New Metal/Polymer Composites for
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`Fused Deposition Modelling
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`Applications
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`By
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`Mostafa Nikzad
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`BSc & MSc (Eng)
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`A thesis submitted in fulfilment of the requirements for
`the degree of
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`Doctor of Philosophy
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`Faculty of Engineering & Industrial Sciences
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`Swinburne University of Technology
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`Hawthorn, Melbourne
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`Australia
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`May 2011
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`Abstract
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`Fused Deposition Modelling (FDM) has been a leading rapid prototyping
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`process but it has been mostly limited to use in making prototypes for design
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`verification and functional testing applications. The commercial process can
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`currently fabricate parts only in limited types of thermoplastics such as ABS
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`and Polycarbonate. Very little efforts have been made to increase the range of
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`FDM materials to include metals or metal based composites for wider
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`application domain beyond just design and verification. This thesis presents
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`new research in this direction by developing novel metal based composites for
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`use in FDM technology.
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`The principal objective of this research is to develop new metal/polymer
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`composite materials for direct use in the current Fused Deposition Modelling
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`rapid prototyping platform with long term aim of developing direct rapid
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`tooling on the FDM system. Using such composites, the direct rapid tooling will
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`allow fabrication of injection moulding dies and inserts with desired thermal
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`and mechanical properties suitable for using directly in injection moulding
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`machines for short term or long term production runs. The new metal/polymer
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`composite material developed in this research work involves use of iron
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`particles and copper particles in a polymer matrix of ABS material, which offers
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`much improved thermal, electrical and mechanical properties enabling current
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`Fused Deposition Modelling technique to produce rapid functional parts and
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`tooling. Higher thermal conductivity of the new metal/polymer composite
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`material coupled with implementation of conformal cooling channels enabled
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`by layer-by layer fabrication technology of the Fused Deposition Modelling will
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`result in tremendously improved injection cycles times, and thereby reducing
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`the cost and lead time of injection moulding tooling.
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`Due to highly metal-particulate filled matrix of the new composite material,
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`injection tools and inserts made using this material on Fused Deposition
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`Modelling, demonstrate a higher stiffness comparing to those made out of pure
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`polymeric material resulting in withstanding higher injection moulding
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`pressures. Moreover, metallic filler content of the new composite allows
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`processing of functional parts with electrical conductivity and in case of using
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`ferromagnetic fillers, namely as fine iron powders, it introduces magnetic
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`properties, which will make FDM-built components suitable for electronic
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`applications specifically whereby electro-magnetic shielding is of high interest.
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`In this research project, a full characterization of the newly developed
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`metal/polymer composites including rheological, thermal, mechanical and
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`electrical properties has been investigated. Mathematical models have been
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`employed in order to predict and optimize the viscous behaviour of
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`metal/polymer composite during the course of deposition through the FDM
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`nozzle.
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`In order to predict the main flow parameters of the metal/polymer composites
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`including pressure, temperature, and velocity fields through the FDM liquefier
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`head, 2-D and 3-D numerical analysis of melt flow behaviour of acrylonitrile-
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`butadiene-styrene (ABS) and Iron composite as a representative metal/polymer
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`material has been carried out using ANSYS FLOTRAN and ANSYS CFX
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`commercial codes. Results of numerical analysis have been verified by the
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`developed empirical mathematical models.
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`A variety of advanced techniques have been employed to fully characterize the
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`newly developed metal/polymer composites in order to successfully process
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`filaments for fabrication of injection mould tooling inserts. Morphological
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`effects of metallic fillers and surfactants as well as variation of volume fractions
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`of constituents on the viscoelastic properties of the new composite material
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`have also been investigated. Filaments of the filled ABS has been fabricated
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`and characterized to verify the possibility of prototyping and direct tooling
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`using the new material on the current FDM machine.
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`Major contributions of the thesis include:
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`• Development of a new metal/polymer composite material for functional
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`parts and rapid tooling solutions on Fused Deposition Modeling
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`platform.
`• Development of mathematical models for predicting viscous behavior of
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`three-component composite flow through capillary extrusion process.
`• Full rheological, thermal, mechanical and electrical characterization of
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`the new metal/polymer composites.
`• Combining experimental and numerical methodology (tools) to predict
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`melt flow behavior of metal/polymer composite through Fused
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`Deposition Modeling.
`• Fabrication of stiff and flexible filaments of the metal-polymer
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`composites as feedstock material for direct rapid tooling via Fused
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`Deposition Modeling.
`• Fabrication of functional parts and inserts of new metal/polymer
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`composites successfully and directly on the FDM3000 system.
`• Production of plastic parts using injection moulding tools made by
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`Direct FDM-based Rapid Tooling Process.
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`Acknowledgment
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`First of all, I would like to express my deepest gratitude to my principal
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`supervisor Professor S.H. Masood for his continuous support and valuable
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`guidance throughout my research work. I would like to also thank my second
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`supervisor, Dr. Igor Sbarski, for his valuable inputs especially on rheological
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`studies, and overall arrangement of experimental works. Initial support of my
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`external supervisor, Dr. Andrew Groth from CSIRO, is also highly appreciated.
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`I acknowledge the financial support in the form of scholarship provided by
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`Swinburne University of Technology and the Commonwealth Scientific and
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`Industrial Research Organisation (CSIRO).
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`My thanks are extended to the people for their help at various stages of my PhD
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`work. Assistance of John Thomas, Adam Webb from Autodesk Moldflow; Dr.
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`Ruether and Dr. Shekibi from CSIRO Energy Technology division; Mike
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`Dundan from Chisholm TAFE; Pejman Hojati from Monash University; Brian
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`Dempster, Mehdi Miri, Girish Thipperudrappa, Dr. Ismet Ilyas, Dr. Wei Song,
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`and Dr. James Wang, from Swinburne University of Technology is highly
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`appreciated.
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` I wish to express my eternal gratitude to my Mum, Dad and Siblings for their
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`endless support, love and encouragement throughout my entire schooling.
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`Last but not least, I would like to thank all my friends and fellow postgraduate
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`students, especially A.B.M. Saifullah and Barbara, whose sincere friendship
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`made the course of my PhD studies fun and enjoyable.
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`Thank You!
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`DECLARATION
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`This thesis contains no material which has been accepted for the award of any
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`other degree or diploma at any university and to the best of my knowledge and
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`belief contains no materials previously published or written by another person
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`or persons except where reference is made.
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`Mostafa Nikzad
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`May 2011
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`Table of Contents
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`Chapter 1 Introduction .................................................................................................. 1
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`1.1. General Background ....................................................................................... 1
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`1.2. Outline of Research Project ............................................................................ 8
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`1.3. Outline of thesis ............................................................................................. 12
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`Chapter 2 RP/RT/RM and Materials Development .............................................. 14
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`2.1.
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`Introduction .................................................................................................... 14
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`2.2. Overview of the Traditional RP Processes ................................................. 17
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`2.2.1. Stereolithography ................................................................................... 17
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`2.2.2. Selective Laser Sintering ....................................................................... 21
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`2.2.3. Three Dimensional Printing ................................................................. 23
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`2.2.4. Laminated Object Manufacturing ........................................................ 24
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`2.2.5. Fused Deposition Modelling Process .................................................. 25
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`2.3. Overview of Emerging Rapid Manufacturing Processes ........................ 29
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`2.3.1. Liquid-based RM Processes .................................................................. 30
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`2.3.1.1.
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`Stereolithography ....................................................................................... 30
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`2.3.2. Powder-based RM Processes ................................................................ 32
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`2.3.2.1.
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`Direct Metal Laser Sintering ........................................................................ 33
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`2.3.2.2.
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`Selected Laser Melting ................................................................................ 34
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`2.3.2.3.
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`Direct Metal Deposition .............................................................................. 35
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`2.3.2.4.
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`Electron Beam Melting................................................................................ 36
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`2.3.3. Solid based RM Processes ..................................................................... 37
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`2.3.3.1.
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`Laminated Object Manufacturing ............................................................... 37
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`2.3.3.2.
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`Fused Deposition Systems .......................................................................... 38
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`2.4. Material Issues in RP & RM ......................................................................... 40
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`2.5. Research Direction in Fused Deposition Modelling ................................. 47
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`2.5.1. New Materials & Process Improvements in FDM ............................. 48
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`2.5.2. Metal-Polymer Composites in FDM .................................................... 55
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`2.5.3. Medical Applications & Rapid Tooling in FDM ................................ 56
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`2.6. Summary ......................................................................................................... 57
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`Chapter 3 New Metal/polymer Composites for FDM ........................................... 59
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`3.1
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`Introduction .................................................................................................... 59
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`3.2 Composite Materials ..................................................................................... 60
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`3.3 Metal/Polymer Composites......................................................................... 62
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`3.3.1
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`Thermoplastic Polymeric Matrices ...................................................... 63
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`3.3.2
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`Particle-reinforced Polymer Composites ............................................ 65
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`3.4
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`Processing of a New Metal/Polymer Composite ..................................... 68
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`3.4.1
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`Preparation of Iron-particulate filled ABS Composite ..................... 68
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`3.4.2
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`Extrusion of the Metal-polymer Composite and Die Swell
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`Phenomenon ......................................................................................................... 73
`VII
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`3.5
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`Fabrication of FDM filament and test samples ......................................... 76
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`Chapter 4 Rheological Properties of Fe/ABS Composites for Fused Deposition
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`Process ........................................................................................................................... 78
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`4.1.
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`Introduction .................................................................................................... 78
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`4.2. Classification of Fluids and Rheological Properties ................................. 79
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`4.3. Rheological Behaviour of Polymer Melts ................................................... 82
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`4.3.1. Steady Simple Shear Flows ................................................................... 82
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`4.3.2. Dynamic Drag Simple Shear Flows ..................................................... 84
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`4.3.3. Shear Free Flows ..................................................................................... 84
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`4.4. Filled Polymer Melts ..................................................................................... 84
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`4.4.1. Metal-Polymer Composite Melt ........................................................... 85
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`4.5. Experimental .................................................................................................. 86
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`4.5.1. Capillary Rheometry.............................................................................. 86
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`4.5.2. Parallel Plate Rheometry ....................................................................... 88
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`4.5.3. Melt Flow Index ...................................................................................... 88
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`4.6. Results ............................................................................................................. 89
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`4.6.1. Discussion................................................................................................ 90
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`4.6.2. Normal Stresses and Die Swell Phenomenon .................................. 114
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`4.7. Viscosity Models for the Composites ....................................................... 115
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`4.8. Summary ....................................................................................................... 117
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`Chapter 5 Mechanical & Electro thermal Properties of Metal/Polymer
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`Composites .................................................................................................................. 121
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`5.1.
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`Introduction .................................................................................................. 121
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`5.2. Micro/nano metal-polymer composites .................................................. 122
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`5.3. Experimental ................................................................................................ 129
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`5.3.1. Stress-Strain behaviour of Iron/ABS composites ............................ 129
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`5.3.2. Morphological properties of ABS-Iron Interface ............................. 133
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`5.3.3. Dynamic Mechanical Analysis ........................................................... 141
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`5.3.4. Thermal Properties of ABS-Iron composites .................................... 151
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`5.3.4.1.
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`Thermal Conductivity ................................................................................ 151
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`5.3.4.2.
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`Heat Capacity ............................................................................................ 155
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`5.3.5. Electrical Conductivity of Iron/ABS composites ............................ 156
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`5.4. Summary ....................................................................................................... 163
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`Chapter 6 A Melt Flow Analysis of Iron/ABS Composites in FDM Process .... 165
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`6.1.
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`Introduction .................................................................................................. 165
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`6.2. Material Characterisation for Boundary Condition Setup .................... 169
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`6.2.1. General Flow Behaviour ...................................................................... 174
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`6.3. Finite Element Analysis .............................................................................. 176
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`6.3.1. Geometry development ....................................................................... 176
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`6.3.2. Problem domain and flow regime definition ................................... 177
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`6.3.3. Meshing ................................................................................................. 178
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`6.3.4. Boundary conditions............................................................................ 180
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`6.4. Results and Discussion ............................................................................... 181
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`6.5. Summary ....................................................................................................... 187
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`Chapter 7 Experimental Trials of Iron/ABS in Fused Deposition Modelling .. 188
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`7.1.
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`Introduction .................................................................................................. 188
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`7.2. Fused Deposition Modelling of Metal/Polymer Composites .............. 189
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`7.3.
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`Industrial Implementation ......................................................................... 199
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`7.4. Summary ....................................................................................................... 207
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`Chapter 8 Conclusions and Recommendations ..................................................... 209
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`8.1.
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`Introduction .................................................................................................. 209
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`8.2. Major Findings & Original Contributions ............................................... 209
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`8.3. Recommendation for Future Work ........................................................... 212
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`References .................................................................................................................... 214
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`Appendix A ................................................................................................................. 237
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`Morphology of Metal/Polymer Composites ......................................................... 237
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`A.1: EDS Result of ABS and Iron (6-9 µm) Composites .................................... 238
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`A.2: EDS Result of ABS and Copper (45 µm) Composites ............................... 239
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`A.3: EDS Result of ABS and Copper (10 µm) Composites ............................... 240
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`A.4: SEM Images of ABS and Iron (6-9 µm) Composites ................................. 242
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`A.5: SEM Images of ABS and Copper (45 µm) Composites ............................. 244
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`A.6: SEM Images of ABS and Copper (10 µm) Composites ............................. 246
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`Appendix B ................................................................................................................. 248
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`Publications from This Research .............................................................................. 248
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`B1: Refereed Journal Papers .................................................................................. 248
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`B2: Refereed Conference Papers .......................................................................... 248
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`List of Figures
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`Figure 1-1: Generic Flow of RP Process ( Kamrani & Nasr 2006) ........................... 2
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`Figure 1-2: Schematic of Stratasys FDM Process ....................................................... 7
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`Figure 2-1: Classification of the current RP-based Tooling .................................... 15
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`Figure 2-2: Material-dependent Rapid manufacturing and Tooling (reproduced
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`from Levy, Schindel & Kruth 2003) ........................................................................... 16
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`Figure 2-3: Schematic of Stereolithography process (Source: Ultra Violet
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`Products, Inc) ................................................................................................................ 18
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`Figure 2-4: Illustration of Direct AIM “Shelling” backfilled with Al-filled Epoxy
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`(Jacobs 2000) .................................................................................................................. 19
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`Figure 2-5: Illustration of Silicon RTV moulding process (Grenda 2006) ............ 21
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`Figure 2-6: Illustration of the SLS process (Subramanian et al. 1995)................... 22
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`Figure 2-7: Illustration of 3DP process (Source: after E.Sachs and E.Cima) ........ 23
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`Figure 2-8: Illustration of the LOM process (Source: Helisys, Inc) ....................... 25
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`Figure 2-9: Fused Deposition Modelling process .................................................... 26
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`Figure 2-10: FDM Liquefier Straight Nozzle ............................................................ 28
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`Figure 2-11: Production of Jewellery and Hearing Aid by Envisiontec
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`Perfactory© ................................................................................................................... 31
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`Figure 2-12: Powder-based RM Processes and the Current Commercial ............ 32
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`Figure 2-13: Rapid Manufactured Parts by DMLS (Source: Morris Technologies
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`Retrieved 2010) ............................................................................................................. 34
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`Figure 2-14: Direct Metal Deposition (Courtesy of the POM Group Inc.) ........... 35
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`Figure 2-15: Arcam Electron Beam Melting Process (Thundal 2008) ................... 36
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`Figure 2-16: Ultrasonic Consolidation of Metal-Matrix Composites (Kong, Soar
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`& Dickens 2004) ............................................................................................................ 38
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`Figure 2-17: Contour Crafting of Structural Ceramic (Khoshnevis et al. 2001) .. 39
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`Figure 2-18: A hierarchy of homogeneous materials system for additive
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`manufacturing .............................................................................................................. 41
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`Figure 2-19: A hierarchy of heterogeneous materials system for additive
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`manufacturing (Bourell, Leu & Rosen 2009) ............................................................ 41
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`Figure 3-1: A simple classification of various types of composites ...................... 62
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`Figure 3-2: Monomers used in thermoplastic ABS .................................................. 69
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`Figure 3-3: Cryogenic grinding of ABS polymer ..................................................... 71
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`Figure 3-4: Single screw extrusion of the ABS-Fe filaments .................................. 74
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`Figure 3-5: Schematic of Polymer Melt Swell ........................................................... 74
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`Figure 3-6: Parallel Plate Rheometry ......................................................................... 74
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`Figure 3-7: Long land length die for suppressing extrusion swell ....................... 75
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`Figure 3-8: FDM filament produced from Iron/ABS composite material. .......... 77
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`Figure 3-9: Test samples produced on FDM3000 from the new Iron/ABS
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`composite and unfilled ABS material (white). ......................................................... 77
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`Figure 4-1: Simple Shear Flow .................................................................................... 79
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`Figure 4-2: Pure viscous non-Newtonian fluids (Yamaguchi 1952) ..................... 81
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`Figure 4-3: Capillary Viscometer ............................................................................... 83
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`Figure 4-4: Rotational Viscometer .............................................................................. 83
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`Figure 4-5: Parallel Plate Rheometry ........................................................................ 88
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`Figure 4-6: Schematic of Polymer Melt Swell ........................................................... 88
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`Figure 4-7: CEAST Melt Flow Indexer ...................................................................... 89
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`Figure 4-8: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. .............................................................................................................................. 91
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`Figure 4-9: Effect of shear rate on the viscosity of various composites of ABS
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`and Ca.St ........................................................................................................................ 92
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`Figure 4-10: Relative viscosity of composites of ABS and varying volume
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`fractions of Ca.St. at different shear rates ................................................................. 92
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`Figure 4-11: Relative viscosity of composites of ABS and varying volume
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`fractions of 45 µm iron ................................................................................................. 93
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`Figure 4-12: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. in 10% filled iron with particle size <10um ................................................... 95
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`Figure 4-13: Shear rate versus viscosity of various composites of ABS and Ca.St
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`in 10% filled iron with particle size <10um .............................................................. 96
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`Figure 4-14: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. in 20% filled iron with particle size <10um ................................................... 97
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`Figure 4-15: Viscosity vs. shear rate for various composites of ABS and Ca.St in
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`20% filled iron with particle size <10um .................................................................. 97
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`Figure 4-16: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. in 30% filled iron with particle size <10um ................................................... 98
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`Figure 4-17: Shear rate versus viscosity of various compounds of ABS and Ca.St
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`in 30% filled iron with particle size <10um .............................................................. 99
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`Figure 4-18: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. in 10% filled iron with particle size <45um ................................................... 99
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`Figure 4-19: Shear rate versus viscosity of various composites of ABS and Ca.St
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`in 10% filled iron with particle size <45um ............................................................ 100
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`Figure 4-20: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. in 20% filled iron with particle size <45um ................................................. 101
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`Figure 4-21: Effect of shear rate on the viscosity of various composites of ABS
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`and Ca.St in 20% filled iron with particle size <45um .......................................... 101
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`Figure 4-22: Flow curves of composites of ABS and varying volume fractions of
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`Ca.St. in 30% filled iron with particle size <45um ................................................. 102
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`Figure 4-23: Viscosity vs. shear rate for various composites of ABS and Ca.St in
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`30% filled iron with particle size <45um ................................................................ 103
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`Figure 4-24: Relative viscosity of composites of ABS and varying volume
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`fractions of Fe of 45 µm and 5%Ca.St. ..................................................................... 104
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`Figure 4-25: Relative viscosity of composites of ABS and varying volume
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`fractions of Fe of 45 µm and 7.5%Ca.St. .................................................................. 105
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`Figure 4-26: Relative viscosity of composites of ABS and varying volume
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`fractions of Fe of 45 µm and 10%Ca.St. ................................................................... 106
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`Figure 4-27: Relative viscosity of composites of ABS and varying volume
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`fractions of Fe for 5% Ca.St. ...................................................................................... 107
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`Figure 4-28: Relative viscosity of composites of ABS and varying volume
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`fractions of Fe for 7.5 % Ca.St. .................................................................................. 108
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`Figure 4-29: Relative viscosity of composites of ABS and varying volume
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`fractions of Fe for 10% Ca.St. .................................................................................... 109
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`Figure 4-30: Relative viscosity of composites of ABS and varying volume
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`fractions of Ca.St for low shear rate with iron particle size of 45 µm ................. 110
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`Figure 4-31: Relative viscosity of composites of ABS and varying volume
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`fractions of Ca.St for high shear rate with iron particle size of 45 µm ............... 110
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`Figure 4-32: Relative viscosity of composites of ABS and varying volume
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`fractions of Ca.St for low shear rate and iron particle size of <10 µm ................ 111
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`Figure 4-33: Relative viscosity of composites of ABS and varying volume
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`fractions of Ca.St for high shear rate and iron particle size of <10 µm .............. 111
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`Figure 4-34: Effect of processing temperature on the viscosity of Fe/ABS
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`composites ................................................................................................................... 113
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`Figure 4-35: Effect of processing temperature on the viscosity of ABS P400 .... 113
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`Figure 4-36: Normal Stress versus Shear Rate for ABS with varying %vol of
`
`Ca.St. ............................................................................................................................ 115
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`Figure 4-37: Relative viscosity of compounds of ABS and varying volume
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`fractions of Ca.St. ........................................................................................................ 118
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`Figure 5-1: Typical tensile stress vs. concentration curves for filled polymers
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`showing upper bound and lower bound responses (Bigg 1987b) ...................... 124
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`Figure 5-2: Stress–strain curves for HDPE/zinc composites with different
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`concentrations of zinc powder: 0% vol (1); 4% vol (2); 8% vol (3); 12% vol (4);
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`16% vol (5); 20% vol (6) (Sofian & Rusu 2001) ....................................................... 124
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`Figure 5-3: Storage Modulus of copper reinforced (a) LDPE, (b) LLDPE, (c
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`)HDPE (Molefi, Luyt & Krupa 2010) ....................................................................... 126
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`Figure 5-4: Loss Modulus of copper reinforced (a) LDPE, (b) LLDPE, (c
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`)HDPE(Molefi, Luyt & Krupa 2010) ........................................................................ 127
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`Figure 5-5: Load vs deformation behaviour of Iron/ABS composites prepared
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`by centrifugal mixing with various volume fractions of Iron powder............... 131
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`Figure 5-6: Stress-strain behaviour of 10wt% Iron filled ABS and virgin ABS
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`used in FDM ................................................................................................................ 132
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`Figure 5-7: Load vs deformation behaviour of ABS-Iron Composites prepared
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`by melt compounding on a twin screw extruder for various volume fraction of
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`Iron powder ................................................................................................................ 133
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`Figure 5-8: (a) Fractured tensile specimen (b) Samples prepared for SEM ....... 134
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`Figure 5-9: Fracture surface of re-processed FDM ABS P400 .............................. 134
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`Figure 5-10: SEM image of fracture surface ABS-Fe(10 vol%)prepared via
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`centrifugal mixing ..........................................................................