UNIVERSITI TEKNIKAL MALAYSIA MELAKA

THE STUDY OF NATURAL RUBBER/POLYETHYLENE

POLYMER MIXING METHOD

Thesis submitted in accordance with the requirements of the

University Technical Malaysia Melaka (UTeM) for the Degree of
Bachelor of Engineering (Honours) Manufacturing (Material Engineering)

By

ROHANI BINTI OSMAN

Faculty of Manufacturing Engineering

March 2008

DECLARATION

I hereby declare that this report entitled THE STUDY OF NR/PE POLYMER
MIXING METHOD is the result of my own research except as cited in the references.

Signature

Authors Name

Rohani binti Osman

Date

28 March 2008

APPROVAL

This report is submitted to the Faculty of Manufacturing Engineering of UTeM as a

partial fulfillment of the requirements for the degree of Bachelor of Manufacturing
Engineering (Material Engineering). The members of the supervisory committee are as
follow:

Muhd.Zaimi Zainal Abidin

(Main Supervisor)
28 March 2008

Dr. Mohd Warikh bin Abd Rashid

(Co-Supervisor)
28 March 2008

ABSTRACT

This research is focused on examining and characterizing the properties of combination

of elastomer which is natural rubber with thermoplastic which is polyethylene.
Improvements in strength of polyethylene (PE) can be sought by melt blending with
natural rubbers (NR). In this study, PE is blended with two types of different NR which
is indoor and outdoor storage. In this research, it is studying about the properties with
two type of polymer which is elastomer and thermoplastic when they are blending
together. The purpose of this research is to improve the thermoplastic elastomer based
on rubber-plastic blends and also to determine their mechanical properties with different
ratio mixing between of them. The ratio percentage blended between natural rubber and
polyethylene that are focused in this work which is 10%, 20% and 30% of natural
rubber. Each percentage of this, were examining their mechanical properties with two
types of testing which are flexure test and tensile test. In the end of this research, NR
indoor is identified as a good NR that can blended properly with polyethylene than NR
outdoor based on the result from mechanical testing.

ABSTRAK

Kajian ini adalah fokus kepada penilaian dan ciri-ciri sifat yang ada pada penggabungan
elastomer iaitu getah natural dengan plastic haba iaitu polietilena. Pembaikan atau
peningkatan dalam kekuatan yang ada pada polyethylene boleh diperoleh melalui
campuran cair bersama dengan getah natural. Dalam kajian ini juga, polietilena
dicampurkan dengan dua jenis getah natural yang berlainan keadaan iaitu getah natural
yang diletakkan didalam rumah (terlindung dari cahaya matahari) dan getah natural yang
diletakkan diluar rumah (terdedah kepada cahaya matahari, hujan dan sebagainya).
Didalam kajian ini, sifat-sifat yang terhasil diantara elastomer dan plastik haba kesan
daripada gabungan kedua-duanya telah dikaji. Tujuan kajian ini dilakukan adalah untuk
memperbaiki atau meningkatkan sifat yang ada pada plastik haba elastomer
berdasarkan campuran yang dilakukan dan juga untuk menentukan sifat-sifat mekanikal
mengikut nisbah campuran yang berlainan. Manakala peratus nisbah campuran diantara
getah natural dan polietilena dalam kajian ini hanya tertumpu kepada 10%, 20% dan
30% dari getah natural. Setiap peratusan ini, dinilai kekuatan mekanikalnya melalui dua
jenis ujian iaitu ujian tegangan dan ujian pelenturan. Di akhir kajian ini, keputusan yang
dicapai adalah getah yang diletakkan didalam rumah adalah lebih bagus dan elok dalam
pencampuran bersama dengan polietilena berbanding dengan getah yang diletakkan
diluar rumah.

DEDICATION

I want to dedicate this research project to my father, Osman bin Husin; who
everlastingly stays in my heart, my mother, Fatimah binti Hj.Isa, my brothers, Arifin
Osman, Muhd Al-Amin Osman and Fauzi Osman, my sisters, Mastura Osman and other
members of my family for their continual support, prayers, understanding and most
importantly patience during my time in graduate school.

ACKNOWLEDGEMENTS

During several steps of ones life, the road seems uphill and full with challenges
and obstacles. While we are traveling along that road, countless times we sigh and then
ask ourselves what is the reason of going through. It is indubitably true about the part of
my life here, in Malacca. Still and all, this journey is enjoyable and memorable because
of helps and kindness from a special group of individuals that I would like to mention as
follows. Not only I have gained much knowledgement about polymers here, but also I
have learned to work and to discipline myself in order to achieve certain important goals
in life.
I would like to express my deepest appreciation to my supervisor, Mr.
Muhd.Zaimi Zainal Abidin, for giving me the opportunity, the support and the guidance,
for his kindness and generosity. They were so enormous and I was very fortunate to be
one of his students. I would also like to thank many faculty members in the Department
of Manufacturing Engineering especially to the entire technician, for their helpful in
providing time and advice support for my research. I express gratitude all my friends in
Faculty of Manufacturing Engineering especially to student Material Engineering, for
their support and encouragement. They have shown that virtue and dignity are much
more important than other things in life and they have taught me not by words but by
examples. I am forever thankful to them. I was taught how to dream the impossible
dream and was given the courage to swim upstream in order to make even a small
difference. I hope that my work will not be the disappointment for them.

TABLE OF CONTENTS

Declaration..

ii

Approval.....

iii

Abstract..

iv

Abstrak

Dedication...

vi

Acknowledgements

vii

Table of Contents

viii

List of Figures.

xi

List of Tables..

xiii

List of Abbreviations, Symbols, specialized Nomenclature...

xiv

1. INTRODUCTION

1.1 .Introduction..

1.2 Problem Statement.......

1.3 Objectives.

1.4 Scope of Project....

2. LITERATURE REVIEW...................................................................................

2.1 Introduction.....

2.2 Elastomer.........

2.2.1 Examples of Elastomer.....

2.2.2 Elastomer Properties Chart...

2.2.3 Natural Rubber......

2.3 Thermoplastic.

19

2.3.1 Polyethylene (PE).....

19

2.4 Polymer Blends..

21

2.4.1 Importance and Characteristics of Polymer Blends...

22

2.4.2 Why Blending....

22

2.4.3 Morphology of Polymer Blends....

24

2.4.4 Thermodynamics of Polymer Blends....

24

2.4.5 Mechanical Properties...

25

2.4.6 Compatibilizers.....

25

2.4.7 Techniques of Blending.....

26

2.4.8 Machinery used for Manufacturing Polymer Blends....

27

2.4.9 Important Blends...

28

3. METHODOLOGY.

29

3.1 Introduction....

29

3.2 Planning of Study...

29

3.3 Process....

31

3.3.1 Mixer Testing....

31

3.3.1.1 Material/Equipment....

32

3.3.1.2 Result ..

33

3.3.1.3 Graph result of mixer process ....

34

3.3.2 Crusher Process.....

37

3.3.2.1 Material/Equipment....

38

3.3.3 Drying Process..

39

3.3.4 Hot Press Process..

39

3.3.4.1 Equipment.......

40

3.3.4.2 Parameter.....

40

3.3.4.3 Result after hot press

41

3.3.5 Sample Cutting...

42

3.3.5.1 Tensile specimen.....

42

3.3.5.2 Flexure specimen.....

44

3.3.6 Mechanical Testing...

45

3.3.6.1 Tensile Test.....

45

3.3.6.2 Flexure Test.....

46

4. RESULT...

48

4.1 Introduction....

48

4.2 Tensile Test for NR/PE blends and Pure PE..

48

4.3 Flexure Test for NR/PE blends and Pure PE.

53

5. DISCUSSION...

57

5.1 Introduction......

57

5.2 Tensile Properties.

57

5.3 Flexure Properties....

61

6. CONCLUSION AND RECOMMENDATION FOR FURTHER WORK.

64

6.1 Conclusion.

64

6.2 Recommendation for Further Work.

65

REFERENCES..

66

APPENDICES

Gantt Chart

68

Table of Tensile Test Result

70

Table of Flexural Test Result

71

LIST OF FIGURES

2.1

Schematic drawing of an unstressed polymer

2.2

Chemical structure of natural rubber

10

2.3

Structure of cyclized rubber

12

2.4

Graph of pH value

15

2.5

Graph of NH3 content

16

2.6

Graph of MST

17

2.7

Fishbone diagram

19

2.8

Structure of polyethylene

20

2.9

Molecule of linear polyethylene

20

2.10

Types of polymer blends

23

2.11

Morphology of polymer blends

24

2.12

Graph of mechanical properties of polymer blends

25

3.1

The flow Chart of Study Planning

30

3.2

Mixer Machine

32

3.3

Sample of PE

33

3.4

Sample of NR after drier

33

3.5

NR mixing with PE

33

3.6

Graph of mixer NR (indoor) 10% with PE 90%

34

3.7

Graph of mixer NR (indoor) 20% with PE 80%

35

3.8

Graph of mixer NR (indoor) 30% with PE 70%

35

3.9

Graph of mixer NR (indoor) 10% with PE 90%

36

3.10

Graph of mixer NR (outdoor) 20% with PE 80%

36

3.11

graph of mixer NR (outdoor) 30% with PE 70%

37

3.12

Crusher machine

38

3.13

Sample from mixing NR and PE

38

3.14

Sample after crusher

38

3.15

Flow of the basic hot press method

39

3.16

Hot press machine model GT-7014-A

40

3.17

PE sample (300 mm x 300 mm x 2 mm)

41

3.18

NR/PE mixing sample (300 mm x 300 mm x 2 mm)

42

3.19

Specimen dimension for tensile test

42

3.20

Cutter machine

43

3.21

Example of tensile specimen

43

3.22

Example of flexure specimen

44

3.23

Universal Testing Machine

45

3.24

Specimen gripped

45

3.25

Flexure machine

47

3.26

Specimen is loaded between a supports span

47

4.1

Comparison strain between NR (indoor) / PE and PE pure

49

4.2

Comparison strain between NR (outdoor) /PE and PE pure

49

4.3

Comparison stress between NR (indoor) / PE and PE pure

50

4.4

Comparison stress between NR (outdoor) / PE and PE pure

50

4.5

Comparison modulus of elasticity between NR(indoor)/PE and PE pure

51

4.6

Comparison modulus of elasticity between NR(outdoor)/PE and PE pure 52

4.7

Comparison strain between NR (indoor) / PE and PE pure

53

4.8

Comparison strain between NR (outdoor) /PE and PE pure

54

4.9

Comparison stress between NR (indoor) / PE and PE pure

54

4.10

Comparison stress between NR (outdoor) / PE and PE pure

55

4.11

Comparison flexure modulus between NR(indoor)/PE and PE pure

56

4.12

Comparison flexure modulus between NR (outdoor)/PE and PE pure

56

5.1

Elongation of PE specimen

59

5.2

NR/PE specimen elongates and breaks off

59

5.3

Force that applied to the specimen

62

LIST OF TABLES

2.1

Comparison between natural rubber latex and synthetic rubber latex

10

2.2

Specification for NR latex concentrate properties

11

2.3

Data of chemical testing

14

3.1

Parameter setting for mixer test (10% NR: 90% PE)

31

3.2

Parameter setting for mixer test (20% NR: 80% PE)

31

3.3

Parameter setting for mixer test (30% NR: 70% PE)

32

3.4

Parameter setting for hot press process

41

3.5

Specimen dimensions for thickness 2mm

43

3.6

Specimen dimensions for flexure testing

44

4.1

Comparison of strain and stress result for NR/PE blends and PE pure

48

4.2

Comparison modulus of elasticity result for NR/PE blends and PE pure

51

4.3

Comparison of strain and stress result for NR/PE blends and PE pure

53

4.4

Comparison of flexure modulus result for NR/PE blends and PE pure

55

5.1

Elongation for each of sample testing

60

5.2

Maximum force for flexure test

62

LIST OF ABBREVIATIONS, SYMBOLS, SPECIALIZED

NOMENCLATURE

TPE

Thermoplastic elastomer

NR

Natural rubber

PE

Polyethylene

HA

High ammonia latex

LATZ

Low ammonia latex

IR

Polyisoprene

IIR

Copolymer of isobutylene and isoprene

CIIR

Chloro Butyl Rubber

BIIR

Brono Butyl Rubber

BR

Polybutadiene

SBR

Styrene butadiene rubber

NBR

buna N.rubber

HNBR

Hydrated Nitrile Rubbers

CR

Chloroprene Rubber

EPM

ethylene propylene rubber

ECO

Epichloroyhdrin rubber

ACM, ABR

Polyacrylic rubber

SI

Silicone rubber

FVMQ

Fluorosilicone rubber

FPM

Fluoroelastomers

FFRM

Perfluoroelastomers

PEBA

Polyether Block Amides

FEPM

Tetrafluoro ethylene

CSM

Chlorosulfonated polyethylene

EVA

Ethylene vinylacetate

TPV

Thermoplastic vulcanizates

NRL

Natural rubber latex

EB

Extensibility

NH3

Ammonia

MST

Mechanical stability time

VFA

Volatile fatty acid number

ISO

International Standard Operation

Hydrogen

Carbon

LDPE

Low-density polyethylene

HDPE

High-density polyethylene

PVC

Polyvinyl chloride

Width

Length

Gage length

Radius

Distance

Strain

Stress

Modulus of elasticity

EL

Elongation

Flexure strength

LNR

Liquid natural rubber

CHAPTER 1
INTRODUCTION

1.1 Introduction
In combining together different materials to form a mixture, there are two major
concerns. One of these is to produce a homogeneous mixture on a global level. The
achievement of compositional homogeneity in a mixing process is said to occur through
distributive mixing. The second concern is to produce as fine a dispersion of the
ingredients as possible (James L.White, 2001). For rubber-plastic blends, they have been
commercialized as thermoplastic elastomers (TPEs). The mechanical and rheological
properties of these blends depend not only on those of constituent polymers but also on
the morphologies of blends. In order to improve the properties of thermoplastic
elastomers based on rubber-plastic blends, one should understand the relationships
between morphology, processing and properties of these materials.

Natural rubber (NR) and polyethylene (PE) are very important industrial elastomer and
thermoplastic, respectively which both are widely used in different industries.
Thermoplastic properties can be imparted into natural rubber (NR) via its melt blending
with any compatible thermoplastic such as polyethylene (PE). Such blend is generally
termed thermoplastic natural rubber and by the physical characteristics exhibit, is
categorized as an elastomer lying between rubbers and plastics (Azizan Ahmad, 2005).
This project is study to obtain the mechanical properties of blends of natural rubber
(NR) with polyethylene (PE). This enables a green material to enter many markets from
which it had previously been precluded for several decades, such as automotive

weatherstrip. Structurally, polyethylene is expected to be more readily compatible with

natural rubber when they are blended together (Azizan Ahmad, 2005).

Thermoplastic elastomers (TPEs) have become very important during last few decades.
Thermoplastic elastomeric compositions based on rubber-plastic blends are becoming
increasingly significant because of their combination of elastomeric properties and ease
of thermoplastic processing to give low-cost end-use products. In order to improve the
properties of thermoplastic elastomers based on rubber-plastic blends, or to find new
rubber-thermoplastic combination to form thermoplastic elastomers, one should
understand the relationships between morphology, processing and properties of these
materials. Thermoplastic natural rubber is being based on blends of NR with
thermoplastic which is polyethylene (PE). It can blend with different ratios and a wide
range of properties can be obtained.

In this study, natural rubber is used as one types of elastomer. It is because hevea-based
natural rubber (NR) is one of the most interesting rubbers, because of its unique
properties in numerous respects and also because of its low price in some tropical
countries, especially in Southeast Asia. Natural rubber latex is stabilized by proteins
layer and fatty acid surfactants/lipids on the surface of the rubber particles which carry a
negative charge. Actually, latex concentrate is divide to two categories which is highammonia latex (HA), preserved with not < 0.61% ammonia and low ammonia latex
(LATZ), preserved with not <0.31% ammonia.

1.2 Problem Statement

Natural rubber (NR) is one of the most interesting rubbers because of its unique
properties in numerous respects. Because of that, NR is blended with another type of
polymer in order to improve their properties. But, the problem is, in what condition or
type of natural rubber is a good quality before blend it with another material. So, in this
study it must to be investigating for getting the good and best quality of properties
natural rubber between indoor and outdoor storage. It is because, the properties of
natural rubber will changes and their quality will decrease time by time. Besides that,
the advantages and disadvantages relationship between natural rubbers blend with
polyethylene also must to be investigate to find a new rubber-thermoplastic
combinations in order to form a good product in future.

1.3 Objectives

i)

To compared their properties between two different condition of natural rubber

which is NR in outdoor storage and NR in indoor storage.

ii)

To determined the stabilization of the natural rubber with different condition.

iii)

To study about the combination of natural rubber with thermoplastic (PE).

1.4 Scope of Project

The blending of polymers provides a powerful route for obtaining materials with
improved property performance. The scope of this project is to produce high quality
blends of natural rubber with thermoplastic which is polyethylene at different condition
of natural rubber such like indoor and outdoor storage. From this research, the type of
suitable condition of natural rubber blended with polyethylene is defined. Besides that,
their mechanical properties with two different ways of testing which is flexure test, and
tensile test are obtained. The high quality blends and their mechanical strength is
depending on the ratio percentage between natural rubber and polyethylene. In this
research, its only concentrate to 10%, 20%, and 30% of natural rubber that blended with
polyethylene.

CHAPTER 2
LITERATURE REVIEW

2.1 Introduction
This chapter is describing the topic of elastomer and thermoplastic, how natural rubber
or elastomer can blend with thermoplastic and answers the following questions:

a) What is elastomer?
b) What is thermoplastic?
c) What is polymer blends?

2.2 Elastomer
The term elastomer is often used interchangeably with the term rubber, and is preferred
when referring to vulcanisates. Elastomer comes from two terms, elastic (describing the
ability of a material to return to its original shape when a load is removed) and mer
(from polymer, in which poly means many and mer means parts). Each link of the chain
is the "-mer" or basic unit that is usually made of carbon, hydrogen, oxygen and/or
silicon. To make the chain, many links or "-mers" are hooked or polymerized together.
They are amorphous polymers existing above their glass transition temperature, so that
considerable segmental motion is possible. At ambient temperatures rubbers are thus
relatively soft (E~3MPa) and deformable. Their primary uses are for seals, adhesives
and molded flexible parts. .(R.Chandra, S.Mishra, 1995)

Figure 2.1: Schematic drawing of an unstressed polymer. The dots represent cross-links.
B is the same polymer under stress. When the stress is removed, it will
return to the A configuration.

Elastomers are usually thermosets (requiring vulcanization) but may also be

thermoplastic (see thermoplastic elastomer). The long polymer chains cross-link during
curing. The molecular structure of elastomer can be imagined as a 'spaghetti and
meatball' structure, with the meatballs signifying cross-links. The elasticity is derived
from the ability of the long chains to reconfigure themselves to distribute an applied
stress. The covalent cross-linkages ensure that the elastomer will return to its original
configuration when the stress is removed. As a result of this extreme flexibility,
elastomer can reversibly extend from 5-700%, depending on the specific material.
Without the cross-linkages or with short, uneasily reconfigured chains, the applied stress
would result in a permanent deformation. .(R.Chandra, S.Mishra, 1995)

2.2.1 Examples of elastomer

2.2.1.1 Unsaturated rubbers that can be cured by sulfur vulcanization:

a) Natural Rubber (NR)
b) Polyisoprene (IR)
i. Butyl rubber (copolymer of isobutylene and isoprene, IIR)
ii. Halogenated butyl rubbers (Chloro Butyl Rubber: CIIR; Bromo
Butyl

Rubber: BIIR)

c) Polybutadiene (BR)
i. Styrene-butadiene

Rubber

(copolymer

of

polystyrene

and

polybutadiene, SBR)
ii. Nitrile Rubber (copolymer of polybutadiene and acrylonitrile,
NBR), also called buna N rubbers
iii. Hydrated Nitrile Rubbers (HNBR) Therban and Zetpol
d) Chloroprene Rubber (CR), polychloroprene, Neoprene, Baypren etc.

2.2.1.2 Saturated Rubbers that cannot be cured by sulfur vulcanization:

i. EPM (ethylene propylene rubber, a copolymer faeces of
polyethylene and polypropylene) and EPDM rubber (ethylene
propylene

diene

rubber,

terpolymer

of

polyethylene,

polypropylene and a diene-component)

ii. Epichlorohydrin rubber (ECO)
iii. Polyacrylic rubber (ACM, ABR)
iv. Silicone rubber (SI)
v. Fluorosilicone Rubber (FVMQ)
vi. Fluoroelastomers (FKM, FPM) Viton, Tecnoflon, Fluorel, Aflas and
Dai-El

vii.Perfluoroelastomers (FFKM)Kalrez
viii. Polyether Block Amides (PEBA)
ix. Tetrafluoro ethylene/propylene rubbers (FEPM)
x. Chlorosulfonated Polyethylene (CSM), (Hypalon)
xi. Ethylene-vinyl acetate (EVA)

2.2.1.3 Various other types of elastomers:

i. Thermoplastic Elastomers (TPE), for example Hytrel, etc.
ii. Thermoplastic Vulcanizates (TPV), for example Santoprene TPV
iii. Polyurethane rubber
iv. Resilin, Elastin
v. Polysulfide Rubber

2.2.2 Elastomer Properties Chart

Physical properties
Polymer Spec.
Gravity
Durometer Range
Tensile Strength, PSI
Elongation, %
Tear Resistance
Weather Resistance
Solvent Resistance:
Aliphatic
Hydrocarbon
Solvent Resistance:
Aromatic
Hydrocarbons
Brittle Point oF
Stiffening Point oF
(avg)
Compression Set
Abrasion Resistance
Flex Resistance

Natural
Rubber
NR

Styrene
Butadiene
SBR

Neoprene
CR

Urethane

0.93

0.93

1.23

1.05

30-100
4000+
To 700
Excels
Fair

30-100
3000
500
Good
Fair

15-95
3000
To 800
Good
Excels

20-100
To 8000
To 650
Excels
Excels

Poor

Poor

Good

Excels

Poor

Poor

Poor

Fair

-80

-80

-50

-60

-40

-35

-10

-20

Good
Excels
Excels

Good
Excels
Good

Fair
Good
Good

Excels
Excels
Good

2.2.3 Natural Rubber

Natural rubber (NR) is used as a type of elastomer to blend with a thermoplastic which
is polyethylene (PE). So, the background of NR and their properties must be
investigated. Actually rubber is a group of industrial material like metals, fibers, wood,
plastics, glass etc. on which the world of modern technology depends. The world
consumption of rubber is in the order of about 16 million tons per annum and has been
increasing in recent years at the rate of about 4% per annum. Out of this about 1/3rd is
man made synthetic rubber mainly produced from petroleum fractions.

The unique and versatile properties of rubber have made it highly indispensable for the
modern way of life. The mobility or speed of movement of the modern world mainly
dependent on rubber; in the form of bicycle tyres to highly sophisticated pneumatic tyres
for motor vehicles and aeroplanes etc. Its importance as strategic material due to its
valuable contribution in defence application is well recognized. The distinguishing of
rubber is its resilience and elasticity. In many of its modern applications rubber is not
used alone but reinforced with textiles, metals etc. Contribution of rubber in the field of
engineering, space research, medical sciences, family planning etc. is vital.(R.Chandra,
S.Mishra, 1995)

Actually, latex has divide by two types which is natural rubber latex and synthetic
rubber latex (nitrile and neoprene). But in this study, a natural rubber latex (C5H8)n is
used for a testing. In its natural state, rubber exists as a colloidal suspension in the latex
of rubber-producing plants. Natural rubber latex (NRL) is a milky fluid that is produced
by the Hevea brazilienis rubber tree found in Africa and Southeast Asia. Often, NRL is
shortened to latex. Natural rubber is "cis 1, 4-polyisoprene" with the chemical structure
of,