I.

TITLE OF PROJECT
Multi-Walled Carbon Nanotube Synthesis from Waste HDPE for the Production of

Molybdenum-MWCNT Reinforced Corrosion Resistant and Strength Enhancing Epoxy

Coating
II.
BACKGROUND
Plastics play an important role in our daily life. They are used in clothing, housing,
automobiles, aircraft, packaging, electronics, signs, recreation items, and medical implants.
Due to their superior properties and low production cost, global production have increased by
6 % (15 million tonnes to 265 million tonnes) from the year 2009 to 2010, confirming the
long term trend of plastics production growth of almost 5% per year over the past 20 years
(Plastics Europe Market Research Group (PEMRG)).
Plastics are any of a large group of materials of high molecular weight that usually
contain a synthetic or semi-synthetic organic substance made by polymerization or
condensation. They are made of compounds and thermoplastic resins that reduce the overall
weight of the product making them suitable for use in different areas, namely packaging.
Plastic packaging of materials are mostly used for only a short span of time therefore
producing waste. In the Philippines, approximately 10.67 million tons to 14.05 million tons
of waste plastics were generated on the year 2000 to 2010 demonstrating periodic increase in
the trend of waste generation (The World Bank Philippine Environment Monitor 2001).
Different countries have been studying ways to improve plastic end-of-life
management. Though plastic waste generation problems are now being addressed through
recovery, energy recovery and recycling, 42.1 % of total waste generation of plastic, still end

up on landfills (Consultic, 2010). In response to this, researchers continue to struggle for a

way not only to recycle plastics but also to up cycle them.
Up cycling is the process of converting waste materials to valuable products. In
earlier years, up cycling of plastics was done only by burning plastics to produce fuel.
Current researches, however, found a way to convert waste polyethylene plastic bags into
carbon materials carbon nanotubes (Pol, 2010).
Carbon nanotubes (CNTs) are very thin lightweight hollow tubes made up of carbon
atoms. A carbon nanotube is like a sheet of graphite that is rolled into a cylinder, with
distinctive hexagonal latticework making up the sheet. Carbon nanotubes are extremely
small; the diameter of one carbon nanotube is one nanometer, which is one ten-thousandth
(1/10,000) the diameter of a human hair. Carbon nanotubes are classified according to their
structures: single-wall nanotubes (SWNTs), double-wall nanotubes (DWNTs), and multi-wall
nanotubes (MWNTs) which have individual properties that make the nanotubes appropriate
for different applications (Johnson).
Carbon nanotubes can be produced from waste High Density Polyethylene (HDPE),
a sturdy and reliable non-leaching translucent plastic, which is widely used in bottles of milk,
juice, shampoo and laundry products. Statistics show that 12% of the total amount of plastics
produced account for HDPE (PEMRG). CNTs produced from HDPE have higher yield as
compared to waste Low Density Polyethylene (LDPE). HDPE feedstock yields highly
graphitic tubes. Conversely, LDPE feedstock yields semi-graphitic tubes which are mixtures
of ordered and disordered carbon nanotubes (Pol and Thiyagarajan).

Carbon nanotubes, due to its unique mechanical, electrical, and thermal properties, as
well as corrosion resistant properties, can be applied in different industriescorrosion
resistance and strength being the focus of this paper.
Corrosion is defined as the destruction or deterioration of a material by direct
chemical or electrochemical reaction with their environment (McFarland). It is a naturally
occurring phenomenon that can cause dangerous and expensive damage- $2.2 trillion, the
annual cost of corrosion worldwide accounting to over 3% of the worlds GDP (World
Corrosion Organization).
Corrosion affects everything from storage tanks, pipelines, bridges, public buildings,
vehicles, water and wastewater systems, and even home appliances. Storage tanks, the
subject of interest of this study, are usually made of steel, a material highly susceptible to
corrosion. Corrosion-related damage is accelerated by factors including the tanks interaction
with interconnected components, corrosive environmental conditions, and stray electric
currents. Over time, uncontrolled corrosion can weaken or destroy components of the tank
system, resulting in holes or possible structural failure, and release of stored products into the
environment. Corrosion poses serious consequences to materials worldwide. It causes waste
of valuable resources, loss or contamination of product, reduction in efficiency, costly
maintenance, and expensive overdesign.

It can also jeopardize safety and inhibit

technological progress. Though it is a natural process that cannot be prevented, intervention

with the correct measures can control it. These control measures include the addition of
corrosion inhibitors.
Corrosion inhibitors are compounds which reduce the rate at which corrosion occurs,
and block early corrosion damage. They can be applied to the material by alloying or by

adding it to the material coating. Existing coating technology however, experience common
failures that eventually lead to corrosion of the coated material. This includes chalking,
blistering, algae & fungi growth, and crating (Building & Construction Authority).

Studies concerning a new series of corrosion control coating containing CNTs is

being developed and made available for end-user sampling. These coatings have enhanced
strength and electrical conductivity due to the inclusion of CNTs, while also incorporating
sacrificial metal particles (e.g., Zn, Al, Mg) for corrosion inhibition via cathodic protection.
CNTs allow sacrificial metal-filled primers to be formulated at much reduced metal content
as compared to traditional systems.

The new hybrid coating technology combines superior physical performance

properties as a barrier coating with a high degree of cathodic protection as a sacrificial
coating. The resulting nanocoating primer provides the foundation for a coating system that
can deliver corrosion protection to a multitude of steel or aluminum surfaceseverything
from fuel storage tanks and bridges to aircraft and ships.

Molybdenum is a refractory metal recognized for its excellent strength at high

temperatures. Molybdates, are non-toxic and are less aggressive oxidants than chromates
toward organic additives that may be used in corrosion inhibiting formulations. Molybdates
are used to inhibit corrosion in water-based hydraulic systems and in automobile engine antifreeze.

Modern corrosion control combines historically proven methods with state-of-the-art

technology to prevent tanks from deteriorating. Corrosion-control strategies are used
individually or in combination with one another. Common strategies include corrosionresistant materials, application of coatings and/or linings as a barrier to the environment,
various forms of cathodic protection to prevent deterioration of tank components in contact
with the soil, and use of inhibiting chemicals in stored substances to control corrosion of the
tank interior. Though, corrosion resistant materials such as Hastelloy, Inconel and Monel
display superior corrosion inhibiting abilities, their expensive price limit their use.
Due to the aforementioned disadvantage, the research aims to produce a cheap and
effective Molybdenum- Carbon Nanotube (Mo-MWCNT) based epoxy coating with
corrosion resistant and strength enhancing capabilities.
III.

OBJECTIVES, RESEARCH QUESTIONS AND HYPOTHESES

The study generally aims to up cycle waste High Density Polyethylene plastics

through the production of Mo-MWCNT reinforced corrosion resistant and strength

enhancing epoxy coating. Specifically, it aims to answer the following problems:
1. What is the production ratio of MWCNT to waste high density polyethylene plastic?
2. Is there a significant difference between purified and unpurified MWCNT in terms of
their corrosion resistant and strength-enhancing characteristics?
Hypothesis: There is a significant difference between the purified and unpurified
MWCNT in terms of their corrosion resistant and strength-enhancing characteristics.
3. Is there a significant difference between pure MWCNT and Mo-MWCNT as epoxy
coating additive in terms of their corrosion resistant and strength-enhancing
characteristics?

Hypothesis: There is a significant difference between the CNT and Mo-CNT in terms
of their corrosion resistant and strength-enhancing characteristics.
4. What ratio of Mo-MWCNT to epoxy coating gives best results with respect to
corrosion-resistant and strength- enhancing properties when applied to aluminum
alloy?
5. Is there a significant difference between the Mo-MWCNT reinforced epoxy coated
aluminum alloy and the control metal (316SST) in terms of their corrosion resistant
and strength characteristics?
Hypothesis: There is a significant difference between Mo-MWCNT reinfirced epoxy
coated aluminum alloy and the control metal (316SST) in terms of their corrosion
resistant and strength characteristics.
6. Is there a significant difference between the Mo-MWCNT reinforced epoxy coated
aluminum alloy and the control epoxy coated aluminum alloy in terms of their
corrosion resistant and strength characteristics?
Hypothesis: There is a significant difference between Mo-MWCNT reinforced epoxy
coated aluminum alloy and the control epoxy coated aluminum alloy in terms of their
corrosion resistant and strength characteristics.

IV.

SIGNIFICANCE
Plastic has become the most common material since the beginning of the 20th century

and modern life. Plastic is useful due to its durability, light weight and low cost at the same
time problematic considering its long life span which takes years for the item to decompose.

This becoming a global issue, researchers are finding a way to reduce the volume of waste
plastics.
Recycling plastics has been one way to reduce waste plastics, though up cycling is a
better option. Waste plastics have been found not only as a source of energy but also as a
source of carbon. Being a source of carbon, researchers used plastic bags to make Carbon
Nanotubes(CNTs).
Carbon nanotubes exhibit properties such as strength and corrosion resistance greater
than other materials. These properties make it a possible additive in the coating used in
industrial tanks such as storage tanks and reactors to enhance its corrosion resistance and
strength properties.

Corrosion problems worldwide are becoming severe with direct annual costs over
$400 billion per year in the US alone. Though current corrosion inhibitors as well as
corrosion resistant materials are commercially available, they are expensive and still pose
problems.
Recent studies regarding CNT-based coatings for corrosion-control applications
generate significant interest within the industry but despite having superior characteristics as
compared to normal epoxy coatings, CNT based coatings are affected by common reasons
for failure of coatings. One of which is due abrasion or impact which removes or damages
the coating therefore creating corrosion site within the material. In response to this, the
research reinforced the coating with Molybdenum to enhance its strength.

In line with the above concerns, this research aims to produce a Molybdenum-Multiwalled Carbon Nanotube reinforced Epoxy Coating which is cheaper, and more lightweight
than conventional chemical coating and gives corrosion resistant and strength enhancing
properties to industrial storage tanks and reactors.

V.

RESEARCH DESIGN AND METHODOLOGY

This study is an experimental research. It aims to investigate the possible cause-and-

effect relationship between research parameters and is accomplished by manipulating,

controlling, and quantifying variables by statistical means.
Variables, namely the ratio of Mo- MWCNT to Epoxy and duration of soaking in
corrosion testing, are manipulated in this research to determine their effect on the properties
of Mo- MWCNT reinforced epoxy coating in terms of its corrosion resistance and strength
enhancing properties. Comparison of the Mo-MWCNT reinforced epoxy coating to the
commercially available 316 SST and the control epoxy coating was also employed.
This study involved the following: collection of waste high density polyethylene
plastics, preparation of catalyst, synthesis of MWCNT, purification of MWCNT, synthesis of
Mo-MWCNT, synthesis of reinforced Mo-MWCNT Epoxy Coating, preparation of metal
specimens, corrosion inhibition testing, and tensile strength testing.
The waste high density polyethylene plastics were washed with water, oven dried,
and reduced into small size. The catalyst was mixed with the substrate forming a composite
which was then placed and heated in a muffle furnace at 850 C. Half of the prepared
composites were purified. Purified and unpurified carbonaceous nanomaterial were mixed

with Ammonium Molybdate and placed in an oven at 180 C for 48 hours. Mo-MWCNT
Epoxy Coating were done through dispersion under ultrasonic system. Characterization of
MWCNT, Mo-MWCNT and Mo-MWCNTEpoxy was done in SEM and FTIR. The test
media were prepared Testing
Data Gathering Tools
Every procedure in the experiment was performed in the Chemical Engineering
Laboratory(I and II) , Natural Sciences Research Unit and in Environmental Research
Laboratory at Saint Louis University. The aluminum alloy sheets which were used as test
specimens were cut and drilled at the Mechanical Engineering Laboratory.
This research is made possible through various sources including books, documents,
articles journals, and previous researches. Several related documents were also obtained
using the internet. Through the help of these aids, factual details were obtained and utilized in
this study.

Data Gathering Procedures

A. Collection of Raw Material
Waste high density polyethylene plastics were collected from the households around
the city of Baguio. The plastic materials were washed, and reduced into small size. The
plastics were then initially air-dried.
B. Preparation of Catalyst

The Ni/Mo/MgO catalyst was prepared by a combustion method. Ethylene glycol,

was used in this work as a combustion additive and to dissolve the metal salts. The right
amounts of Mg(NO3)26H2O, (NH3)6Mo7O244H2O, Ni(NO3)26H2O were dissolved in
Ethylene glycol to yield the molar ratios Mg/Mo/Ni/Ethylene glycol = 1.0/1.2/0.1/1.0. The
solution was subsequently placed in a muffle heated at 650 C for 10 minutes. Finally,
faintly green, foamy materials were obtained and ground to fine powders.
C. Synthesis of Multi-walled Carbon Nanotubes
The catalyst was mixed with the substrate to form a composite. The composite was
then placed in a crucible and heated in a muffle furnace at 850 C for 5 min. After cooling to
room temperature the produced black powder materials were obtained and ground to fine
powders.

D. Purification of Multi-walled Carbon Nanotubes

In purification of the sample, the raw material was first heated under an air
atmosphere at 400 C for 2 hours and then stirred in dilute HCl to remove the catalyst. The
sample was finally washed with deionized water and dried in oven.

E. Carbon Nanotubes characterization through Scanning Electron Microscopy (SEM)

The nanostructure and morphology of CNTs were observed under scanning electron
microscopy.
F. Carbon Nanotubes characterization through Electrical Conductivity

Approximately 4 mg of the carbonaceous nanomaterials was dissolved in 20 mL of

methanol assisted by sonication. The solution was then transferred to a beaker and
evaporated at a temperature of 40 to 45 C. A layer covering the whole bottom of the beaker
was formed and its conductivity across the diameter measured using a two probe diameter
and a standard digital multimeter.

G. Synthesis of Ammonium Molybdate- Multi-walled Carbon Nanotubes

100 mg carbon nanotube with 10 mL deionized water and homogenized about 5
minutes by an ultrasonic system. Then 20 mL of saturated solution of ammonium molybdate
hepta hydrate was prepared. Both prepared solutions was mixed and transferred to a vessel
which was sealed and placed for 48 hours in an oven at 180 C. The precipitate was filtered,
rinsed, dried, and then analyzed.
H. Mo-MWCNT characterization through Fourier Transform Infrared (FTIR)
The binding of Multiwalled Carbon Nanotubes and molybdenum were observed using the
Fourier Transform Infrared System.
I. Preparation of Mo-MWCNT Epoxy Nanocomposites Solution
For the preparation of the colloidal solution, 1% and 1.5% wt Mo-MWCNT were added
to the epoxy. The solution was then subjected to an ultrasonic system for 24 hours.

J. Preparation of Test Media

4000ml each of 2N HCl and 2N H2SO4 solutions were prepared using analytical grade
HCl, H2SO4 and distilled water. The resulting solutions were kept in stoppered reagent
bottles.

K. Preparation of Metal Specimen

For the samples preparation, the samples were polished with 800 grit sand papers,
degreased with absolute ethanol, sonicated in acetone and distilled water for 5 min. The pretreated samples were kept over a hot plate at 200 C for 10 min to eliminate the moisture and
entrapped air from the surfaces of substrate.
L. Metal Specimen Coating
Coating was conducted by dipping the aluminum alloy substrates into the Mo-CNT
epoxy coating at ambient temperature and environmental condition.
The aluminum alloy was immersed into the coating for 25 s to allow the wetting. In order
to obtain a stain-free surface, the specimens were slowly pulled out of the solution.
M. Corrosion Testing
The Mo-MWCNT-epoxy coated aluminum alloys were soaked in 2N H 2SO4 and 2N HCl
solutions for a period of 1 month. Data were recorded in a daily basis
N. Strength Testing
The strength of the coated aluminum sheet was subjected to tensile test and fatigue test in
order to estimate the additional strength given by the Mo-CNT based epoxy coating.
O. Treatment of Data
After the experimentation was conducted, the data collected were subjected to
computational and statistical analysis.
Percentage Yield
In the determination of percentage yield of HDPE and CNT, the following equation
was used:
Yield=

CNT produced
x 100
HDPE feed

Analysis of variance and Tukeys Honest Significant Difference Test

In the determination of the existence of a significant difference in the inhibition
efficiencies of the varied concentrations of the extract, the results were statistically

treated using the One- way Analysis of Variance(ANOVA) and Tukeys Honest
Significant Difference (HSD) Test.