opposed to the neat resin system. The neat resin system reaches the gel point at about 230 seconds where as the nano-modified resin system with 4 wt% Cloisite 20A reaches the gel point in 106 seconds. Clearly, there is an increase in the reaction rate. This is agreement with the results obtained in the literature, where it is seen that the addition of clays in epoxy and polyester based systems has a catalytic effect. This means that the polymerization reaction proceeds much quickly. DSC results shown in section 4.6 will be used to verify these observations. However, it is important to mention that a decrease in the gelation time for an already fast acting system poses significant problems in terms of characterization and manufacturing.

59

1000

Viscosity (Pa.s)

100

10

0 wt% Cloisite 20A 4 wt% Cloisite 20A

1 0 50 100 Time (s)

Figure 4-8: Viscosity as a function of curing time until the gel point. Tests were carried out under oscillation mode at 40C.

150

200

250

4.4. Storage modulus

4.4.1. Determining the LVR (linear viscoelastic region)

The DMA tests were conducted under constant displacement mode. In order to use DMA to accurately determine mechanical properties and develop morphological relationships, the material must be deformed at an amplitude that is within the linear viscoelastic region of the material. Within the linear viscoelastic region, the materials response is independent of the magnitude of the deformation and the materials structure is maintained in tact (unbroken). Characterization of the material within the linear region yields a more accurate picture of the structure of the polymer. Therefore, any differences in the structure of polymers can easily be measured as differences in the dynamic mechanical properties. Special care should be given when selecting an amplitude for a DMA test. As a general rule of thumb, solids are linear at strains less then 0.1% (0.001 strain units). However, this is a general rule and may not apply to all samples so the 60

linear region may require verification. The linear region can be measured for a material using a strain sweep test. In a strain sweep test, the frequency of the test is fixed and the amplitude is incrementally increased. To determine the linear viscoelastic region, the storage modulus is plotted against the amplitude (in log scale) as the amplitude is the control variable, as show in Figure 4-9. The test was carried out 25C with the sample containing 3 wt% Cloisite 20A, in order to determine the linear viscoelastic region. As seen in Figure 4-9 the R580-ZPE-14 resin system has a linear region between the amplitude of 8 m and 25m, between which the storage modulus remains unchanged. Therefore, the displacement control tests were carried out at amplitude of 15m (approximate mid point of the LVR).

2.55 2.5 Storage Modulus (GPa) 2.45 2.4 2.35 2.3 2.25 1 10 Amplitude (m)
Figure 4-9: Storage modulus as function of amplitude at 25C. The sample contains 3 w% of Cloisite 20A prepared using ultrasonication for 60 minutes at 50C.

LVR Range 15 m

100

1000

4.4.2.

Effect of post cure

This section will briefly identify the effects of post cure on the storage modulus and loss modulus values. The sample was prepared first using 3 wt% Cloisite 20A as described in 61

section 3.2.3. This was used for testing to determine the effect of no post cure. Another sample prepared with same procedure as described earlier but then was post cure with a temperature ramp to 150C at 3C/min. The results are shown below in Figure 4-10. As seen below, there is a slight effect on the values from storage modulus and the loss modulus due to post curing. From the results below, we observe about a 10% decrease in both storage modulus and loss modulus at 30C. This is slightly surprisingly, as one would expect higher storage modulus as result of post curing (due to increased stiffness). However, the trend and behaviour is the same for both samples, indicating no obvious preference of one method over the other. Therefore, for future results, no post cure shall be applied.

3.5 3 Storage Modulus (GPa) 2.5 2

Storage modulus - post cure Storage modulus - no post cure Loss modulus - post cure Loss modulus - no post cure

180 160 Loss Modulus (MPa)

62

140 120 100 80 60 40 20 30 50 70 90 110 130 150 Temperature (C) 170 190 0 210

1.5 1

0.5 0

Figure 4-10: Effect of post curing on storage modulus and loss modulus for samples made with 3 wt% Cloisite 20A. The tests were carried out at 25C.

4.4.3.

Effect of nanoclays on storage and loss modulus

The storage modulus of the UP/LPA/clay polyester was measured using the DMA in single cantilever beam mode. The results are shown in Figure 4-11. Increasing the clay content has a stiffening effect on the storage modulus, although this effect decreases with increases in temperature. There is a significant improvement in the storage modulus as the clay content is increase from 0 wt % to 5 wt% (from 2.73 GPa to 3.15 GPa). This improvement of the flexural modulus was already observed and explained by several factors [40, 76]. It is known that these clays have high elastic modulus and high aspect ratio which contribute to the improvement of the material. It was also found that due to the mismatch of the CTE of the resin and the clay, a compression zone of a few nanometers was created around the nano-particles [76]. These compression zones improve the stress transfer between the polymer and the nanoclays thereby improving the modulus. Figure 4-13 along with Table 4-2 clearly shows about 16% increase in the storage modulus with only 5 wt% addition of nanoclays. The error bars shown in Figure 4-13 (and elsewhere) were calculated from the standard deviation calculated from the data set. Therefore, as seen in the literature, only a small amount of nanoclays can cause significant improvement in the storage modulus.

63

4.0
5 wt% Cloisite 20A

3.5 Storage Modulus (GPa) 3.0 2.5 2.0 1.5 1.0 0.5 0.0 30 40 50 60 70 80 90 100 Temperature (C)

4 wt% Cloisite 20A 3 wt% Cloisite 20A 2 wt%Cloisite 20A 0 wt% Cloisite 20A

110

120

130

140

Figure 4-11: Storage modulus as a function of temperature with the addition of Cloisite 20A. Samples were prepared by using ultrasonication for 60 minutes at 50C.

180 160 140 Loss modulus (MPa) 120 100 80 60 40 20 0 30 40 50 60 70 80 90 100 Temperatue (C) 110 120 130 140
5 wt% Cloisite 20A 4 wt% Cloisite 20A 3 wt% Cloisite 20A 2 wt% Cloisite 20A 0 wt% Cloisite 20A

Figure 4-12: Loss modulus as a function of temperature with the addition of Cloisite 20A. Samples were prepared by using ultrasonication for 60 minutes at 50C.

64

3.50

Storage Modolus (GPa)

3.25

3.00

2.75

2.50 0 1 2 3 4 5 Clay Content (%)

Figure 4-13: Increasing trend of the storage modulus with increase in clay content measured at 30C Table 4-2: Percentage increase in the storage modulus at 30C with addition of Cloisite 20A1

Cloisite 20A Content Storage modulus (GPa) Percentage change (%) 0 2 3 4 5 2.71 0.065 2.98 0.036 3.00 0.031 3.13 0.035 3.15 0.051 0.00 9.65 10.50 15.29 16.00

Errors are calculated from the standard variation for the data set

65

4.5. Glass transition temperature

4.5.1. Establishing evaluation criteria for the glass transition temperature (Tg)

The glass transition temperature is defined in many different ways. Some of these ways are; the onset point of the loss in storage modulus curve, half length of the storage modulus curve, peak of the tan delta curve or the peak of loss modulus. All these measurements can be made from the data obtained during the displacement control tests using the DMA. Although, some papers are found where the Tg is measured using the DSC, majority of the researchers prefer using the onset of drop in modulus or the half length of storage modulus curve, as the glass transition temperature. Figure 4-14 shows the method of evaluating glass transition temperature using the storage modulus and loss modulus curves. The onset point and the half length of the storage modulus curve, which is measured using the universal analysis software is defined as the glass transition temperature. Similarly, the peak of the loss modulus curve is identified using the software and is defined as another means to measure the glass transition temperature. It can be clearly seen these techniques provide different values for the glass transition temperature with the most conservative value obtained using the onset of drop in storage modulus. The values obtained using the half length method and the peak of loss modulus method are very close to each other. The following section will discuss the effects of adding nanoclays on the glass transition temperature using each of these methods, while comparing the general trend obtained. One of the other method common used to identify the Tg is the peak of tan delta curve. However, results obtained for the tan delta curves from the DMA show some unusual behaviour. As seen from Figure 4-15, there seems to be an initial increase (marked as unusual behaviour when compared to the literature) followed by a peak. Secondly, when we compare the values obtained by the methods outlined above, the value obtained by tan delta method is significantly higher. Therefore, in the following section only the first three methods (onset of drop in storage modulus, half length of storage modulus and peak of loss modulus) shall be used to identify the Tg.

66

3 2.5 Storage Modulus (GPa) 2 1.5 1 0.5 0 30 40 50 60

Storage Modulus Loss Modulus

160 Peak point: 104.53C 140 Loss Modulus (MPa)

67

120 Onset Point: 72.03C 100 80 Half length: 103.03C 60 40 20 0 70 80 90 100 110 120 130 140 Temperature (C)

Figure 4-14: Evaluation of glass transition temperature using storage modulus and loss modulus. The sample contains 0 wt% Cloisite 20A prepared using ultrasonication for 60 minutes at 50C.

0.3 0.25 0.2 Tan Delta 0.15 0.1 0.05 0 30 50 70 90 110 130 150 Unusual behaviour

Peak Point: 151.46C

170

190

210

Temperature (C)
Figure 4-15: Tan delta curve for 0 wt% Cloisite 20A prepared using Ultrasonication for 60 minutes at 50C. The peak of tan delta curve is known to correspond to the glass transition temperature.

68

4.5.2.

Effect of nanoclays

Table 4-3 shows the glass transition temperatures obtained using three different criteria, that is: onset of drop in storage modulus, half length of storage modulus and peak of loss modulus. It seen clearly that the trend is similar for all three criteria. All these criteria show a general trend of decrease in the Tg with increase in the clay content. As expected, the onset of the storage modulus provides the most conservative value for the glass transition temperature. For applications, this value is most critical and therefore, the onset point of drop in storage modulus will be used as the evaluation criteria (as is also preferred by many researchers). Figure 4-16 shows the results from using the onset of drop in storage modulus criteria and Table 4-4 shows the change in value for the glass transition temperature for the nanocomposite. As discussed in section 2.3.3 some researchers show improved glass transition temperature while some show a reduction both of which can be linked to the molecular interaction of the clay and the resin. The glass transition process is related to molecular motion at a structural level, which involves several molecular segments, Tgs are considered to be affected by both molecular packing and chain conformation (chain rigidity and linearity). Figure 4-16 shows that the Tg decreases as the clay content is increased. The lowest Tg was observed for 4 wt% of Cloisite 20A (-11.58C) as seen from Table 4-4. In general, an increase in Tg has been linked to the strong adhesion between polymer and the clays. This strong adhesion restricts the motion near the organic-inorganic interface, which may shorten the polymer chain (increase in thermal stability). On the same note, a decrease in Tg has been linked to the weak adhesion between the clay particles, which generally results in lower cross-link density and longer polymer chains which causes a decrease in the Tg. Lower reactivity of resin (shown by results in the following section) generally results in lower cross linking density of the cured resin (and longer polymer chains) which are less thermally stable than shorter chains. Since loss modulus is defined as the energy dissipated into heat when a material is deformed, an increase in the loss modulus with increase in clay content as shown in Figure 4-12 signifies less thermally stable longer

69

polymer chains and lower cross linked density that was caused due to the reduced reactivity.
Table 4-3: Glass transition temperature as measured from three different criteria

Cloisite 20A Content 0 2 3 4 5

Half Length of Storage Modulus (C) 103.03 0.4325 101.97 0.4525 99.89 0.1750 98.47 0.2725 100.70 0.3550

Onset point of drop in storage modulus (C) 72.30 0.1850 72.02 0.3300 69.61 0.2800 60.72 0.3100 63.47 0.3150

Peak of loss modulus (C) 104.10 0.2150 103.29 0.3800 102.59 0.2050 98.20 0.4000 99.50 0.2050

For the R580 resin system used in this research, it is clear that the addition of Cloisite 20A has a decreasing trend for the Tg of the nanocomposites. This is because Tg can be significantly decreased by addition of nanoclays into the polymer matrix. Smaller molecules of the clays embed themselves between the polymer chains, increasing the spacing and free volume, and allowing them to move past one another even at lower temperatures.

70

74 72 70 68 66 64 62 60 0 1 2 3 Clay Content (%) 4 5

Table 4-4: Glass transition values measured using the half length criteria of the storage modulus

Temperature (C)

Figure 4-16: Glass transition temperature as a function of clay content at 30C. The onset of loss in storage modulus is used as the evaluation criteria

Cloisite 20A Content Glass transition temperature (C) 0 2 3 4 5 72.30 0.1850 72.02 0.3300 69.61 0.2800 60.72 0.3100 63.47 0.3150

Change (C) 0.00 -0.28 -2.69 -11.58 -8.60

4.6. Cure Kinetics

There are two factors which have opposite influences on the thermal stability of polyester-clay nanocomposites. Firstly, as most papers have proven that the addition of nanoclays to resin system have decreased their cure reactivity [56, 86], which can be also

71

demonstrated by the decreased glass transition temperatures, as shown in Figure 4-16. Secondly, some researchers have shown [72] silicate layers have a property to show good barrier to gases such as oxygen and nitrogen, they can insulate the underlying materials and slow the mass loss rate of decomposition products. Figure 4-17 clearly shows a reduction in the total heat of reaction (calculated from the area under the heat flow curve and normalized with the mass of resin for different clay loadings). This reduction in heat of reaction can be traced to the intercalation of clay particles within the resin which prevents cross-linking leading to lower reactivity. Lower reactivity of resin generally results in longer polymer chain (and lower cross linking density of the cured resin) which are less thermally stable than shorter chains. Since loss modulus is defined as the energy dissipated into heat when a material is deformed, an increase in the loss modulus with increase in clay content as shown in Figure 4-11 signifies less thermally stable longer polymer chains and lower cross linked density that was caused due to the reduced reactivity. Hence, the reduction of total heat of reaction, increase in modulus and reduced glass transition temperature are all results of structural effects caused due to the intercalation/ exfoliation of clays. These effects cause an increase in the length of the polymer chain and reduce the reactivity. Figure 4-19 shows the heat flow curves for the nanocomposite resin system with different nanoclay content. As seen from the curves, the onset temperature of the cure reaction and the peak, both shift to a lower temperature. This has been seen in the literature and it confirms the explanation that the addition of nanoclays to the resin has a catalytic effect, initiating the cure reaction at an earlier stage because of the longer polymer chains that are thermally less stable. Figure 4-18 shows the cure rate as a function of the degree of cure. The cure rate was calculated using the heat curves from the DSC and applying the following equation:

72

& & d (qbaseline qin ) m sample = dt H R (1 0 ) Where is the degree of cure, & qbaseline is the heat flow rate at the base line in J/s & qin is the heat flow rate from the resin sample from the DSC in J/s msample is the mass of the resin only in g HR is the total heat of reaction in J/g

Eq. 4-1

The degree of cure, is calculated by integrating the cure rate and the time. The graph shows the broadening and reduction of the cure rate as the clay content increases. Therefore, as seen in many of the previous work, the addition of nano-particles in the resin has a catalytic effect while decreasing the cure activity of the resin system.

400 Total heat of reaction (J/g) 360 320 280 240 200 0 1 2 3 4 5 Clay content (%)
Figure 4-17: Total heat of reaction as a function of clay content when using ultrasonication for 60 minutes at 50C.

73

0.0014 0.0012 0.001 Cure rate (1/s) 0.0008 0.0006 0.0004 0.0002 0 0 0.2 0.4 0.6 0.8 1 Degree of Cure
Figure 4-18: Cure rate as a function of degree of cure for various clay content mixed using ultrasonication for 60 minutes at 50C.

5 %wt Cloisite 20A 3 wt% Cloisite 20A 2 wt% Cloisite 20A 0 wt% Cloisite 20A

3.6 3.1 2.6 Heat flow (J/g) 2.1 1.6 1.1 0.6 0.1 -0.4 0 20 40 60 80 Temperature 100 120 140
5 wt% Cloisite 20A 3 wt% Cloisite 20A 2 wt% Cloisite 20A 0 wt % Cloisite20A

Figure 4-19: Heat flow curves for nanocomposites synthesized using ultrasonication for 60 minutes at 50C.

74

4.7. Volumetric Shrinkage

Volumetric shrinkage has been known to play an important role in the surface finish of the composite parts. Section 4.7.1 discusses the results of the effect of nanoclays on shrinkage, where as section 4.7.2 discusses styrene and LPA effects

4.7.1.

Effect of nanoclays on pre-formulated and pre-promoted resin

As explained in Section 3.2.5, the volumetric cure shrinkage of the resin was measured with a modified rheometer procedure. In step 1, no normal force was applied because the resin was still in its liquid state. It was assumed that there was no cure shrinkage, as is confirmed by the constant gap value. In step 2, the target force value of 0.1 N was reached after approximately 240 seconds (~4 minutes). The cure shrinkage or LPA expansion should cause a change in this normal force, which would be adjusted through the gap between the plates. However, as seen from Figure 4-20 the resin system under investigation does not show any shrinkage control (no typical phase separation and micro cracking behaviour is observed). This is believed to be so because the pre-formulated and the pre-promoted system do not under go the phase separation stage which is believed to be the driving mechanism for shrinkage control. However, further investigation into this is recommended as future work. Figure 4-20 also shows the result when R580 was mixed with 4 wt% of nanoclays using the optimum mixing method (OMM). As seen there is no significant improvement (only about 3% reduction) in the shrinkage control mechanism. This is because the nanoclays are believed to be useful in increasing the phase separation effect rather than initiating it. This means, that for nanoclays to have a significant impact on volumetric shrinkage, it is necessary to first have a phase separation mechanism. The nanoclays are then believed to be attracted to the LPA rich region, where they increase the reaction rate, causing an earlier on set of microvoid formation that causes an earlier onset of the shrinkage control mechanism. Six identical tests were conducted to check the volumetric shrinkage and similar results were obtained. Further investigation was halted due to insufficient

75

shrinkage control behaviour. Therefore it is important to first establish a working UP/LPA/St processing parameter for this resin system before adding the clays. However, it would be interesting to mix these clays with a UP/St/LPA system that has already shown some shrinkage control. Even though significant shrinkage control mechanism is not observed for these systems, there is a significant decrease in the volumetric shrinkage. The pre-formulated resin has volumetric shrinkage of about 11% where as the pre-formulated resin has a volumetric shrinkage of about 7-8%. This suggests that even though the clays in themselves do not have a great impact, they certainly provide some benefits in terms of the volumetric shrinkage. The pre-formulated resin R580-ZPE-14 does not show any shrinkage control and hence it will be useful to investigate the effect of styrene and LPA on the shrinkage control mechanism for this pure resin without the LPA, styrene and cobalt. Previous studies [44, 45] have studied the effects of styrene and LPA on the shrinkage control mechanism. Therefore, in due to time constraints and the scope of this research, only a few preliminary tests have been conducted to re-emphasize these effects and show how they affect the shrinkage control mechanism.

4.7.2.

Effect of LPA and styrene on shrinkage control of the base resin

As mentioned earlier, this section will discuss some preliminary results of the effect of styrene and LPA on the base resin used for the pre-formulated R580-ZPE-14. The base resin used was T580-63 also manufactured by AOC. The LPA used to for these tests was LP40-A containing 60% styrene and manufactured by Ashland. The choice of LPA and its initial value was used after studying Landrys work [94]. As mentioned in section 3.2.5, these tests were carried out at an isothermal temperature of 80C. Figure 4-21 shows the effects of adding LPA to the base resin. As it can be seen, with 15% LPA, the shrinkage reduces to about 6%. When the LPA quantity was increased from 15% to 25% the final volumetric shrinkage remains about the same. However, there is a slight hint of the shrinkage control mechanism (due to phase separation and micro cracks). The shrinkage control effect is seen as you see a sudden drop in shrinkage during the isothermal cure. Although, the final shrinkage remains the same, it can be concluded

76

that LPA/St interaction has changed (no microscopy tests were conducted but several literature papers [17, 60] could be found to confirm this) causing some phase separation and micro cracks.

14 12 Volumetric shrinkage (%) 10 8 6 4 2 0 0 1000 2000 Time (s) 3000

0 wt% Cloisite 20A 4 wt% Cloisite 20A

4000

5000

Figure 4-20: Volumetric shrinkage (shown as positive) for the R580 resin system and modified R580 system with 4 wt% Cloisite 20A at 40C

Similarly, Figure 4-22 shows how changing the styrene content affects the shrinkage of the base resin. As seen below in the figure, changing the styrene content by 5% displays a difference in the shrinkage behaviour. As discussed in section 2.3.4, the shrinkage behaviour during the curing of UP resin is dependent on the unique and optimum mix of UP/St/LPA. These properties have been extensively studied before and are highlighted in section 2.3.4. The results presented in Figure 4-21 and Figure 4-22 clearly shows how these parameters affect the shrinkage. Therefore, these results compliment the suggestions made in the previous sections in regards to the need to establish a good UP/St/LPA resin system. It is important to note here that these results are only preliminary findings and further investigation would be required to establish the optimum mixture of UP/St/LPA resin system using this base resin.

77

14

12

15%LPA+35%St 25% LPA + 35%St T580-63

Volumetric Shrinakge (%)

10

0 0 500 1000 1500 Time(s) 2000 2500 3000 3500

Figure 4-21: Effect of LPA on shrinkage control of T580-63 (base resin for R580-ZPE-14) at 80C
14
15%LPA+35%St 15%LPA+30% St T580-63

12

Volumetric Shrinkage (%)

10

0 0 500 1000 1500 Time(s) 2000 2500 3000 3500

Figure 4-22: Effect of styrene on shrinkage of T580-63 (base resin for R580-ZPE-14) at 80C

78

5. Conclusion
There are three main research objectives related to: a) Studying various synthesizing techniques and learning how to identify a suitable synthesizing technique, b) studying two mixing techniques under various conditions and alterations of parameters in order to develop an optimum mixing method (OMM), (c) using the OMM, study the effects of nanoclay content on the resin physical and mechanical properties. a) Synthesizing nanocomposites: As mentioned earlier, three synthesizing techniques were available for use with the pre-formulated resin. However, only simultaneous mixing was appropriate as solvent mixing involved heating and causing the evaporation of the solvent. This might have caused styrene evaporation hence was not considered. Similarly, sequential mixing could not have been employed as the resin was already preformulated. b) Developing the optimum mixing method (OMM): It was seen that increasing time (for ultrasonication) and the number of passes (for TRM) increased the dispersion of the clays into the resin. Increasing the shearing effect by means of reducing the roller distance also increases dispersion Two primary factors, styrene evaporation and increase in exfoliation, influenced the viscosity during the mixing procedure. It was found that the TRM samples showed more increase in viscosity when compared to the ultrasonication samples. But from the X-ray analysis ultrasonication showed better dispersion. Therefore it can be concluded that the dominant factor in the increase of viscosity of TRM samples was the styrene evaporation. There was less than 0.1% change in mass observed for ultrasonication samples, indicating minimum styrene evaporation. It was seen that the dominant factor in viscosity increase for TRM mixing changes from styrene evaporation to increased exfoliation. Therefore it TRM provides a potential in sequential mixing.

79

The optimum mixing method (OMM) was developed. Ultrasonication at 50C for 60 minutes gave improved dispersion and was selected to apply for further investigation on the effect of nanoclays on physical and mechanical properties. It can be concluded that TRM is not suitable for polyester systems containing styrene, as the dramatic increase in viscosity causes a decrease in exfoliation. c) Nanoclay effects: It has been clearly seen that adding nanoclays had increased the viscosity of the resin mix. It has been suggested that the increased clay-resin interactions leads to this Upto16% increase in storage modulus has been observed for 5 wt% clay content. This has been linked to the high elastic modulus and aspect ratio of the clay particles Glass transition temperature, which has been the area of debate amongst many researchers, has been decreased. This and the decrease in cure activity as seen from the DSC results has been due reduction in cross-link density and longer, thermally less stable polymer chains.

5.1. Future Work

Synthesizes of nanocomposites have been under investigation for several years especially with epoxy resins. This research have opened up a new window towards synthesizes of nanocomposites using unsaturated polyester resin. The future work involved could look into two basic areas: a) Sequential mixing of polyester resin: As pointed out in this research, TRM could be a useful tool in the dispersing nanoclays within the nanocomposite system. It is seen that synthesizes and mixing technique has a significant effect on the final morphology and hence the behaviour of the nanocomposites. Styrene-free polyester resin could be initially used to disperse the clays and then studied for the required mechanical and physical properties.

80

b) Resin characterization models TEM samples to verify and confirm the XRD results Develop cure kinetics model and viscosity models from DSC and rheometer data. Develop cure shrinkage model from rheometer data (or an alternate method) after establishing a valid UP/LPA/St combination Use well characterized resin to manufacture panels and measure surface roughness for the final finished part Apply the methodology of design of experiments to identify the nanoclays and additives for best surface finish. c) Preform characterization: Resin characterization was extensively performed, but it is also needed to characterize the preform as it has an effect on the surface quality of the parts: Identify the preform characteristics (surface veil and structural mat) to investigate. Measure preform fibre diameter, fibre volume fraction and orientation distribution. Investigate fibre preform variability. Relate the preform characteristics to the surface finish of RTM panels.

81

6. References

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APPENDIX A Test plan for optimum mixing method (OMM) and resin characterization

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Experimental plans for the mixing nanoclay with UP Phase I Verification of optimal conditions Objective: To verify which of the two mixing methods give better result for dispersion using the X-ray diffraction method Ultrasound parameters to be considered: Frequency kind Mixing Methodology Amount of clays Power (amplitude) Temperature Time

Suggested line of Action: Frequency to be used is degassing (sinusoidal). Ultrasound (constant frequency) is not used because previous literature results show better dispersion with sinusoidal frequency setting Two mixing methods are to be used. Nanoclays in LPA and nanoclays in UP resin. 4 wt% clay will be used to make sure the effects of clays are clearly visible when comparing it with three roll mill (TRM) Temperature will be fixed at 50C To ensure temperature rise due to ultrasonication does not interact with the results. Amplitude is fixed at the machine The time used shall be 60 minutes to ensure appropriate dispersion (in accordance to previous literature data) The effects of the two mixing methodology will be studied by using the shrinkage tests. 94

Three Roll Mill (TRM) parameters to be considered Speed of rotation Amount of nanoclays Distance between rollers Temperature Number of cycle

Suggested line of Action: Speed of rotation is fixed 5% nanoclay will be used to compare with ultrasonication results Distance between rollers shall be adjusted. Best of the results will then be compared to the best results from ultrasonication Temperature will be constant at 25C as for ultrasonication Number of cycle will be varied to study dispersion

Table A 1: Parameter comparison of ultrasonication and TRM mixing methods

Ultrasonication Frequency type: Sinusoidal or constant frequency Power (amplitude): Constant

TRM Speed between the rollers: Constant Distance between the rollers: Varied for three different distances

Temperature: 50C Mixing time: Varied for two different times Clay content: constant at 4 wt%

Temperature: 25C Number of passes: Varied for two different number of passes Clay content: constant at 4 wt%

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Table A 2: Test plan to determine optimum mixing method (OMM)

Tests for optimum mixing method (OMM) 4% Cloisite20A clay will be used as the clay content Amplitude on the Ultrasound is fixed X-ray diffraction tests will be used to analyze results for dispersion The variables X,Y,Z define spacing between the middle and back rollers in m The numbers 1,2,3 define the distance between middle and front rollers in m Sample Name Variable Frequency/ Temp Time/ No. # 1 2 3 4 5 6 7 8 9 10 11 LPA-clay Mixture (ultrasonication) Resin-Clay Mixture (ultrasonication) Spacing X1 (TRM) Spacing Y1 (TRM) Spacing Z1 (TRM) Spacing X2 (TRM) Spacing Y2 (TRM) Spacing Z2 (TRM) Spacing X3 (TRM) Spacing Y3 (TRM) Spacing Z3 (TRM) Roller Spacing Roller Spacing Roller Spacing Roller Spacing Roller Spacing Roller Spacing Roller Spacing Roller Spacing Parameter Mixing Methodology Mixing Methodology Roller Spacing Spacing Degassing (pulsation) Degassing (pulsation) Back X Front 1 Back Y Front - 2 Back Z Front 3 Back X Front 2 Back Y Front - 2 Back Z Front 2 Back X Front 3 Back Y Front 3 Back Z Front 3 25 3 Cyc 25 3 Cyc 25 3 Cyc 25 3 Cyc 25 3 Cyc 25 3 Cyc 25 3 Cyc 25 3 Cyc 25 3 Cyc 50 30 min 50 Of Cycle 60 min

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Measure the dispersion for the two methods Choose the best results from the two mixing tools Compare the two mixing tools and identify the optimum conditions. Conclusion: A mixing methodology and optimum condition has been established. This is now OMM (Optimum mixing method). Phase II Effect of nanoclay content on rheological properties, cure kinetics, storage modulus, glass transition temperature and volumetric shrinkage Objective: To study the effect of the nanoclay content on volumetric shrinkage using the OMM established in Phase I Parameters are used as established in Phase I
Table A 3: Resin Characterization tests summary

Tests for Effect of Nanoclays OMM established earlier will be used to study effects of nanoclays Sample # 0 2 3 4 5 0 wt% Cloisite 20A 2 wt% Cloisite 20A 3 wt% Cloisite 20A 4 wt% Cloisite 20A 5 wt% Cloisite 20A Clay weight Clay weight Clay weight Clay weight Sample Name Variable Parameter Clay weight DSC, Shrinkage, DMA (Storage modulus, Tg) DSC, Shrinkage, DMA (Storage modulus, Tg) DSC, Shrinkage, DMA (Storage modulus, Tg) DSC, Shrinkage, DMA (Storage modulus, Tg) DSC, Shrinkage, DMA (Storage modulus, Tg) Validation Tests

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APPENDIX B Preliminary DSC and shrinkage results on T580-63 pure resin

98

Dynamic Scan at 10C/min

Cure Rate Degree of Cure

4.0E-03 3.5E-03 Cure Rate (/s) 3.0E-03 2.5E-03 2.0E-03 1.5E-03 1.0E-03 5.0E-04 0.0E+00 0
Max DOC 0.99 Total heat of reaction: 377 J/g

1 0.8 0.6 0.4

Peak: 74C

0.2 0 200 400 600 800 1000 1200 1400 1600 1800 2000 Cure Time (sec)

Figure B 1: Dynamic DSC scan at 10C/min for T580-63 with 3% cobalt 1% and MEKP catalyst

Degree of Cure (-)

99

2.0E-03 1.8E-03 1.6E-03 1.4E-03 1.2E-03 1.0E-03 8.0E-04 6.0E-04 4.0E-04 2.0E-04 0.0E+00 0

1 Degree of Cure (%)

100

0.8
Cure Rate Degree of Cure

Cure Rate (/s)

0.6 0.4 0.2

0 300 600 900 1200 1500 1800 2100 2400 2700 3000 Cure Time (sec)

Figure B 2: Dynamic DSC scan at 3C/min for T580-63 with 3% cobalt 1% and MEKP catalyst

Dynamic scan at 3C/min Cure Rate 2.0E-03 1.6E-03 Cure Rate (/s) 1.2E-03 8.0E-04 4.0E-04 0.0E+00 0 Degree of Cure 1 Degree of Cure (-)
101

0.8 0.6 0.4 0.2 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 Cure Time (sec)

Figure B 3: Dynamic DSC scan at 3C/min for T580-63 with 1.5% cobalt 1% and MEKP catalyst

Dynamic Scan at 3C/min

Cure Rate Degree of Cure

2.0E-03 1.6E-03 Cure Rate (/s) 1.2E-03 8.0E-04 4.0E-04 0.0E+00 0

Initial peak Total heat of reaction: 355 J/g Peak: 94C Max DOC 0.99

1 Degree of Cure (%)

102

0.8 0.6 0.4 0.2

0 300 600 900 1200 1500 1800 2100 2400 2700 3000 Cure Time (sec)

Figure B 4: Dynamic DSC scan at 3C/min for T580-63 with 1.5% cobalt 1% and MIBKP catalyst

Isothermal Scan at 75C Cure Rate 3.5E-03 3.0E-03 Cure Rate (/s) 2.5E-03 2.0E-03 1.5E-03 1.0E-03 5.0E-04 0.0E+00 0
Initial reaction observed as well Fast reaction with peak at 150 sec

Degree of Cure 1 Degree of Cure (%)

103

0.8 0.6 0.4 0.2

0 300 600 900 1200 1500 1800 2100 2400 2700 3000 Cure Time (sec)

Figure B 5: Isothermal scan at 75C for T580-63 resin + 1.5% cobalt 3% + 1.5% MIBKP

7 6 Volumetric Shrinkage % 5 4 3 2 1 0
0 0.1 0.2 0.3 0.4 DOC 0.5 0.6 0.7 0.8

Figure B 6: Volumetric Shrinkage results as a function of DOC for T580-63 resin with 1.5% Cobalt 3% and MIBKP at 75C,

104