T.C.

 
MARMARA UNIVERSITY
INSTITUTE FOR GRADUATE STUDIES IN
PURE AND APPLIED SCIENCES

PRODUCTION OF ABS WIRE MATERIAL FOR RAPID

PROTOTYPING MACHINES

Özgür KIRELLİ

THESIS
FOR THE DEGREE OF MASTER OF SCIENCE
IN
MECHANICAL ENGINEERING

SUPERVISOR

Asst.Prof. Dr. Bülent EKİCİ

İSTANBUL 2008
 T.C.
MARMARA UNIVERSITY
INSTITUTE FOR GRADUATE STUDIES IN
PURE AND APPLIED SCIENCES

ACCEPTANCE AND APPROVAL DOCUMENT

PRODUCTION OF ABS WIRE MATERIAL FOR RAPID PROTOTYPING

MACHINES

The jury established by the Executive Board of the INSTITUTE FOR

GRADUATE STUDIES IN PURE AND APPLIED SCIENCES on .............
(Resolution no:.......) has accepted Mr. ÖZGÜR KIRELLİ’s thesis titled “
Production of Supply Material for of  ABS Wire Material for Rapid Prototyping Machine
”as Master of Science thesis in Master Science of Mechanical Engineering.

Advisor : Assit. Prof. Dr. Bülent EKİCİ

1. Member of the jury : Prof. Dr. A.Kerim KAR
2. Member of the jury : Prof. Dr. Mustafa KURT

Date :

APPROVAL
Mr. Özgür KIRELLİ has satisfactorily completed the requirements for the
degree of Master of Science of Philosophy in Master Science of Mechanical
Engineering at Marmara University. The Executive Commitee approves that he be
granted the degree of Master of Science on (Resolution no: )

DIRECTOR OF THE INSTITUTE

 
ACKNOWLEDGMENT

First and foremost, I would like to thanks you to my supervisor, Assit. Prof Dr.
Bülent EKİCİ for his valuable support and help and encouragement throughout this
thesis.

Along to my master education, thank you my collogue, my friend Mechanical

Engineer Murat YATAN for valuable ideas and great support.

During to preparation and the writing of the thesis, I would like to thank you to my
cousin Material Engineer Elif TAŞTABAN , my dear friend Material Engineer Emre
YAVUZ and Burcu GÜRDAL because of helping me to finish this thesis with their
knowledge and support.

Also I would like to thank you to Chemical Engineer Kübra CEBECİOĞLU for
suppling material and for guiding to my thesis.

Finally, I would like to deepest gratitude for their endless support and understanding
to my father Arif KIRELLİ, my mother Necla KIRELLİ and my dear sister Başak
KIRELLİ. I would like to dedicate this thesis to my mother Necla KIRELLİ for her
great understanding and trust through my master education.

i
CONTENTS

PAGE
ACKNOWLEDGMENT……...……………………………………….i
CONTENTS….………………………………………….……………..ii
SUMMARY..………………………………………………..................iv
ABSTRACT…………………………………………………….……...v
ÖZET……..…………………………………………………….……...vi
SYMBOLS…...…………………………………………..…………... vii
ABBREVIATIONS ……….…………………………………………viii
FIGURES……….………………...……………….…………….…….ix
TABLES ………………………...……………………………...…..….x
I. INTRODUCTION.………….……………………………………….1
II. POLYMERS AND ABS PROPERTIES..............……………........3
II.1 POLYMERS …………………………………...…………………….…....3
II.1.1 Polymer Structure ……………………..…………………….….…...4
II.1.2 Polymer properties ………..………….….…………………..…..….4
II.1.2.1Crystallinity…………………………………………………...4
II.1.2.2Tensile strength ……………………….…….………………..5
II.1.2.3 Young's Modulus of Elasticity………………………….……5
II.1.2.4 Transport Properties ………………………………...……….5
II.1.2.5 Melting point …………………….………………….…….....5
II.1.2.6 Boiling point …………………….…….…………….….…....6
II.1.2.7 Glass transition temperature …………………….…..……....6
II.1.2.8 Chain length …………………….………………….………..7
II.1.3 Chemical properties of polymers ..………..………………….……....7
II.1.4 Polymer characterization ………………..………………….……….8
II.1.5 Polymer degradation ……………………..………………….………9
II.1.6 Polymerization ……………………..…….…...…………....………10
II.1.6.1 Chain-growth …………………………….………...….……11

ii
 II.1.6.2 Step-growth …………………………………………..……13
II.2 ENGINEERING THERMOPLASTICS ………………..……...…......15
II.2.1 Introduction ………………………..………...……...…………....15
II.2.2 History of development of Thermo plastics ……..…....………….16
II.2.3 Properties of Thermoplastics ……..………………..……....……..17
II.1.3.1 Physical Properties……………..………….……….…....…21
II.1.3.2 Electrical Properties …………………………….….…...…25
II.1.3.3 Thermal Properties ……………………………….……..…25
II.1.3.4 Mechanical Properties …………………………….…….…26
II.1.3.5 Rheological Properties ………………………….….………27
II.1.3.6 Chemical Resistance …………………………..…………..…28
II.2.4 Processing of Thermoplastics ...………………………..….….........28
II.2.5 Summary of Mechanical, Thermal, and Electrical Properties……...33
II.2.6 Future ………………………..……………..…..…….…….….…...37
II.3 INTRODUCTION TO ABS RESINS…………….....…………………39
II.3.1 Properties of ABS ……………………..…………….…….….…....40
II.4 DESCRIPTION OF THE FDM …….………....………………….........41
II.4.1 Mechanical Properties of FDM ABS ………………..….....…….…44
II.4.2 Example Design Project Applications ……..……..………………...47
II.5 EXTRUSION PROCESS ………………….………....…………….…...50
II.5.1 Extruder ………………..…………………………..………....….…51
II.5.1.1 Obtaining the melting temperature right ……………...…..…52
II.5.1.2 Extrusion pressure and extrusion speed ………….……….…52
III. PRODUCTION AND TESTING IF NEW MATERIAL…..…..54
III.1 MATERIAL TESTS OF ABS MATERIALS FOR RAPID
PROTOTYPING MACHINE………………………….…………………....54
III.1.1 Using Materials in Rapid Prototyping Process for Studies …….....54
III.2 PLASTICS CHARACTERIZATION AND SELECTION BY TESTS
………………….…….………….………….……….……….……………55
III.2.1 Strength Test of the Plastics ………………………….……………55
III.2.2 Elongation Test………………….….…………………………..….56
III.2.3 Mold Flow Index Test of Samples …………………….…….……57
III.2.4 Hardness Test …………………….…………………………….…59

iii
 III.2.5 SEM Scanning Electron Microscope Imaging.................................61
III.2.6 XRD X-ray Scattering Techniques …………………………….…62

III.3 PREPARATION OF ABS MATERIALS .…..…………………..…...63

III.4 FABRICATION OF NEW MATERIAL ………………..….….…….64
IV. TEST RESULT OF ABS WIRE SAMPLES…. ...................….66
IV.1 TENSILE STRENGTH TEST RESULTS OF SAMPLES ….….......68
IV.2 MFI TEST RESULTS OF SAMPLES…………………………….….69
IV.3 EXPERIMENT MEASUREMENTS OF HARDNESS TEST .….....71
IV.4 DISCUSSION .…………………………………………………...…….72

V. CONCLUSION AND RECOMMENDATIONS ………......….74

REFERENCES……………………..……………………….……....75
APPENDIX….……….……………………...……….……….…..…77
CV…………………………………………...………………….…....82

iv
   
ABSTRACT
Production of  ABS Wire Material for  Rapid Prototyping 
Machine

Our aim is producing of supply materials for Rapid Prototyping machine and
improving materials properties . With the production of supply material in Turkey,
which is exported, costs are decreased and escape from foreign dependence.
This thesis investigates processes of support material and using of these
materials in rapid prototyping machine. For production and selection to right
material, we have to get information about production, processing and using of ABS
(Acrylonitrile Butadiene Styrene).
First, general information about polymers is given in Theoretical
Investigation. Then, thermoplastics are described in detail. Hereafter, detailed
information is given about ABS. At the end of the theoretical investigation part,
process of Rapid Prototyping process FDM (Fused Deposition Modeling) and
extrusion process of ABS will be explained.
There are a lot of important points for production of supply material. We have
to select the right material. There are too many types of material that used in Rapid
Prototyping Machine. And there are a lot of important points such as Tensile
strength, tensile modulus, elongation, melting temperature and mold flow index.
Another point is smooth surfaces on these molds. Rough surfaces prevent ejection of
the injection molded part and play a role in the overall quality of the final part.
In experimental study, experiments are made on samples which have different
properties. We produced ABS material for rapid prototyping machine. First, we
purchased raw ABS materials from producers. That is the most important point
which effects overall process. Then, we made extrusion process with extrusion
machine. We have to know the physical properties of material to using in machine.
Prototyping process is very sensitive process which can be affected by many
disturbances. When we know physical values of samples of ABS, we realize the
production is good or not.

v
ÖZET
Hızlı Prototipleme Makineleri için ABS Tel Malzeme Üretimi
Tezin amacı Hızlı prototipleme makinelerinde kullanılan maddelerin
Türkiye’de üretilmesi ve kullanılan malzemelerin iyileştirilmesidir. Amacımız,
Yurtdışından ithal edilen malzemelerin Türkiye’de üretilmesiyle beraber;
maliyetlerinin düşürülmesi ve dışa bağımlılıktan kurtulunması, kullanılan
malzemelerin iyileştirilerek daha iyi ürünler üretilmesi.
Bu tez hızlı prototipleme makinelerinde kullanılan malzemelerin üretimini ve
kullanımını incelemektedir. Doğru malzemeyi seçip ondan gerekli boyutlarda
malzemeyi üretebilmek için, prototip makinelerinde hammadde olarak kullanılan
malzeme ABS (Acrylonitrile Butadiene Styrene) ‘nin üretimi, işlenmesi ve kullanımı
hakkında bilgi sahibi olmak gerekiyor.
Tezde öncelikle polimerler hakkında teorik incelemelere yer verildi. Ondan
sonra polimerlerin, ABS’ninde içinde olduğu, termoplastikler anlatıldı. ABS’nin
üretim methotları kullanım alanları ve özellikleri incelendi. Teorik inceleme kısmının
en sonunda, hızlı prototipleme yöntemlerinden tezle ilgili olan yöntem FDM (Fused
Deposition Modelling) ayrıntılı olarak anlatıldı. Bu kısımda son olarak, hızlı
prototipleme makinelerinde kullanılmak için ABS malzemeyi işlediğimiz ekstrüzyon
incelendi. Tezin deneyler ve sonuçları kısmında, değişik firmalardan alınan değişik
özelliklere sahip ABS örneklerine testler yapıldı. Böylelikle istenilen malzemenin
özelliklerini ve firmalardan alınan ABS’ lerin arasında karşılaştırma imkanı doğdu.
Bu testlerle malzemelerin içerikleri, çekme mukavemeti, sertliği, erime sıcaklıkları
ve akış endeksleri incelendi. Bir diğer önemli özellik olan yüzey pürüzsüzlüğü
yapılan kalıplar ve hassas ekstrüzyon işlemiyle elde edildi. Böylelikle doğru
malzemeyi seçip bundan istenilen boyutlarda malzeme çekildi. Hızlı prototipleme
makinesinde denenip sonuçları irdelendi.
Hızlı prototipleme işlemi çok hassas bir işlem olduğundan kullanılan
malzeme birinci öncelikle işlemin ve sonucun kalitesini etkileyen etmendir.
Malzemelerin fiziksel ve termal özelliklerini bilip karşılaştırma imkanımız
olduğunda bu işlem için kullanılması gereken doğru ABS malzemeyi seçmiş,
böylelikle tezimizin amacına ulaşmış olduk.
06, 2008 Özgür KIRELLİ

vi
SYMBOLS

E : Young’s Modulus
F : Force
Tm : Melting Temperature
Tg : Glass Transition Temperature
W : Load
ρ : Density

vii
ABBREVIATIONS

ABS : Acrylonitrile Butadiene Styrene

DTUL : Deflection Temperature Under Load
FDM : Fused Deposition Modeling
H2O : Dihidrojen Monoksit (Water)
IV : INTRINSIC VISCOSITY
HDT : The Heat Deflection Temperature
LOI : The Limited Oxygen Index
MPa : Mega Pascal
MFI : Mold Flow Index
PC : Polycarbonate
Psi : Pounds per square inch
PVB : Polyvinyl Butyral
PVC : Polyvinyl Butyral Chloride
RP : Rapid Prototyping
UV : Ultraviolet Rays

viii
FIGURES

PAGE
FIGURE II.1 Structure of Polypropylene ….………………………….……..3
FIGURE II.2 Polymerization of ethylene….…………………………….…..12
FIGURE II.3 The Historical Development of Synthetic Thermoplastic
Resins …………………………………………………………………….…..17
FIGURE II.4 Production Volumes And Prices For Volume Units For
Thermoplastics………………………………………………………….……..33
FIGURE II.5 Modulus vs Notched Iizod of Engineering Thermoplastics…..34
FIGURE II.6 Tensile strength vs HDT of engineering thermoplastics ……..35
FIGURE II.7 Monomers in ABS polymer……..……..……..……..………...39
FIGURE II.8 Three-dimensional model of a wine glass .……………….…..42
FIGURE II.9 Wine glass as seen in catalyst as cross-section, from front, and in
perspective view ……..……..……..……..……..……..……..……..………...42
FIGURE II.10 Dimension FDM machine and view of build in progress …...43
FIGURE II.11 FDM Machine ….…………………………….………….…..44
FIGURE II.12 FDM Fabricated Water Wheel Bucket …………………...…48
FIGURE II.13 FDM Using Paintball IR Tank ….……………………..…….49
FIGURE II.14 Extrusion Process.…………………………….………….…..50
FIGURE II.15 Extrusion Machine.…………………………….………….…51
FIGURE II.16 Extrusion Screw Design.………………………………….….52
FIGURE III.1 MFI Machine .…………………………………………….….57
FIGURE III.2 Hardness Test Machine .………………….……………….…60
FIGURE III.3 Extrusion Machine.…………………………….…....…….….63
FIGURE IV.1 Sample1 and Sample 3 after MFI Test.……………………...70
FIGURE IV.2 Sample after MFI Test.…………………….…..………….….70

ix
TABLES

 
PAGE
Table II.1 RelationShips Between Poylmer Properties and Morphology …………..15
Table II.2 Producers and Trade Names of Engineering Thermoplastics………….19
Table II.3 Producers and Trademarks of Thermoplastic Polyesters ………..…….21
Table II.4 Producers and Trademarks of ABS Materials …………….……..…….22
Table II.5 Properties, Units and Standard Methods of Measurement …...…..…....24
Table II.6 Sites for Engineering Thermoplastics…………………………………..31
Table II.7 Chemical Resistance of Engineering Thermoplastics………………….36
Table II.8 Material Properties (Stratasys)…………………………..……………..46
Table IV.1 Properties of Original Materials………………….…………..…….….65
Table IV.2 MFI Test Results …………………….………….…………..…….…..69

x
 I. INTRODUCTION
The fused deposition modeling (FDM) is one of the most widely used rapid
prototyping systems in the world. The main reasons of its increasing popularity and use
have been its reliability, safe and simple fabrication process, low cost of material, and
the availability of a variety of building thermoplastics. Ever since the first FDM system
was launched in early 1990s, the Stratasys Inc has been marketing improved FDM
systems on a regular basis. However, research has also been going on in universities and
research institutions around the world to increase its applications, to develop new
materials and to improve the FDM process [1].
The FDM systems, developed by Stratasys Inc, currently fabricate parts in
elastomers, Acrylonitrile Butadiene Styrene (ABS) and investment casting wax using the
layer by layer deposition of extruded material through a nozzle using feedstock
filaments from a spool. Most of the parts fabricated in these materials can be used for
design verification, form and fit checking and patterns for casting processes and medical
application. New materials for FDM are needed to increase its application domain
especially in rapid tooling and rapid manufacturing areas. ABS material can be produced
in feed stock filament form of required size, strength and properties in Turkey.
Our aim is producing of supply materials for Rapid Prototyping (RP) machine and
improving materials properties and its using in Turkey. With the production of supply
material in Turkey, which is exported, costs are decreased and escape from foreign
dependence.
This thesis investigates processes of support material and using of these materials
in rapid prototyping machine. For production and selection to right material, we have to
get information about production, processing and using of ABS.
First, general information about polymers is given in Theoretical Investigation.
Then, thermoplastics are described in detail. Hereafter, detailed information is given
about ABS. At the end of the theoretical investigation part, process of Rapid Prototyping
process FDM and extrusion process of ABS will be explained.

1
 There are a lot of important points for production of supply material. We have to
select the right material. There are too many types of material that used in Rapid
Prototyping Machine. And there are a lot of important points such as Tensile strength,
tensile modulus, elongation, melting temperature and mold flow index. Another point is
smooth surfaces on these molds. Rough surfaces prevent ejection of the injection molded
part and play a role in the overall quality of the final part.
In experimental study, experiments are made on samples which have different
properties. We produced ABS material for rapid prototyping machine. First, we
purchased raw ABS materials from producers. That is the most important point which
effects overall process. Then, we made extrusion process with extrusion machine. We
have to know the physical properties of material to using in machine. Prototyping
process is very sensitive process which can be affected by many disturbances. When we
know physical values of samples of ABS, we realize the production is good or not.

2
 II. GENERAL BACKGROUND
II.1 POLYMERS
A polymer is a substance composed of molecules with large molecular mass
composed of repeating structural units, or monomers, connected by covalent chemical
bonds. The word is derived from the Greek, πολυ, polu, "many"; and μέρος, meros,
"part". Well known examples of polymers include plastics, DNA and proteins. A simple
example is polypropylene whose repeating unit structure is shown at right.

Polypropylene

Poly (1-methylethylene) except where noted otherwise, data are given for
materials in their standard state (at 25 °C, 100 kPa)
Figure II.1

While "polymer" in popular usage suggests "plastic", the term actually refers to a
large class of natural and synthetic materials with a variety of properties and purposes.
Natural polymer materials such as shellac and amber have been in use for centuries.
Biopolymers such as proteins (for example hair, skin and part of the bone structure) and
nucleic acids play crucial roles in biological processes. A variety of other natural
polymers exist, such as cellulose, which is the main constituent of wood and paper.
Typical synthetic polymers are Bakelite, neoprene, nylon, polyvinyl chloride (PVC),
polystyrene, polyacrylonitrile and polyvinyl butyral (PVB). Polymers are studied in the
fields of polymer chemistry and polymer science [2].

3
 II.1.1 Polymer Structure
The structural properties of a polymer relate to the physical arrangement of
monomers along the backbone of the chain. Structure has a strong influence on the other
properties of a polymer. For example, a linear chain polymer may be soluble or
insoluble in water depending on whether it is composed of polar monomers (such as
ethylene oxide) or nonpolar monomers (such as styrene). On the other hand, two
samples of natural rubber may exhibit different durability even though their molecules
comprise the same monomers. Polymer scientists have developed terminology to
precisely describe both the nature of the monomers as well as their relative arrangement
[6]:

II.1.2 Polymer properties

Types of polymer 'properties' can be broadly divided into several categories based
upon scale. At the nano-micro scale are properties that directly describe the chain itself.
These can be thought of as polymer structure. At an intermediate mesoscopic level are
properties that describe the morphology of the polymer matrix in space. At the
macroscopic level are properties that describe the bulk behavior of the polymer.

The bulk properties of a polymer are those most often of end-use interest. These are
the properties that dictate how the polymer actually behaves on a macroscopic scale [6].

II.1.2.1 Crystallinity

When applied to polymers, the term crystalline has a somewhat ambiguous usage.
In some cases, the term crystalline finds identical usage to that used in conventional
crystallography. For example, the structure of a crystalline protein or polynucleotide,
such as a sample prepared for x-ray crystallography, may be defined in terms of a
conventional unit cell composed of one or more polymer molecules with cell dimensions
of hundreds of angstroms or more.

A synthetic polymer may be described as crystalline if it contains regions of three-

dimensional ordering on atomic (rather than macromolecular) length scales, usually

4
arising from intramolecular folding and/or stacking of adjacent chains. Synthetic
polymers may consist of both crystalline and amorphous regions; the degree of
crystallinity may be expressed in terms of a weight fraction or volume fraction of
crystalline material. Few synthetic polymers are entirely crystalline[1].

II.1.2.2 Tensile strength

The tensile strength of a material quantifies how much stress the material will
endure before failing [4] [5]. This is very important in applications that rely upon
polymer's physical strength or durability. For example, a rubber band with a higher
tensile strength will hold a greater weight before snapping. In general tensile strength
increases with polymer chain length [2].

II.1.2.3 Young's Modulus of elasticity

Young's Modulus quantifies the elasticity of the polymer. It is defined, for small
strains, as the ratio of rate of change of stress to strain. Like tensile strength this is highly
relevant in polymer applications involving the physical properties of polymers, such as
rubber bands [2].

II.1.2.4 Transport Properties

Transport properties such as diffusivity relate to how rapidly molecules move

through the polymer matrix. These are very important in many applications of polymers
for films and membranes[3].

II.1.2.5 Melting point

The term "melting point" when applied to polymers suggests not a solid-liquid
phase transition but a transition from a crystalline or semi-crystalline phase to a solid
amorphous phase. Though abbreviated as simply "Tm", the property in question is more
properly called the "crystalline melting temperature". Among synthetic polymers,
crystalline melting is only discussed with regards to thermoplastics, as thermosetting
polymers will decompose at high temperatures rather than melt [6].
5
 II.1.2.6 Boiling point

The boiling point of a polymer substance is never defined due to the fact that
polymers will decompose before reaching theoretical boiling temperatures.

II.1.2.7 Glass transition temperature

A parameter of particular interest in synthetic polymer manufacturing is the glass

transition temperature (Tg), which describes the temperature at which amorphous
polymers undergo a second order phase transition from a rubbery, viscous amorphous
solid to a brittle, glassy amorphous solid. The glass transition temperature may be
engineered by altering the degree of branching or cross-linking in the polymer or by the
addition of plasticizer [6].

In general, polymeric mixtures are far less miscible than mixtures of small molecule
materials. This effect is a result of the fact that the driving force for mixing is usually
entropics, not energetics. In other words, miscible materials usually form a solution not
because their interaction with each other is more favorable than their self-interaction but
because of an increase in entropy and hence free energy associated with increasing the
amount of volume available to each component. This increase in entropy scales with the
number of particles (or moles) being mixed. Since polymeric molecules are much larger
and hence generally have much higher specific volumes than small molecules, the
number of molecules involved in a polymeric mixture are far less than the number in a
small molecule mixture of equal volume. The energetics of mixing, on the other hand,
are comparable on a per volume basis for polymeric and small molecule mixtures. This
tends to increase the free energy of mixing for polymer solutions and thus make
solvation less favorable. Thus, concentrated solutions of polymers are far rarer than
those of small molecules.

In dilute solution, the properties of the polymer are characterized by the interaction
between the solvent and the polymer. In a good solvent, the polymer appears swollen
and occupies a large volume. In this scenario, intermolecular forces between the solvent
and monomer subunits dominate over intramolecular interactions. In a bad solvent or

6
poor solvent, intramolecular forces dominate and the chain contracts. In the theta
solvent, or the state of the polymer solution where the value of the second virial
coefficient becomes 0, the intermolecular polymer-solvent repulsion balances exactly
the intermolecular monomer-monomer attraction. Under the theta condition the polymer
behaves like an ideal random coil [6].

II.1.2.8 Chain length

Polymer bulk properties are strongly dependent upon their structure and mesoscopic
behavior. A number of qualitative relationships between structure and properties are
known.

Increasing chain length tends to decrease chain mobility, increase strength and
toughness, and increase the glass transition temperature (Tg). This is a result of the
increase in chain interactions such as Van der Waals attractions and entanglements that
come with increased chain length. These interactions tend to fix the individual chains
more strongly in position and resist deformations and matrix breakup, both at higher
stresses and higher temperatures. Chain length is related to melt viscosity roughly as
1:103.2, so that a tenfold increase in polymer chain length results in a viscosity increase
of over 1000 times [5].

II.1.3 Chemical properties of polymers

The attractive forces between polymer chains play a large part in determining a
polymer's properties. Because polymer chains are so long, these interchain forces are
amplified far beyond the attractions between conventional molecules. Different side
groups on the polymer can lend the polymer to ionic bonding or hydrogen bonding
between its own chains. These stronger forces typically result in higher tensile strength
and melting points.

The intermolecular forces in polymers can be affected by dipoles in the monomer

units. Polymers containing amide or carbonyl groups can form hydrogen bonds between
adjacent chains; the partially positively charged hydrogen atoms in N-H groups of one

7
chain are strongly attracted to the partially negatively charged oxygen atoms in C=O
groups on another. These strong hydrogen bonds, for example, result in the high tensile
strength and melting point of polymers containing urethane or urea linkages. Polyesters
have dipole-dipole bonding between the oxygen atoms in C=O groups and the hydrogen
atoms in H-C groups. Dipole bonding is not as strong as hydrogen bonding, so a
polyester's melting point and strength are lower than Kevlar's (Twaron), but polyesters
have greater flexibility.

Ethene, however, has no permanent dipole. The attractive forces between

polyethylene chains arise from weak van der Waals forces. Molecules can be thought of
as being surrounded by a cloud of negative electrons. As two polymer chains approach,
their electron clouds repel one another. This has the effect of lowering the electron
density on one side of a polymer chain, creating a slight positive dipole on this side. This
charge is enough to actually attract the second polymer chain. Van der Waals forces are
quite weak, however, so polyethene can have a lower melting temperature compared to
other polymers [9].

II.1.4 Polymer characterization

The characterization of a polymer requires several parameters which need to be
specified. This is because a polymer actually consists of a statistical distribution of
chains of varying lengths, and each chain consists of monomer residues which affect its
properties.

A variety of lab techniques are used to determine the properties of polymers.

Techniques such as wide angle X-ray scattering, small angle X-ray scattering, and small
angle neutron scattering are used to determine the crystalline structure of polymers. Gel
permeation chromatography is used to determine the number average molecular weight,
weight average molecular weight, and polydispersity. Thermal properties such as the
glass transition temperature and melting point can be determined by differential
scanning calorimetry and dynamic mechanical analysis. Pyrolysis followed by analysis
of the fragments is one more technique for determining the possible structure of the
polymer[9].

8
 II.1.5 Polymer degradation
Polymer degradation is a change in the properties - tensile strength, colour, shape,
etc - of a polymer or polymer based product under the influence of one or more
environmental factors such as heat, light or chemicals. It is often due to the hydrolysis of
the bonds connecting the polymer chain, which in turn leads to a decrease in the
molecular mass of the polymer. These changes may be undesirable, such as changes
during use, or desirable, as in biodegradation or deliberately lowering the molecular
mass of a polymer. Such changes occur primarily because of the effect of these factors
on the chemical composition of the polymer. Ozone cracking and UV degradation are
specific failure modes for certain polymers[6].

The degradation of polymers to form smaller molecules may proceed by random

scission or specific scission. The degradation of polyethylene occurs by random scission
- that is by a random breakage of the linkages (bonds) that hold the atoms of the polymer
together. When heated above 450 Celsius it degrades to form a mixture of hydrocarbons.
Other polymers - like polyalphamethylstyrene - undergo 'specific' chain scission with
breakage occurring only at the ends. They literally unzip or depolymerize to become the
constituent monomer[6].

However the degradation process can be useful from the view points of
understanding the structure of a polymer or recycling/reusing the polymer waste to
prevent or reduce environmental pollution. Polylactic acid and Polyglycolic acid, for
example, are two polymers that are useful for their ability to degrade under aqueous
conditions. A copolymer of these polymers is used for biomedical applications such as
hydrolysable stitches that degrade over time after they are applied to a wound. These
materials can also be used for plastics that will degrade over time after they are used and
will therefore not remain as litter.

9
 II.1.6 Polymerization

In polymer chemistry, polymerization is a process of reacting monomer molecules

together in a chemical reaction to form three-dimensional networks or polymer chains
[7]. There are many forms of polymerization and different systems exist to categorize
them.

The main categories are

• Chain-growth polymerization
• Step-growth polymerization

In chemical compounds, polymerization occurs via a variety of reaction

mechanisms which vary in complexity due to functional groups present in reacting
compounds[8] and. In more straightforward polymerization, alkenes, which are a
relatively stable due to σ bonding between carbon atoms form polymers through
relatively simple radical reactions; conversely, more complex reactions such as those
that involve substitution at the carbonyl atom require more complex synthesis due to the
way in which reacting molecules polymerize.[8]

As alkenes can be formed in somewhat straightforward reaction mechanisms, they

form useful compounds such as polyethylene and polyvinyl chloride (PVC) when
undergoing radical reactions, which are produced in high tonnages each year due to their
usefulness in manufacturing processes of commercial products, such as piping,
insulation and packaging. Polymers such as PVC are generally referred to as "singular"
polymers as they consist of repeated long chains or structures of the same monomer unit,
whereas polymers that consist of more than one molecule are referred to as "co-
polymers".

Other monomer units, such as formaldehyde hydrates or simple aldehydes, are able
to polymerize themselves at quite low temperatures (>-80oC) to form trimers;[8]
molecules consisting of 3 monomer units which can cyclize to form ring cyclic
structures, or undergo further reactions to form tetramers, or 4 monomer-unit

10
compounds. Further compounds either being referred to as oligomers in smaller
molecules. Generally, because formaldehyde is an exceptionally reactive electrophile it
allows nucleophillic addition of hemiacetal intermediates, which are generally short
lived and relatively unstable "mid stage" compounds which react with other molecules
present to form more stable polymeric compounds.

Polymerization that is not sufficiently moderated and proceeds at an undesirably fast

rate can be very hazardous. This phenomenon is known as Hazardous polymerization
and can cause fires and explosions[9].

II.1.6.1 Chain-growth

Chain-growth polymerization or addition polymerization involves the linking

together of molecules incorporating double or triple chemical bonds. These unsaturated
monomers (the identical molecules which make up the polymers) have extra internal
bonds which are able to break and link up with other monomers to form the repeating
chain. Addition polymerization is involved in the manufacture of polymers such as
polyethylene, polypropylene and polyvinyl chloride (PVC). A special case of addition
polymerization leads to living polymerization[8].

The main characteristics are:

Polymerization process takes place in three distinct steps:

1. Chain initiation, usually by means of an initiator which starts the chemical

process. Typical initiators include any organic compound with a labile group: e.g. azo (-
N=N-), disulfide (-S-S-), or peroxide (-O-O-).
2. Chain propagation[8]
3. Chain termination, [8]which occurs either by combination or
disproportionation. Termination, in radical polymerisation, is when the free radicals
combine and is the end of the polymerisation process.

• Some side reactions may occur, such as: chain transfer to monomer, chain
transfer to solvent, and chain transfer to polymer.
11
 • Unlike condensation polymerisation (also known as step-growth
polymerization):
o high molecular weight polymer is formed at low conversion
o no small molecules, such as H2O, are eliminated in this process
• New monomer adds on the growing polymer chain via the reactive active centre
which can be a
o free radical in free radical addition polymerisation
o carbocation in cationic addition polymerisation
o carbanion in anionic addition polymerisation
o organometallic complex in coordination polymerisation
• The monomer molecule can be a
o unsaturated compound like ethylene or acetylene which make them
reactive, see vinyl polymer
o Alicyclic compound, see ring-opening polymerisation
• Given special reactants and reaction conditions an addition polymerization can
be considered a living polymerization.
• Above a certain ceiling temperature, no polymerisation occurs[8].

In the polymerization of ethylene, its pi bond is broken and these two electrons
rearrange to create a new propagating center like the one that attacked it. The form this
propagating center takes depends on the specific type of addition mechanism. There are
several mechanisms through which this can be initiated. The free radical mechanism was
one of the first methods to be used. Free radicals are very reactive atoms or molecules
which have unpaired electrons. Taking the polymerization of ethylene as an example,
the free radical mechanism can be divided in to three stages: chain initiation, chain
propagation and chain termination[9].

Polymerization of ethylene
Figure II.2

12
 Free radical addition polymerization of ethylene must take place at high
temperatures and pressures, approximately 300°C and 2000 At. While most other free
radical polymerizations do not require such extreme temperatures and pressures, they do
tend to lack control. One effect of this lack of control is a high degree of branching.
Also, as termination occurs randomly, when two chains collide, it is impossible to
control the length of individual chains. A newer method of polymerization similar to
free radical, but allowing more control involves the Ziegler-Natta catalyst especially
with respect to polymer branching [9].

Other forms of addition polymerization include cationic addition polymerization

and anionic addition polymerization. While not used to a large extent in industry yet due
to stringent reaction conditions such as lack of water and oxygen, these methods provide
ways to polymerize some monomers that cannot be polymerized by free radical methods
such as polypropylene. Cationic and anionic mechanisms are also more ideally suited for
living polymerizations, although free radical living polymerizations have also been
developed[9].

II.6.2 Step-growth

Step growth polymers are defined as polymers formed by the stepwise reaction
between functional groups of monomers. Most step growth polymers are also classified
as condensation polymers, but not all step growth polymers (like polyurethanes formed
from isocyanate and alcohol bifunctional monomers) release condensates. Step growth
polymers increase in molecular weight at a very slow rate at lower conversions and only
reach moderately high molecular weights at very high conversion (i.e. >95%).

To alleviate inconsistencies in these naming methods, adjusted definitions for

condensation and addition polymers have been developed. A condensation polymer is
defined as a polymer that involves elimination of small molecules during its synthesis,
or contains functional groups as part of its backbone chain, or its repeat unit does not
contain all the atoms present in the hypothetical monomer to which it can be degraded
[7].

13
 II.2 ENGINEERING THERMOPLASTICS
II.2.1 Introduction
The development of plastic materials is one of the most successful stories of the
twentieth century. In the sixties, plastics represented a small fraction of the total annual
consumption of materials, but 20 years later they surpassed metallic materials (mostly
iron-based) in terms of consumed volume. At the end of the century, plastics reached the
astonishing total amount of 150 million metric tons produced per year. Of this amount,
70% is comprised by the so-called commodity plastics , 11% by thermoset resins, 7% by
elastomers, and 12% by engineering thermoplastics[9].
The definition of engineering plastics is rather arbitrary. In the last edition of this
encyclopedia they were defined as thermoplastic resins, neat or filled, which maintain
dimensional stability and most mechanical properties above 100◦C and below 0◦C. In
such a definition, engineering plastics are obviously intended as engineering
thermoplastics and the terms are used interchangeably. They encompass plastics that can
be formed into parts suitable for bearing loads and able to withstand abuse in thermal
environments traditionally tolerated by metals, ceramics, glass, and wood. A more
general definition defines engineering plastics as those high performance materials that
provide a combination of high ratings for mechanical, thermal, electrical, and chemical
properties. This article adopts this latter definition, with the following three restrictions:
[9] thermoplastics considered here are generally produced on an industrial scale; [10]
with some exceptions, their predominant application is as solid parts or films, not fibers
or cellular materials; and [11] sophisticated derivations of commodities, like reinforced,
widely used in engineering applications are excluded. Following these guidelines, Table
1 was compiled; occasionally, copolymers, blends, and reinforced polymers are
included. The materials have been arbitrarily grouped by considering the most
representative heteroatom present in their chemical structure.
These materials are discussed in general in this article and in more detail in articles
devoted to the various polymers. Cross references are provided. The selection of
polymer families treated here is somewhat arbitrary. For instance, fluoropolymers are
more functional materials than engineering materials, and acrylic resins suffer enough
14
thermal instability to be considered by some authorsas outside the border of engineering
plastics. However, PTFE (together with some copolymers) and PMMA have been
considered because of their notoriety and some specific engineering applications.

Table II.1 RelationShips Between Poylmer Properties and Morphology

In Table II.1, the qualitative dependence of some properties of polymeric materials

as a function of their morphological state is reported. Such properties are determined
directly or indirectly by the different response of chains to solicitations (chemical,
thermal, and so on) when they are in an ordered arrangement or in a random one. Totally
crystalline (100%) polymers are impossible to obtain because of the unavoidable
presence of chain folds; further, the crystallinity degree can change under the effect of
thermal, mechanical, or chemical operations.

15
 II.2.2 History of development of Thermoplastics
The development of engineering thermoplastics began in the thirties and is still
continuing. The first patent on polyamide (nylon) was obtained by Carothers in 1931.
Before the second World War, acrylic and polyester resins were discovered, as well as
styrene-based copolymers (ABS) and PTFE. The latter was brought to full production in
1950 as Teflon by DuPont. In the same year, polycarbonates were introduced by General
Electric and acetal resins by Celanese. In the period of 1960–1980, most of the actual
high performance polymers were developed, among them were polyimides, PES, PPS,
PEEK, and PEI, as well as other engineering resins such as PPO and PBT. At that time,
the potential of development of novel engineering plastics was overestimated, and when
it was realized that the volume growth was not so fast, the introduction of new families
slowed down. Several factors contributed to this change of attitude, from the growing of
costs necessary for the introduction of a new material, to a lower demand of materials
studied for structural applications, and finally to the competition of tailored grades of
existing polymers (also commodity plastics, like PP), new blends, and reinforced
materials. Furthermore, the time from the invention of a new polymer structure to the
achievement of the industrial stage remained quite high (10– 12 years), in spite of the
experience accumulated in such processes. Thus, from an originally forecasted 25% of
the whole plastics market, engineering plastics cover only 10% roughly. It remains true
that the growth rate is higher than that of commodities, but this expands their total
fraction only very slowly. In Figure II.3, the chronological development of commercial
thermoplastic polymers is sketched, taking into account commodities nearer to
engineering polymers (in properties) [11,12]. The figure shows that most of the
engineering thermoplastics were introduced industrially in the 1950–1980 period. The
new flourishing in the nineties was partly enhanced by some particular events, like the
development of metallocene catalysts, which rendered convenient the fabrication of new
materials like sPS and COCs, and the availability of the monomer for PEN.

16
 Figure II.3 The Historical Development of Synthetic Thermoplastic Resins.
The reported years indicate the presumed entry in the market. [6]

Table 2 reports for each polymer family the most important producers and
corresponding trade names, with the aim of helping the reader to identify materials.
Some books are dedicated to this task [12–15], which is complicated by ongoing
mergers and selling of operations, resulting in changed connections between producers
and trade names.

II.2.3 Properties of Thermoplastics

Some material properties are intrinsic to the chemical substance under investigation;
others depend on the processing operation, which confers a shape and orientation to the
material. Because some processing is often necessary to prepare testing specimens,
intrinsic properties can be difficult to measure. Some properties acquire relevance only
when the final article is manufactured and strictly depend on the specific use of the
article. Properties have been distinguished as performance, maintenance, or aesthetic
properties [9]; however, this classification is extremely subjective. Herein, mainly
intrinsic and processing properties are considered, divided into four conventional
groups: physical, electrical, thermal, and mechanical. Several of such properties change
remarkably depending on the morphology (amorphous or semicrystalline materials) or

17
for the presence of fillers and reinforcing fibers. It is impossible to report the properties
of all the grades present on the market; it was estimated that more than 5300 grades of
engineering plastics were offered by producers in 1997 [13]. Thus, the more
representative of them are described in discussions of specific polymers. In Table II.2,
the most representative properties are reported, together with the proper SI units and, if
existing, the respective standard measurement method. Several books describe the
methods in more detail [11,12,16].

18
Table II.2 Producers and Trade Names of Engineering Thermoplastics

19
Table II.2 (cont’d) [7]

20
 II.2.3.1 Physical Properties
Physical properties include density, properties connected to their combustion
tendency (flammability and oxygen index), optical properties (refractive index and
yellow index), and the ability to absorb water. Density ρ, ie, the mass per unit volume,
depends on the nature of atoms present in the chemical structure and the way molecules
(chains) pack together. Polyolefins, composed of C and H only, have densities in the
range 0.85–1; organic polymers containing heteroatoms rarely have densities higher than
[2]. Conformations and crystalline phases strongly influence density. Crystalline phases
are generally more dense than amorphous phases, an average ρc/ρa ratio of 1.13 ± 0.08
has been determined [9].

Table II.3 Producers and Trademarks of Thermoplastic Polyesters [6]

Table II.3 Producers and Trademarks of Thermoplastic Polyesters

The Limited Oxygen Index (LOI) test determines the minimum oxygen fraction in

an oxygen/nitrogen mixture able to support combustion of a candle-light sample under

specific test conditions. The LOI test is necessary but not sufficient for determining the

21
burning behavior of polymers in real conditions. For this task, specific flammability tests
have been established on an empirical basis. The most widely used test is UL94,
elaborated by Underwriters Laboratories, rating the ability of a material to extinguish a
flame once ignited [15]. In decreasing order, the UL94 degrees are V-0, V-1, V-2,
andHB, based on a specific specimen thickness.
Only a few high performance polymers, like polyetherimides, have been classified
as inherently nonflammable (ie, V-0); other polymers can reach a good classification
after the addition of specific additives, ie, flame-retardants, in the material formulation.

Table II.4 Producers and Trademarks of ABS Materials [7]

The refractive index n measures the deviation of light when passing through matter
and is expressed as sin(i)/sin(r), where i and r are the angles of incident light and
refracted light, respectively. It is closely linked to molecular structure of polymers and
contributes to their optical properties, like clarity, haze, birefringence, color,
transmittance, and reflectance. Most of engineering plastics considered here are opaque
and/or inherently colored, with the exceptions of PC, PMMA, and COC. For them, when
used in optical applications, the yellow index (YI) is relevant. Yellow index indicates the

22
degree of departure of an object color from colorless or from a preferred white toward
yellow and is determined from spectrophotometric data.

Water absorption indicates the increase of weight of a polymer after immersion in

water under specified conditions of temperature and time. Generally, it is referred to 24
h at room temperature (23◦C) and is expressed as a percentage with respect to the initial
weight. If water is absorbed by a polymer, drying is required before processing
operations because the presence of water at high temperatureresults in uncontrolled
degradation of the material and consequently poor performance. This is the case of PET
and other polyesters.
Some polymers like polyamides absorb water from air humidity and hold water
molecules rather firmly by hydrogen bonding. Absorbed water causes a slow variation of
properties like electrical characteristics, mechanical strength, and dimensions. For this
reason, polymers or specific grades insensitive to water must be employed in moist
environments[13].

23
Table II.5 : Properties, Units and Standard Methods of Measurement [7]

24
 II.2.3.2 Electrical Properties
Electrical properties include dielectric constant, dielectric strength, dissipation
factor, and volume resistivity. All of them depend on temperature and water absorption.
The (relative) dielectric constant is the ratio of the capacitance of a condenser formed by
two metal electrodes separated by a suitable layer of the material considered and the
same separated by dry air. The dielectric strength measures the dielectric breakdown
resistance of a material under an applied voltage. The applied voltage value just before
breakdown is divided by the specimen thickness. Thus, because the result depends on
thickness, this value must be specified. The dissipation factor, also called loss tangent, measures
the tangent of the difference angle between 90◦ (ideal angle for a perfect dielectric material)

and the true angle at which an alternating current leads the voltage. It is equivalent to the
ratio of current dissipated into heat and current actually transmitted. The volume
resistivityis the electrical resistance of a unit cube of a given material when an electrical
potential is applied to two opposite faces of the cube[14].

II.2.3.3 Thermal Properties

Thermal properties include some transitions like melting temperature and glass
transition transition temperature, the heat deflection temperature (HDT), specific heat
capacity, thermal conductivity, coefficient of thermal expansion, and upper working
temperature. The melting temperature Tm is the temperature at which a solid becomes a
liquid (or, on cooling, at which a liquid solidifies). For polymeric materials, Tm is often
a temperature range rather than a single value; however, its point value should represent
the maximum temperature at which crystallites exist. Amorphous polymers do not
exhibit a Tm. The glass-transition temperature Tg is the temperature at which a solid,
rigid, and brittle polymer becomes rubbery by loosening remarkably its rigidity.
Mechanical properties are also reduced at Tg, and other properties like volume, thermal
expansion coefficient, and specific heat capacity change noticeably. Being kinetic in
nature, Tg occurs over a temperature range (depending, for instance, on cooling rate)
and is hardly visible in some polymers.[12]
HDT measures the temperature at which a specimen is deformed a specific amount
(eg, 0.25 mm) under a given load (usually, 0.45 or 1.82 MPa), applied in a three-point

25
arrangement. HDT is also called Deflection Temperature Under Load DTUL and should
not be interpreted as a safe temperature for continuous operation (which is usually
somewhat lower). The specific heat capacity represents the amount of heat necessary to
increase the temperature of a unit mass of a substance by one degree. Depending on its
definition at constant pressure or at constant volume, it is indicated as cp or cv,
respectively. Thermal conductivity represents the amount of heat conducted per unit of
time through a unit area of a material of unit thickness having a difference of one degree
between its faces. The thermal expansion coefficient represents the change in volume (or
length) accompanying a temperature unit variation and is of great importance in molding
operations of plastic articles, having mold shrinkage as a practical effect.
The upper working temperature is a purely empirical indication at which a given plastic
can be expected to perform safely and satisfactorily. It is generally lower than HDT [13].

II.2.3.4 Mechanical Properties

Mechanical properties include tensile properties (modulus and strength), flexural
properties (modulus and strength), compressive strength, elongation at break, impact
resistance, hardness, and friction coefficient. Other relevant properties are creep and
fatigue but it is difficult to find comparative data among materials.

The tensile modulus (also elastic, or Young’s modulus) E is the stress-to strain ratio
within its proportional limit for a material under tensile loading (in practice, the initial
slope of the stress–strain curve). The tensile strength represents the maximum tensile
stress observed when the specimen is being pulled. It may or may not coincide with the
ultimate strength, ie, the tensile stress at specimen failure. In tough materials it can be
equal to the yield stress. The flexural modulus is the stress-to-strain ratio within its
proportional limit for a material under bending load conditions. It measures the stiffness
of a material. The flexural strength is the ability of a material to flex without permanent
deformation or breaking. The elongation at break is equal to tensile strength at failure
multiplied by 100. It is expressed as a percent of the original length of the specimen. The
impact strength (or impact resistance) represents the ability of a material to resist
physical breakdown when subjected to a rapidly increasing force and is accepted as a

26
comparison guide for toughness (see IMPACT RESISTANCE). It depends strongly on
the type of test used. The most widely used test in the field of plastics is Izod; the
Charpy test is less common. The Izod test requires specimens of thickness from 3.18 to
12.7 mm, preferentially notched following the test method prescriptions. A weighted
pendulum arm released from a fixed height strikes the specimen in a specified way. The
Izod impact energy is measured by dividing the energy lost by the pendulum
(presumably absorbed by the specimen) by the specimen thickness [13].
Hardness, defined as the resistance of a material to local deformation, is connected
in a complex way to mechanical properties, elasticity, and plasticity. Hardness cannot be
defined unambiguously and depends strongly on the test adopted for its determination. It
is usually characterized by the combination of three parameters, ie, scratch resistance,
abrasion resistance, and identation under load. For the identation test, different Shore
and Rockwell scales are in use, Rockwell M and Rockwell R being the most popular for
engineering plastics [10]. The scale depends on the combination of load and indentor
dimensions. The friction coefficient represents the resistance of surfaces of solid bodies
in contact with each other to sliding or rolling. It is represented as k = F/w, where F is
the force necessary to move one surface with respect to the other one, and w the load
exerted on them.
II.2.3.5 Rheological Properties
Rheological properties , describing the deformation of materials under stress and
concerning their flow properties, must be considered in all processing techniques for the
fabrication of plastic articles. In order to give operators necessary rheological
information, melt viscosity vs shear plots are commonly included in Data Sheets
provided by plastics producers. Here only a few properties connected to rheology are
considered, ie, intrinsic viscosity (IV) and melt-flow index (MFI). Intrinsic viscosity
measures the capability of a polymer in solution to increase the viscosity of the solution
itself. Because IV increases with molecular mass, it is an indication of this last property.
The MFI (or simply melt index) measures the isothermal resistance to flow through an
extrusion plastometer commonly referred to as melt indexer. Practically, the amount of
matter forced by a given load to pass in 10 min through a standard die is determined.
Melt-flow index can be considered as a single-point test (ie, resistance to flow at a single

27
shear rate). Every plastics processing technology operates at a defined MFI range as
follows (2): 5–100 g/10 min for injection molding, 5–20 g/10 min for rotational
molding, 0.5–6 g/10 min for film extrusion, and 0.1–1 g/10 min for blow molding and
profile extrusion.
II.2.3.6 Chemical Resistance
Chemical resistance is less rigidly defined than the properties discussed previously.
Measurement methods include immersion in selected vapors or liquids of a test
specimen, then determining the variation of mechanical properties after and before
treatment. Optical properties are also considered, particularly in the case of transparent
materials. The test results are generally indicated as excellent, good, fair, or poor, or are
given other arbitrary scale units. Chemical agents are chosen in order to simulate
possible real situations: strong and weak acids, alkalis, saline solutions, hydrocarbons
(aliphatic oraromatics), oils and greases, alcohols, aldehydes, ketones, etc. Engineering
plastics are generally difficult to dissolve in most solvents. Strictly correlated to
chemical resistance is weathering resistance, where a combination of a particular
environment, temperature, time, and uv irradiation is considered, also with cyclic
experiments.

II.2.4 Processing of Thermoplastics

Processing of thermoplastic materials can be classified into four main categories:
extrusion, post-die processing, forming, and injection molding [9–11]. In an extruder,
the polymer is melted and pumped into a shaping device called a die, through which the
material is forced to assume a particular shape. The pumping action is done by a single-
screw or by a twin-screw device, the configuration of which is essential for a suitable
result. Extruders are very often used at the end of the polymerization reactor in order to
obtain polymer pellets by chopping an extruded strand. Extruders are also currently used
to mix in the proper additives for the polymer, to obtain intimately mixed polymer
blends, to devolatilize the material from the monomers or solvent residues, and in some
special cases as a chemical reactor (reactive extrusion). For example, polyetherimide is
prepared at the industrial level by reactive extrusion. Depending on the extrusion die
geometry, final articles can also be obtained, including sheets, films, pipes, rods, and

28
profiles of various geometries (T, double T, C, and so on). Coating on wires can be
done, as well as coextrusion of two or more layers. Post-die processing includes a
number of operations carried out at the exit of the extruder die in a free-surface way.
Examples of such processes are fiber spinning, film blowing, and sheet forming. The
shape and dimensions of the extrudate material are determined by the rheological
properties of the melt, the die dimensions, the cooling conditions, and the take-up speed
(relative to the extrusion rate).
Forming processes use a mold to confer the final form to the article. Blow molding
is widely used in the manufacture of bottles or other containers for liquids, widely using
engineering polymers like PET and PC. Essentially, an extruded cylindrical parison is
inflated with a gas until it fills the mold cavity. A good equilibrium between the melt
strength of the resin under low shear conditions (parison stability) and the flow
properties under high shear conditions (blowing) are essential for obtaining a
satisfactory result. In thermoforming, a polymer sheet is heated to a temperature above
its Tg (or sometimes above Tm) and then pressed into the female part of the mold by
means of a suitable plug or by vacuum pulling. Simple-shape articles such as trays can
be obtained. In compression molding, an amount of polymer is heated at the proper
temperature and then squeezed by means of the male part of the mold into the mold
cavity. Injection molding is the most commonly used processing technique for
engineering thermoplastics. Typically, the polymer pellets are melted and the melt
pulled forward by means of a screw as in extrusion, so filling a mold under appropriate
pressure. The shape of the mold, the number and relative location of the injection
devices, and the mold cooling rate determine, together with the intrinsic properties of the
material, the final quality of the molded articles. Very complex article shapes can be
obtained by this technique. A viscosity of the resin around 10,000 Pa·s and a shear rate
of 100 s−1 are needed for a convenient operation. The main problem in injection
molding is shrinkage, caused by the volume changes during transition from the melt to
the solid. The typical shrinkage of semicrystalline polymers during processing is around
1–4%, compared to 0.2–0.8% for amorphous polymers (17). To reduce the problem,
crystallinity could be maintained low, but this is to the detriment of mechanical
properties. A compromise should be used. For polymers which crystallize slowly, like

29
PET, it is preferable to allow the polymer to reach the maximum crystallization degree
by the use of nucleating agents. If the shrinkage amount is different in different volume
portions of the fabricated part, warpage of the part itself can be observed. Interpolymer
Competition The properties of engineering thermoplastics span a wide range, and there
are many overlapping situations among resins. To select the right polymeric material for
a specific application is a hard job because the forest of commercial polymers has
become so crowded. Books have appeared to guide the materials engineer in the
selection of thermoplastic materials, with the help of a dedicated software [13].
Four main groups of technical considerations must be made in order to make the
right choice, ie, mechanical, electrical, environmental, and appearance. In addition, two
other elements are important, ie, cost and specifications (eg, imposed by a government
body or by a corporation). The environmental considerations include the operating
temperature, the chemical environment, the weathering exposure, and humidity degree.
The appearance includes style, shape, color, transparency, and surface finish of the
fabricated object. Mechanical and electrical considerations must include both short-time
and long-time values, and also the effects of environment on such properties. Also,
appearance can vary under service conditions. The necessary information must be
provided by different actors, that is, the material supplier, the processor, the processing
equipment supplier, and the product designer/producer.
Depending on the particular application, numerous properties should be considered
during the selection of the best candidate. Further, every property has a different
importance, and thus a different weight on the final choice. Property values reported
here are representative; several of them vary over a wide range depending on several
factors, like the nature and amount of fillers, the possible occurrence of
copolymerization, etc. Also, some data are not available in the current literature and
others are difficult to describe with just one figure. This is particularly true for
rheological data reported in data sheets as flow curves viscosity vs temperature curves,
etc. Similar difficulties arise for creep curves (related to long-term mechanical
resistance) and shrinkage and warpage of fabricated parts, strongly dependent on the
geometry and thickness of the part itself. The internet has made it easier to access data
about polymer grades actually produced

30
 In the final selection of the best material for the fabrication of a specific object,
a compromise is generally made by choosing the material which shows an optimized
balance of the most relevant properties. In addition to some particular

Table II.6 Sites for Engineering Thermoplastics [20]

properties, like transparency and the question of processability (which involves complex
issues as rheology, shrinkage, and surface finishing), in most of the applications of
engineering thermoplastics, the following characteristics and properties are considered:
price, mechanical properties, thermal properties, electrical properties,and chemical
resistance.
The price of a thermoplastic resin is basically determined by the cost of preparation,
which in turn strongly depends on the cost of reagents (monomers, catalysts, etc), the
complexity of the manufacturing process, and the dimension of production plants.
Aliphatic polyketones, for instance, are made from very cheap rawmolecules as
ethylene, propylene, and CO; their cost is determined by the need for expensive

31
catalysts, based on Pd complexes, and the relatively complex production plant. On the
other hand, PEN, which can easily be prepared in the same reactors used for PET,
suffers from the difficult availability of its basic monomer dimethyl 2,6-naphthalene
dicarboxylate. Most engineering polymers contain aromatic monomers, which are
difficult to synthesize and polymerize, with slow and sophisticated mechanisms
(condensation, substitution, oxidative coupling).
Roughly, commodities are priced at US$0.5–1/kg, engineering polymers in the
range of US$1–5/kg, and high performance polymers the range of US$5–50/kg. The
current prices fluctuate following market conditions and can be found as a price range,
for most materials, in technical journals like Plastics Technology. In Figure II.4, the
prices of engineering thermoplastics are reported as a function of annual production
volume, confirming, with a few exceptions, the inverse relationship between the two
parameters. The price is reported in U.S. cents per volume unit, more significant than the
corresponding price per mass unit. The unfilled materials have a density ranging from
1.02 g/mL for COCs to 2.18 g/mL for PTFE. However, the density of most engineering
thermoplastics falls around 1.15– 1.45 g/cm3. The price/volume relationship does not
work when a low volume material can be produced in a captive way in a plant used also
for producing a higher volume polymer. This is the case of polyarylates, some aliphatic
polyamides, and polysulfones[14].

32
 Figure II.4 Production Volumes and Prices For Volume Units For Thermoplastics
[19]

Fig.II.4. Production volumes and prices for volume units for thermoplastics
considered in this compilation. The dashed line represents an arbitrary border between
engineering and high performance thermoplastics.

II.2.5 Summary of Mechanical, Thermal, and Electrical Properties

The most representative mechanical properties are elastic (or tensile) modulus,
tensile strength, flexural modulus, and toughness. Flexural modulus is particularly
interesting, because it represents the stiffness of the material; unfortunately, data are not
available for all materials. However, because flexural modulus values are mostly of the
same order of magnitude of tensile modulus values, the latter can be used for
comparison purposes. Toughness is approximately described by Izod impact strength.
Figure II.5 reports elastic moduli and Izod strengths of engineering thermoplastics.
Data ranges are particularly wide for toughness data. The figure shows that for any
application, a wide number of combinations of stiffness and toughness is available in the
field of engineering thermoplastics. Further, reinforcing practice with fibers, minerals, or

33
other fillers is largely applied in order to enhance the mechanical and thermal properties.
Most of the materials treated here are offered in the market in a large number of
reinforced grades. Such a practice also influences the cost of the material, and this is
particularly relevant when the cost of the matrix is higher than the cost of the filler.
Figure II.5 shows the increase of modulus values that can be obtained by adding glass
fibers to several polymers.

Fig. II.5 Modulus Vs Notched Izod Of Engineering Thermoplastics. [19]

Heat-deflection temperature does not correspond to the practical use temperature;

however, it has been widely used in the plastics industry to compare the physical
response of materials to temperature at a single–load level. In Figure II.5,HDTvs tensile
strengths at two different loads are reported. Both groups of data roughly show a
proportional trend that can be ascribed to the fact that in many cases the molecular
structure of the chain influences, in the same sense, the mechanical and thermal
properties.
The electrical properties of engineering thermoplastics are generally excellent. In
specific applications, like cable and wire coatings, electrical or electronic parts, etc,

34
demanding values are requested. On the other side, electrical conductivity can be
increased by adding particular fillers like metallic powders.[17]

Chemical Resistance. Chemical resistance belongs to environmental

considerations because the accidental or expected exposure of a material to the
action of chemicals or solvents can have relevant short-and long-term influence

Figure.II.6. Tensile strength vs HDT of engineering thermoplastics. [17]

35
 Table II.7 Chemical Resistance of Engineering Thermoplastics [7]

Table II.7 summarizes the resistance of polymers against the most common families
of chemicals and solvents. As expected, fluoropolymers show the best response against
the whole range of chemicals considered. Chemical resistance values reported in the
table are indicative because they can be significantly affected by exposure length and
temperature. In practice, chemical resistance testing under end-use conditions is
suggested.

36
 II.2.6 The Future
Thermoplastic materials have now pervaded every important aspect of the human
life, from food management (through packaging) to clothing (through synthetic
fibers), ground and air transportation, office equipment, health (medical instruments and
devices, artificial prostheses), entertainment (audio and video reproduction components),
sports goods, and so on. Applications of thermoplastic materials, both commodities and
engineering thermoplastics, will continue to expand at the expense of other materials
like glass, metals, wood, and ceramics. Moreover, the time between the laboratory
synthesis of a new polymer and its industrial production remains high [17], thus
discouraging the introduction of new materials. The expected expansion of the
engineering thermoplastics market is of the order of 12% per year in the next three years
[14]. Interestingly, the most significant threat to engineering polymers comes from some
commodities, like polypropylene, which in some reinforced (but also unreinforced)
grades reach the performance of some engineering materials.

37
 II.3 Introduction to ABS Resins

Acrylonitrile butadiene styrene, or ABS, (chemical formula (C8H8·

C4H6·C3H3N)n) ABS is an acronym for the engineering polymer acrylonitrile-butadiene-
styrene. Contrary to what the name suggests, ABS is rarely made by simply reacting
acrylonitrile, butadiene, and styrene; intermediate stages are usually necessary. Nor is
the polymer structure homogenous; multiple phases are usually present. In 1970, there
were hundreds of patents to make ABS, 89 of which described a different series of
chemical reactions. Today, it is estimated that there are over 2300 grades of ABS resins
available commercially.[19] Almost all of these are produced by unique processes.

It is a copolymer made by polymerizing styrene and acrylonitrile in the presence of

polybutadiene. The proportions can vary from 15 to 35% acrylonitrile, 5 to 30%
butadiene and 40 to 60% styrene. The result is a long chain of polybutadiene criss-
crossed with shorter chains of poly(styrene-co-acrylonitrile). The nitrile groups from
neighboring chains, being polar, attract each other and bind the chains together, making
ABS stronger than pure polystyrene. The styrene gives the plastic a shiny, impervious
surface. The butadiene, a rubbery substance, provides resilience even at low
temperatures. ABS can be used between −25 and 60 °C. The properties are created by
rubber toughening, where fine particles of elastomer are distributed throughout the rigid
matrix.

Production of 1 kg of ABS requires the equivalent of about 2 kg of oil for raw

materials and energy. It can also be recycled

38
 End products made from ABS have properties passed on from each of the three
components.
• Acrylonitrile makes the plastic hard, heat resistant and chemical resistant.
• Styrene adds rigidity, strength, and processibility.
• Butadiene makes the plastic more elastic, increasing the impact performance
and toughness of the plastic[11].

Figure II.7 Monomers in ABS polymer [11]

39
 II.3.1 Properties of ABS
The mechanical properties of ABS are comparable to resins that cost far more. It is
easy to process in standard injection molding, extrusion, thermoforming, and blow
molding machines, which make up the majority of the plastic processing sales volume. It
has high gloss, can be easily colored, has minimal shrinkage during molding, and is
scratch-resistant making it aesthetically pleasing both after processing and through the
life of the part.[9] It is considered to be one of the most versatile engineering
thermoplastic resins.[11] Common ABS products are telephones and computer housings,
appliance housings, helmets, automotive panels, and pipe.
With all the benefits of ABS come a few drawbacks. First, ABS degrades when
exposed to heat, light, and oxygen. Without any modifications, this excludes ABS
resins from use in outdoor or other harsh environments. With the addition of stabilizers,
pigments, or protective coatings, this problem can be partially overcome.[11] However,
added steps and materials increase processing time and cost of manufacturing. For this
reason, the primary uses of ABS are found indoors or in UV protected environments.
Another disadvantage of ABS is that nearly all grades are opaque. This problem
has been partially overcome by newer grades of ABS that graft methyl methacrylate
onto a special styrene-butadiene substrate, which makes the polymer transparent. This
special modification makes these polymers more expensive than standard ABS. It has
found limited use in medical applications.
Major disadvantage of ABS is its susceptibility to degradation during processing.
When many thermoplastics are exposed to heat (near melting temperature), they may
bend or stretch, but they suffer little chemical degradation. Polyethylene is an example
of such a plastic. ABS, on the other hand, will slowly degrade over time.[9] Its
mechanical properties are reduced as it is exposed to high temperatures, as in
processing. ABS has a strong thermal history, meaning that there is a limit to the
number of times it can be reprocessed without significant loss of mechanical
properties.[11] Because of the short cycle times in injection molding, extruding, and
blow molding, this only becomes a factor in regrind or recycling. However, in rotational
molding, with inherently long heating cycles, this disadvantage is important.

40
 II.4 DESCRIPTION OF THE FDM

Created in 1989 by Scott Crump, Fused Deposition Modeling, or FDM, was one of
the first commercially viable rapid prototyping technologies. Now a part of Stratasys
Inc., [19] FDM has become an ideal solution for a diverse range of prototyping needs.

Today there is an array of materials available for extrusion in the various FDM
machines they include: ABS plastic, polycarbonate, polyphenylsulfone, and proprietary
UV plastic. Depending on the machine used objects can be as large as 59.9 x 50.0 x 59.9
cm. Default coloration for the material is white or clear. ABS can be ordered in any
custom pantone color or in any of the 5 basic colors including black, red, blue, green,
and yellow. In addition to the model material the FDM process also uses a temporary
break away or water soluble support material laid down to attach the model to the build
platform and bolster interior parts, negative space, holes, overhangs, and undercuts. The
cost of material varies slightly depending on the quantity purchased and the vendor but
averages USD 250 per cartridge for both model and support. With 878 cubic centimeters
in a new cartridge the cost of material to build models is approximately USD 0.27 per
cubic centimeter.

The FDM process begins with a three-dimensional model. This model must be
completed, without geometry issues such as flipped “normals” or “naked edges”, within
a solid or modeling environment such as Auto CAD, PRO E, or Rhinoceros (Figure
II.8). The native three-dimensional model file format is then exported as a
Stereolithography or STL file format extension. The STL file is then opened in Catalyst
(Figure II.9), the software package supplied with the FDM Dimension modeler, so it can
be prepared for prototyping. Once in Catalyst the model can be oriented either by
surface selection or degree input to minimize supports, thus minimizing cost and time of
build. Depending on the degree of detail and function of the model build style can be
changed from draft to standard resulting in slice layers that are .33 and .245 mm
respectively. The model’s interior style can be built “solid” with no hollow interior
space or “sparse” where minimal scaffolding like threads are build within internal spaces

41
resulting in a semi-hollow part, again affecting cost and build time. After selecting the
build and support style for the model an analysis procedure begins resulting in the
establishment of a CMB file. The CMB file consists of multiple standard files generated
by creating slices, supports, boundary curves, and tool paths for the model.

Figure II.8: Three-dimensional model of a wine glass as seen in Rhinoceros

Figure II.9: Wine glass as seen in Catalyst as cross-section, from front, and in
perspective view.

Slices are created horizontal to the x axis dividing the STL file into a stack of two-
dimensional part boundary contours. Once the slices are compiled the support material is
generated automatically. The design and location of the support material is dictated by
the geometry of the model. After slicing and support generation boundary curves, or
closed curves used to define a region in the xy plane, are completed. Two different types

42
of boundary curves are found in the analysis of a model: part boundary curves, which
are a result of slicing, and support boundary curves which are a result of support
generation. Finally tool paths, the data used to describe extrusion tip positioning is
produced. The model is then shown in its sliced state with color coded representation of
its supports and boundary curves. Models can be examined further, if need be, by
stepping through each consecutive slice layer to determine if model and support material
exist in the proper places. The model is then placed on a graphic representation of the
build table and can be saved or sent to the machine for prototyping. If saved, the model
can later be merged with other pending jobs to maximize platform use. If sent to the
machine, via a network connection, an approximate build time is supplied. The status of
the machine, material, and build time remaining can be monitored via a designated IP
address as well as directly on the machine interface.

In the building process (Figures II.10), the FDM machine feeds a continuous thread
of material through a heated nozzle, approximately 138°C, where it melts almost to the
point of liquefaction. The heated thread extrudes according to the tool paths created in
the CMB file. Once the material is extruded from the nozzle it immediately hardens in
its temperature-controlled environment and adheres to the layer beneath it. This additive
process occurs for each slice layer until the entire part has been deposited. Part build
time varies according to geometry size but falls roughly at 5.5 minutes per cubic
centimeter.

Figures II.10 Dimension FDM machine and view of build in progress

43
 Figure II.11 FDM Machine
Once the building cycle is complete the part can be removed from the machine
immediately. The part is released from the build platform and all supports are either
broken away or dissolved in an ultrasonic tank depending on the type of support material
used. There is no further post-processing needed. Many of the model materials in FDM
are suitable for sanding, priming, painting, and machining.

II.4.1 Mechanical Properties of FDM ABS

The properties of FDM-deposited ABS differ from those of cast ABS because of the
deposition process. [20] The FDM process lays down beads (or roads) or semi-molten
plastic, so the material is, unlike cast ABS, anisotropic. The bead orientation (raster
direction), bead width and the amount of spacing between adjacent beads (air gap) all
affect the mechanical properties. The materials testing reported in Ahn was performed
on FDM (Stratasys 1998 model) P400 ABS specimens with various raster orientations
and two air gaps. Injection-molded ABS specimens had a tensile strength of about 26
MPa, while FDM ABS specimens with roads oriented in the direction of tensile stress
had a tensile stress of about 20 MPa. If the load is applied with the beads alternating in
layers at +45° and -45°, the tensile strength was reduced to about 12 MPa. The lowest
44
tensile strength occurred for beads oriented at 90° to the loading (the build plane
perpendicular to the load direction). Tensile strength under this condition was about 3
MPa. Air gap affected tensile strength as well, with specimens constructed with a
negative air gap (adjacent beads slightly overlapping) being stronger than specimens
with the beads just touching (zero air gap). Compressive strength was found to be about
40 MPa for injection-molded ABS P400, about the same when the build layer plane was
oriented in the load direction, and about 35 MPa when the build layer plane was
perpendicular to the load. Bead width, color and model temperature had negligible effect
on the tensile strength. Another paper reported tensile testing results for ABS deposited
by a Stratasys 1650 RP machine. This paper indicated the highest ultimate and yield
strengths (at 0° orientation) at 20.5 and 16.3 MPa respectively, and ultimate and yield
strengths at ±45° orientation at 13.7 and 10.3 MPa. The weakest orientation was in this
case the 45° orientation (no alternating bead angle in adjacent layers), with ultimate and
yield strengths of only 7.0 and 6.6 MPa. For comparison, 6061-O wrought aluminum
alloy has a tensile strength of 124 MPa. [20]

Useful guidelines for use of FDM ABS plastic in structural elements:

1. Build parts such that tensile loads will be carried axially along the fibers.
2. Be aware that stress concentrations occur at radiused corners. FDM roads exhibit
discontinuities at such transitions.
3. Use a negative air gap to enhance strength and stiffness.
4. Consider the following issues on bead width:
• Small bead width increases build time, but improves surface quality.
• Wall thickness should be an integer multiple of bead width to avoid air gaps.
5. Consider the effect of build orientation on part accuracy.
• Two-dimensional slices closely reproduce geometry.
• Three-dimensional layer stacking creates linear approximations.
6. Be aware that tensile-loaded areas fail more easily than compression-loaded
areas.

45
 The manufacturer of the machine used at Penn State Altoona, Stratasys, lists the
material properties (converted from USCS units; no indication was made of the bead
orientation in which specimens were tested). [20]

Other material properties of ABS (injection molded, medium-impact grade) include

specific gravity of 1.03-1.06 g/cc, hardness of Rockwell R102-115 (a fairly high
hardness for a thermoplastic polymer), and a deflection temperature under flexural load
of 455 kPa of 93.3-104.4°C (a fairly low heat deflection temperature). [21] FDM ABS is
thus suitable as a structural element for low load, low-temperature applications,
especially where weight savings and the ability to quickly fabricate complex,
dimensionally-accurate parts are desirable qualities.

Table II. 8 Material Properties (Stratasys)

Notched Peak
Peak Flexural Tensile Break
Build Izod Impact Tensile
Liquifier Flexural Module Modulus Elongation
Material Type Speed Strength Stress
Temp (°C) Stress Average Average Average
(cm/sec) Average Average
(MPa) (GPa) (GPa) (%)
(J/m) (MPa)
ABS FDM 290 5.08 114.8 34.3 1.21 21.6 1.64 3.18
Polycarbonate
340 5.08 100.4 76.3 1.46 52.6 1.96 3.6
FDM
ABS
Injection - - 133.4 62.1 2.21 30.3 1.86 50-95
Molded
Polycarbonate
Injection - - 640.5 93.1 2.31 65.5 2.48 120
Molded

46
 II.4.2 Example Design Project Applications

The Electromechanical Engineering Technology design course, , requires

students to design and construct a device that draws on both their electrical and
mechanical backgrounds, and involves some form of computer control. The course is
offered in the last semester, and typically involves teams of two, who develop a
project proposal, plan and track the project using project management software,
make several oral presentations on their progress, and submit regular status reports
and interim and final reports.[22] The final week of the class includes oral
presentations on the projects before an audience of faculty, students, advisory board
members, family members and other guests from the community. The FDM has
become a major element in the design and fabrication phases of the projects. Serving
to illustrate how the FDM was used in capstone design projects are a load-lifting
waterwheel system and radio-controlled, infrared-targeting paintball tanks. The
projects were performed during the 2002-2003 and 2003-2004 academic years,
respectively..

In a project to compete in the 2003 ASME Student Design Contest, and as part
of their design project, a team of two designed and built a water wheel. The wheel
was designed to have the water buckets arranged on a belt, suspended vertically
between two pulleys. The water wheel lifted a cart filled with uncooked rice,
simulating a water-powered mine ore lifting system. The water buckets had to be
light and uniform, and shaped carefully to enable smooth flow and balance, including
holes for attachment to the belt and an overflow notch. The FDM was used to
fabricate buckets for the wheel (Figure 11, including a US half-dollar coin, diameter
30.6 mm, for scale), and to make the “ore” cart, which had to be lightweight and
dimensionally accurate as well.

47
 Figure II.12 : FDM Fabricated Water Wheel Bucket [21]

Two teams in 2003-2004 designed and built paintball-shooting tanks as part of

their capstone design course. The tank chassis were remote controlled (radio
frequency). A turret on each tank, carrying infrared emitters and detectors and the
paintball gun, automatically aimed and fired on the opponent tank as the teams
remotely maneuvered the chassis. Both teams agreed on the emitter specifications,
and the rules of the actual competition. Both teams used the FDM to fabricate a
housing (Figure 12, including a U.S. half-dollar coin for scale) for the infrared
detectors. An array of five IR detectors are arranged in an arc, and the signal strength
from the detector array is used to automatically control the turret azimuth and signal
for the gun firing (when the side-shielded center detector is on) as the tank chassis is
maneuvered. The application made good use of the FDM’s ability to quickly produce
a lightweight structure in a complex shape, where load requirements were low. The
second team used the FDM to fabricate a brush holder for a slip ring to connect the
turret electronics to the chassis.

48
 FDM ABS Housing
IR Detector Port

Figure II.13: FDM Using Paintball IR Tank [21]

49
 II.5.EXTRUSION PROCESS:

Extrusion is a processing technique for converting thermoplastic materials in

powdered or granular form into a continuous uniform melt, which is shaped into
items of uniform cross-sectional area by forcing it through a die. Extrusion end
products include pipes, profiles for construction, automobile, and appliance
industries or raw material like in this thesis. Extrusion is perhaps the most important
plastics processing method today.
A simplified sketch of the extrusion line is shown in Figure II.14. It consists
of an extruder into which is poured the polymer as granules or pellets and where it is
melted and pumped through the die of desired shape (in this thesis it is circular with
1.8 mm diameter). The molten polymer then enters a sizing and cooling trough or
rolls where the correct size and shape are developed. From the trough, the product
enters the motor-driven, rubber-covered rolls (puller), which essentially pull the
molten resin from the die through the sizer into the cutter or coiler where final
product handling takes place.

Figure II.14 Extrusion Machine [20]

50
 II.5.1 Extruder
Figure II.15 is a schematic representation of the various parts of an extruder.
It consists essentially of the barrel, which runs from the hopper (through which the
polymer is fed into the barrel at the rear) to the die at the front end of the extruder.
The screw, which is the moving part of the extruder is designed to pick up, mix,
compress, and move the polymer as it changes from solid granules to a viscous melt.
The screw turns in the barrel with power supplied by a motor operating
through a gear reducer. The heart of the extruder is the rotating screw (Figure 8). The
thread of an extruder screw is called a flight, and the axial distance from the edge of
one flight to the corresponding edge on the next flight is called the pitch. The pitch is
a measure of the coarseness of the thread and is related to the helix.

Figure II.15 Extrusion Machine [20]

We trying to reach filament of ABS with 1,8 mm diameter. It is very hard to

obtain this dimension about long time. Electric current which come from city lines
directly affect the speed and pressure of extruder.

We bought 7 different types of ABS plastic materials and we extrude them

51
into filament which have diameter 1,8mm. But because of hardness of process we
can not reach regular diameters all of filament.
There are a lot of problems which we have to cope with. These problems are;

II.5.1.1. Obtaining the melting temperature right

This is the hardest part of extrusion process. We have to know the melting
and extrusion temperature true.

All material has a Molt Temperature and Melt Temperature range. In general
speaking, the melt temperature for easily-flow grades will be taken from the bottom
of the range, or for more viscous grades, from the top of the range.

Figure II.16 Extrusion Screw Design [20]

II.5.1.2. Extrusion pressure and extrusion speed

This is another important part. We have to adjust the pressure and speed of
the extrusion screw. In this subject, extrusion design is very important. Depend on
that, it directly affects the extrusion process.

52
 Extrusion pressure directly affects the quality of final part. The pressure
should be high enough for extruding plastic without any undesirable cavity. The
speed of screw affects directly the pressure at the extrusion point and quantity of
extruded plastic per second. If we increased the pressure and speed more than
desirable, we cannot reach the cylindrical profile.

53
 III. PRODUCTION AND TESTING OF NEW
MATERIAL
III.1 MATERIAL TESTS OF RAPID PROTOTYPING MACHINE ABS
MATERIALS
Our aim is producing of supply materials for Rapid Prototyping machine and
improving materials properties and its using. With the production of supply material
in Turkey, which is exported, costs are decreased and escape from foreign
dependence.
This studies processes to support the use of thermo plastics filament in rapid
prototyping. First, we got different types of ABS material from domestic and
international plastic producer.
In first part of study, we decide to make test on samples. We made first the
Tensile Test, secondly Mold Flow Index test which is the most important properties
of plastic for FDM process and at the end Hardness Test.
On the other hand, smooth surfaces of strings are critical. Rough surfaces
prevent ejection of the injection molded part and play a role in the overall quality of
the final part. And also affect the FDM process, it cause problems in rapid
prototyping machine.

III.1.1 Using Materials in Rapid Prototyping Process for Studies

ABS: All systems in the FDM line-up offer ABS as a material option, and nearly
90% of all FDM prototypes are produced in this material. Users report that the ABS
prototypes demonstrate 60-80% of the strength of injection molded ABS. Other
properties, such as thermal and chemical resistance, also approach or equal those of
injection molded parts. This makes ABS a widely used material for functional
applications.
Polycarbonate: Use of a new RP material available for FDM — polycarbonate
is growing rapidly. The additional strength of polycarbonate produces a prototype
that can withstand greater forces and loads than the ABS material. Some users
believe that this material produces a prototype that demonstrates the strength
characteristics of injection molded ABS.
Other materials: While not as widely used as ABS, there are other specialty
materials for

54
 III.2. PLASTICS CHARACTERIZATION AND SELECTION BY TESTS
When we want to use plastic materials, we select plastic which is most useful for
us. We have to think and select the most suitable material. There are some properties
of plastic which help us in selection.

III.2.1 Strength Test of the Plastic

One of the most important properties of material is strength. Strength of material
give us the bounds of using. Strength is a mechanical property that you should be
able to relate to, but you might not know exactly what we mean by the word "strong"
when we're talking about polymers. First, there is more than one kind of strength.
There is tensile strength. A polymer has tensile strength if it is strong when one pulls
on it.
Stress-strain behavior is another important property. The description of stress-
strain behavior is similar to that of metals, but a very important consideration for
polymers is that the mechanical properties depend on the strain rate, temperature, and
environmental conditions.
Mechanical properties change dramatically with temperature, going from glass-
like brittle behavior at low temperatures to a rubber-like behavior at high
temperatures.
Tensile strength is important for a material that is going to be stretched or under
tension. Fibers need good tensile strength. Then there is compressional strength. A
polymer sample has compressional strength if it is strong when one tries to compress
it.
The ability of a material to resist breaking under tensile stress is one of the most
important and widely measured properties of materials used in structural
applications. The force per unit area (MPa or psi) required to break a material in such
a manner is the ultimate tensile strength. The rate at which a sample is pulled apart in
the test can range from 0.5 to 50 cm per minute and will influence the results. T

55
 III.2.2 Elongation Test
But there's more to understanding a polymer's mechanical properties than merely
knowing how strong it is. All strength tells us is how much stress is needed to break
something. It doesn't tell us anything about what happens to our sample while we're
trying to break it. That's where it pays to study the elongation behavior of a polymer
sample. Elongation is a type of deformation. Deformation is simply a change in
shape that anything undergoes under stress. When we're talking about tensile stress,
the sample deforms by stretching, becoming longer. We call this elongation, of
course.
There are a number of things we measure related to elongation. Which is most
important depends on the type of material one is studying. Two important things we
measure are ultimate elongation and elastic elongation .
Ultimate elongation is important for any kind of material. It is nothing more than
the amount you can stretch the sample before it breaks. Elastic elongation is the
percent elongation you can reach without permanently deforming your sample. That
is, how much can you stretch it, and still have the sample snap back to its original
length once you release the stress on it.

The ultimate elongation of an engineering material is the percentage increase in

length that occurs before it breaks under tension. Ultimate elongation values of
several hundred percent are common for elastomers and film/packaging polyolefins.
Rigid plastics, especially fiber reinforced ones, often exhibit values under 5%. The
combination of high ultimate tensile strength and high elongation leads to materials
of high toughness.
We made the extrusion process in private company. We made ABS raw material
for RP machine which material is long filament. They have to be in diameter of 1.8-
1.9mm and it is very hard to obtain. Thereupon, material selection and prepare to
using is very hard. We use their thin filaments for tensile test.

56
 III.2.3. Mold Flow Index Test of Samples

In Rapid Prototyping process, melting of ABS plastic is the most important

process. Melt Flow Rate measures the rate of extrusion of thermoplastics through an
orifice at a prescribed temperature and load. It provides a means of measuring flow
of a melted material which can be used to differentiate grades as with polyethylene,
or determine the extent of degradation of the plastic as a result of molding.

Figure III.1 MFI Machine

57
 Common Melt Flow Rate Conditions by Material

200ºC/5.0kg
Acrylonitrile-butadiene-styrene 230 ºC /3.8kg
220 ºC /10

We made test with ASTM D1238 standards under 5kg and 200ºC in Technical
Education Faculty in Marmara University.
Experiment is done on the following system.
1. We cut samples small pieces about 3mm long and up to 2mm diameter
cylindrical pieces.
2. Then we put them in to machine and wait about 10 minutes to melt,
3. After than with the help of weight Abs plastic started melt down on the cap.
4. Every 10 minutes we took melted plastic
5. Measure their weights with a sensitive device.

58
 III.2.4 Hardness Test

First, all samples of ABS material cut about 1cm pieces. Then, we melt them in
oven which is in M.Ü. Material Science Engineering Laboratory. All of samples
warm to 285ºC which is melting degree, we prepared test sample. A measure of the
indentation resistance of elastomeric or soft plastic materials based on the depth of
penetration of a conical indentor. Hardness values range from 0 (for full penetration)
to 100 (for no penetration). Full penetration is between 2.46 and 2.54 mm (0.097 and
0.100 in) depending on the equipment used.

Experiment Setup:

We used the Zwick Shore hardness test equipment with ASTM D2240 DIN
53505 standards.

Experiment is done on the following system.

1. We cut samples small pieces about 3mm long and up to 2mm diameter
cylindrical pieces.
2. Then we put them cap and put them in to oven on melting temperature

3. After than we cut the top of melted material to reach true values in test.

4. And we took 10 hardness values of each sample under 15 kg weight.

59
 Figure III.2 Hardness Test Machine

III.2.5 SEM Scanning Electron Microscope Imaging

SEM is a type of electron microscope that images the sample surface by

scanning it with a high-energy beam of electrons in a raster scan pattern. 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. This particular type of microscope is
exceedingly useful.

The types of signals made by an SEM can include secondary electrons, back
scattered electrons, characteristic x-rays and light (cathodoluminescence). These
signals come from the beam of electrons striking the surface of the specimen and
interacting with the sample at or near its surface. In its primary detection mode,
secondary electron imaging, the SEM can produce very high-resolution images of a
sample surface, revealing details about 1 to 5 nm in size. Due to the way these
images are created, SEM micrographs have a very large depth of focus yielding a
characteristic three-dimensional appearance useful for understanding the surface

60
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, secondary electron imaging, such as the
micrograph taken of pollen shown to the right. Characteristic x-rays are the second
most common imaging mode for an SEM. X-rays are emitted when the electron
beam removes an inner shell electron from the sample, causing a higher energy
electron to fill the shell and give off energy. These characteristic x-rays are used to
identify the elemental composition of the sample. Back-scattered electrons (BSE)
that come from the sample may also be used to form an image. BSE images are often
used in analytical SEM along with the spectra made from the characteristic x-rays as
clues to the elemental composition of the sample.

We made two SEM on original materials. Two material seem very similar in
SEM images in Appendix 2.

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 III.2.6 XRD X-ray Scattering Techniques
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 materials and thin films. 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.

We made two XRD test for analyzing the percentage of polymers which
compose ABS.
Result of XRD is %15 Acrylonitrile % 60 Butadiene % 25 Styrene in Appendix
3 and Appendix 4

62
 III.3 PREPARATION OF ABS MATERIALS
We produced ABS strings for rapid prototyping machine. First, we purchase raw
ABS materials from producers. Then, we made extrusion process with extrusion
machine. Then we have to know the physical properties of material to using in
machine. Prototyping process is very sensitive process which can be affected by
many disturbances. When we know physical values of samples of ABS, we can
realize the production is good or not.

Figure III.3 Extrusion Machine

63
 III.4 FABRICATION OF NEW RAW MATERIAL

The filaments used in FDM process need to be of specific size, strength and
properties. A single-screw extruder machine was used to produce such filaments. The
single screw extruder is one of the most important types of extruders used in the
polymer processing industry. Its key advantages include its relatively lower cost,
simple design, ruggedness, reliability, and acceptable performance.

A single screw extruder was selected to fabricate the filaments from the ABS
material. The ABS granule is fed into the feed hopper. The ABS material flows by
gravity from the feed hopper down into the extruder barrel. As the material flows, it
fills the annular space between the extruder screw and barrel. Since the barrel is
stationary and the screw is rotating, the frictional forces will act on the material, both
on the barrel as well as on the screw surface. As the material moves forward, it will
heat up as result of frictional heat generated and conducted from the barrel heaters.

When the temperature of the ABS material exceeds the melting point, a thin film
of ABS material, will form at the barrel surface. This is where the plasticising action
starts. As the ABS material moves forward, the amount of solid material at each
location will reduce as a result of melting. When the entire solid ABS has
disappeared, and the end of the plasticising zone has been reached then the melt-
conveying zone starts. In the melt-conveying zone, the ABS material is simply
pumped to the die. Since the die exerts a resistance to flow, a pressure is required to
force the material through the die. This is referred to as the die head pressure. The
die head pressure is determined by the shape of the die, temperature of the ABS
material melt, the flow rate through the die, and the rheological properties of the
composite melt. The extruding filament exiting the die is then carried away by a
conveyor belt, whose speed matches the output flow rate.

During extrusion, a phenomenon, sometimes referred to as die swell, occurs.

Actually, it is not the die but the polymer that swells. The elastic behavior of the
polymer melt is largely responsible for the swelling of the extrudate upon leaving the
die. This is primarily due to the elastic recovery of the deformation of the metal–
polymer composite in the die. A die with a short land length will cause a large

64
amount of swelling, while a die with long land length will reduce the amount of
swelling. Therefore, the land length of die was increased from 5 to 10 mm, which
leads to decrease the extrudate swelling. Because of swelling, the diameter of die
used was taken to be smaller than the required diameter of the filament.

The die diameter was 1.65 mm and the resulting diameter of filament formed
was in the range of 1.78–1.85 mm due to the extrudate swelling. Therefore, the
geometry of exit flow channel is generally different from the required product
geometry. Thus using the proper geometry of the die and appropriate volume of flow
parameters, flexible winding filaments of desired diameter and tolerance were
produced.

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 IV. TEST RESULT OF ABS WIRE SAMPLES
We made tests on ABS materials which is selected and used for FDM machine.
In the first phase of our study, we made tests on 6 samples. Two of these samples are
original raw materials which are using for FDM machine. We find 4 more samples
from domestic and international suppliers according to properties which are given by
original ABS supplier.

Table IV.1 Properties of original materials [2]

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 Test Samples:
We have five different production and one support material which use in the
machine. Then we give them number to realize and do test easily.
1- ) Sample 1 have a very smooth surface after extrusion from domestic supplier.
2- ) Sample 2 include ABS and some rubber material from Resinex-BYM. (See
appendix for detail information)
3- ) Sample 3 is the original material which came from Stratasys USA
4- ) Sample 4 is newest one we bought from DOW (See appendix for detail
information)
5- ) Sample 5 is the ABS which have rough surface from Resinex-BYM with
code: MAGNUM ABS 3904
6- ) Sample 6 is the support material of machine which is made by different
mixture of PC we made some test on it for future works.

67
 IV.1 TENSILE STRENGTH TEST RESULTS OF SAMPLES
We made tensile strength test on 5 of these samples for determine and compare
each other. Tests are made 10 times for each material and took average of values to
get rid of errors. Sample 4 couldn’t tested.

Maximum Force Maximum Strength Elongation

Sample 1 156 N 49,5 MPa %100

Sample 2 152 N 48,5 MPa %6
Sample 3 (Original) 158 N 50,1 MPa % 70,8
Sample 5 161 N 51,5 MPa % 34
Sample 6 154 N 48,5 MPa %9

As a result we can see that second sample is not suitable for use.
During the test, sample 3 was deformed perfectly .Other samples deformed
preparedly, after plastic deformation on some place usually other part of sample
didn’t being plastic deformation and usually breaks down with first deformed place.
On the other hand, elongation is the other point of material. After elastic
deformation, plastic deformation started and especially first and third sample along
more than others.

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 IV.2 MFI TEST RESULTS OF SAMPLES

TABLE IV.2 MFI TEST RESULTS

Experment Sample 1 Sample 2 Sample 3 Sample 4 Sample 5

No
1 0,942 g 1,380 g 1,630 g 3,320g 1,248g
2 0,861 g 1,433 g 1,578 g 3,355g 1,253g
3 0,811 g 1,417 g 1,578 g 3,365g 1,278g
4 0,784 g 1,380 g 1,530 g 3,475g 1,245g
5 0,750 g 1,370 g 1,516 g 3,600g 1,259g
6 0,720 g 1,375 g 1,525 g 3,505g 1,243g
7 0,700 g 1,379 g 1,560 g 3,452g 1,257g
8 0,689 g 1,335 g 1,510 g 3,338g 1,272g
9 0,710 g 1,350 g 1,530 g 3,290g 1,243g
10 0,730 g 1,332 g 1,520 g 3,315g 1,248g

0,7697 1,3891 1,5477 3,4015 1,2546

Average
g/10min g/10min g/10min g/10min g/10min

69
 We can see the melted materials.

Sample 1 Sample 3
Figure IV.1 Sample1 and Sample 3 after MFI Test

On the other hand, we could see the materials how they melt. And we can see
melted pieces they melt well or not. In first and third samples were melting is so
good and there were little cavity in materials. But in fifth sample it wasn’t melted so
well, there were some cavities in melted material.

Figure IV.2 Sample 5 after MFI Test

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 IV.3 EXPERIMENT MEASUREMENTS OF HARDNESS TEST

1. Sample’s average hardness value is 26

2. Sample’s average hardness value is 27
3. Sample’s average hardness value is 24
4. Sample’s average hardness value is 24
5. Sample’s average hardness value is 27
6. Sample’s average hardness value is 28
Each value is average of 10 tests.

Results
In the experiment results, we see that hardness values of the materials are quite
similar. In other words, Selected ABS materials’ hardness values are so close to each
other. In order to reach the true values of samples we made test 10 times and take the
average values.
In first phase of the study, mechanical tests are done on 6 types of samples.
Following results are taken:

71
 IV.4 DISCUSSION

MFI
(Mold
Strength Elongation Hardness Using in RP Supplier
Flow
Index)
Domestic
Sample 1 49,5 Mpa 0,78 gr/min 100% 26 Not applicable
Supplier
Good,
Some
Sample 2 48,5 Mpa 1,81 gr/min 6 27 Problems Resinex-BYM
occurs in RP
process
1,54
Sample 3 50,1 Mpa 70,8 24 Original ABS Stratasys USA
gr/min
Very soft flow
Sample 4 ---- 3,40 gr/min ----- 24 for RP, DOW
not applicable
Very hard flow
Sample 5 51,5 Mpa 1,25gr/min 34 27 in RP, Resinex-BYM
not applicable
Sample 6 48,5Mpa ---- 9 28 Original PC Stratasys USA

72
 According these results, only sample 2 is applicable for using in RP machine. But when
we use this sample in FDM machine, it creates problems in FDM process. We investigate the
problem in process and we find out ,problem occurs because of the dimension of sample. ABS
strings should have 1.8-1.9mm diameter. Because of the extrusion process it is very hard to
get it. In some sample, this diameter can be more than 2mm and it cause blockage in the FDM
machine.
We made die for this undesirable samples and process once more of ABS strings. We
heat die to operation temperature for ABS and reduce the diameter to desirable values. But we
couldn’t reach the required results after this operation.
In the second phase of our study, we search new material which can be used in FDM
without any problem. According to conversation and meeting with one international supplier,
they suggested trying a new sample (Appendix 2).
We made strings for FDM machine with new ABS material and we used in FDM
machine and we reached good results. We produced one sample prototype with new ABS
material, and there is no problem about 2 hours operation. Final product which made by new
ABS material is quite similar with original one.

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 V. CONCLUSION AND RECOMMENDATIONS
A new raw material for FDM machine has been successfully produced and tested for
direct rapid tooling application using the FDM rapid prototyping process.
Characterization of this material displays desirable mechanical properties, offering fabrication
of flexible feedstock filaments for producing functional parts and
tooling directly on the FDM system. This material has quite similar properties like strength,
mold flow property and availability. These properties can help to establish the upper limits for
the process ability of filament in terms of the particle size and the volume fraction of filler
content.

Composites consisting of large as high tensile modulus as original raw material, tensile
stress and elongation are quite enough for using, most important and the hard part is the
extrusion process. When comparing new material with original raw material, main difference
is color of the ABS. And it can be changed in extrusion process with adding colorant.

Application of this new raw material in rapid tooling using the FDM system has shown
that good qualities parts and very clear process. The material is especially suitable for direct
rapid tooling application.

In this work, we find out production of raw material for FDM machine in Turkey is
available. With the production in Turkey, big money saves in Turkey and foreign dependence
is finished.

For improve this thesis, optimization can be done in extrusion process and different type
of ABS and PC material can produced and use in FDM machine.

74
REFERENCES

[1]International Union of Pure and Applied Chemistry, et al. (2000) "IUPAC Gold Book"
Retrieved on 11 May 2007 from "IUPAC Gold Book" on http://goldbook.iupac.org/

[2] Clayden, J.: Greeves, N. et al. (2000), p1450-1466

[3] http://www.polymerchemistryhypertext.com/(08.06.2008)

[4] Masood SH. Intelligent rapid prototyping with fused deposition (2003).

modelling. Rapid Prototype (1996);2(1):24–32.

[5] Meyers .: Chawla. Mechanical Behavior of Materials, Prentice Hall, Inc. 1999, pg. 41.

[6] Brandrup, J.; Immergut, E.H.; Grulke, E.A.; eds Polymer Handbook 4th Ed. New York:
Wiley-Interscience, (1999).

[7] CAS: Index Guide, Appendix IV (© 1998).

[8] International Union of Pure and Applied Chemistry, et al. "IUPAC Gold Book" Retrieved
on 11 May 2007 from "IUPAC Gold Book" on http://goldbook.iupac.org/ (2005)

[9] D. W. Van Krevelen, Properties of Polymers, 3rd ed., Elsevier, Amsterdam, the
Netherlands,(1990).

[10] D. V. Rosato, Rosato’s Plastics Encyclopedia and Dictionary, Hanser, Munich, (1993).

[11] W. V. Titow, Technological Dictionary of Plastics Materials, Elsevier Science Ltd.,

Kidlington, Oxford, (1998).

[12] D. P. Bashford, Thermoplastics Directory and Databook, Chapman & Hall, New York,
(1997).

[13] C. P. MacDermott and A. V. Shenoy, Selecting Thermoplastics for Engineering

Applications, 2nd ed., Marcel Dekker, Inc., New York, (1997).

[14] J. Brandrup, E. H. Immergut, and E. A. Grubke, eds., Polymer Handbook, 4th ed., John
Wiley & Sons, Inc., Chichester, (1999).

[15] J. A. Brydson, Plastics Materials, 6th ed., Butterworth-Heinemann Ltd., Oxford, (1995).

[16] D. G. Baird and D. I. Collias, Polymer Processing, John Wiley & Sons, Inc., Chichester,
(1998).

[17] J. M. Charrier, Polymeric Materials and Processing, Hanser, Munich, (1990).

[18] World-Wide Web URL http://cede.psu.edu/StudentGuide., (01.05.2008).

[19] World-Wide Web URL http://www.rhino3d.com., (01.10.2007).

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[20] Ahn, Sung-Hoon, Michael Montero, Dan Odell, Shad Roundy and Paul K. Wright.
Anisotropic Material Properties of Fused Deposition Modeled ABS. Rapid Prototyping, Vol.
8, No. 4, (2002), pp. 248-257.

[21] http://www.buildfdm.com/data/product_brief_matspecs.pdf., (05.07.2008).

[22] IDES, Inc. IDES Prospector Pro. <http://ppro.ides.com> (05.08.2008).

76
APPENDIX

APPENDIX 1
Technical Sheet of Sample 7

77
APPENDIX 2
Scanning Electron Microscope Imaging (Sample 3)

78
APPENDIX 3
XRD X-ray Scattering Techniques Results of Sample 3

79
APPENDIX 4
XRD X-ray Scattering Techniques Results of Sample 6

80
APPENDIX 5
Technical Sheet of Sample 6

Applications • Information technology equipment

• Electrical parts
• Other structural/internal parts

Physical Properties(1) Test Method English Units SI Units

Specific Gravity ASTM D 792 1.33 1.33
Melt Flow Rate, 300°C/1.2kg ASTM D 1238 5 g/10 min 5 g/10 min
Mold Shrinkage, Linear Flow ASTM D 955 0.002-0.004 in/in 0.002-0.004 mm/mm
Mechanical Properties(2)
Tensile Strength at Break ASTM D 638 14,500 psi 100 MPa
Tensile Elongation at Break ASTM D 638 4.0 % 4.0 %
Tensile Modulus ASTM D 638 870,000 psi 6,000 MPa
Flexural Strength ASTM D 790 24,650 psi 170 MPa
Flexural Modulus ASTM D 790 797,500 psi 5,500 MPa
Thermal Properties
Deflection Temperature Under Load ASTM D 648
264 psi (1.8 MPa), annealed 289°F 143°C
66 psi (0.45 MPa), unannealed 293°F 145°C
264 psi (1.8 MPa), unannealed 284°F 140°C
Vicat Softening Point ASTM D 1525
50°C/hr, 50N 302°F 150°C
120°C/hr, 10N 320°F 160°C
Ball Indentation Temperature IEC 60335-1 >275°F >135°C
CLTE, flow, -40 to 80°C ASTM D 696 14x10-6 in/in/°F 25x10-6 mm/mm/°C
CLTE, cross flow, -40 to 80°C ASTM D 696 29x10-6 in/in/°F 51x10-6 mm/mm/°C
Electrical Properties
Dielectric Strength, 1.6mm thickness ASTM D 149 >692 V/mil >28 kV/mm
Dielectric Constant, 1.6mm, 10Hz to 1 MHz ASTM D 150 3.1 3.1
Dissipation Factor, 10 Hz ASTM D 150 50x10-4 50x10-4
100 Hz 25x10-4 25x10-4
1MHz 160x10-4 160x10-4
Volume Resistivity, 1.8mm thickness ASTM D 257 1x1016 ohm-cm 1x1016 ohm-cm
Surface Resistivity ASTM D 257 3x1014 ohm 3x1014 ohm
Comparative Tracking Index IEC 60112
At 3mm thickness 175 V 175 V
Flammability(3)
UL94 Classification at
1.5 mm UL94 V-0 V-0
Limiting Oxygen Index ASTM D 2863 35 % 35 %
Glow Wire Temperature, 1.0-3.0 mm thickness IEC 60695-2-10 1,760°F 960°C
Processing Conditions
Drying Temperature, 3 to 4 hours 250°F 120°C
Melt Temperature 555 to 600°F 290 to 315°C
Mold Temperature 175 to 240°F 80 to 115°C

81
CV

ÖZGÜR KIRELLİ

Arifiye mah. Hüseyin Cahit sok.

Aydın apt. 1/5 Eskişehir
Gsm Tel: 0532 598 45 63
E-Mail: [email protected]

PERSONAL INFORMATION

Birth Place : Eskişehir

Birth Date : 26.11.1980
Marital Status : Single
Citizenship : T.C
Military Obligation : Finished (May 2006)

EDUCATION

2004 - : Marmara University , İstanbul

Mechanical Engineering (English) Graduation Program

1998 - 2004 : Marmara University , İstanbul

Mechanical Engineering (English) Undergraduation
Program

1995-1998 : Cumhuriyet High School, Eskişehir

1994-1995 : Orhan Oğuz High School (English Preparetion),

Eskişehir

1992-1994 : Cumhuriyet High School , Eskişehir

1987-1992 : Millizafer Primary School

WORK EXPERIENCE AND INTERNSHIPS

01.02.2007 - : Siemens A.Ş. Energy (R&D specialist)

01.10.2004 -30.05.2004 : Lecturer Laboratory Assistance, Introduction to

Computer Systems and Computer Programming (FORTRAN)

01.09.2003 -12.09.2003 : Aygaz A.Ş. Genel Müdürlüğü

18.07.2003 - 28.08.2003 : Arçelik A.Ş Eskişehir Refrigerator Factory

05.07.2002-13.08.2002 : Ford-Otosan İnönü Engine Factory

82
 03.07.2001 - 02.08.2001 : Marmara University, Mechanical Engineering
Department

FOREIGN LANGUAGUES

Good command of English

German (Beginner)

COMPUTER
I-deas 8,9,10 , Autocad R14, Autocad 2000, Mechanical Desktop 5.0/6.0,
Fortran 90-95, MS Office 2000 , Windows 98/NT/2000/XP,
Matlab,Lingo,Solidworks(beginner).

LICENSES AND CERTIFICATES

* GRID Management Systems 1999

* Class-B driving license
* Festo Pneumatics, Electropneumatics and Hydraulic Certificates (3 Days)

INTERESTS

* Cinema , Classical Music, Guitar

* Football, Swimming , Basketball
* Racing , Engine and Design Technologies

SOCIAL ACTIVITIES

* Marmara University Mechanical Engineering Club Management Board

President, 2004
* Marmara University Mechanical Engineering Club Management Board Vice-
President, 2003
*Marmara University Mechanical Engineering Club Management Board
Member 1999-2002
* ASME International (American Society of Mechanical Engineers)
Marmara University Student Section Management Board Member, 2003
* Marmara University Cariyer Step Organization Committe 1999-2003

REFERENCES

Çetin ARBATLI, Porsuk Ticaret A.Ş., Manager (Retired) ,Eskişehir

Mehmet COŞAR ,Siemens A.Ş. Energy, Group Manager, İstanbul

83