STUDY OF THE MEDIUM DENSITY POLYETHYLENE MECHANICAL

MILLED WITH THE GRAPHITE POWDER

CHEAH WOI LEONG

PROPOSAL

DEPARTMENT OF PHYSICAL SCIENCES

FACULTY OF SCIENCE AND TECHNOLOGY
UNIVERSITI MALAYSIA TERENGGANU
2010
 TABLE OF CONTENTS
Pages
TITLE PAGE i
TABLE OF CONTENTS ii
LIST OF TABLES iii
LIST OF FIGURES iv
LIST OF APPENDIX v
LIST OF ABBREVIATIONS vi

CHAPTER 1 INTRODUCTION
1.1 Research Background 1
1.2 Problem Statement 2
1.3 Objectives 2

CHAPTER 2 LITERATURE REVIEW

2.1 Polyethylene-graphite nanocomposite 3
2.2 Graphite 4
2.3 Polyethylene (PE) 4
2.4 Medium Density Polyethylene (MDPE) 6
2.5 Mechanical Milling Method 8

CHAPTER 3 METHODOLOGY
3.1 Location of research 9
3.2 Experiment
3.2.1 Sample Preparation 9
3.2.2 Characterization 10
3.2.3 Compounding process (composite) 10
3.2.4 Injection Moulding 10
3.2.5 Analysis 11
3.3 Instrument
3.3.1 Thermogravimetric Analysis 11
3.3.2 X-Ray Diffraction 12
3.3.3 Fourier Transform Infrared Spectroscopy 13
3.3.4 Testometric MODEL 350/500 14
3.3.5 4 Point Probe 14
3.4 Process Flow Chart 15

CHAPTER 4 EXPECTED RESULTS 16

REFERENCES 17
APPENDIX 19

ii
 LIST OF TABLES

Tables No. Page

3.1 Instruments and method 9

iii
 LIST OF FIGURES

Figures No. Page

2.1 Polyethylene chain with side branches 6

3.1 Condition for constructive interference 11
3.2 Sample preparation and etching process 13

iv
 LIST OF APPENDIX

Tables No. Page

A1 commercially produced metallocenes 17

A2 Gantt chart proposal 2010 20

v
 LIST OF ABBREVIATIONS

Abbreviations

DENT Double Edge Notched Tensile

FNCT Full Notched Creep Tensile
FTIR Fourier Transform Infrared Spectroscopy
HDPE high density polyethylene
IUPAC International Union of Pure and Applied Chemistry
MA Mechanical Alloying
MD Mechanical Disordering
MDPE Medium Density Polyethylene
mf mass at the end of temperature, T
MG Mechanical Grinding
ML percentage loss of mass
MM Mechanical Milling
ms mass at the start, before heating
PE Polyethylene
PE100 PE water pipes ISO 4427, an HDPE material
PMC Polymer Matrix Composite
PTFE polytetrafluoroethylene
RPM Revolutions per minute
SCG Slow crack growth
SEM Scanning electron microscope
Tg low glass transition temperature
TGA Thermogravimetry
XRD X-ray diffraction

vi
 CHAPTER 1

INTRODUCTION

1.1 Research Background

Many researchers do relate the conductivity to polymer matrices with respect to the
presence of polymer groups, polymer surface tension and different blends of polymer.
One influencing factor that has not been dealt with is the compatibility of polymer
matrix with conductive filler, which does have a substantial effect on conductivity.

Carbon black is the most widely used conducting filler. However, short carbon fiber
also has its own characteristics due to its high conductivity in polymer matrix. It is of
great importance when high conductive system is required. By studying electrical
conductivity of high density polyethylene-carbon fiber composites mixed with
different concentrations of carbon black. (Zhang et al. , 2007)

Therefore, MDPE-Graphite composite will be produced in this research and its

characteristic will be determined. This research have 2 stage, which is preparation and
processing of samples, compounding process and characterization. In the preparation
and processing of samples, carbon nanostructure can be produced by mechanical
milling of the graphite powder. After that , the change in crystallinity of graphite
during milling will be examine by using X-ray diffraction (XRD), Scanning electron
microscope(SEM). In compounding process, MDPE mix with graphite powder by
using Haake polylab mixer. After mixer two samples, characterize the MDPE-graphite
composite by using the Fourier Transform Infrared Spectroscopy (FTIR), X-ray
diffraction (XRD), Scanning electron microscope (SEM), and Thermogravimetry
(TGA).

1.2 Problem Statement

According to the research of Hamouda et al. (2006). Creep fracture by slow crack
growth is studied in a medium density polyethylene at 60 ̊C and 80 ̊C. Whereas
elastic–plastic fracture mechanics load parameters fail to provide a unique
temperature-independent correlation, that of the fracture mechanics for creeping solids
is proved to be relevant since this parameter correlates very well with the time to
failure.

Slow crack growth (SCG) behaviour has been investigated under creep conditions in a
medium density ethylene–butene copolymer (MDPE) on both axisymmetrical Full
Notched Creep Tensile (FNCT) and Double Edge Notched Tensile (DENT) samples
tested at 60 ̊C. Fracture Mechanics for Creeping Solids approach was attempted for
the present medium density polyethylene used for gas-pipe networks. The creep load
parameter was reported to correlate with the time to failure on laboratory specimens as
well as on pre-cracked tube under internal pressure. (Hamouda et al. , 2008)

Therefore, a typical experiment proposes by mixing the graphite powder with the
MDPE to produce the PMC. These experiments carry out the result for extend the
lifetime of slow crack growth and increase the tensile of the PMC.

1.3 Objective

1) To obtain the fine size graphite powder by mechanical milling.

2) To prepare mixture of the MDPE with the milled graphite by compounding
process.
3) To study of the characteristic of the MDPE mix with the mechanical milled
graphite powder.

2
 Chapter 2

LITERATURE REVIEW

2.1 Polyethylene-graphite Nanocomposite

This research conducted a mixture of both a new and modified research. The research
will carry out the characterization of the MDPE-graphite composite and determine the
chemical properties and mechanical properties. Some of the researchers have also
spent time on studying the effect of the other polymer matrix composite of mechanical
milled with the graphite powder.

Besides, several researchers have finished their research for preparation of

polystyrene/graphite nanosheet composite. According their research, Graphite, which
is naturally abundant, has been widely used as an electronically conducting filler for
preparing conducting polymer composites in the last decades. A new process for the
dispersion of graphite in the form of nanosheets in a polymer matrix was developed
via in situ polymerization of monomer at the present of sonicated expanded graphite
during sonication. The process fabricated electrically conducting polymer/graphite
nanocomposite films with much lower percolation threshold and much higher
conductivities than those of composites made by conventional methods. The graphite
nanosheets prepared via powdering the expanded graphite might also be used as a
conducting nanofiller for many other polymers. (Chen et al., 2003)
2.2 Graphite

In recent years, The raw materials most frequently used in graphite manufacturing are
some types of coke, carbon black and natural graphite, which are ground, sieved and
added to a binder. The paste at this stage is homogenized and placed in molds or
passed through drawing frames, sufficiently compacted. The material is then baked
slowly, protected by coke powder, at a temperature of at least 1000 ◦C for complete
elimination of volatile particles from the binder and to transform the remaining
particles into coke.

In principle, graphite is normally classified by grain size. The grain size is used as a
criteria because most of the other properties and characteristics of graphite are related
directly or indirectly to the grain size and orientation. Nowadays, the market offers
graphite classes with average grain sizes under 1µm up to 20µm.

Due to its low mechanical strength, graphite is considered to be easily machined.

However, complications arise in the cutting of this material due to the layered
crystalline structure and, particularly, the extremely abrasive behavior of graphite,
which leads to a shortened tool life for tools without coating. (Schroeter et al. , 2006)

2.3 Polyethylene (PE)

Polyethylene is an organic semicrystalline, thermoplastic polymer with excellent

chemical resistance, thermal stability, and high spinnabilty. Thus, it is a very
important polymer for producing engineering plastics and fibers. It has a low glass
transition temperature (Tg) since strong intermolecular cohesive forces are absent.
Polyethylene has a low cost and therefore there is considerable interest in increasing
its strength. Polymer/ layered inorganic hybrids offer the potential for improvement in
mechanical, thermal, optical and physico- chemical properties. The word
‘nanocomposite’ refers to composites whose reinforcement has at least one dimension
in the nanometer scale. Because the building blocks of a nanocomposite are nanoscale,
they have enormous surface area leading to high interfacial area between filler and
matrix. Unique properties of the nanocomposite are attributed to the interactions at the
interfaces.

4
Polyethylene (PE) is a natural, organic, thermoplastic homopolymer which does not
melt at one particular temperature into a clean liquid. Instead it becomes increasingly
soft and ultimately turns into a very viscous, tacky molten mass. It has a low Tg as
strong intermolecular cohesive forces are absent and the substituent group (CH2)
present in it is not bulky. PE is a polymer consisting of long chains of the monomer
ethylene (IUPAC name ethene). Polyethylene is classified into several different
categories based mostly on its density and branching. The mechanical properties of PE
depend on variables such as the extent and type of branching, the crystal structure, and
the molecular weight. (Kosuri et al. , 2008)
Some classifications of PE include:

·Ultra high molecular weight PE (UHMWPE)

·High density PE (HDPE)
·Cross-linked PE (PEX)
·Medium density PE (MDPE)
·Linear low density PE (LLDPE)
·Low density PE (LDPE)
·Very low density PE (VLDPE)

The applications of polyethylene are based on its properties. Sometimes a given

application is based on a specific property, but more often an application is based on a
combination of properties. PE is unbreakable and this property is used in the
manufacture of house wares and toys. It’s cheap, tough and moisture resistant nature
makes it ideal for packaging films and squeeze bottles, PE laminates and coatings,
textiles: Cheap, tough and moisture resistant. PE shows remarkable ability in the sense
of tackling large strains without fractures and without excessive permanent
deformation and it is also able to do at extremely low temperatures due to its sub
ambient Tg. Low water absorption, low water transmission, high dielectric strength,
high tensile strength, lightweight, chemical inertness, resistant to fungi and other
organisms are other key properties. (Kosuri et al. , 2008)

Application of polyethylene can refer to the Table A1.

5
2.4 Medium Density Polyethylene (MDPE)

Medium-density polyethylene, MDPE, is a semi-crystalline thermoplastic polymer

which has been increasingly used for fabrication of plastic pipes for water and gas
distribution systems. (Peres et al. , 2010)

MDPE viscoelastic characteristics at room temperature, it is susceptible to long term

creep fracture by means of a slow stable crack growth mechanism. (Brown, 2007)

According to the research of Mohammad (2008), he investigated the sole effect of

each parameter and their combination on maximum stress produced in MDPE gas
pipes and their sockets which are made from PE100. MDPE can be used for water
pipe, gas pipe, MDPE plastic pipe and so on. It is known that MDPE pipes offer many
advantages over traditional ductile iron and steel pipes. These advantages include
flexibility, coilability, high ductility, light weight, corrosion resistance, and reduced
installation costs. These features provide both performance and economic benefits
which in turn have made MDPE pipes popular in ploughing-in and trenchless
technology applications.

6
Figure 2.1 shows a schematic picture of such a side branching chain; the branches
radiate three-dimensionally, just as the branches of a tree point in all directions from
various places along the trunk. The presence of such side branches is a reason for
variations in a number of important physical properties (such as density, hardness,
flexibility or melt viscosity), which distinguish polyethylene resins. Chain branches
also become points in the molecular network where oxidation may take place. (Wan et
al. , 2006)

Figure2.1: Polyethylene chain with side branches.

7
2.5 Mechanical Milling Method

Two different terms are commonly used in the literature to denote the processing of
powder particles in high-energy ball mills. Mechanical Alloying (MA) describes the
process when mixtures of powders (of different metals or alloys/compounds) are
milled together. Material transfer is involved in this process to obtain a homogeneous
alloy. On the other hand, milling of uniform (often stoichiometric) composition
powders, such as pure metals, intermetallics, or prealloyed powders, where material
transfer is not required for homogenization, has been termed Mechanical Milling
(MM). The destruction of long-range order in intermetallics to produce either a
disordered intermetallic or an amorphous phase has been referred to as Mechanical
Disordering (MD). The advantage of MM/MD over MA is that since the powders are
already alloyed and only a reduction in particle size and/or other transformations need
to be induced mechanically, the time required for processing is short. For example,
MM requires half the time required for MA to achieve the same effect. Additionally,
MM of powders reduces oxidation of the constituent powders, related to the shortened
time of processing. Some investigators have referred to MM as Mechanical
Grinding(MG). (Suryanarayana, 2001)

8
 Chapter 3

METHODOLOGY

3.1 Location of research

The research will be conducted at Laboratory of Basic Physics (MFA) in Department

of Physical Sciences, Faculty of Science and Technology, University Malaysia
Terengganu (UMT).

3.2 Experiment
3.2.1 Sample Preparation

Graphite will be put inside grinding jar of the instrument ball-mill Retsch PM 100.
The grinding jar is arranged eccentrically on the sun wheel of the planetary ball mill.
It will grind the graphite into nanosized graphite particles. This mill have 20 grinding
balls. It will perform 20, 40, 60, 80, 100 hour milling time for mill the graphite be the
grain size. However, the milling time was restricted due to heating and therefore each
alternate 30 min were used for milling and then cooling. After finish milling, graphite
powder will be obtained from the ball milling.
3.2.2 Characterization

Every 20 hours alternate of ball milling, little grain size of powder will be taken out
and do the characterization by using the X-ray diffraction (XRD) to determine the
crystalline size and using the Scanning electron microscope (SEM) to determine the
graphite morphology.

3.2.3 Compounding process (composite)

In this process, MDPE will mix with the graphite by using the HAAKE Polylab
system. The blending process will carry out 5 samples; each sample will use 0wt%,
1wt %, 2wt%, 3wt%, 4wt% mix with the MDPE. The materials were compounded
into different mixture ratios of graphite content in MDPE. The MDPE will compound
at 180℃ and 170RPM for 20 min. Firstly, the MDPE will add to the mixer until the
MDPE fully melt and be liquid, and then the graphite powder is added until the
mixing torque become stabilized.

3.2.4 Injection Moulding

After a complete blending, the compound will be compact and form into tensile bar
shape by using injection moulding machine, HAAKE Minijet ΙΙ. When the compound
were shape into the tensile bar, it easy for the analysis.

10
3.2.5 Analysis

Lastly, MDPE-graphite composite be produced. Testing and analysis were perform on

this stage. Table below shows several characterizations method and description in this
research.

Table3.1 : Instruments and method

Method
Thermogravimetry (TGA)
X-ray diffraction (XRD)
Fourier Transform Infrared
Spectroscopy (FTIR)
Testometric MODEL 350/500
Four Point Probe
Description
Determine change of weight in relation of
the change of temperature
Investigation of the fine structure of matter
Determine the type of bonds which are
present in a compound
Tensile test
Determine the conductivity

3.3 Instrument
3.3.1 Thermogravimetric Analysis (TGA)

TGA is a branch of thermal analysis, which examines the mass change of a sample as
a function of temperature in the scanning mode or as a function of time in isothermal
mode. TGA is used to characterize the decomposition and thermal stability of
materials under variety of conditions and to examine the kinetics of the physico-
chemical processes occurring in the samples. It is used to compare the behavior of
polymer with or without additives Thermogravimetry is used to measure the mass or
change in mass of a sample as a function of temperature or time or both. Changes of
mass occur during sublimation, evaporation, decomposition, and chemical reaction,
magnetic or electrical transformations. In TGA, the change of mass of a specimen is
measured either absolutely in milligrams or relatively as a percentage of the starting
mass, and plotted against temperature or time. Plastics may change mass in one or
more steps. The percentage loss of mass ML is calculated from the masses ms (at the
start, before heating) and mf (at the end of temperature, T) using the following
equation:

11
 ms− mf (3.1)
ML = × 100%
ms

TGA measurements were carried out in a TGA 6 Perkin-Elmer analyzer under a

nitrogen atmosphere. Around 10 mg of sample was used. The measurements were
performed from 50-800°C at a heating rate of 10°C/ min. (Kosuri et al. , 2008)

3.3.2 X-Ray Diffraction

X-ray diffraction is a tool for the investigation of the fine structure of matter. This
technique had its beginnings in von Laue’s discovery in 1912 that crystals diffract
Xrays, the manner of the diffraction revealing the structure of the crystal. At first, x-
ray diffraction was used only for the determination of the crystal structure. Later on,
however, other uses were developed and today the method is applied not only to
structure determination but to such diverse problems as chemical analysis and stress
measurement, to the study of phase equilibria and the measurement of particle size, to
the determination of the orientation of one crystal or the ensemble of orientations in
polycrystalline aggregate.

X-ray diffraction is based on Bragg’s law which is given by the formula

nλ = 2dsinθ (3.2)
where,
λ= wavelength
θ= Bragg’s angle
d= d-spacing between planes

Figure3.1: condition for constructive interference

12
Bragg’s law states the essential condition which must be met if diffraction is to occur.
N is called the order of reflection, it may take on any integral value consistent with
sinθ not exceeding unity and is equal to the number of wavelengths in the path
difference between rays scattered by adjacent planes. Therefore, for fixed values of λ
and d, there may be several angles of incidence θ1, θ2, θ3 … at which the diffraction
may occur corresponding to n=1,2,3…
Debye Scherrer’s formula is used to calculate the crystallite lamella size. Scherrer’s
equation is given as Crystallite Lamella size= 0.9 λ/(B cos θ) Where, B is full width
half maxima in nm. (Kosuri et al. ,2008)

3.3.3 Fourier Transform Infrared Spectroscopy (FTIR)

Fourier transform infrared spectroscopy is another form of infrared spectroscopy

which does not bombard the samples using infrared radiation of individual
wavelengths. Instead, FTIR uses sends out a pulse of beam which contains the
information of all infrared wavelengths. The beam is transmitted through the sample,
and the transmitted beam results in an interferogram. The interferogram is then
deciphered to obtain the infrared absorbance of the compound.

FTIR spectroscopy uses an interferometer which generates the pulse of beam which
transmits information of all infrared wavelengths. The beam produced by the infrared
source and is split by a beamsplitter into two perpendicular beams. One of the beams
will reflect on a fixed mirror while the other beam will reflect off a mirror mounted
onto a moving part. The moving mirror will then move a few millimeters away from
the source. As the two beams meet and collide with each other interference of the
beam will occur and produces an interferogram. The interferogram is transmitted
through the sample and absorption of infrared wavelength will occur. Transmitted
radiation is collected and is analyzed to obtain the infrared spectrum.

13
3.3.4 Testometric Model 350/500

Testometric Model 350/500 design and manufacture a comprehensive range of

materials testing machines and software for evaluating the mechanical properties and
performance of materials. It has two type of this model, there are AT range of stand-
alone universal strength testing machines and the CT range of universal strength
testing machines. Testometric machine can done the testing including tensile test, wet
strength and puncture of tissue, board tests include flat, ring edge and the etc.
Accessories for paper testing include a wide range of grips and fixtures for paper
testing and all are compliant to international standards.

3.3.5 Four Point Probe

Four point probes method is a simple apparatus for measuring the resistivity of
semiconductor samples. By passing a current through two outer probes and measuring
the voltage through the inner probes allows the measurement of the substrate
resistivity. The sheet resistivity of the top emitter layer is very easy to measure
experimentally using a "four point probe". A current is passed through the outer
probes and induces a voltage in the inner voltage probes. The junction between the n
and p -type materials behaves as an insulating layer and the cell must be kept in the
dark.

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 3.4 Process Flow Chart

Preparation of samples-mill graphite (20, 40, 60, 80,100 hr)

Characterization graphite XRD

SEM

Compounding process

MDPE MDPE MDPE MDPE

+ + + +
MDPE
1wt% 2wt% 3wt% 4wt%
graphite graphite graphite graphite

Analysis

TGA XRD FTIR Testometric 4 Point PRobe/Impedance Spectroscopy

Figure 3.2 : Sample preparation and compounding process

15
 Chapter 4

EXPECTED RESULTS

Graphite transforms to an amorphous phase by ball milling, the average size reach
from 3nm to 8nm after 60 hour milling.

When MDPE mix with the graphite, crystallinity will increase and structure will be
more close packing. When crystallinity increases, hardness will increase. Tensile
modulus increasing from 1.9 to 3.2 GPa, the tensile strength will increase from 16 to
24MPa and the strain to failure decrease from 30% to 5% as the composition increases
from 0 to 10wt% graphite powder.

Carbon act as filler added to the MDPE, thermal stability values increase as the filler
volume fraction increases alignment of the microfibers in the direction of the heat
flow increases the thermal conductivity.
 REFERENCES

Peres, M. F. , Schön, C.G. & Tarpani, J.R. 2010 Effect of precracking method on KIc
results for medium-density polyethylene tested under cryogenic condition.
Journal of Polymer Testing 29 : 667–673

Brown, N. Intrinsic lifetime of polyethylene pipelines. 2007. Polymer Engineering

and Science. doi:10.1002/pen :477–480

Mohammad Shishesaz1 & Mohammad Reza Shishesaz . 2008. Applicability of

Medium Density Polyethylene Gas Pipes in Hot Climate Areas of South-west
Iran. Iranian Polymer Journal. 17 (7), 503-517

Zhang , W. , Dehghani-Sanij , A. A. & Blackburn, R.S. 2007 Carbon based

conductive polymer composites. J Mater Sci. 42: 3408–3418

Schroeter , R. B. , Kratochvil, R. & Gomesb, J. D. O. 2006 High-speed finishing

milling of industrial graphite electrodes. Journal of Materials Processing
Technology. 179: 128–132

Chen, G.H. , Wu, C.L. , Weng, W.G. , Wu, D.J. & Yan, W. L. 2003. Preparation of
polystyrene/graphite nanosheet composite. Journal of polymer
Communication. 44: 1781–1784

Hamouda, H. B. H. , Laiarinandrasana ,L. & Piques, R. 2006. Fracture mechanics

global approach concepts applied to creep slow crack growth in a medium
density polyethylene (MDPE). journal of Engineering Fracture Mechanics.
74: 2187–2204

Hamouda, H. B. H. , Laiarinandrasana ,L. & Piques, R. 2008. A local approach to

creep fracture by slow crack growth in an MDPE: Damage modeling.
International Journal of Pressure Vessels and Piping 86: 228–238

Kosuri, D & Tech, B. 2008. Polyethylene-layered double hydroxides and

montmorillonite nanocomposites: thermal, mechanical and flame retarddance
properties. Thesis University Of North Texas

17
Wolak, J. E. 2005. Polyolefin miscibility: Solid-state NMR investigation of phase
behavior in saturated hydrocarbon blends. Dissertation Degree of Doctor of
Philosophy. North Carolina State University.

Dhoot, S.N. , B.S. & M.S. 2004. Sorption And Transport Of Gases And Organic
Vapors In Poly(Ethylene Terephthalate). Dissertation Degree of Doctor of
Philosophy. University of Texas, Austin.

Suryanarayana, C . 2001. Mechanical alloying and milling. Journal of Progress in

Materials Science, 46: 1-184

Wan Aizan & Rahman, W.A. 2006. Design of silane crosslinkable high density
polyethylene compounds for automotive fuel tank application. Thesis of
project IRPA. Faculty of Chemical and Natural Resource Engineering,
Universiti Teknologi Malaysia

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 APPENDIX

Table A1: commercially produced metallocenes

Source: Wolak, Justyna Ewa. 2005. Pg:103

19
Table A2: Gantt Chart for FYP

Month
No. Task 2010 2011
JUL AUG SEP OCT NOV DEC JAN FEB MAR APR
1 Literature Review
2 Title Selection & Submission
3 Writing Proposal
4 Proposal Submission
5 Proposal Presentation
6 Lab work 1 (Preparation)
7 Lab work 2 (Compounding)
8 Writing Progress Report 1
9 Writing Progress Report 2
10 Thesis Writing
11 Submit Final Draft
12 Final Presentation
13 Thesis Submission

20