SWELLING BEHAVIOR OF NATURAL RUBBER VULCANIZATE FILLED WITH

CARBONIZED GROUNDNUT HUSK AND CARBON BLACK

BY
ELETA KATE WILLIAMS

MATRIC NO AST/2161208034

SUBMITTED TO THE DEPARTMENT OF POLYMER TECHNOLOGY

SCHOOL OF APPLIED SCIENCE AND TECHNOLOGY AUCHI POLYTECHIC,
AUCHI,
EDO STATE

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE AWARD OF

HIGHER NATIONAL DIPLOMA (HND) IN POLYMER TECHNOLOGY

September 2014

CERTIFICATION
This is to certify that this project work on swelling behavior of natural rubber (NR) vulcanizate
filled with carbonized groundnut husk was performed and written by ELETA KATE
WILLIAMS of department of polymer technology of higher national diploma (HND)
certificate

______________________
DR MRS F.A. AKPA

__________________
DATE

(PROJECT SUPERVIOR)

______________________
MRS UGBESIA, S.O

___________________
DATE

PROJECT CO-ORDINATOR

_______________________

____________________

MR IDIAGHE J .A

DATE

(HEAD OF DEPARTMENT)

ii

DEDICATION
This project wok is dedicated to God most high whose divine grace is unspeakable to my
success in life.

iii
ACKNOWLEDGEMENT
The long year dream is now a reality my first gratitude go to my lord God almighty , for his
guidance, protection , substance , provision and all for giving me divine health, wisdom,
knowledge and understanding favor, encouragement throughout the course of study.
My thankS also goes to my supervisor Dr Mrs. F. A .O AKPA. My profound gratitude goes to
Mr. Ekebafe L .O for his full support throughout my project and for his contribution during
the course of my study. Also my gratitude to Engr AYO DADA for his support, MR FESTUS
INEGBEDION. My thank also goes to MR IKHIDE his for help and assistance, MR
MOMOH F. P, My thanks also goes to all the staff of polymer technology department that
influence and contribute to my academic success. Most especially MR EKEBAFE .L .O May
God enriches you with your heart desires. Amen
My gratitude goes to the head of the department MR IDIAGHE J .A.
Am ever indebted to my mother MRS ANTHIANS .O. for her support, spiritually, prayerfully,
financially, love and care I pray the Lord enlarge her coast. Also MR WILSON ONORIADE
and MR MIKE IRALE for their support for the success for my academic work.
Finally, I appreciate and acknowledge the presence of God in my life; spirit, soul, and body
for give me favors ability and enablement to pass through the program successfully. I also
acknowledge the assistance of all my course mate 2012/2014 scission.

iv

ABSTRACT
This research work is aimed at studying the swelling behavior of natural Rubber (N.R)
vulcanizates filled with groundnut husk carbon and carbon black respectively. Eight formulation
tables were drawn, four containing carbon black and four containing carbonized groundnut husk
at different loading capacity. The vulcanizates were prepared based on the formulations. The
swelling behavior vulcanizates were studied using the solvents: petrol, diesel, kerosene, and
water to determine the swelling index at 100ml of each of the solvent. The essence of the test is
to determine the stability of the vulcanizates to attack by these solvents and other material alike,
which the vulcanizates may come in contact with in every day application. From the result
obtained, it was observed that vulcanizates with low filler loading have very high swelling
index obviously due to low interaction between the filler and the polymer matrix leading to very
low cross link density. Which means at low filler loading the vulcanizate will not be suitable for
petro chemical industrial application except at high filler loading.

TABLE OF CONTENT
Title page

Certification

ii

Dedication

iii

Acknowledgement

iv

Abstract

Table of content

vi-vii

CHAPTER ONE
1.0

Introduction

1.1
1.2

Purpose /objective Of The Study

Statement of problem

2
2

1.3

Significance Of Study

1.4 scope of study

CHAPTER TWO

2.1

Natural Rubber

2.2

Sources of Natural Rubber

2.3

Method of Producing Natural Rubber

2.4

Processing Of Natural Rubber

2.5

Properties/Application of Natural Rubber

2.6

Fillers

2.7

Characteristic of Filler

2.8

Uses of fillers

10

2.9

Types of Filler

13

vi

2.10 Main effect of filler characteristics on vulcanizate properties

18

2.11 source of filler

18

2.12 Rubber Compounding Ingredients

20

CHAPTER THREE
3.0

materials and method

24

3.1

material and sources

24

3.2

Method

25

3.3

preparation of carbonized groundnut husk powder as filler

25

3.4

characterizations of the fillers (CB 330 and CGNH)

25

3.6

compounding of N.R at varying filler loading

28

3.7

modification of formulation

30

3.8

stages of processing

30

3.9

molding and vulcanization

31

CHAPTER FOUR
4.0

Result

33

4.1

test

33

CHAPTER FIVE
5.0

Discussion, Conclusion and recommendation

38

5.1

Discussion

37

5.2

Conclusion

39

5.3

recommendation

39

REFERENCE

vii

CHAPTER ONE
1.0

INTRODUCTION
Many people have tried to use various agricultural by-products as fillers in compounding.

These fillers are either use raw or modified. In this work, the carbonized groundnut shell are
compare with carbon black to see the comparative study of thermal stability of compounded
rubber. The rapid increase in the range of manufactured products following world war (2) two
resulted directly from the development of broad range of new fibers, plastic elastomers,
adhesive, and resins. These new material are polymers and their impact on our way of life is
almost incalculable [allcock and lampe1990]. The demand for polymers in many applications
has experience a steady growth over the years. In developed countries of Europe and America,
the volume of polymer used is more than that of metals or ceramics [Akpa2005]. Rubber, being
a major form of polymers has not been left out. Rubber in its raw state have virtually no
engineering application, it is necessary to appropriately compound them in order to obtain good
processing characteristics, and the desire cure properties in the finished products [catchy 2000].
It is not surprising, therefore that more than 50% of all chemist and chemical engineers, large
numbers of physicist and mechanical engineers and nearly all materials scientists and textile
technologist are involved with research or development work with polymers.

Rubber as one of the classes of polymers have found great valued in many application including
engineering, sport and leisure and domestic. In its raw state, rubber may not be good enough for
any useful application, so there is the need for the addition of additives which help to enhance
the properties. Among the additives are filler. Carbon black is the major filler used in rubber
industry. Today there are lots of research going on to find an alternative (local source) for it.
Advances are being made into the use of other agricultural by-products, such as rice husk,
groundnut shell, rubber seed shell, etc[Bryson 1955]. These materials are used in their raw form
or they are modified before used.
1.1

PURPOSE/OBJECTIVE OF STUDY
1.
2.
3.
4.

Preparation of carbonized groundnut husk

Characterization of carbonized groundnut husk
The use of carbonize groundnut husk to compound natural rubber
The determination of the swelling properties of the vulcanizate
The purpose of this study is to study the swelling behavior of the carbonized groundnut
shell and carbon black filled natural rubber compounds

1.2 STATEMENT OF PROBLEM

Apart from the base polymer, fillers are the next material in terms of volume that is
required in the rubber industry.

The most commonly use fillers include carbon black, china clay, calcium carbonate, etc
of all these fillers, carbon black is the one that is mostly used for rubber products expect where
colour is of priority.
This carbon black is mostly imported which make it to be expensive due to our weak
naira and secondly, it is from petroleum a source which is non-renewable and between the next
15 years coming it may get exhausted. There is the need to sort for alternate material from local
material with little modification.
1.3

SIGNIFICANCE OF THE STUDY

The significance of this study is to assess the swelling behavior of natural rubber vulcanizate
filled with carbonized groundnut husk as to provide an alternative to carbon black by using
locally sourced fillers.
1.4

SCOPE OF STUDY

This work is limited to swelling behavior of natural rubber vulcanizate filled with carbon black
and carbonized groundnut husk in solvents

CHAPTER TWO
2.0

LITERATURE REVIEW

2.1 NATURAL RUBBER

Rubber also India Rubber redirect here for other uses. Rubber is generally classified
as natural and synthetic rubber a gummy substance, isolated from the white fluid of rubber trees
with minor impurities of other organic compounds plus water forms of poly-isoprene that are
useful as natural rubber are classified as elastomeric. Rubber is harvested mainly in the form of
latex from certain trees. The latex is a sticky, milky colloid drawn off by making incision into
the bark add collecting the fluid in vessels in a process called tapping. The latex then is
refined into rubber, rubber ready for commercial processing. Natural rubber is used extensively
in many application and products, either alone or in combination with other materials. In most
of its useful forms, it has a large stretch ratio, high resilience, and is extremely water proof (4).
NR is hydrocarbon with empirical formula (C5H8) n where n is 95,000 to 10,500. The
(C5H8) is gutta-percha in contrast to natural rubber however, gutta-percha is hard and very
brittle at home temperature and this noticeable difference is attributed to the structural
arrangement about the double bonds in the two (C5H8) Isomers. While in natural rubber, the
arrangement is in Cis form, in gutta percha the arrangement is in Trans form.

CH3
CH2

= C - CH = CH2
n
( Isoprene) ( Poly-isoprene)

2.2

SOURCES OF NATURAL RUBBER

Sometimes called (Para rubber) is the tree Hevea brasiliensis. The only other place under

cultivation as a commercial rubber source is guayule (parthenium argentatum), shrub native to

the arid region of Mexico and the SW United States.
2.3 METHOD OF PRODUCING NATURAL RUBBER
In the collection of natural rubber latex, the hevea brasiliensis tree wounded by cutting
the latex vessel in the bank, by a controlled operation called TAPPING. The most common
tapping method used is the half spiral system, from left to right way around the tree trunk at an
angle of 30o to the horizontal.
5

Tapping is achieved with a special curved knife (tapping knife) which flow along the
groove to the end of the cut where spout conduct it to a collecting cup attached to the tree. The
cup may contain a preservative such as Ammonia (NH3) to prevent the latex from coagulating
at the latex receiving station. The latex is strained through a sieve to remove coagulum and bark
particle as well as dirt. The latex is then transferred to the main factory for onward preparation
to dry rubber.
2.4 PROCESSING OF NATURAL RUBBER
Natural rubber is coagulated latex from certain types of rubber tree e.g. hevea brasiliensis
and manufactured in a factory. Rubber got its name when English scientist Joseph Priestly
observed that it could rubout pencil marks (source: RMA).
Rubber is a polymer, which is a chain of monomers or small molecules. Natural rubber
has only monomers of isoprene. While synthetic rubber can contain any of several types of
monomer, but those must be derived from petroleum. The processors mix different chemicals
with the rubber, depending on its ultimate use. In 1839, U.S. inventor Charles Good year
determined that heating rubber with surfer resulted in a stronger product that was more stable
over a wide range of temperatures. He called this process vulcanization and further discovered
that he could quicken the process by adding other substances. Vulcanization strengthens rubber
into a stronger matrix. Natural rubber is processed by first taking the sap from a cut in the tree,
next, processors flatten it into sheets.
6

To make the sheets workers blend, latex from various sources and sometime mix with water and
coagulants. Then the latex is passed through grooved rollers to produce sheets of rubber that are
allowed to dry. On small rubber plantations, these sheets are visually inspected; they are tested
technically in large operations. After imperfections are removed, the sheets are baled together
with talc in between to keep them from sticking to each other. Block rubber goes through the
same initial stages, but is chopped up and pressed into bales (source: UACTAD).
Synthetics rubber is made by mixing two by product of petroleum fining, butadiene and
styrene. They are mixed with soapsuds to make liquid latex, which as then dried into bits and
passed into bales. About 70 percent of all rubber is synthetic. The industry can vary the
chemical formula of synthetic rubber to adapt it to different applications (source: RMA)
2.5 PROPERTIES / APPLICATION OF NATURAL RUBBER
Rubber exhibits unique physical and chemical properties. Rubbers stress strain behavior
exhibits the Mullins effect and the Payne effect, and is often modeled as hyper-elastic.
Rubber strain crystallizers
Owing to the presence of a double bond in each repeat unit, Natural rubber is susceptible to
vulcanization and sensitive to ozone cracking.

The two main solvents for rubber are turpentine and naphtha (petroleum). The former has been
in use since 1964 when Giovanni Fibroins is credited with the discovery of naphtha as a rubber
solvent in 1779.
Because rubber does not dissolve easily, the material is finely divided by shredding prior to its
immersion.
An ammonia solution can be used to prevent the coagulation of raw latex while it is being
transported from its collection site.
2.6 FILLERS
These are usually solid additives that are incorporated into polymer to modify its physical
(mechanical) properties. Fillers help to increase modulus and hardness and to reduce creep and
most time to reduce the cost of end product. It also help in electrical in solution and heat
deformation resistance. They are powdered or short fibred materials such as wood flow, glass
fibred, silicon and silicates. CaCo2, MgCo2 as be stores e.t.c. others may be rein-enforcing e.g.
carbon black and also groundnut shell. Plastics that are used as structural engineering materials
contained rein-enforcing agent and a more recently use rein-enforcing agent is graphic fibred
which is a common additive used in application call for a proved mechanical properties (2)

2.7 CHARACTERISTIC OF FILLER

The interaction of particular filler with an elastomeric is dependent on a number of
factors.
Namely:
1.
2.
3.
1.

Intensity
Extensity
Geometrical
INTENSITY
The intensify factor is the specific activity of this solid surface per square centimeter

interface, determined by the physical chemical nature of the filler surface and to some extent
that of the elastomers (3)
2. The EXTENSITY FACTOR is the total amount surface area of the filler per cubic
centimeter compound in contact with that elastomer.
3. GEOMETRICAL FACTOR
(a) The surface of the filler, which can be determined by it empty (void) volume under
standardized packing conditions.

(b) The porosity of filler usually a minor factor which can varied over a wide range with
carbon black because the weight of the individual spongy particles is lower than those of the
solid particles. The number of particles sizes per cubic centimeter of
Compound at a given weight loading is greater for spongy particle than the solid particle (3)
2.8

USES OF FILLERS
Filler are used in various forms for various Purposes. Before the application of fillers,

much consideration such as cost, process ability, compatibility and ability to withstand adverse
condition must be evaluated for better product property. Filler cannot be used to the best
advantage in polymer unless there is a good adhesion between them. In particular, the filler
particle polymer interface will not be stress bearing and therefore provides a point of
mechanical weakness, fillers can be used to achieve the following effect.
a. COST REDUCTION
Certain filler can be applied to reduce cost in opaque P.V.C Compounds for mixing and
processing. Examples of filler used are coconut shell, wood flour, rice husk, groundnut shell. In
other words filler are used as cheapeners for products.

10

b. HARDNESS AND MODULUS

The hardness of a material gives a measure of the modulus at low strain and usually
expressed in I.R.H.D particulate fillers play an important role in the hardness and modulus of a
vulcanisate. Generally fillers especially reinforcing fillers increase the modulus and hardness of
a Vulcanisate.
c. STRENGTH
Fillers are useful in impacting the product property of strength when incorporated into
polymers such as NR, SBR, low gum strength polymer require fine particle size carbon black
and silicas give the highest strength for rubber especially when they are well dispersed.
d. ABRASION AND TEAR RESISTANCE
Fillers are used in areas where resistance to abrasion and tear are desired, as the
resistance to abrasion increases with optimum resistance occurring in the region of 5Ophr, nonblack filler can also give this effect.
e. ELECTRICAL PROPERTIES
Fillers can be used to improve

electrical insulation properties clay and carbon blacks,

are example of fillers applicable for this purpose.

11

f. DEFORMATION RESISTANCE
Fillers are also used to improve heat deformation resistance of cables in its manufacture
to lengthen its service life.
g. BRITTLENESS
The incorporation of filler such as glass fibred, wood flour in high impact polystyrene
can help to reduce brittleness in the compound.
h. MACHINE ABILITY
With the careful incorporation of fillers to vulcanizates that can be improvement in
machine ability and thermal conductivity but may some cases inhibit cure. All forms of metal
fillers can be used to this effect.
I. PIGMENTATION
Filler is applicable as colorant, in some case final products need not to be coloured.
Fillers like carbon blacks given considerable black pigment
j. FLAME RETARDANCE
Most filler are used as flame and fire breakers; certain fillers like Aluminum tri-hydrate
are self-extinguishing. These kinds of fillers do not initiate or contribute to fire attack.

12

TYPES OF FILLER
These are the three main types of fillers, these include:
1) Particulate filler
2) Ruinous filler
3) Fibrous filler
PARTICULATE FILLER
Particulate filler are divided into reinforcing filler and inert fillers. The inert filler may affect
the physical properties when incorporate into a polymer. e.g. the addition of inert filler onto
plasticized PVC compound will reduce die swell on extension, increase modules and hardness,
improve electrical insulation properties and reduces tackiness. Inert fillers will also usually
reduce the cost of a compound to greater extent. Among the filler used such filler should be
insoluble in any liquid with which the polymer compound is liable in contact. Chemicals type of
filler is available in a numbers of grades and differs in the following ways:
(1) Particle shape and porosity
(2) Average particle size and size of the surface
(3) Chemical nature of the surface
(4) Impunities
13

It has been observed that when employed in the elastomeric system the finer the particles size,
the higher the value of such properties as tensile strength modules, and hardness. They can
function in a number of ways in a polymer matrix.
(1) Improve where an abrasion characteristics of the matrix
(2) Increase the heat deformation temperature of the matrix
(3) Reduce solvent and gas permeability in the matrix
(4) Increasing lubrication properties of the matrix
(5) Electrical insulation properties (reduces)
(6) Viscosity increase
(7) Specific gravity increase
(8) Transparency (decrease)
RESINGEOUS FILLER
When particulate filler are added to rubber, there is a considerable increase in the viscosity and
the filler properties becomes extremely poor. In order to facilitate processing by improving
flow, plasticizer is added but the level of plasticizer is required to be kept low. It is because of
this, resinous filler are used in rubber.

14

The resinous have a further advantage, testing of the rubber compound is little affected. There is
equally little or no heart build up the case with the particle filler as loading is increased.
The resinous filler commonly used are,
Styrene-butadiene (50/50 resin)
Phenolic phenol +formaldehyde resin.
FIBROUS FILLER
There are generally fibers of cotton rayon, wood, carbon asbestos etc. the fiber used have a
higher modulus than resin in which they are embedded so that when the composite of resin+
fiber is stained In the place of the fibrous layer, the bulk of the stress is taken out by the fiber.
REINFORCING FILLER
Generally, reinforcing filler re those additions which increase the tensile strength, tear strength,
modulus, hardness and abrasion resistance of rubber compound vulcanization in which are
incorporated.

15

NON BLACK REINFORCING FILLER

However for light color product meeting specification was very tasking as the non black filler
up to 1945 were non reinforcing, hence, it become imperative than non black filler use for light
color goods give more reinforcing properties in other to be used in non-self reinforcing
elastomers such SBR, NBR, EPDM.
The experience as resulted in the development of non black filler for the production of rubber
article with improved physical properties such as
Increasing hardness, tensile, strength, tear strength and operation resistance.
The following constitute some of the non black reinforcing filler presently in use in the rubber
industry are silica, zinc oxide natural silica, hydrated precipitated silica, Hydrated aluminum
hydroxide etc.
NON BLACK NON REINFORCING FILLER
These are the inner material (dilutes) mainly used reduce compounding cost and cheapen or
extend the material. Example include
BARITES;
An inner material used to reduce cost: it is an attractive candidate for chemical resistance
compound for tank lining.
16

TALCUM (TALC FRENCE CHALK)

Mica powder naturally washed and grounded to about 200-300. Due to its lamellar structure
can substantially reduce gas permeation and also impact good resistance to heart. This consists
mainly of silicate of magnesium and aluminum used as inert filler in heat resistance compound
for gasket battery cases and auto clawing joints. Talc is now mostly used as a dusting agent to
prevent uncured stock from sticking to themselves and other surfaces.
NON BLACK SEMI REINFORCING FILLER
Some of these include:
TREATED WHITINGS
These are precipitate CaCo3. The particle of which has been coasted with 3% of a serrate. They
are quite valuable materials to fill gap between non reinforcing whiting at one hand and
reinforcing silicon on the other hand.
As semi - reinforcing filler, giving product of moderate cost goods appearances with fairly
high resistance and tears strength. They are used in the high grade colour mechanical goods.
Others include a timony trioxide maximum flame resistance and precipitated whiting at high
loading.

17

2.10 MAIN EFFECT OF FILLERS CHARACTERISTIC ON VULCANISATE

PROPERTIES.
PARTICLE SIZE
An increase in the surface activity (physical absorption) result in high abrasion resistance,
higher absorptive properties, higher bond rubber and lower hysteresis
SURFACE ACTIVITY An increase in surface activity (physical adsorption) result in higher
modulus at the higher strain 300% upward,
Higher abrasion resistance and higher adsorption properties higher bound rubber and lower
hysteresis.
2.11 SOURCE OF FILLERS
FILLERS FROM MINERAL DEPOSIT
Examples of filler gotten from material deposit are barites which are gotten from coarse ground
natural day. Also are china derived from natural deposit example includes soft clay and hard
clay.
FILLER FOM FIBROUS MATERIAL
Examples of filler of source from fibrous material are wood flour from hard wood which are
firmly grounded to give fine grades of filler.
18

Others include wood flour, asbestos which are naturally occurring siliceous fibers both the
shorter fibers and the grounded material as filler for flame (.heat resistance material) like gasket
and shoe.
FILER FROM ORGANIC MATERIAL
Example of filler source from organic material are phenolics resins, doka nut shell, rice husk
etc. the source doka shell is dried and grounded to a fine powder, sieve to particles size between
75-150mm. others includes coconut fiber, mango shaft etc.
PERSITENT STRUCTURE
An increase in persistence structure (omisionery) results in lower extrusion shrinkage,
higher modulus at low and medium strain up to 300%, higher viscosity, higher hysteresis and
longer incorporation time. Higher electrical conductivity is found for higher structure blacks.
This property is interrelated with surface activity. Structure changes on filler without surface
activity (graphitized black), showing the effects indicated above only rather faulty at constant
high activity. The structural effects are pronounced.
POROSITY
Porosity results in higher viscosity and higher electrical conductivity in the case of
carbon black.

19

2.12 RUBBER COMPOUNDING INGREDIENTS

The manufacture of rubber products required the addition of many different types of
chemical compounds and materials to the rubber. These additional materials are called
compounding ingredients or rubber additives. Compounding therefore is the operation of
bringing together all the ingredients required to mix a batch of rubber compound. They are
often added to facilitate processing, improve the properties of the rubber and reduce cost. The
rubber in its raw state is not suitable for use in any given application. Rubber is, for example,
visco-elastic in nature. They have a tendency towards both plastic and elastic behaviors. This
tendency gives rise to creep which is adverse to engineering and other application. Rubbers
are also very sensitive to changes in temperature. They exhibit thermo plasticity within a limited
range of temperature most rubbers are soluble in a wide range of organic solvents. These factors
impose severe limitations on the usefulness of the rubber material for a particular application
the base polymer or blend has to be selected according to the final properties required. Some of
the compounding ingredients are:
I. RUBBER
Raw rubber, whether it is the natural hydrocarbon or synthetic, in the dry or latex form, is
compound with various other materials to change it from a soft plastic material to a strong, nonplastic and even hard Substance. A blend of two rubbers may also be used in the rubber
compound formulation.
20

ii. VULCANIZING AGENT

Vulcanization is a chemical process, which brings about the formation of cross-links
between the long polymer chains. The three-dimensional structure produced restricts the free
mobility of the molecules and gives products having reducing tendency to crystallize improved
elasticity and substantially increased modulus and hardness. The original and more commonly
used vulcanizing agents are organic peroxides such as dicumyl peroxide and benzyl peroxides,
metal oxide such as zinc oxide and magnesium oxide.
Poly-functional amines are used in the vulcanization of fluorocarbon rubber. The process
of sulphur vulcanization is only possible if raw rubber has double bond or unsaturation in its
molecules. For saturated rubbers, a small amount of unsaturation is usually introduced to make
it sulphur Vulcanizable.
iii. ACCELERATORS
Accelerators are compounding ingredients used to speed up the rate of cure, they are
added to reduce cure time to an economic level examples are biphenyl-guanidine (DPG),
mercaptobenzothiazole (MBT) Zinc diethyl dithiocarbonate (ZDC).
iv. ACTIVATOR
Activators are compounding ingredients which activate the accelerator and make them
more soluble and efficient during vulcanization.
21

They consist of organic activator (zinc oxide) and organic activator (stearic acid). The
zinc oxide is soluble in the stearates which act as a vehicle. These increase cross link density
but do not speed up the rate of cure.
v. ANTIDEGRADANTS
Anti-degradant is a general term used to describe materials added to rubber which retard
deteriorates of rubber product during

service life. Double bond although vital for sulphur

vulcanization of rubber provides the weak link as far as degradation by oxygen and ozone is
concerned. Rubber containing high amount of unsaturation such as NR, SBR, are more prone to
Oxidative degradation or attack by ozone than elastomer containing low amount of unsaturation
such as EPDM. The groups of protective agents used in the rubber industry fall into:
1. Amines and their derivatives e.g.
a. Phenyl A- napthylamine (PAN)
b. Phenyl B- naphitonlamine (PBN)
c. N, iso- propyl N-phenyl, P-phenylene diamine (IPPD).
2.

Phenol and their derivative e.g. Bis (2 hydroxyl 3- t-buty1 5 methyl phenyl)

methane.

22

vi. PLASTICIZER
These are materials used in rubber to facilitate the mixing and processing of rubber
compounds. They act as; lubricants during processing operation and accelerate the plasticization
of the raw rubber. These materials include resins, mineral and vegetable oils, waxes and organic
peptizing agent: Plasticizers must be compatible with the rubber so as to function effectively
into the compound.

23
CHAPTER THREE
3.0

MATERIALS AND METHOD

3.1

MATERIAL AND SOURCES

S/NO

MATERIALS

SOURCES

Natural rubber

Rubber

research

institute

iyanomo, Benin city, Edo State.

2
3
4

Stearic acid
Zinc oxide
Sulphur

British drug house limited

British drug house limited
Juhros Nig (Ent) NO_ 21 B str.

Off wine Rd Benin city

Tetra methyl thiarman ;;
;; ;; ;;

disulphide (TMTD)
Mercaptobenzyl thiozle ;;

;;

;;

;;

disulphide (MBT)
7
8
9

Carbon black (N330)

Groundnut shell
TMQ

;; ;; ;; ;;
Auchi, Edo State
British drug house limited

24
3.2

METHOD

The major materials required in this work are groundnut shell, Natural rubber and compounding
ingredients.
3.3

PREPARATION OF THE CARBONIZED GROUNDNUT HUSK POWDER AS

FILLER.
The groundnut husks were washed with water and sundried to remove sand particle and
moisture. The groundnut husks were carbonized at a temperature of 300 0c of one (1) hour using

a muffle furnace. The carbonize groundnut husks were grinded pass through a metal sieves in
order of 150 micro (um) with a shaker, the fine powder particle for the carbonize groundnut
husks that passes through the sieves were collected and characterized before used for
compounding and also with carbon black in order to compared the swelling behavior with
different solvent
3.4

CHARACTERIZATION OF THE FILLER

Filler are characterized in terms of P H, Bulk density determination, Iodine adsorption, loss on
ignition.
pH Determination
The pH of the carbonized groundnut husk (CGNH) samples were
Determined using ASTMD 1512 method, 1983 by immersing 1.0g samples in 50.0ml of
25
deionised water in a 250ml beaker. The mixture stirred for 15minutes and both the filler and
was heated for 25minutes and added to cool before adding another 50ml of deionizer water
making it 100ml and was stirred of 5minutes.The pH meter was inserted on both the filler to
determine the reading and values were read. Transfer the results to the chapter for results and
discussion
For carbon black
7.92pH
For carbonized groundnut husk
8.11Ph
ASH CONTENT
The weight of the crucible were noted before the test sample were filled to the crucible and
were place inside the oven at a temperature of 400 o c for hours. At the expiration of the time,
the crucible (moisture cans) were removed from the oven and place into a dissector to before it

was re-weighed and the valves were noted for both carbon black and carbonized groundnut
husk filler.
Bulk Density Determination
Bulk Density of the carbonized groundnut husk was determined by the tampering procedure
described by Ahmedna et al, 1997. Accurately weighed samples of the CGNH were poured into
a uniform cylinder of cross sectional area and were then tapped several times until there was no
change in the volume occupied. This volume was then recorded and the bulk density calculated.
Determination of the Loss on Ignition
Loss on ignition (LOI) refers to the mass loss of a combustion residue whenever it is heated in
an air or oxygen atmosphere to high temperatures. The loss on ignition of carbon black and
carbonized groundnut husk was determined gravimetrically, in accordance to the procedure
described in ASTM D7348, 1983 and expressed in terms of percentage. Loss on Ignition is a
test used in inorganic analytical chemistry, particularly in the analysis of minerals. It consists of
strongly heating ("igniting") a sample of the material at a specified temperature, allowing
volatile substances to escape, until its mass ceases to change.
26
This may be done in air, or in some other reactive or inert atmosphere. The simple test typically
consists of placing a few grams of the material in a tared, pre-ignited crucible and determining
its mass, placing it in a temperature-controlled furnace for a set time, cooling it in a controlled
(e.g. water-free, CO2-free) atmosphere, and predetermining the mass. The process may be
repeated to show that mass-change is complete.
Determination of the Moisture Content
The moisture content of carbon black and carbonized groundnut husk filler sample was
determined by method described in ASTMD 1509, 1983 at 125 C. This method was used to
determine the percentage of water in a sample by drying the sample to a constant weight. The
water content is expressed as the percentage, by weight, of the dry sample. The moisture sample
was determined by weighing the rubber seed shell and record as wet weight of sample; the
wet sample was dried to a constant weight, at a temperature not exceeding 115C using suitable

drying equipment (drying oven). The sample was allowed to cool and then weighed again, and
recorded as the dry weight of sample
Calculation
The moisture content of the sample is calculated using the following equation:
%W = A - B 100

------------------------- 2

_____
A
Where:
%W = Percentage of moisture in the sample,
A = Weight of wet sample (grams), and
B = Weight of dry sample (grams)

27
3.5

COMPOUNDING
Compounding of natural rubber with carbonized groundnut husks filler and carbon

black. The formulation used for the compounding of natural rubber, carbon black filler and
carbonized groundnut husks filler
Formulation used for compounding natural rubber ingredient of carbon black N330
PPHR

ingredient
Natural

100

100

100

100

rubber

Stearic acid
Zinc oxide
TMTD
MBT
Processing oil
TMQ

5
3.5
1.5
3
5
1.5

5
3.5
1.5
3
5
1.5

5
3.5
1.5
3
5
1.5

5
3.5
1.5
3
5
1.5

Filler(CB)N3

20

30

40

50

3.5

3.5

3.5

3.5

3O
Sulphur

28
Formulation used for compounding N.R ingredient of carbonized groundnut husk. CGNH
PPHR

100
5
3.5
1.5
3
5
1.5
20
3.5

100
5
3.5
1.5
3
5
1.5
30
3.5

100
5
3.5
1.5
3
5
1.5
40
3.5

100
5
3.5
1.5
3
5
1.5
50
3.5

INGREDIEN
T
Natural rubber
Stearic acid
Zinc oxide
TMTD
MBT
processing oil
TMQ
Filler(CGNH)
Sulphur

3.6 COMPOUNDING OF NATURAL RUBBER AT VARYING FILLER LOADING.

The design of the formulation for the compounding is shown in table above. The fillers used
were varied with different loading capacity to check on their influence on the natural rubber
product.

29
3.7 MODIFICATION OF FORMULATION
With the 100g of the base polymer it is not possible to form a band and a bank of rubber
on the roll nip, through which other ingredients can be added to the rubbers. So this made it
easier to modify the formulation and consequently, a batch factor of 7 was used in the
modified formulation used.
3.8 STAGES OF PROCESSING
a. WEIGHING
The natural rubber and all the required additives were weighed with a weighing balance
according to the modified formulation stated.
b. MASTICATION
The mastication of natural rubber was carried out on two roll mill in order to enhance the
processing of the natural rubber due to its high viscosity. The mastication continued for about 5
minutes until a uniform band were formed round the front roll.

c. COMPOUNDING
The compounding ingredients were added to the masticated rubber in a sequential order.
The ingredients were added to the rubber bank that is formed on the nip of the rolls. The mixing
operation was done with the following order as shown below

30
Stages of mixing
time of mixing (minutes)
Mastication
5
ZnO
3
Stearic acid
3
Half filler and processing oil
3
Remaining half filler and processing oil
4
TMQ
2
MBT and sulphur
3
Duration
25minutes
After proper mixing the compound was than sheeted out from the rolls and live for a
minimum of 24 hours for proper homogenization of the compounding ingredient before curing.
3.8 MOULDING AND VULCANIZATION
The compression molding system was used in the curing of the material fed into the
mould cavity is soften, shaped and vulcanized in the mould. The mould was preheated and
robs with silicon oil to act as mould releasing agent. The material was fed into the mould
cavity and placed in the hydraulic pressing machine (15tonnes). Temperature was applied for
6 minutes for flat sheets and the mould was however, opened for an instant, to allow for
escape of any entrapped gas produced during cross linking .

31
The cure test pieces were removed from the mould after the stipulated time and allowed
to cool after a week the test piece produce were cut by a cutter machine in a round tin circle
and was ready for testing.

32
CHAPTER FOUR
4.1
4.2

TEST
SOLVENT TEST: Transfer to chapter on methodology

Solvents used in the assessing the swelling behavior of the vucanizate are petrol , diesel ,
kerosene and water the test sample that were cut were weighed to know their initial weight and
were immersed into 100ml of the different solvents with a sealed containers for 24hours.
Where are the results for the characterization of the carbonized groundnut husk and
carbon black. They should be presented here.
RESULT
5. CARBON BLACK (N330) SWELLING CAPACITY IN FILLER LOADING
SOLVENT
A(70)
B(140)
C(210)
D(280)
PETROL
40.2
25.3
50.1
1.2
DIESEL
6.1
7.2
7.6
5.5
KEROSENE 20.3
24.7
15.2
8
WATER
0.3
0.1
0.2
0.2
SWELLING INDEX (Y axis) AGAINST FILLER LOADING (X axis)
CARBONIZED GROUNDNUT HUSK (SWELLING CAPACITY IN FILLER
LOADING)
SOLVENT
A(70)
B(140)
C(210)
D(280)
PETROL
7.2
26.2
32.7
0.9
DIESEL
6.8
6.9
9.2
6.6
KEROSENE 22.1
17.30
35.9
23.2
WATER
0.3
0.2
0.1
0.2
SWELLING INDEX (Y axis) AGAINST FILLER LOADING (X axis)
FIGURE 1.UPTAKE OF SOLVENT IN THE VULCANIZATE IN DIFFERENT FILLER
LOADING IN PETROL

33

60
50
40
CARBONIZED
GROUNDNUT HUSK

30

CARBON BLACK
20
10
0
A(70)

B(140)

C(210)

D(280)

FIGURE 2.UPTAKE OF SOLVENT IN THE VULCANIZATE IN DIFFERET

FILLER LOADING IN DIESEL

10
9
8
7
6
5

CARBONIZED
GROUNDNUT HUSK

CARBON BLACK

3
2
1
0
A(70)

B(140)

C(210)

D(280)

35
FIGURE 3. UPTAKE OF SOLVENT IN THE VULCANIZATE IN DIFFERENT
FILLER LOADING INKEROSENE

40
35
30
25
CARBONIZED
GROUNDNUT HUSK

20

CARBON BLACK

15
10
5
0
A(70)

B(140)

C(210)

D(280)

FIGURE4. UPTAKE OF SOLVENT IN THE VULCANIZATE IN FILLER LOADING

IN WATER
0.35
0.3
0.25
0.2

CARBONIZED
GROUNDNUT HUSK

0.15

CARBON BLACK

0.1
0.05
0
A(70)

B(140)

C(210)

D(280)

36
CHAPTER FIVE

5.1
5.2
EFFECT

DISCUSSION, CONCLUSION AND RECOMMENDATIONS

DISCUSSION
OF

SOLVENT

TREATMENT

/DIMENSIONAL

CHANGES

OF

VULCANIZATES
The effect of solvent treatment on equilibrium swelling of the vulcanizates in various
solvents is presented in the Figures1, 2, 3, and 4 above. it was observed that in the vulcanizates
containing carbon black filler, the solvent up take was reduced from the filler loading 70 - 280
and increase in from 140- 210, why carbonized groundnut husk vulcanizate reduced in swelling
index with filler loading from 140 -280 and then increase from 70 - 210 due to the enhance
interfacial bonding between the filler and the rubber [reference] . The nature of the fillers, as
well as the porosity of the filler, extent of crosslink density characteristics were revealed from
the solvent interaction with the vulcanizates. Thus it is clear that equilibrium solvent up take
can provide information regarding the efficiency of interfacial bonding [reference]. This is
compared to the solvent up take of the vulcanizates containing carbon black.
The percentage increase in the equilibrium swelling for the vulcanizates cured at different
filler loading at 70, 140, 210, and 280 at 100ml in petrol, diesel, kerosene and water are shown
in the above graphs.

37

It was observed that the petrol and diesel in the vulcanizates in carbonized groundnut
husk has higher swlling index to that for carbon black in Figure 1 and 2, why in Figure 3 the
vulcanizates in carbon black swells more than the vulcanizates in carbonized groundnut husk on
filler loading in 70,210,280 why that of 140 the vulcanizates in carbonized groundnut husk
swells more. In water it has equal level of both the vulcanizates except in 140, and 210 of filler
loading that have minor different in the vulcanizates. The solvent can diffuse into the polymer
mostly through a direction parallel orientation. At low filler loading (70) the solvent absorption
of the vulcanizates with carbon black in Figure 1, petrol was higher when compared with that of
210 filler loading in the vulcanizates. As filler loading increases, the number of filler in a unit
volume increases and therefore the rate absorption also decreases and the penetrate molecule
finds it difficult to diffuse into the polymer and therefore the swelling have better result in the
loading of filler in vulcanizates of carbon black of 280 on petrol, diesel and kerosene why that
of the vulcanizates of carbonized groundnut husk in diesel of 210 have good swelling also why
the other filler loading in the vulcanizates have poor swelling. Although during swelling
dimensional changes are shown by both the vulcanizates on carbon black and carbonized
groundnut husk vulcanizates on the above Figure.1, 2, 3, and 4.
5.2

CONCLUSION
Equilibrium swelling observed in the vulcanizates with petrol, diesel, kerosene followed

by water increases as the filler loading decreases showing increased filler polymer matrix
interaction and hence increased cross link density.
38

The vulcanizates containing water absorbed less solvent compared to those of petrol,
diesel and kerosene which absorbed higher solvent of the filler and rubber due to the bonding
type between the water (hydrogen bonding) and the vulcanizates (covalent bonding).
The reason why the following solvent petrol, diesel, kerosene and water are use in the
vulcanizates is to test for the interaction between the solvent and the vulcanizates i.e. when it is
use for automobile equipment like tyre, engine sitter e.t.c. when come in contract with these
solvent petrol, diesel, kerosene and water so as to know the interaction between the solvent and
the vulcanizates. The interaction determines the shelf life i.e. to test how long the polymer is
going to sustain it use as car tyre, engine sitter e.t.c. The swelling behavior of this vulcanizates
determines the level of industrial and type of application of the vulcanizates.
5.3

RECOMMENDATION

Further work should be done in accessing the thermal stability of vulcanizates to determine the
electrical properties of the vulcanizates and also to determine the ability of the vulcanizates to
bio degradable when they come in contact with micro-organism.
It is recommended that for vulcanizates produced from groundnut husk shell high filler loading
should in industrial application of the materials where they might come in contact with solvents
and chemicals.

39

The referencing style is not numbering as below but APA method which
is alphabetical rearrangement of the references in other of the name of
the first author in the articles References inside the work should be
like : Allcock and Lampe (1990). Your referencing inside the work is a
mixture of numbering and APA style and is very wrong. Stay put with
APA method both inside and reference of the work.
REFERENCE
1. Allcock, H.R and Lampe, F.W (1990); contemporary polymer chemistry second Edition
prentice-Hall lnc, New Jersey.pp
2. Akpa, F. A.O (2005): the synthesis and conversion process of polymers. Jireh Publishers
3.
4.
5.
6.

Benin City pp
Katchy, E.M (2000): introduction to polymer technology EL Demark, Enugu pp
Abc Heinz Hermann Greve Rubber Bad referencing
Market stud: filler Ceresane Research Bad referencing
Blow. C. M. Rubber Technology and Manufacturer 3 rd edition Butter worth London

(1971); 178
7. Idiaghe J.A 2004 physical testing of polymer Jonado computer Auchi pp.
8. Principles and Techniques of Polymer Blends and Composites. Year Page 8
9. Chika, M.A (2001) Student Project (HND11), Application of Filler Mixture for the
Thermal Stability of Natural Rubber. Auchi Polytechnic Auchi.pp.
10. Solomon. G and Amerongen G J V 1948 Rubb. Chem. Technol.21-67
11.Ansell Mwaikanmbo L Y2002
Title of article J.Appl. Polym .Sci 84

Your referencing is very few, if you know what you are doing. A project should have at least 20
references at your level. Add more references from materials used and site them appropriately
inside the work.

40