Characterization of Cockle Shells as Particle Reinforcement

for Recycled Polyethylene and Extraction of Silica

BY

OLADIPO Ayobami Alice

(140406002)

A FINAL YEAR PROJECT REPORT SUBMITTED TO THE DEPARTMENT OF

METALLURGICAL AND MATERIALS ENGINEERING
FACULTY OF ENGINEERING
UNIVERSITY OF LAGOS, AKOKA, YABA

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF

BACHELOR OF SCIENCE (B.Sc. HONS.) DEGREE IN METALLURGICAL AND
MATERIALS ENGINEERING

Supervised by:
Dr. J.O. Agunsoye (Associate Professor)

NOVEMBER, 2019
 CERTIFICATION
This is to certify that the research work titled “Characterization of Cockle Shell as Particle
Reinforcement for Recycled Polyethylene And Extraction of Silica” was carried out by,
OLADIPO Ayobami Alice with Matriculation Number: 1404006002, in partial fulfilment for
the award of Bachelor of Science (Hons) degree in Metallurgical and Materials Engineering.

--------------------------------- ---------------------------
A.O. Oladipo Date
(Student)

--------------------------------- ----------------------------

Dr. J.O. Agunsoye Date

(Project Supervisor)

--------------------------------- ----------------------------
Prof. S.O. Adeosun Date
(Head of Department)

--------------------------------- ----------------------------
Prof. J. A. Omotoyinbo Date
External Examiner

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 DEDICATION
This project is dedicated foremost to God Almighty for his favor and recurring grace upon my
life especially during the period of conducting this research.

Also, I would like to dedicate this report to my parents, siblings and everyone who contributed
to the success of my project research.

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 ACKNOWLEDGEMENT
My gratitude goes to the Almighty God for granting me wisdom, opportunity, provision and
grace throughout my undergraduate study and also for the partial completion of my final year
project.

I am sincerely grateful to my beloved parents and my siblings for their love and support.

I want to appreciate my supervisor, Dr. J.O. Agunsoye who has been understanding and
supportive throughout my research period. I also want to acknowledge his patience and
impactful knowledge via constructive criticism during this project.

I am grateful to the entire members of the Department of Metallurgical and Materials

Engineering for their continuous effort in installing industrial knowledge into the
undergraduates to become a better and professional engineer.

Finally, my appreciation goes to my colleagues who have been so supportive and helpful, God
bless you all for your extended support.

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 ABSTRACT
Cockle shells an agro-waste material with unique properties are alternative particulate
reinforcement to fiber reinforcement for polymer composites (recycled polyethylene) due to
their ability to eliminate anisotropic behavior of the fiber reinforcement, cockle shells also
contains substantial amount of some other useful elements. The prominent environmental
pollution causes by these wastes remains a challenge and also the mechanical limitation of fiber
reinforcement harness this study. This study characterized cockle shells as particle
reinforcement for recycled polyethylene composite and also extracted silica from the
particulate cockle shells. Polyethylene reinforced composites with filler of 150µm particle size
was produced by compounding and compression molding method at 1500 - 2000C, the
mechanical properties was found to vary with hardness value, modulus of elasticity and flexural
strength optimized at 20%, low wear rate was found at this 20% due to high hardness. The
tensile strength and impact energy was found to increase significantly with increasing filler
content. The inconsistency in the mechanical properties was attributed to improper filler
dispersion as a result of limitation in the production. This was supported by the SEM
micrograph of the 10% and 50%. XRD and XRF analysis of the cockle shell indicate calcium
silicate as the most prominent compound and also the presence of silica and some other useful
element in the composition respectively. The extraction of silica via the process of acid and
base treatment was used to obtain 0.56% yield where the low yield was as a result of effect
from the pH stability and acid treatment effect. Result shows that the process of extraction
involving calcination would give more yield. Finally from the investigation, it is evident that
the selection of percentage of filler content suitable for the polymer composite depends on the
properties required for various engineering application. Also, the silica extracted can further
be processed to obtain silicon which is a useful material in the manufacturing of solar panels
and insulating materials.

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TABLE OF CONTENTS
CERTIFICATION .................................................................................................................... i

DEDICATION..........................................................................................................................ii

ACKNOWLEDGEMENT ..................................................................................................... iii

ABSTRACT ............................................................................................................................. iv

LIST OF FIGURES ...............................................................................................................vii

LIST OF TABLES ............................................................................................................... viii

1.0 INTRODUCTION......................................................................................................... 1

1.1 Background of Study................................................................................................... 1

1.2 Statement of the Problem ............................................................................................ 4

1.3 Justification/Significance of the Study........................................................................ 4

1.4 Aim and Objectives ..................................................................................................... 5

1.5 Scope of the study ....................................................................................................... 5

1.6 Limitations .................................................................................................................. 5

1.7 Abbreviations and Acronyms ...................................................................................... 6

CHAPTER TWO ..................................................................................................................... 8

2.0 LITERATURE REVIEW ............................................................................................ 8

CHAPTER THREE ............................................................................................................... 20

3.0 MATERIALS AND METHOD ................................................................................. 20

3.1 Materials .................................................................................................................. 20

3.2 Equipment ............................................................................................................. 20

3.3 Methods .................................................................................................................... 23

3.3.1 Cockle Shell Preparation.................................................................................... 23

3.3.2 Synthesis of Recycled Polyethylene and Cockle Shell Particulate Composite 24

3.3.3 Mechanical Tests ............................................................................................... 25

3.3.4 Microstructural Analysis ................................................................................... 27

3.3.5 Preparation and Purification of the Cockle Shell Powder ................................. 27

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 3.3.6 Extraction of Silica from Sodium Silicate ......................................................... 27

CHAPTER FOUR .................................................................................................................. 28

4.0 RESULTS AND DISCUSSION ...................................................................................... 28

4.1 Mechanical Property Characterization ...................................................................... 28

4.1.1 Impact Energy .................................................................................................... 28

4.1.2 Hardness Analysis .............................................................................................. 29

4.1.3 Wear Resistance Analysis .................................................................................. 30

4.1.4 Tensile Strength and Young Modulus ............................................................... 31

4.1.5 Flexural Strength ................................................................................................ 33

4.2 Microstructural property Characterization ......................................................... 34

4.2.1 Phase Identification of the Cockle shell powder using XRD ............................ 34

4.2.2 Compositional Analysis of the Cockle Shell Powder using XRF...................... 35

4.2.3 SEM/EDS Characterization ............................................................................... 36

4.3 Extraction of Silica Analysis................................................................................... 38

CHAPTER FIVE ................................................................................................................... 40

5.0 CONCLUSION AND RECOMMENDATION ........................................................ 40

CONCLUSION ................................................................................................................... 40

RECOMMENDATION ..................................................................................................... 41

REFERENCES ....................................................................................................................... 42

APPENDIX ...................................................................................................................... 47

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LIST OF FIGURES

Figure 1.1: Cockle Shells sourced from Badagry Beach, Lagos 2

Figure 2.1: (a) continuous fibers (b) discrete (chopped) fibers (c) woven fabric 3

Figure 3.1: (a) Briquetted Recycled Polyethylene (b) Cockle Shells 20

Figure 3.2: (a) Sieve (b) Electronic Weighing Balance (c) Two Roll Mill (d) Hydraulic
Compressive Molding Machine 22

Figure 3.3: (a) Universal Testing Machine (b) Portable Hardness Tester (c) Universal Instron
Machine (d) Hounsfield Balanced Izod Impact Machine 23

Figure 3.4: (a) Powdered Cockle Shells (b) Sieving of Cockle Shell Powder 24

Figure 3.5: Test Coupons 25

Figure 4.1: Impact Energy Variation with Varying Loading of the Cockle Shell Particle 28

Figure 4.2: Hardness Value Variation with Varying Cockle Shell Powder Loading 30

Figure 4.3: Wear Rate Variation at Varying Cockle Shell Particle Loading 31

Figure 4.4: Tensile Strength Variation with Varying Cockle Shell Powder Loading 32

Figure 4.5: Young Modulus Variation with Varying Cockle Shell Powder Loading 33

Figure 4.6: Flexural Strength Variation at Varying Cockle Shell Particle Loading 34

Figure 4.7: XRD Spectrum of the Cockle Shell Powder Particles 35

Figure 4.8: SEM/EDS Micrograph of 10% loading RPE/CS Composite 37

Figure 4.9: SEM/EDS Micrograph for 50% Loading RPE/CS Composite 38

Figure 5.0: Extraction sequence product at each stages 39

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LIST OF TABLES
Table 2.1: Chemical Analysis of Cockle Shells using XRF 9

Table 2.2: Summary of Literature Review 16

Table 3.1: Test Coupon Formulation 25

Table 4.1: Chemical Analysis of Cockle Shells using XRF 36

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1.0 INTRODUCTION
1.1 Background of Study
According to Hammajam et al., (2013), composite is composed of two or more materials which
are the matrix (polymer) and filler/reinforcement (agro-waste), the author reported that the
properties of this composite were improved due to the additive properties of the reinforcement
(s).

The most prevalent superior composites materials are polymer matrix composites. The
composites may be reinforced with fibers or particulate such as polymer thermosetting
(polyester, epoxy etc.) or thermoplastics (PVC, Nylon, Polystyrene, polyethylene etc.) and
these can be made into various shapes and sizes for the requirement. It poses good mechanical
characteristics like high strength, stiffness, good resistance and good corrosive resistance even
though they can make simple manufacturing principles with low cost. Because of these
characteristics most of the researches were focused on the composite material (Kumar et al.,
2017)
Polyethylene plays crucial role in polymer thermoplastic composites production because of it
suitable characteristics such as temperature resistance, melt flow index and density.
Polyethylene reinforced with rice husk, barley husk, palm kernel are few examples from several
studies (Hammajam et al., 2014).
In Nigeria and Lagos in particular, with a growing population of estimated number of 14
million people (2019 World Population Review) proper disposal and general management of
agro-waste as remain a major challenge despite concerted effort by Lagos Waste Management
Authority (LAWMA). Most of this agricultural waste constitute serious environmental hazard
which if not checked maybe capable of reducing life expectance of an average citizenry, there
is a huge gap to be fill in terms of the utilization by way of recycling through processing and
conversion of some of these agricultural wastes to useful engineering materials for the benefit
of the mankind. The number of Agro-waste are numerous and almost inexhaustible but to
mention a few egg shell, coconut shell, palm kernel shell, orange peel, cockle shell etc. which
are common waste material readily available in our local community in particular, there is
scarcity of literature on the use of cockle shell as a reinforcement for composite production in
Nigeria and Lagos in particular, this cockle shells are commonly found in large quantity around
sea shores mostly beaches in Lagos and its environs.

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Cockle shell (anadara granosa) is the shell or one of the shell valves of a cockle, although
many small edible bivalves are loosely called cockles, true cockles are species in the family
cardiidae having rounded or heart-shaped shells with radiating ribs as shown below.

Figure 1.1: Cockle Shells sourced from Badagry Beach, Lagos

True cockles live in sandy, sheltered beaches throughout the world. These cockles are available
in large quantity unattended to, from the analysis it was observed that the composition of cockle
shell contains mainly almost 96% of calcium carbonate and some others useful element.
Because of the high percentage of calcium carbonate (which is a primary raw material of
limestone) in cockle shells, it can be properly analyzed and utilized as a substitute material in
building and construction, ceramic tiles etc. Studies also shows that cockle shell contains some
appreciable amount of silica (Mohamed et al., 2012; Hoque et al., 2013), when the particulate
is treated with an acid it increases the appreciable amount of silicate upon purification and then
silica can be extracted by treating with a base. This silica can be used in various engineering
application for example silica is used for coating solar panels.

Cockle shells are known for their notable mechanical and thermal properties attributed to
morphological (crystalline) and elemental structures. According to Al-Zubaidi et al., (2015),
cockle shells are generally composed of calcium carbonate of prismatic layers giving the shell
structure a high strength, low mass and low coefficient of heat conductivity.

Furthermore, Hammajam et al., (2013), reported from various studies that when the agro-waste
were processed with polymer material, it gave a superior property than it (polymer and agro-

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waste) individual properties. The use of agro-waste polymer composite has found its increasing
significant in the building and construction industries and automobile industries.

Polymer composite can be reinforced either with fiber or particulate. In the reinforcement of
polymer composite with particulate there are two common particulate configurations mainly
Micron and Nano particles size with a characteristics large surface area. For reinforcement with
fiber, there are three common fiber configuration namely continuous fibers, discrete (chopped)
fibers and woven fabric as shown below respectively, in this case the tensile strength properties
vary with direction i.e. highly anisotropic in nature, this implies that the optimal strength is
achieved in the aligned direction of the fiber axes. Thus this anisotropic property limit their
uses in engineering application where well distributed strength is required in the adjoining
direction (James F. Shackelford, Introduction to Materials Science for Engineers, Seventh
Edition. Pg. 398).

(a)

(b)

(c)

Figure 1.2: (a) continuous fibers (b) discrete (chopped) fibers (c) woven fabric

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Furthermore, according to Hammajam et al., (2013) some difficulties associated with the use
of fiber as reinforcement in polymer composite were enumerated, this includes to mention a
few, the problem associated with husks like decomposition in the ground, difficulty in digestion
and low nutritional value for animals necessitate alternative utilization and also it has been
reported by some investigators that its poor compatibility of fibers with hydrophobic
thermoplastics result to poor mechanical properties of the resultant material.

1.2 Statement of the Problem

Water sachets waste are usually found littered on the streets of Lagos, Nigeria; this constitute
environmental pollution, they are not biodegradable, even if gathered and burnt, can cause air
pollution. The clogging of this water sachets waste results to flooding and thus create heavy
traffic congestion within the metropolitan, Lagos thereby increasing the loss of man hour and
lead to low productivity which may have direct effect on the GDP of the nation, bearing in
mind that Lagos provides substantial tax base for federal government.

Cockle shells which is an agro-waste also constitute environmental pollution especially around
the beach areas. It is clear that these two waste materials are problems in terms of
environmental pollution. Hence, an attempt was made to address the environmental pollution
effect of these two waste materials and likewise the mechanical effect of the filler particulate
on a polymer composite.

1.3 Justification/Significance of the Study

The anisotropic properties that is associated with the fiber reinforced composite is one of the
motivation for the researcher to attempt to characterize cockle shell as particle reinforcement
in recycled polyethylene polymer composite, the use of particulate (at Micron level) as
reinforcement to a reasonable degree will eliminate the anisotropic nature characterized by
fiber-reinforced polymer composite. It is envisaged that the excellent interfacial bonding of the
processed particulate cockle shell and the molten recycled polyethylene at 2000 will produce a
better interfacial bonding and provide a composite blend without anisotropic properties thereby
furthering it use as a viable engineering material.

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1.4 Aim and Objectives
The aim of this study is to characterize cockle shell as particle reinforcement for recycled
polyethylene and the extraction of silica from the cockle shell particulate.

The specific objectives are

1. Sourcing and processing by washing, drying, grinding and sieving the cockle shell into
150μm particle size
2. Compounding of the recycled polyethylene with the grinded cockle shell by melting
between (1500 – 2000C)
3. Compression of the compounded blend at 2000C
4. Characterization of the mechanical properties of the compounded composite
5. Extraction of silica from the particulate cockle shell

1.5 Scope of the study

1. This study utilizes briquetted recycled polyethylene as a matrix
2. Particle size of 150μm by sieving
3. Compounding and Compression Method at a temperature range of (1500 -2000) using
Two Roll Mill and Hydraulic Compressive Molding
4. Assessment of the Mechanical Properties (Tensile, Hardness, Wear, Flexural and
Impact)
5. Analysis of the Microstructure of the surface using SEM
6. Calcination of the powdered cockle shells to 5000C using a muffle furnace
7. Purification of the sample with HCL
8. Extraction of silica from silicate

1.6 Limitations
1. Incessant power failure during the compounding process affects the product output of
our sample and also production rate
2. Inadequate access to some equipment to aid quick and proper research
3. Time constraints.

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1.7 Abbreviations and Acronyms
Al - Aluminum

ASTM - American Society of the International Association for Testing of Materials

C - Celsius

CaC - Calcium Carbide

CaCO3 - Calcium Carbonate

CaO - Calcium Oxide

cm2 - Centimeter Squared

CO2 - Carbon dioxide

CSP - Cockle Shell Particle

GDP - Gross Domestic Profit

GSP - Groundnut Shell Particle

HCL - Hydrochloric Acid

Kg - Kilogram

LAWMA - Lagos State Waste Management Authority

LOI - Loss of Ignition

M - Molarity

m/s - Meter per Seconds

mg - milligram

Mg - Magnesium

Min - Minutes

mm - Millimeter

MME - Metallurgical and Materials Engineering

MPa - Megapascal

Na - Sodium

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Na2SiO3 - Sodium Silicate

NaOH - Sodium Hydroxide

PVC - Polyvinylchloride

RLDPE - Recycled Low Density Polyethylene

SEM - Scanning Electron Microscope

Si - Silicon

Sr - Strontium

UNILAG - University of Lagos

wt. - Weight

XRD - X-ray Diffraction

XRF - X-ray Fluorescence

% - Percentage

° - Degree Centigrade

µm - Micrometer

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CHAPTER TWO

2.0 LITERATURE REVIEW

Agricultural waste is of great abundance and it creates environment pollution due to attraction
of insect that are harmful to human health, odor it generates when abandoned and left
unattended to and so on. The applications of this agro-waste has been widely explored in
engineering and science due to the limitation caused by environmental pollution. The
utilization of these waste materials into valuable industrial products brings about increase in
gross domestic product (GDP) in the nation by creating jobs, recycling, reducing waste disposal
issues and also contribute to knowledge by local entrepreneur. Examples of agricultural waste
includes and not limited to rice and wheat husk, rice and wheat straw, sugarcane leaf and
bagasse, corn cob, cockle shells, periwinkle shells, snail shells, egg shells, bamboo wood,
sawdust.

Cockle shells are agro-waste found readily available in large quantity around the sea shores,
mostly beaches in Nigeria. This shells are being dumped and left untreated and unattended to,
this cause unpleasant smell and disturbing view to the surrounding and also a threat to human
life.

Cockle shell also known as ‘Anadara granosa’ is commonly name for a group of (mostly)
small, edible, heart-shaped, jumping or leaping saltwater clams, marine bivalve molluscs.
Cockle Sea shells are inorganic in nature, they are exoskeletons of molluses such as clams,
oysters and many others (Hoque et al., 2013 and Alebiosu et al., 2016). Cockle shells are of
uniform size, obliquely spherical, possess distinct radiating ridges or ribs and are brittle in
nature (Columbia Encyclopedia, 2016). Cockle can also be said to be one of the most common
types of sea shells. It is easily found on almost every beach of the world.

In Malaysia recently, it was found that cockles shell is one of the most common sources of
calcium carbonate and also the potential biomass resource for bone repair material especially
made for cancer patients, due to their low cost and availability these seashells which contained
approximately 95-99% by weight of CaCO3 can easily fulfil the increase in demands of
biomaterials and also be applied for quite a number of engineering application (Mohamed et
al., 2012 and Hoque et al., 2013).

Different analyses (chemical, microstructure and mechanical) has been investigated by

researcher on the utilization of sea shells (cockle shells) as basic substitute for construction

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materials and also for multipurpose application. The analysis of crystal structure using XRD
pattern shows that the main reflections (peak distribution) of the pure cockle shells powder
consist of aragonite phase of CaCO3. Aragonite, which is a type of crystal form of calcium
carbonate, is known to be more suitable for material in plastic, glass fiber and other industrial
application due to it hardness properties. Aragonite seems to be the predominating phase other
than calcite and vaterite. (Al-Zubaidi et al., 2015)

Cockle shells are known for their notable mechanical properties attributed to morphological
(crystalline) and elemental structures, the prismatic layers of calcium carbonate give the shell
structure high strength, low mass and low coefficient of heat conductivity.

The chemical analysis using XRF conducted on a prepared cockles shell powder illustrates that
the predominant elements is calcium carbide and less quantities of other elements. The
estimation of these elements is presented in Table 2.1 below. The Table 2.1 shows the
compositional analysis carried out by Al-Zubaidi et al., (2015) and Mohamed et al., (2012)
using XRF, from this it is evident that cockle shells contains some appreciable amount of
silicon.

Table 2.1: Chemical Analysis of Cockle Shells using XRF

Author Element % ratio

CaC Al Si Sr Mg Na Others

Al-Zubaidi et al. 97.23 1.02 0.63 0.34 0.54 - 0.24

Mohamed et al. 98.99 - 0.078 - 0.51 - < 0.1

Saffanah K. M. et al., (2017) discussed the previous use of cockle shell containing aragonite
CaCO3 in tissue engineering and also upon studying, it was concluded that the addition of
cockle shell is a good substitute biomaterial in bone tissue engineering application due to its
physicochemical characteristics.

Several researchers have carried out work in the use of agro-waste as fillers in polymer
composite. Due to the general high stiffness ability of some inorganic particles than polymer

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matrices, the addition of either micro- or nano- particles can readily improve it Young’s
Modulus, however the strength is strongly dependent on the bonding/adhesion interface that is
the stress transfer between the matrix and the particles, for good interfacial bonding strength is
improved but reduces by adding particles for poor bonded particles.
However, several studies shows that impact/fracture toughness increases by adding particles in
some polymers like polyethylene and polypropylene. Polyethylene filled with calcium
carbonate particles has been reported by Fu and Wang to show enhanced / improved impact
toughness (S-Y Fu et al., 2008).

Venkatakrishnan et al., (2017) reported that the applied stress is to be distributed among the
fibers that is, the applied stress must be transferred across the filler-matrix interface in a
polymer matrix composites which is the most important function of the matrix. The bonding
strength at the fiber matrix interface has a major effect on the mechanical behavior of composite
materials, Thus for full strength of fiber reinforcement, bonding must be maximized in other
to make accurate characterization of interfacial bonding in the composite material.

Islam and Islam, (2015) study show that when the sawdust-reinforcement was treated
chemically, the mechanical properties of the polymer composites were found to improve
compared to the untreated sawdust-reinforced polymer composites, this was suggested to be as
a result of better fiber-matrix interfacial bonding/adhesion due to the chemical treatment of
the reinforcement, the research was further characterize using scanning electron microscopy
(SEM) to study the surface morphology of the fractured surface of the composites.

Ekwedigwe et al., (2015) evaluated the effect of bean pod ash particles on the properties of
recycled low density polyethylene (RLDPE) composites. The mechanical properties of the
composites were determined shows that the optimum values of flexural strength were obtained
at 140˚C, 12 minutes, 40 wt% filler loading and 6 Mpa. The hardness values, tensile and
bending strengths of the composite increased by increasing loading variation of beans pod ash
particles to RLDPE composites.
Microstructural analyses shows a fairly uniform distribution of the bean pod ash particles in
the microstructure of the composites which is the major factor that effect the improvement in
the mechanical properties which agrees with Venkatakrishnan et al., (2017). The obtained
results of the developed composites have shown that the beans pod waste could be used as a
biodegradable eco-friendly reinforcement.

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Usman et al., (2016) researched on alkaline treated and untreated groundnut shell (GSP) used
to reinforce recycled polyethylene to produce GSP-recycled polyethylene composites
improved mechanical properties and biodegradability. Tensile and hardness showed an
improvement in mechanical properties of the treated fiber composites. SEM micrographs
showed that treated fibers in the polymer matrix has uniform distribution; this explained the
observed improvement in the mechanical properties of treated GSP-recycled polyethylene
composites.

Atuanya C. U. and Obele, C. M. (2016), studied the Optimization of Process Parameter for
Sawdust/Recycled Polyethylene Composites. The mechanical results show that those factors
made different effects on the tensile strength of the composites. The optimized process
conditions obtained are as follows: press time 7 min, press temperature 180˚C, sawdust/RLDPE
60:40%, press pressure 40kg/cm2. The average tensile strength of the optimized composite
board was 13.991 MPa. The composite board met the standard for general purpose applications.

Agunsoye et al., (2012) Studied the Mechanical Behaviour of Coconut Shell Reinforced
Polymer Matrix Composite. The morphology and mechanical properties of coconut shell
reinforced polyethylene composite was establish and the effect of the particles on the
mechanical properties of the composite produced shows that the hardness of the composite
increases with increase in coconut shell content though the tensile strength, modulus of
elasticity, impact energy and ductility of the composite decreases with increase in the particle
loading from 0% - 25%. Scanning Electron Microscopy (SEM) of the composites (with 0% -
25% particles) surfaces indicates poor interfacial interaction between the coconut shell particle
and the low density polyethylene matrix. They reported that the study exploits the potential of
agro-based waste fiber in Nigeria as an alternative particulate material for the development of
a new composite.

Agunsoye et al., (2012) also studied the effects of Palm Kernel Shell on the Microstructure and
Mechanical Properties of Recycled Polyethylene/Palm Kernel Shell Particulate Composites in
other to assess the possibility of using it as a new material for engineering applications.
Mechanical properties of the composites were analysed and it shows that the hardness of the
composite increases with increase in filler loading and the tensile strength of the composite
increased to up to 5vol% filler loading. Scanning electron Microscopy (SEM) of the composites

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surfaces (micrograph) indicates fairly interfacial adhesion between the palm kernel shell
particles and the RLDPE matrix. Agunsoye et al., 2012 concluded that the composites
produced with 150 μm particle size have the best properties of the entire grade. Hence the grade
can be used for interior applications such as car seat, dash board, and car interior for decorative
purposes or other interior parts of automobile where high strength is not considered a critical
requirement.

Hammajam, Abba. (2014) investigated the potential properties of agro waste fiber (millet
husk) reinforced with high density polyethylene thermoplastic composites. The fiber loading
effects as well as fiber sizes were also investigated. Different fiber sizes were applied. The
composites were prepared by the use of internal mixer, followed by compression molding
process. Using up to 40 wt % of fiber loading, the results indicate an increase in the bending
strength and modulus as the fiber loading increased. He observed that impact strength decrease
considerably as fiber loading increases.

Ahmed et al., (2015) studied the effect of sugarcane bagasse fiber on the properties of recycled
high density polyethylene, the tensile strength and modulus were improved after
compatibilities between the fiber-matrix due to better interfacial bonding where the elongation
at break and impact strength was found to decrease rapidly with increasing fiber loading
compared to the high density polyethylene.

Agunsoye J. O. and Aigbodion V. S. (2013) worked on the Morphological and mechanical

properties of bagasse filled recycled polyethylene bio-composites, the study shows that the
uniform distribution of the bagasse particles in the microstructure of the polymer composites
is responsible for the improvement in the mechanical properties. Thus improved rigidity and
hardness values of the composites, tensile and bending strengths of the composite increased
with increasing loading rate to the maximum of 20 wt. % Uncaburized bagasse particle and 30
wt. % Carburized bagasse particle. Though the impact energy and fracture toughness decreases
with wt. % bagasse particles the study shows that the developed composites have better
properties at the 30 wt. % bagasse additions, and for optimum service condition, carbonized
bagasse particles addition should not exceed the range of 30% weight. Based on the observation
obtained in this study, they recommended that these grades of composites can be used in the
production of low strength car bumpers and other structural applications.

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Mohamad et al., (2017) research on the effect of Cockle-Shells Powder on Recycled
Polypropylene Reinforced used for Lightweight and Green Tiles, the mechanical properties
shows that the high tensile strength value at 5 wt. % CSP of the composite is due to good filler-
matrix interactions, which enable more stress to be transferred from the matrix to the fillers
during external loading. For the 30 wt. % the tensile strength tends to decrease thus poor
bonding this may be due to the non-uniform distribution of particles in the matrix.

S. PANTHAPULAKKAL et al., (2005) studied the enhancement of processability of rice husk

filled high-density polyethylene composite profiles. The research concluded that the
mechanical properties of the rice husk filled HDPE composite profiles with different loadings
of coupling agent and processing aid was improved. The tensile strength, flexural strength of
the composites with a reduction in the Processability was enhanced. Also, observation show
that the addition of processing aid resulted in a reduction in the strength and stiffness of the
composites and the effect is at a higher content of processing aid in the formulation.

Agunsoye J. O. et al., (2013) investigated the effects of silica ceramic particle sizes on the
properties of recycled polyethylene composites. From the various observations made, it
showed that the silica based ceramic used as fillers for the LDPE-PC composite can be sued as
the wear property of the composite significantly improved. The grain size of the ceramic affects
the mechanical properties of the composite i.e. the smaller the grain size, the tougher the
material becomes and also, the higher the impact values.
The incorporated silica based ceramic particles play a crucial role in improving the thermal
stability by acting as effective physical barriers against the thermal decomposition in the
polymer composites. The fairly uniform distribution of the silica ceramic particles in the
microstructure of composites is the major factor responsible for the improvement in the thermal
and wears properties.

Jia Ying Tong et al., (2014) Studied the mechanical and morphology properties of recycled
HDPE composite using rice husk filler. Based on the research, an increased tensile properties
and flexural properties of the composite was observed as the RH fiber in the composite
increased. The impact strength of the composites decreases as the RH loading increased. The
study also enumerate that the addition of coupling agent used in the research improved the
interfacial bonding between the filler and the matrix polymer. The filler is more brittle
compared to the matrix. Therefore, this causes the impact strength in the composite to decrease.

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The microstructural analysis done using SEM showed that there were no clear gaps between
RH fibers and recycled HDPE matrix, indicating good interface bonding.
This indicates that the efficiency of the mixing which was attributed to a good interfacial
interaction between RH fibers and matrix.

Agunsoye J. O. et al., (2017) did experimental investigation and theoretical prediction of tensile
properties of delonix regia seed particle reinforced polymeric composites. It was concluded
new polymer composites through incorporation of delonix regia seed particle into RLDPE
exhibits a good predictability of the tensile properties Maximum enhancement in tensile
strength was recorded at 4wt.% of delonix regia seed particle addition. Disclosing an approach
to wealth creation through waste recycling.

Anselm O. O. and Joseph N. A., (2013). Characterize and compared the mechanical behavior
of agro fiber-filled high-density polyethylene bio-composites. The effects of four agro fibers
(corn cob, rice hull, flax shive, and walnut shell flour) performances were compared with
commonly used wood flour filler. Investigation showed that high-density polyethylene
composites filled with agro fiber at high filler content of 65 wt% has improved mechanical
properties. The flexural strength, flexural modulus, and un-notched Izod impact strength
increased with filler loading at the 65 wt% level for all composites, but there was little
difference in both properties among the composites from various fiber types. The results of the
study concluded that agro fiber-filled high-density polyethylene composites can be used as
reinforcements for engineering value-added bio-composite materials.

Different studies has shown that Silica can be extracted from rice husk using the chemical
treatment methods; taking into consideration that solubility of amorphous silica is very low at
pH < 10 and increases sharply at pH >10. For this causes, the silica may be extracted in pure
form by dissolving it in the base state and then deposited in acidic conditions (low pH) (Kamath
& Proctor, 1998).

Rafiee et al. (2012) also produced nanosilica from rice husk. By acid treatment of the rice husk
was followed by thermal combustion under controlled conditions to yield 22.50% ash with
90.469% silica. Nanosilica was prepared by reflux technique, the extracted silica was treated
with acide and then dissolved in NaOH, the solution was deposited into acidic solution to
precipitate silica.

14 | P a g e
Novie Permatasari et al., (2016) reviewed agricultural wastes as a source of silica material.
This study reported several sources of silica derived from agricultural waste, such as rice husk,
rice straw, corn cobs, and bagasse. In addition, the study discussed also about the method of
isolation of silica from agricultural waste, and its application as a catalyst.

Majumder C. B. et al., (2014) describes the treatment of rice husk with acid and base, namely,
hydrochloric acid and sodium hydroxide to yield precipitates of silica. The study speculated
that a simple non-conventional method for extracting silica in the amorphous form is based on
alkaline extraction followed by acid precipitation. Rice husk ash was prepared and washed with
acid in other to remove the mineral impurities. Further, it was treated with sodium hydroxide
to form sodium silicate solution. The silicate solution formed was titrated with hydrochloric
acid and precipitation (in the form of gel) formation takes place below pH 10.

Adebisi J.A. et al., (2017) reviewed the potential of producing solar grade silicon nanoparticles
from selected agro-wastes. This study highlights the viability of using abundant agricultural
wastes in Nigeria to produce nano-sized solar grade silicon employing methods that will require
less energy. Details of previous silicon (nanoparticles) synthesized from agricultural wastes by
different researcher were dissected and the various method of production were highlighted.

Silica is the starting material for silicon production. It is found naturally as quartz which is an
abundant mineral. It is the major component of sand and rock. It has also been confirmed that
it could be synthesized from sodium silicate (Sudirmana et al., 2012).

15 | P a g e
Table 2.2: Summary of Literature Review

AUTHOR WORKDONE FINDINGS

Ekwedigwe et al., Mechanical properties Tensile strength was found to

(2015) evaluation of RLDPE with increase up to 40% filler loading
bean pod ash particulate
Increased hardness but decreased
flexural strength and impact strength

Islam and Islam (2015) Characterized treated sawdust Increased young modulus, flexural
reinforced with RPE strength and hardness to up 30%

Decreased tensile strength, impact

and elongation break with
increasing filler loading

Usman et al., (2016) Studied the effect of treated Tensile strength increased up to
groundnut shell powder on the 20%wt. of the TGSP Increased
mechanical properties of RPE hardness

Abdulrahman & Characterized RLDPE with Tensile strength was increased up to

Haruna, (2015) egg shell particulate 10%

Elongation at break decreased with

increasing filler loading but high at
10% and 25%

Decreased flexural strength

Hussien, Salim & Evaluated the mechanical Decreased tensile strength and
Suitan (2011) properties of HDPE hardness upon increasing filler
with/reinforced with egg shell loading

16 | P a g e
 Increased impact and elongation
break as filler loading increases

Atuanya et al., (2016) Studied the optimization of The mechanical results show that
process parameter for factors like time, temperature and
sawdust/recycled polyethylene pressure made different effects on
composites the tensile strength of the
composites.

Agunsoye et al., Studied the mechanical Increased hardness

(2012) behaviour of coconut shell
Decreased tensile strength, modulus
reinforced polymer matrix
of elasticity, impact energy and
composite
ductility

Agunsoye et al., Studied the effects of palm Increased hardness up to 5%

(2012) kernel shell on the
microstructure and mechanical
properties of recycled
polyethylene/palm kernel shell
particulate composites

Hammajam Abba, Investigated the potential Bending strength and modulus of

(2014) properties of agro waste fiber elasticity increased
(millet husk) reinforced with
Impact strength decreased
high density polyethylene
thermoplastic composites

Ahmed et al., (2015) Studied the effect of sugarcane Increased tensile strength and
bagasse fiber on the properties modulus of elasticity
of recycled high density
Elongation at break and impact
polyethylene
strength decreased

17 | P a g e
Agunsoye and Morphological and Mechanical properties increased up
Aigbodion (2013) mechanical properties of to 20wt% for the Uncaburized
bagasse filled recycled bagasse and 30wt% for the
polyethylene bio-composites carburized bagasse

Impact energy and fracture

toughness decreased

Mohammed et al., Research on the effect of Increased tensile strength up to 5%

(2017) cockle-shells powder on and then decreased from 30%
recycled polypropylene
reinforced used for lightweight
and green tiles

Saffanah K. M. et al., discussed the previous use of it was concluded that the addition of
(2017) cockle shell containing cockle shell is a good substitute
aragonite CaCO3 in tissue biomaterial in bone tissue
engineering engineering application due to its
physicochemical characteristics

S. Studied the enhancement of The tensile strength, flexural strength

PANTHAPULAKKAL processability of rice husk of the composites with a reduction in
et al., (2005) filled high-density the Processability was enhanced.
polyethylene composite
The higher addition of processing aid
profiles
resulted in a reduction in the strength
and stiffness of the composites

Jia Ying Tong et al., Studied the mechanical and Increased tensile and flexural
(2014) morphology properties of properties of the composite as the RH
recycled HDPE composite fiber in the composite increased.
using rice husk filler
Impact strength decreases as the RH
loading increased.

18 | P a g e

Rafiee et al. (2012) Produced nanosilica from rice
husk
Novie Permatasari et Reviewed agricultural wastes
al., (2016) as a source of silica material
Majumder C. B. et al., Describes the treatment of rice
(2014) husk with acid and base,
namely, hydrochloric acid and
sodium hydroxide to yield
precipitates of silica
Adebisi J.A. et al., Reviewed the potential of
(2017) producing solar grade silicon
nanoparticles from selected
agro-wastes
Improved interfacial bonding
between the filler and the matrix
polymer, The efficiency of the
mixing was attributed to the cause of
the good interfacial interaction
Acid treatment of the rice husk
followed by thermal combustion
under controlled conditions yield
22.50% ash with 90.469% silica.
ThE study reported several sources
of silica derived from agricultural
waste, such as rice husk, rice straw,
corn cobs, and bagasse. In addition,
the study discussed also about the
method of isolation of silica from
agricultural waste, and its application
as a catalyst
The study speculated that a simple
non-conventional method for
extracting silica in the amorphous
form is based on alkaline extraction
followed by acid precipitation
The study highlights the viability of
using abundant agricultural wastes in
Nigeria to produce nano-sized solar
grade silicon employing methods
that will require less energy
19 | P a g e
CHAPTER THREE
3.0 MATERIALS AND METHOD
3.1 Materials
The briquetted recycled polyethylene was obtained from an open market in Ojota, Lagos State,
Nigeria.

The cockle shell was sourced from Badagry Beach, Badagry, Lagos State, Nigeria. Others
includes HCL, NaOH, litmus paper, filter paper, funnel, burner, distilled water, beaker was
obtained from a chemical shop in Bariga and Ojota.

(a) (b)

Figure 3.1: (a) Briquetted Recycled Polyethylene (b) Cockle Shells

3.2 Equipment

Equipment used in this research includes:

 Local Grinding Machine

 Sieve (Met. & Mat. Lab.)

 Electronic Digital Weighing Balance

20 | P a g e
 Two Roll Mill

 Hydraulic Compressive Molding Machine

 Universal Testing Machine, Model: SAUMYA D2

 Portable Hardness Tester, Model: LEEB (type D)

 DIN Abrasion Tester, Model: FE05000

 Universal Instron Machine, Model No: 3369

 Hounsfield Balanced Izod Impact Machine, Serial No: 3915

 Scanning Electron Microscope (SEM)

 Heat Treatment Furnace

 Burner / Heater

 Funnel, Filter, Beaker and Litmus Paper

(a) (b)

21 | P a g e
 (c) (d)

Figure 3.2: (a) Sieve (b) Electronic Weighing Balance (c) Two Roll Mill (d) Hydraulic
Compressive Molding Machine

(a) (b)

22 | P a g e
 (c) (d)

Figure 3.3: (a) Universal Testing Machine, Model: SAUMYA D2 (b) Portable Hardness Tester,
Model: LEEB (type D) (c) Universal Instron Machine, Model No: 3369 (d) Hounsfield
Balanced Izod Impact Machine, Serial No: 3915

3.3 Methods
3.3.1 Cockle Shell Preparation
The cockle shells sourced from the beach were washed and sun dried. The clean dried cockle
shells were then crushed, grinded and secured in a tight container to avoid air moisture into the
grinded particulate, this was taken to MME Laboratory, UNILAG and sieved to a particle size
of 150 μm.

23 | P a g e
 (a) (b)

Figure 3.4: (a) Powdered Cockle Shells (b) Sieving of Cockle Shell Powder

3.3.2 Synthesis of Recycled Polyethylene and Cockle Shell Particulate Composite

The composite test coupons were produced by a compounding and compressive molding
method, the compounding process involves addition of the briquetted recycled polyethylene
into the rolling mill, while the rolls rotate counter clockwise to each other for a period of (7-10
minutes) and at a temperature range of (150°C – 200°C), upon achieving a paste form of the
matrix, the filler material was introduced manually as the rolls rotates and proper mixing was
done to obtain homogeneity. The percentage of cockle shell particulate was varied as shown
below in Table 3.1 with an interval of 10 vol.% for a particle size of 150μm.
Immediately after compounding the paste was inserted into a metallic molds of various
dimensions per ASTM standards for mechanical test, then the covered molds were subjected
to a hydraulic press (the compressive molding) at 2000C for 30 minutes to enable it cure.

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Table 3.1: Test Coupon Formulation
Content Weight percentage % (g)

Control Coupon 2 Coupon 3 Coupon 4 Coupon 5 Coupon 6

BRPE 100 100 100 100 100 100

CSP 0 10 20 30 40 50

Figure 3.5: Test Coupons

3.3.3 Mechanical Tests

3.3.3.1 Tensile Test
Tensile test was carried out according to ASTM D636, on the Universal Testing Machine,
Model: SAUMYA D2. A load was applied continuously throughout on the test coupons with
nominal dimension of 80 x 15 x 4 mm at a speed rate of 60 mm/min. The tensile strengths were
determined from the graph result of load versus elongation taking the average for 2 coupons
each per filler loading.

25 | P a g e
3.3.3.2 Hardness Test

Hardness test was carried out in accordance with ASTM A956 using a LEEB Portable (type
D) Hardness Tester, scale value HLD (HV). The test coupons were indented on the surface
with a pin at different locations and the average of the results were taken from the display of
the tester.

3.3.3.3 Impact Test

The impact energy test was carried out on Hounsfield Balanced Izod Impact Machine, Serial
No: 3915 in accordance with ASTM D6110-10: Standard Test Method for determining the
Impact Resistance of Notched Specimens of Plastics. The test coupons were prepared and
inserted, then the hammer was thrown smartly and the readings were observed from the pointer,
the impact energy were determined by taking the average of 2 coupons each per filler loading.

3.3.3.4 Flexural Test

Flexural test was carried out in accordance with ASTM on Universal Instron Machine, Model
No: 3369 to determine the resistance to bending. A 3-Point bending configuration was used
with specimen nominal dimension of 12.84 x 4.5 mm and a support span of 65 mm. The flexural
strength was determined from the graph plot of flexural stress versus flexural stain.

3.3.3.5 Wear Test

The wear abrasion test was carried out in accordance with ASTM D5963-04 with a DIN
Abrasion Tester, Model No: FE05000 to determine the resistance to surface abrasion. The test
coupon was shaped/machined to a surface area of 16mm diameter and the roller with surface
area of 150 x 460 mm moves at a speed 0.32 m/s with the abrasion sheet P60 at a number of
revolution of 40/min and an applied load of 10N. The initial and the final weight of the coupons
were taken.

The weight loss of the coupons was determined by the differences in weight measured before
and after each test. A parameter referred to as wear rate used to define the wear rate in terms
of the weight loss was calculated using Equation (5).

Weight loss (W) = ( Initial weight - final weight ) g [1]

Abrasion distance = (Sliding speed x Time) m [2]

Weight loss (W)

Wear rate = (Abrasion Distance (D)) g/m [3]

26 | P a g e
3.3.4 Microstructural Analysis
The Scanning Electron Microscope with Model No: JSM-7600F was used to view the surface
morphology of the 10% CSP and 50% CSP test coupons, this is to check the interfacial bonding
and homogeneity of the composite samples. The preserved cockle shell was also taken for XRD
test for phase identification and XRF test for elemental identification.

3.3.5 Preparation and Purification of the Cockle Shell Powder

The preserved cockle shell powder was calcined to 5000C at 100C/minutes for 4hours to aid
the escape of CO2 via thermal decomposition of CaCO3 to CaO and CO2 . Two methods firstly,
the used of the preserved CSP and secondly the calcined CSP were used with the same quantity.
900g of CSP was treated with 400cl of 6M HCL to remove impurities by stirring and heating
at 1000C for 1hour, the solution was cooled and filtered with filter paper to recover the solid
and the liquid was discarded, the solid filtrate was washed with distilled water (pH7) to remove
any other acidic content and dried by heating in the oven at 1500C for 1hour.

1000C
Cockle Shell Powder + 6HCL SiO2 (Impure) [4]

3.3.6 Extraction of Silica from Sodium Silicate

The purified solid filtrate was stirred continuously with 50cl of 2M NaOH and heated for 2
hours at 1000C. The suspension was cooled and filtered and discarding the solid, the filtrate
solution Na2SiO3 (Sodium Silicate) was then cooled at room temperature. The solution was
mixed and stirred with HCL to give a pH7 or less (acidic or neutral) thus precipitation of pure
silica and for complete precipitation the solution was kept at room temperature for 24 hours.
The solution was decanted, washed with distilled water and dried in the oven at 1000C for 12
hours.
1000C
SiO2 (Impure) + 2NaOH Na2SiO3 + H2O [5]

Room temp.
Na2SiO3 + 2HCL SiO2 + 2NaCl +H2O [6]

27 | P a g e
CHAPTER FOUR

4.0 RESULTS AND DISCUSSION

4.1 Mechanical Property Characterization
4.1.1 Impact Energy
The average impact energy of five different samples (varying filler loading) with respect to the
control sample is presented in Fig. 4.1, the inserted error bar indicate the standard deviation of
the energy absorbed. Impact strength is the ability of a material to absorb energy before
fracture. Observation in Fig. 4.1 is an enhancement in the amount of energy absorbed by the
RPE/CS particulate composites. The energy absorbed increased from 7.52J to 9.11J with
increase loading rate from the polymer to the composite.

Figure 4.1: Impact Energy Variation with Varying Loading of the Cockle Shell Particle

An increase in the concentration of the filler increased the ability of the composite to absorb
and dissipate more energy thereby increasing the toughness, thus, impact strength increased.
This may be due to/relate to the fact that when the cockle shell powder is loaded it act like
plasticizer therefore giving room for more deformation. Also the fine dispersion of the

28 | P a g e
particulate in terms of the particle size might contribute to it as also observed by Hussien, Salim
& Suitan (2011).

4.1.2 Hardness Analysis

The variation in the hardness values for RPE/CS composites at different loading rate is shown
in Fig. 4.2 below, the inserted error bar indicate the standard deviation of the hardness value,
observation showed a decreased hardness value. Hardness is the resistance of a material to
localized deformation and this depends on the distribution of the reinforcement in the matrix
as reported by Ismail et al., and Premalal et al., (2002). As shown in Fig. 4.2, the hardness
values of the composite decreased sharply up to 10% loading from the control (149HV) which
is the highest. The hardness value increased from 10% up to 20%, with the 20% being the
optimum. It is worth noting that the hardness value of 20% loading were only slightly different
than RPE.

The hardness value decrease up to 30% and then increased up to 50%. This inconsistent values
can be attributed to inhomogeneous wetting of the cockle shell powder by the RPE matrix as
similarly observed by Islam and Islam (2015). This is a surface property such as the presence
of voids. The hardness of 20% being the optimum compare to the other loading may be as a
result of a little bit better dispersion than the rest.

29 | P a g e
 Figure 4.2: Hardness Value Variation with Varying Cockle Shell Powder Loading

4.1.3 Wear Resistance Analysis

The wear rate of the RPE/CS composites at different loading rate in terms of abrasion distance
is represented in Fig. 4.3 below, it was observed that the presence of cockle shell particles in
the polymer matrix increased the wear rate drastically up to 10%. The wear rate decreased
greatly from 10% to 20%, where at 20% the wear rate is equal to that of the RPE. This may be
attributed that the composite at 20% is as hard as the RPE (see Figure 4.2) which was also
observed by Agunsoye et al., (2013). Generally, an increase in hardness values of materials
causes a decrease in their wear rates. An increase occur from 20% to 30% which also agrees
with Figure 4.2 as the hardness decreased, 30% to 40% showed a constant wear rate and then
decreased up to 50%.

30 | P a g e
 Figure 4.3: Wear Rate Variation at Varying Cockle Shell Particle Loading

Furthermore, it was observed that particle reinforcement is more effective in decreasing wear
rate than short and long fiber reinforcements (Malhotra, Sheikh, & Rani, 2012).

4.1.4 Tensile Strength and Young Modulus

According to previous reports, tensile properties depend on several factors: material properties,
method of composite preparation, sample condition, speed of testing, void content, and volume
percent of reinforcement (Razali et al., 2016).

The variation in the tensile strength of RPE/CS composite with varying loading is presented in
Fig. 4.4. From observation, the tensile strength increased from 0% up to 10%, at 20% the tensile
strength slightly decreased, implying that a brittle fracture occurred in the material, that is little
or no plastic deformation and this can also be due to improper distribution/dispersion of the
filler content (during composite preparation) in the interface causing weak interfacial bonding.
An increase from 30% to 50% show a gradual and rapid improved tensile strength which may

31 | P a g e
be due to good stress propagation or distribution, this is a prerequisite to better performance of
the composite under tensile loading.

Figure 4.4: Tensile Strength Variation with Varying Cockle Shell Powder Loading

However, for the young modulus as shown in Fig. 4.5, an increment up to 20% was observed,
with the optimum being at 20% loading, thereby high stiffness. A sudden decrease from 20%
up to 50% loading may have occur due to increase in the resistance of composite material to
plastic deformation and this verified the increase in tensile strength from 20% to 30% in Fig.
4.4.

Similar observation from Hussien, Salim & Suitan (2011), expatiated that decrement in
modulus of elasticity can refer to increase in the resistance of material to deformation. He
enumerated the effect of filler addition in correspondent to increase in the modulus, thus
exhibiting high stiffness compared to the polymeric material.

32 | P a g e
 Figure 4.5: Young Modulus Variation with Varying Cockle Shell Powder Loading

4.1.5 Flexural Strength

The flexural strength of different RPE/CS composite material with respect to filler loading is
represented in Figure 4.6. From observation, the flexural strength decreased upon filler content
loading up to 10% and increased rapidly up to 20%. The 20% provided an optimal flexural
strength. The decrease of the flexural strengths as the cockle shell particles increased beyond
20% is due to the interference of particles in the mobility or deformability of the matrix. This
interference was created through the physical interaction and immobilization of the polymer
matrix in the presence of mechanical restraints, thereby reducing the strength (Atuanya et al.,
2014).

33 | P a g e
 Figure 4.6: Flexural Strength Variation at Varying Cockle Shell Particle Loading

At a high filler loading, the formation of the micro-filler (agglomeration) is found due to the
difficulties in achieving a homogeneous dispersion of the filler at high filler loading and cockle
shell agglomerate. All these may relate to the improper composite preparation or impurities
inclusion.

4.2 Microstructural property Characterization

4.2.1 Phase Identification of the Cockle shell powder using XRD
The XRD pattern of the cockle shell powder particles revealed that, the major diffraction peaks
are 32.14˚, 46.6˚, 31.71˚, 47.998˚ and 39.73˚ and their inter-planar distance are 2.79Å, 1.95Å,
2.82Å, 1.90Å and 2.27Å. Their relative intensity of X-ray scattering are 56.46, 26.25, 100.00,
10.12 and 21.68 and phases at these peaks are (Ca2(SiO4)) Calcium Silicate, (CaCO3) Calcium
Carbonate, (Ca2(SiO4)) Calcium Silicate, (Al4Si3C6) Aluminum Silicon Carbide, (Mg2(SiO4))

34 | P a g e
Magnesium Silicate respectively (Figure 4.7). The result showed that Calcium Silicate had the
highest percentage of all the compound and element present as revealed by the XRD analysis.

Figure 4.7: XRD Spectrum of the Cockle Shell Powder Particles

4.2.2 Compositional Analysis of the Cockle Shell Powder using XRF

The test was carried out in Faculty of Natural & Agricultural Sciences, XRD & XRF Facility,
Department of Geology, University of Pretoria 0002, South Africa. The sample was prepared
as boric acid powder briquettes. The ARL Perform'X Sequential XRF and Uniquant software
was used for analyses. The software analyses for all elements in the periodic table between Na
and U, but only elements found above the detection limits were reported. The values were
normalized, as no LOI was done to determine crystal water and oxidation state changes.

35 | P a g e
Table 4.1: Chemical Analysis of Cockle Shells using XRF

Element SiO2 CaO Al2O3 Na2O Others

Normalized 35.00 44.44 17.80 2.70 3.92
Value

The XRF chemical composition of the cockle shell powder particles is represented in Table
4.1, XRF analysis confirmed SiO2, Al2O3, Na2O and some others were found to be major
constituents of the powder. Silicon dioxide and alumina are known to be among the hardest
substances. Some other oxides viz. CaO, K2O, Na2O, Fe2O3 were also found to be present in
traces.

4.2.3 SEM/EDS Characterization

Morphology of the 10% and 50% RPE/CS composites by SEM/EDS is showed in Figure 4.8
and Figure 4.9 respectively. Figure 4.8 shows the SEM micrograph of the 10% loading while
Figure 4.9 shows the SEM micrograph of the 50%.

Morphological study showed that the cockle shell as a reinforcement had smooth spherical
surfaces and more surface area for interaction. There is poor dispersion of the cockle shell
particle in the polymer matrix as a result of limitation encountered from production
mixing/blending. This was also observed by Jia Ying Tong et al., (2014). The interaction
between the particles and the matrix was not as good as shown in the SEM in Figure 4.8 and
4.9. Morphological results clearly show that there is improper intimate mixing of cockle shell
particles with the polymer matrix in the composites. This is responsible for the inconsistency
in the mechanical properties analysed above. Particles-matrix interface plays an important role
in composite properties. A strong particles-matrix interface bond is critical for high mechanical
properties of composites

36 | P a g e
Figure 4.8: SEM/EDS Micrograph of 10% loading RPE/CS Composite

37 | P a g e
 Figure 4.9: SEM/EDS Micrograph for 50% Loading RPE/CS Composite

4.3 Extraction of Silica Analysis

From the process carried out it was observed that the second method of extraction which
involved the calcination of the powder particle, will yield more than without calcination. This
is because the decomposition that took place during the process to an extent displace some
amount of CO2, thereby reducing the amount of impurities and thus less acid volume needed
for purification. The choice of calcination temperature of 5000C was based on the structural
properties of silica where above 5700C silica start to form crystalline structure which are more
complex silica.

During the extraction process, it was also observed that the pH value of the solution consisting
the sodium silicate and hydrochloric acid (HCL) has an effect on the formation of the silica

38 | P a g e
gel. This was also observed by Novie Permatasari et al., (2016), gelation occurs more slowly
at pH less than 4 and more rapidly at pH7. When gelation formation occur slowly the sodium
ions diffuse rapidly out of the gel matrix therefore lower sodium content unlike the rapid
formation at pH7 and at pH above 7 gel formation becomes unstable and dissolved completely.
Observation shows that this influence the poor yield obtained for both process method due to
limitation of equipment necessary to stabilize the pH value therefore using litmus paper.

Acid treatment was also observed to affect the yield of the silica obtained. From Fig. 5.0 which
represented a brief sequence of the process, shows that the gel formation at stage three starts to
dissolve after a certain period of time to from amorphous silica particles. Therefore further
research can also be done to review this study by initial processing of the cockle shell powder
with base.

Yield percentage ratio

𝑓𝑖𝑛𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡
× 100% [7]
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡

5𝑔
× 100% = 0.56%
900𝑔

Extraction of Silica
NaOH Treatment from Silicate using Silica
Calcined ash HCL Particle
•Precipitation/Fil
•Acid Treatment tration •Initiation of Silica Formation
•Washing and Precipitate
Filtration

Figure 5.0: Extraction sequence product at each stages

39 | P a g e
CHAPTER FIVE
5.0 CONCLUSION AND RECOMMENDATION
CONCLUSION
The mechanical and microstructural characterization of the recycled polyethylene reinforced
with cockle shell powder particulate composite as analyzed in chapter four can then be
illustrated as follows:

1. The filler loading addition was found to increase with impact energy.
2. The hardness value was found to decrease inconsistently, with 20% loading giving an
optimum hardness value of 139.5 HV with a slight deviation from the control which is
insignificant.
3. The inconsistence in the hardness value which is an inverse proportionate to wear rate
resulted into low wear rate at 20% with a value of 0.0025 mg/m.
4. Cockle shell powder particle addition resulted an increase in the tensile strength 56.7
to 320.4 MPa with a slight deviation at 20%, which therefore caused an optimal
modulus value at this loading rate. Modulus of elasticity decrease as filler content
increase beyond 20%.
5. The flexural strength of the composites was found to decrease as filler content increase
with an exception to the 20% filler content which shows a rapid high flexural strength
of 10.96 MPa.
6. The study of the RPE/CS composite at 10% and 50% loading rate microstructure
indicated smooth spherical and large area surface for interaction for the cockle shell
powder particle but also showed fair dispersion of the cockle shell powder particle in
the polymer matrix. This gave rise to the inconsistent mechanical properties.
7. The microstructural analysis of the cockle shell powder using XRD and XRF verified
the presence of silica inclusion as a constituent in the composition.
8. Extraction of the silica yielded 0.56% of the total weight percent.

Finally from the investigation, it is evident that the selection of which filler content for the
polymer composite depends on the properties required for various engineering application.
Also, the silica extracted can further be processed to obtain silicon which is a useful material
in the manufacturing of solar panels and insulating materials.

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RECOMMENDATION
1. Proper production/ sample preparation should be ensured during further investigation
using the cockle shell powder particulate a reinforcement.
2. Varying particle size can also be investigated for broader utilization of this agro-
waste.
3. Further/continual investigation should be carried out on the extraction process of
silica from the powder particle.

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 (mm)

EB (%)
STRAIN
STRAIN

TS (MPa)
YM (MPa)
YM (kg/cm2)
APPENDIX
APPENDIX A

LENGTH (mm)

ELONGATION
ELONGATION

AT MAXIMUM
AT YIELD (mm)
Tensile Readings

STRESS (kg/cm2)
STRESS (kg/cm2)
80

3.88 15.02108 153.17 0.02875 2.3 56.74872 578.6667 2.17 0.00375 0.3
CSP LOADING

0.5 3.187212 32.5 0.01125 0.9 254.977 2600 13 0.005 0.4

10.13 10.52564 107.33 0.04625 3.7 78.45445 800 2 0.0025 0.2

12.13 13.5991 138.67 0.04875 3.9 274.5906 2800 3.5 0.00125 0.1

1.75 4.184564 42.67 0.0175 1.4 75.12013 766 3.83 0.005 0.4

7.25 17.70128 180.5 0.0475 3.8 52.17221 532 1.33 0.0025 0.2

4.13 11.00029 112.17 0.04125 3.3 104.3444 1064 1.33 0.00125 0.1

3 14.38364 146.67 0.03 2.4 25.88997 264 0.33 0.00125 0.1

13.75 0.459939 4.69 0.01375 1.1 11.76817 120 0.6 0.005 0.4

4.25 10.86888 110.83 0.0425 3.4 248.4391 2533.333 19 0.0075 0.6

0.75 1.863293 19 0.0225 1.8 52.56448 536 0.67 0.00125 0.1

1.75 4.184564 42.67 0.0175 1.4 320.3883 3267 32.67 0.01 0.8

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Control control 10% 10% 20% 20% 30% 30% 40% 40% 50% 50%
APPENDIX B
Wear Readings
Weight loss (g)
Weight Wear Rate (g/m) @
Sample Initial Final Difference Abrasion Distance 40m
Control 0.9 0.8 0.1 0.0025
10% CSP 0.9 0.7
0.2 0.005
20% CSP 0.8 0.7
0.1 0.0025
30% CSP 1.2 1
0.2 0.005
40% CSP 1.1 0.9
0.2 0.005
50% CSP 0.9 0.8
0.1 0.0025

APPENDIX C
Hardness Test Readings
Specimen Readings 1 (HV) Readings 2 (HV) Average (HV)
Control 143 162 153
Control 171 118 145
10% 153 115 134
10% 136 125 131
20% 176 105 141
20% 135 140 138
30% 141 113 127
30% 126 112 119
40% 152 128 140
40% 132 111 122
50% 157 122 140
50% 126 119 123

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