Introducion Chapter one

1.1 General
In the second half of the twentieth century, the great population increase
worldwide together with the need of people to adopt improved conditions of
living led to a dramatically increase of the consumption of plastics. Because
plastics are light, durable, hygienic and economic, they are making them
suitable for a wide variety of applications including food and product
packaging, car manufacturing, agriculture and housing products (1-4).
Plastics are made up of long chain molecules called polymers. Polymers
are made when naturally occurring substances such as coal, natural gas and
oil are transformed into other substances with completely different properties
(5-7)
. On the other hand, these polymers can then be made into granules,
powders and liquids, becoming the raw materials for plastic products. The
world’s annual consumption of plastic materials has increased from around 5
million tons in the 1950s to nearly 100 million tones yearly (8-11).There is a
vast plastic products waste stream that reaches each year to the final recipients
creating a serious practice of handling such waste streams is to incinerate
them with energy recovery or to use them for land-filling. Waste is now a
global problem, and one that must be addressed in order to solve the world's
resource and energy challenges (12-14). Disposing of the waste to landfill is
becoming undesirable due to legislation pressures (waste to landfill must be
reduced by 35% over the period from 1995 to 2020), rising costs and the poor
biodegradability of commonly used polymers (15, 16).
Hence, recycling seems to be the best solution. Japan is pursuing measures to
create a recycling-oriented society in order to achieve sustainable
development. Since the Basic Law for Promoting the Creation of a Recycling-
oriented Society was enacted in 2000, a number of recycling-related laws
have been enacted, come into force, been reviewed and amended (17-20).

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Introducion Chapter one

1.2 Types of plastics

There are two main types of plastics classified as thermoplastics
and thermosetting polymers.
1-Thermoplastics can repeatedly soften and melt by applying enough
heat otherwise; it hardened when it cooled. Thus, it is possible
converted into new products. For examples polyethylene, polystyrene
and polyvinyl chloride are among others.
2- Thermosets or Thermosetting polymers can melt and take shape only
once. They are not suitable for repeated heat treatments; therefore after they
have solidified, they stay solid. For examples phenol formaldehyde and urea
formaldehyde (21-22).
The plastics industry has voluntarily devised a coding system which makes
plastics easier. The Society of the Plastics Industry (SPI) established a resin
identification code in 1987, which contains a number, surrounded by the
“chasing arrows” recycling symbol, followed by an abbreviation for the
specific plastic it represents. The use of this code has subsequently been
adopted by legislation in 39 states in USA. This identification code is
imprinted on most plastic packages manufactured in the United States in order
to aid in the identification of plastics for recycling. The six most common
types of plastic can easily be recycled. Table (1-1) shows these 6 types of
plastics with their identification code, general properties and common uses(4).

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Introducion Chapter one

Table (1-1): Types of plastics and common uses

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Introducion Chapter one

1.3 Recycling of Plastics

Recycling of plastics should be carried in such a manner to minimize the
pollution level during the process and as a result to enhance the efficiency of
the process and conserve the energy. The use of post-consumer recycled
plastics for food packaging applications emerged in the 1990s and was driven
by the interest of industry in mitigating the solid waste problems that were
partly contributed to plastic packaging. The use of recycled plastics for food
packaging has continued in recent years and will likely increase due to the
high price of crude oil, a feedstock for the petrochemicals used in the
manufacture of plastics, as well as the recent advances in plastic recycling
technologies that allow improved quality and safety of post-consumer
recycled plastics intended for food packaging applications (23-26).

1.4- Methods of Recycling Plastic

The recycling of waste polymers can be carried out in many ways. In
generals, four main approaches have been proposed such as (27-30):

1.4.1- Primary Recycling

This is refers to the manufacturer recycling of the clean and
uncontaminated scrap material of controlled history. This process remains the
most popular as it ensures simplicity and low cost, dealing however only with
the recycling of clean uncontaminated single-type waste.

1.4.2- Mechanical Recycling (or Secondary Recycling)

In this method, the polymer is separated from its associated contaminants
and it can be readily reprocessed into granules by conventional melt
extrusion. Mechanical recycling includes the sorting and separation of the
wastes, size reduction and melt filtration. The basic polymer is not altered
during the process. The main disadvantage of this type occurs because the

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Introducion Chapter one

molecular weight of the recycled resin is reduced due to chain scission

reactions caused by the presence of water and trace acidic impurities.
Strategies for maintaining the polymer average molecular weight during
reprocessing include intensive drying, reprocessing with degassing vacuum,
the use of chain extender compounds, etc.
1.4.3- Chemical or Feedstock Recycling (Tertiary Recycling)
The chemical recycle has been defined as the process leading in total
depolymerization the polymer to the monomers, or partial depolymerization
to oligomers and other chemical substances. The monomers could
subsequently re-polymerize to regenerate the original polymer.

1.4.4-Energy Recovery (Quaternary Recycling)

Energy recovery refers to the recovery of plastic’s energy content.
Incineration aiming at the recovery of energy is currently the most effective
way to reduce the volume of organic materials. Although polymers are
actually high-yielding energy sources, this method has been widely accused
as ecologically unacceptable owing to the health risk from air born toxic
substances e.g. dioxins (in the case of chlorine containing polymers).
The scheme of recycling polymers can be shown below in Figure (1-1)(27).

Scheme (1-1): The Polymer Recycling Techniques

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Introducion Chapter one

1.5 The Type of Plastic Recyclable

Polymers that will be able to recycling includes ; poly(ethylene
terephthalate) (PET), polypropylene (PP), polystyrene (PS), low density
polyethylene (LDPE), high density polyethylene (HDPE), poly(vinyl
chloride) (PVC), polycarbonate (PC), poly(methyl methacrylate) (PMMA)
and nylon(31,32).
In the present work, two types of plastic products have been studied include:
1-Waste water bottles that content poly (ethylene terephthalate) (PET).

2-Waste food dishes content polystyrene (PS).

1.5.1 Poly (Ethylene Terephthalate) PET

One of the most familiar types of plastic packaging is made from a plastic
called polyethylene terephthalate or “PET" for short. PET introduced to
consumers as the plastic soft drink bottle in the 1970s, then PET quickly
gained acceptance among bottlers and consumers (33-35). Because PET have
lightweight, economical and shatter proof, PET plastic offered unique
marketing and lifestyle benefits. PET plastic is now used as a packaging
material for a whole range of consumer products in addition to carbonated
beverages. These bottles and containers, known as “custom-PET” containers
are used to package such consumer products such as spring water, liquor,
juice, peanut butter, salad dressing, dish detergent, mouthwash, household
cleaners and tennis balls ….etc.(36-39). The SPI resin identification for PET is
(code1) (40-42), as shown in Table (1-1).

1.5.1.1 Chemical Recycling of Polyethylene Terephthalate (PET)

The chemical nature of polyethylene terephthalate permits easy recyclability
by all known recycling methods. Recycling of PET has become an important
process from the environmental point of view and it has given commercial
opportunity due to wide spread use and availability of PET bottles, packages
and fibers (43, 44).
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Introducion Chapter one

While mechanical recycling is well established, chemical recycling is

highly dependent on the manner in which the depolymerization is carried out.
PET is a polyester with functional ester groups that can be cleaved by some
reagents, such as water (hydrolysis), alcohols (alcoholysis), acids (acidolysis),
glycols (glycolysis), and amines (aminolysis) (45-50).
Thus, chemical recycling processes for PET are divided as follows:
(i) Hydrolysis, (ii) Glycolysis, (iii) Methanolysis, and (iv) other processes.
The different process options for chemical recycling of PET waste may be
categorized as following (51-54):
(i) Regeneration of base monomers (methanolysis for dimethyl terephthalate
(DMT) and hydrolysis for producing pure Terephthalic acid (TPA) and
ethylene glycol (EG)).
(ii) Conversion into oligomer 997mers (glycolysis or solvolysis).
(iii) Use of glycolyzed waste for value-added products.
(iv) Conversion into specialty chemicals by aminolysis or ammonolysis.
(v) Conversion into specialty intermediates for use in plastics and coatings
Post-consumer PET bottles are generally sorted out as a material recovery
facility, compressed into bales, washed and converted to clean dried flake.
The feed purity requirements of the intended use of the recycled PET are
making recycling more challenging. Generally contaminants are not allowed
in fiber or bottle applications due to breakage and aesthetic considerations.
During recycling thermal and oxidative degradation products cause yellowing
and diminishing of mechanical properties of the product (55-58). In the present
study we used two methods for recycling PET: Glycolysis and aminolysis.

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Introducion Chapter one

1.5.2 Polystyrene (PS)

Polystyrene (PS) is the most employed aromatic thermoplastic polymer.
PS finds a wide range of application from food contact packaging to thermal
(59)
insulator in buildings . Among several recycling processes exploited, the
most used is direct remanufacturing through milling, washing, drying, and
moldings but this is possible only for uncontaminated waste (59, 60). Otherwise
aromatic feedstock are usually obtained from catalytic refining of oil
fractions, indeed the safeguarding of energy and material content of waste PS
is a key point for saving oil stocks(83). PS and specially contaminated PS may
be disposed through chemical recycling and among these methods the
preferred one focus on the conservation and valorization of the phenyl moiety
widely present in PS(61,62) .

1.5.2.1 Types of Polystyrene Accepted for Recycling

Polystyrene is used in two types ; Solid forms such as coffee cups and
Expanded forms such as; housing uses and commercial construction,
foodservice products like cups, plates, trays, etc (63,64).
Both expanded and solid PS wastes have been successfully recycled in
extruded plastic timber-lumber. Recycled PS is used to produce plant pots and
desk items such as pen, pencils, etc. As with other types of plastic materials,
PS recycling takes place after consideration by the industry of a number of
issues including eco-efficiency, availability, corporate social responsibility,
product quality, hygiene aspects, and trace ability (65-69).

1.5.2.2 Recycling of polystyrene Products

The waste expanded polystyrene (EPS) can be recycled in many ways once
it comes to the end of its life. The choice of a recycling method is based on
technical, environmental and economic considerations (70,71).
The waste EPS recycling mainly has three kinds of methods include:

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Introducion Chapter one

(i) Material recycling, which is reducing EPS in volume by heating, solvent,

or friction at first, and then PS can be recovered as an ingot or pellet, and
reused into raw material, daily products, and construction material and so
on.
(ii)Chemical recycling, which is aimed at recovering the styrene monomer to
reuse as chemical resource.
(iii) Thermal recycling, an effective method for the contaminated waste
EPS, by which the waste EPS can be used for energy generation through
combustion (72-75).

1.5.2.3 Chemical Recycling of PS

Chemical recycling of synthetic polymers is one of important targets for
modern society that consumes a great deal of fossil resources. It is desired to
develop the degradation technique of polymers by which useful materials can
be recovered (76-78).
One of the attractive chemical recycling processes is the catalytic degradation
of polystyrene. This process enables to get styrene monomer at relatively low
temperature with a high selectivity (79-81).
In the present study waste polystyrene recycling by grafting with different
active organic groups Such as: acylation, sulfonation and Maleic anhydride
addition.

1.6 Recycled Polymers Survey

The Recycled-PET bottles and Recycled polystyrene were used in different
applications. Recycled-PET is used in bottles for non-food like household
chemicals or cleaners and it used for the manufacture of polyester fibers then
used to make clothing, either directly or as a filling fiber in anoraks and
bedding. Recycled PS is used as Thermal insulation, light switch plates and
Cameras or video cassette casings (82-87).

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Introducion Chapter one

The first recycling technology of waste plastic was represented by a

company called St. Jude Polymers in 1976(33). Waste PET-bottles can be
recycling by different ways which in accordance give variable products that
can be introduced as starting ingredients for synthesis of many other
polymers. Some of the recognized techniques have been reported in different
researches and reviews journals.
S.R. Shukla et al, in 2008 had recycled waste PET in to useful textile
auxiliaries by depolymerization of waste PET-bottles by using a glycolysis
(37)
route in the presence of sodium sulfate as a catalyst . Other applications
were represented by M.Sarker and M.Rashid, in 2013(39), they used thermal
(39)
degradation of waste PET-bottles and LDPE for fuel production . P.k.Roy
(40)
et al, 2013, were produced polyurethane from waste PET-bottles . S.
Makkam and W.Harnnarongchai, 2014, modified mechanical properties of
(41)
recycled PET by reactive extrusion . Jeane Dullius et al ,in 2006(44), used
post-consumer PET in alkyd resin synthesis for coatings, replacing a fraction
of phthalic anhydride (PA) and ethylene glycol (EG) of conventional
synthesis for post-consumer PET.
R. López-Fonseca et al , in 2010(45), were used glycolysis method of PET
waste by using excess ethylene glycol in the presence of different simple
chemicals acting as catalysts, namely zinc acetate, sodium carbonate, sodium
bicarbonate, sodium sulphate and potassium sulphate.
Yong Yang et al, in 2001(48) ,were used the Methanolysis method for
recycling the waste PET-bottles, the reaction was carried out in a stainless
stirred autoclave at temperatures of 523-543 K, pressures of 8.5-14.0 MPa,
and with a weight ratio of methanol to PET from 3 to 8. The solid products
mainly composed of dimethyl terephthalate and small amounts of methyl-(2-
hydroxyethyl) terephthalate, bis-(hydroxyethyl) terephthalate, dimers and
oligomers were analyzed by high performance liquid chromatography
(HPLC) techniques.

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Introducion Chapter one

Magda E. Tawfik et al, 2010(50), were studied aminolytic degradation of

PET waste in the presence of dibutyl tin oxide (DBTO) as a catalyst. The
process proceeds at 1900C and under atmospheric pressure.
Li Shen et al, 2010, study assesses the environmental impact of polyethylene
terephthalate (PET) bottle-to-fiber recycling using the methodology of life-
cycle assessment (LCA)(56). The chemical and physical properties of resins
can be modified depending on the reagents that used, also the ratio between
them and the method of synthesis chosen.
Cuong N. Hoang et al, in 2013(88), were used the aminolysis of PET-bottles
waste by used ethylenediamine (EDA). While N.D. Pingale et al, in 2009(89),
have de polymerize the PET-bottles waste via aminolysis method using
excess of ethanolamine. The reaction was carried out under non-conventional
microwave energy in the presence of different simple chemicals as catalysts
namely, sodium acetate, sodium bicarbonate and sodium sulphate. D.
(90)
Spaseska et al, in 2010 , de polymerize the PET-bottles waste via alkaline
hydrolysis using sodium hydroxide and trioctyl methyl ammonium bromide
(TOMB) as catylst.
In the present study, recycled PET and recycled PS were used as oil spill
cleanup and as Corrosion inhibitors.

1.7 Corrosion
Corrosion is the destructive attack of a material by reaction with its
(91)
environment . Corrosion is a chemical or electrochemical oxidation
process, in which the metal transfer electrons to the environment and
undergoes a valance change from zero to a positive value. The serious
consequences of the corrosion process have become a problem of worldwide
significance(92-95). Corrosion might cause plants shutdown, waste of valuable
resources, loss or contamination of product reduction in efficiency, costly
maintenance, and expensive overdesign. Corrosion also harms safety and
inhibits technological progress (96, 97).
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Introducion Chapter one

The several and different aspect of corrosion problems combined with the
distributed responsibilities that associated with such problems leads to
increase the complexity of the subject (98, 99).
Corrosion control is achieved by recognizing and understanding corrosion
mechanisms, using corrosion-resistant materials and altering designs, also by
using protective systems, devices, and treatments. Major corporations,
industries, and government agencies have established groups and committees
to look after corrosion-related issues, but in many cases the responsibilities
are spread between the manufacturers or producers of systems and their users.
Such a situation can easily breed negligence and be quite costly in terms of
dollars and human lives (100-102).

1.7.1 Corrosion Inhibiter

Corrosion inhibitors are chemical compounds that, when added in small
concentration to a corrosive environment, effectively decreases the corrosion
rate. These inhibitors will reduce the corrosion rate of either anodic oxidation
or cathodic reduction, or both. The inhibitors themselves form a protective
film on the surface of the metal.
It has been assumed that the inhibitors are adsorbed into the metal surface
either by physical (electrostatic) adsorption or Chemisorption (103-105). Physical
adsorption is the result of electrostatic attractive forces between the organic
ions and the electrically charged metal surface. While the Chemisorption is
the transfer, or sharing of the inhibitor molecule by forming a coordinate-type
bond(106,107). The adsorbed inhibitor reduces the corrosion rate of the metal
surface either by delay the anodic dissolution reaction of the metal, or by
inhibited the cathodic evolution of hydrogen, or both. Inhibitors can be used
at pH values of acid from near neutral to alkaline (108-111). Generally inhibitors
can be classified in many different ways according to the followings:
(i) Their chemical nature (organic or inorganic substances).
(ii)Their characteristics (oxidizing or non-oxidizing compounds).
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Introducion Chapter one

(iii) Their technical field of application (pickling, descaling, acid cleaning,

cooling water systems, and the like)
The most familiar and application of inhibitors in oil industries,
petrochemicals plants, automobile cooling systems and boiler feed waters
(137,138)
.

1.7.2 Inhibitor Evaluation

The efficiency of an inhibitor can be expressed by a measure of this
improvement according to the following equation (113,114).

%= × …. (1-1)

Where
IE = Inhibitor Efficiency
CR₀ = corrosion rate of the uninhibited system
CR= corrosion rate of the inhibited system
In general, the efficiency of an inhibitor increases with an increase in
inhibitor concentration (e.g., a typically good inhibitor would give more than
95% inhibition at low concentrations). The cooperation between different
inhibitors and the environment being controlled is often present, and mixtures
are the usual choice in commercial formulations.
The scientific and technical corrosion literature has descriptions and lists of
numerous chemical compounds that exhibit inhibitive properties. But only
very few of them are actually used in practice due to the desirable properties
of an inhibitor that might be extend beyond those simply related to metal
protection only. It should be taken to considerations the cost, toxicity,
availability, and environmental friendliness of inhibitors (115-120).

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Introducion Chapter one

1.7.3 Classification of Inhibitors

Corrosion inhibitors were used to reduce metal corrosion even in small
additions in aggressive media. Corrosion inhibitors change the kinetics of
electrochemical reactions that bring about corrosion, so that the corrosion
process rate retards significantly. The Corrosion inhibitors classification as
following(121,122):

1.7.3.1 CorrosionInhibitors According to their Designation

These inhibitors were subdivided into five classes (123-127):
(i) Inhibitors in acid solution. The use of corrosion inhibitors in acid
environments is one of the most effective alternatives for the protection of
metallic surfaces against corrosion. The corrosion of metals in acid
solutions have a wide range of substances, such as halide ions, carbon
monoxide, and many organic compounds, particularly those containing
elements (nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium).
(ii)Inhibitors in alkali solution, generally in alkali solutions environments
organic inhibitors were used especially those containing polar functions
with nitrogen, oxygen or sulfur in the conjugated system.
(iii) Inhibitors in neutral solution. Typical inhibitors for near-neutral
solutions are the anions of weak acids, like chromate, nitrite, benzoate,
silicate, phosphate, and borate. The reasons of using those compounds
based on the corrosion of metals in neutral solution as compared with the
acidic solution can be explained in two important respects. First in air-
saturated neutral solutions, the main cathodic reaction is the reduction of
dissolved oxygen, whereas in acid solution the main cathodic reaction is
the hydrogen evolution. Secondly corroding metal surfaces in acid
solution are oxide-free, whereas in neutral solutions metal surfaces are
covered with films of oxides, hydroxides, or salts. Therefore inhibitors
must reduce the solubility of these species.

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Introducion Chapter one

(iv) Inhibitors in non-aqueous liquid media. Oil is a good example for non-
aqueous liquid media. Organic compounds are used as typical oilfield
corrosion inhibitors function by forming a film or protective barrier
between metal and the corrosive fluid either because of their anodic,
cathodic or mixed type behavior.
(v) Inhibitors of atmospheric corrosion. The metal is easily suffered from
atmospheric corrosion due to the variation of temperature and humidity
during transport and storage. The use of volatile corrosion inhibitors
(VCIs) is one of the most effective and convenient methods for preventing
corrosion of metals and equipment during storage and transportation.
Organic compounds having significant vapour pressure act as efficient
inhibitors for corrosion under vapour phase condition even in presence of
water vapour in the air

1.7.3.2 Classification of Corrosion Inhibitors According to Chemical

Reactions
corrosion inhibitors can be classify according to chemical reactions into three
groups (123,127,128).
(i) Anodic inhibitors are chemical substances that form a protective layer
of oxide film on the surface of metal, causing resistance to corrosion.
These inhibitors particularly alter the anodic reactions in a chemical
cell, forcing the metallic surface into the passivation region. Anodic
inhibitors are also known as passivators. For convenience, anodic
inhibitors can be considered in two groups, highly oxidizing like
chromate, nitrite, orthophosphate, nitrite, ferricyanide and nitrate that
can passivize steel are called oxidizing ions(8), and as anodic inhibitors
called passivation inhibitors. They cause a large anodic shift of the
corrosion potential, forcing the metallic surface into the passivation
range.

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Introducion Chapter one

(ii) Cathodic inhibitors Cathodic either slow the cathodic reaction itself or
selectively precipitate on cathodic areas to increase the surface
impedance and limit the diffusion of reducible species to these areas.
Cathodic inhibitors can provide inhibition by three different
mechanisms:
a) As cathodic poisons.
b) As cathodic precipitates.
c) As oxygen scavengers.
The major cathodic reaction in cooling systems is the reduction of oxygen.
O2 + 2H2O + 4e-→ 4OH-……….(1-2)
Cathodic inhibitors are classed as safe because they do not cause
localized corrosion. Zinc ions are used as cathodic inhibitors because of
the precipitation of Zn(OH)2 at cathodic sites as a consequence of the
localized high pH .
(iii) Mixed inhibitors work by reducing both the cathodic and anodic
reactions. They are typically film forming compounds that cause the
formation of precipitates on the surface blocking both anodic and
cathodic sites indirectly. The most common inhibitors of this category
are the silicates and the phosphates
1.7.3.3 Classification of Corrosion Inhibitors According to their Physical-
Chemical Properties and Protection Principle into two groups (129-132).
(i) Volatile corrosion inhibitors: Temporary corrosion protection is
designed to prevent the corrosion of metal surfaces of equipment
during transport and storage. The use of volatile corrosion inhibitors is
an effective and convenient means. The VCIs contain anticorrosive
chemicals, which extend their corrosion properties to a metal surface
by volatilization within an enclosed space.
(ii) Contact and creep inhibitors of atmospheric corrosion: Contact
corrosion inhibitors are the substance whose protecting effect is

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Introducion Chapter one

exhibited only on direct application on the metal surface. Many of

them migrate via diffusion and undergo creeping.
1.7.3.4 Classification of Corrosion Inhibitors According to their Chemical
Structure in to two groups (133-137)

(i) Organic inhibitors

Organic inhibitor are applied extensively to protect metals from corrosion in
many aggressive acidic media (e.g., in the acid pickling and cleaning process
of metals). Different kinds of organic compounds are used as corrosion
inhibitors for iron alloys in various acid media such as aromatic compounds
with positively charged amine groups, Sodium sulfonates, phosphonates, or
mercaptobenzotriazole (MBT) are used commonly in cooling waters and
antifreeze solutions.
(ii) Inorganic inhibitors
Inorganic inhibitor usually are called passivators, which that defined as
inorganic oxidizing substances (e.g., chromates, nitrites, or molybedates) that
passivize the metal and shift the corrosion potential several tenths of volt in
noble direction .The passivator is reduce over a large cathodic area of the
metal surface to an extent not less than that necessary to form a chemically
equivalent passive film at small residual anodic areas
1.8 Methods of Corrosion Measurements
There are many different methods for corrosion measurements in order to
evaluate the corrosion inhibitors such as (123,138-146):
1)Electrochemical Impedance Spectroscopy (EIS)

2) Tafel Plots

3) Linear Polarization Resistance (LPR)

3) weight loss methods

4) Coulometry

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Introducion Chapter one

In this study the first two techniques were used to evaluate the preperd
compounds as corrosion inhibitors.

1.8.1 Electrochemical Impedance Spectroscopy (EIS)

The term impedance refers to the frequency dependent resistance to current
flow of a circuit element (resistor, capacitor, inductor, etc.).
Electrochemical Impedance Spectroscopy (EIS) has many advantages in
comparison with other electrochemical techniques. During EIS experiments, a
small amplitude ac signal is applied to the system being studied. Therefore, it
is a non-destructive method for the evaluation of a wide range of materials,
including coatings, anodized films and corrosion inhibitors. It can also
provide detailed information of the systems under examination; parameters
such as corrosion rate, electrochemical mechanisms and reaction kinetics,
detection of localized corrosion, can all be determined from these data. The
classical electrochemical techniques present measurements of currents,
electrical charges or electrode potentials as functions of time (which can also
be related to the electrode potential). In contrast, Electrochemical Impedance
Spectroscopy (EIS) presents the signal as a function of frequency at a constant
potential.
This technique measures the impedance of a system over a range of
frequencies, and therefore the frequency response of the system, including the
energy storage and dissipation properties, is revealed. Often, data obtained by
EIS is expressed graphically in a Nyquist plot or a Bode plot as shown in
Figures (1-1) and (1-2).

Impedance is the opposition to the flow of alternating current (AC) in a

complex system. A passive complex electrical system comprises both energy
dissipater (resistor) and energy storage (capacitor) elements. If the system is
purely resistive, then the opposition to AC or direct current (DC) is simply

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Introducion Chapter one

resistance. Impedance assumes an AC current of a specific frequency in Hertz

(cycles/s).
Impedance: Z = E/I ………. (1-3)
E = Frequency-dependent potential
I = Frequency-dependent current

While Ohm’s Law: R = E/I ………. (1-4)

R = impedance at the limit of zero frequency

Often, EIS reveals information about the reaction mechanism of an

electrochemical process: different reaction steps will dominate at certain
frequencies, and the frequency response shown by EIS can help identify the
rate limiting step.

This often poses some problems in understanding what is happening because

electrochemists try to think in terms of time, not frequency. On the other
hand, in optical spectroscopy, nobody thinks that light consists of the
sinusoidal oscillations of electric and magnetic vectors of various frequencies,
phases, and amplitudes. In spectroscopy, we used to think in terms of the
frequency domain (wave number, frequency, or some related functions as
wavelength) and that what we observed was the Fourier transform of the
optical signal (138-141).
Electrochemical impedance spectroscopy is a recent tool in corrosion. The
inhibition efficiency obtained from the charge transfer resistance is calculated
by(141):

………… …… (1-5)

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Introducion Chapter one

Rt and Rt/inh are the charge transfer-resistance values with and without
inhibitor, respectively.

Electrochemical impedance is the response of an electrochemical system

(cell) to an applied potential. An equivalent circuit Figure (1- 3) was used in
simulation of the impedance data. In this circuit, Cdl is the double layer
capacitance Rt is the interfacial charge-transfer resistance, L is the inductance,
and RL is the inductive resistance.

Figure (1-1) Nyquist plot

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Introducion Chapter one

Figure (1-2) Bode Plot

Figure (1-3) Electrochemical Impedance Model used to Fit the

Experimental Data

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Introducion Chapter one

1.8.2 Tafel Plot

A Tafel plot is performed on a metal specimen by polarizing the specimen

about 300mv anodically (positive-going potential) and cathodically (negative-
going potential) from the corrosion potential Ecorr. The potential can be
"stepped" in staircase wave form if desired.

The resulting current is plotted on a logarithmic scale. The corrosion current

icorr, is obtained from a Tafel plot by extrapolating the linear portion of the
curve to Ecorr. The corrosion rate can be calculated from icorr by using the
following equation(142-146) :

CR = 0.13×Icorr × (E.W.)/d ………… (1-6)

Where: CR= Corrosion rate measured by mille inch per year (mpy)

E.W.= equivalent weight of corroding species (g/eq).

D= density of the corroding species (g/cm3).

Icorr =corrosion current density (μA/cm2).

Figure( 1-4 ) Tafel Plot for Corrosion Rate Determination

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Introducion Chapter one

1.9 Literature Survey

Many studies for using the corrosion inhibitors for many metals and alloys
concerned on using aromatic compounds like hetero cyclic compounds which
that have no dissolved in water. It has been recognized that nitrogen and
sulfur-containing organic compounds act as inhibitors for Cu dissolution. M.
Valipour et al, in (2014) (92), evaluation of the corrosion process for estimating
the service life of concrete structure is of great importance to civil engineers.
In this paper, the effects of different exposure conditions (i.e., tidal and splash
zones) on macrocell and microcell corrosion of rebar in concrete were
examined on concrete specimens with different w/c ratios in the Persian Gulf
region. Experimental techniques such as macrocell corrosion rate
measurement, Galvanostatic pulse, electrical resistivity, half-cell potential
measurement, and numerical techniques were used to determine the corrosion
(93)
rate and time-to-corrosion-initiation of rebar. J. Kim et al,(2009) , This
paper focuses on techniques of improving refinery reliability, availability and
profitability. Our team developed a corrosion control document (CCD)
database system for refinery process. This system includes a method for
defining and measuring the component risk and it also provides a powerful
tool for managing many of the important elements of a refinery plant. The
simulation has been applied for this system to find the critical component
without direct measurement and experiment. A. Alvarez-Pampliega et
(95)
al,(2014) , This work studies the corrosion behaviour of Al-containing
metal coated steel. Odd random phase mul-tisine electrochemical impedance
spectroscopy (ORP-EIS) is used for monitoring the corrosion evolutionunder
continuous immersion in a NaCl solution. This technique allows a rapid
screening of corrosion pro-cesses due to the reduced measurement time with
respect to conventional single sine techniques. A. Wierzbicka-Miernik et al,
(2015) (96), studied the Corrosion behavior of lead-free SAC-type solder alloys
in liquid media. The main goal of this study was to investigate the corrosion
resistance of ternary Sn–Ag–Cu (SAC) alloys in the air-saturated aqueous
23
Introducion Chapter one

solutions of NaCl (including sea water) and containing NO-3, SO4-2, Cl- ions of
concentration equivalent to those in acid rains. J. Yang et al. (2006) (105)
,
studied Corrosion protection of iron in water by activated
carbon fiber (ACF) ,in this work activated carbon fiber (ACF) was modified
and employed to prevent iron corrosion in industrial water supply and
(107)
circulation system. S. Huanhuan et al, (2011) , Studied of corrosion
protection of the composite films on A356 aluminum alloy, Composite films
were fabricated on A356 aluminum alloy by combined anodizing and rare
earth deposition. The corrosion protection effect and corrosion behavior of the
composite films in 3.5% NaCl solution were studied by electrochemical
impedance spectroscopy (EIS).
(138)
A. Chetouani al el, (2011) , measured corrosion inhibiter by using
(139)
Impedance spectroscopic. S.Zelinka et al, (2009) , used Electrochemical
impedance spectroscopy (EIS) as a tool for measuring corrosion of polymer-
coated fasteners used in treated wood, In this study, a common technique for
measuring the corrosion performance of polymer-coated metals,
electrochemical impedance spectroscopy (EIS), was used to evaluate
(141)
commercial fasteners in a water extract of treated wood. H. Ma, (2003) ,
Impedance spectroscopic study of corrosion inhibition of copper by
surfactants in the acidic solutions, the inhibitive action of the four surfactants,
cetyltrimethylammonium bromide (CTAB),
sodium dodecyl sulfate, sodium oleate and polyoxyethylene sorbitan
monooleate (TWEEN-80), on the corrosion behavior of copper was
investigated in aerated 0.5 mol.dm-3 H2SO4 solutions, by means of
electrochemical impedance spectroscopy.

24
Introducion Chapter one

1.10 Oil Spill

Oil is one of the important sources of energy in the modern industrial
world which has to be transported from the source of production to many
places across the globe through oceans and inland transport. During
transportation the chance of oil spillage over the water body occurs due to
accidents or by deliberate action during wartime that causes severe
environmental pollution (147,148).

Oil spill is the release of a liquid petroleum hydrocarbon into the

environment, especially in marine areas due to the human activity into the
ocean or coastal waters, but spills could also occur on land. Oil spills may
also be due to releases of crude oil offshore platforms, drilling rigs, and wells,
as well as spills of refined petroleum products (1149, 1150).

An important part of the field of oil spill control is the analysis of oil in
various media. Oil analytical techniques are a necessary part of the scientific,
environmental, and engineering aspects of oil spills.Analytical techniques are
used extensively in environmental assessments of fate and effects. Laboratory
analysis can provide information to help identify an oil if its source is
unknown or what its sources might be.With a sample of the source oil, the
degree of weathering and the amount of evaporation or biodegradation can be
determined for the spilled oil (151-153).

25
Introducion Chapter one

Figure(1-5 ) Formation and Movement of Various Types of

OSAs in Marine Systems

1.10.1 Oil Spill Clean up

There are many methods for oli spill cleanup include ; bioremediation in
which microorganisms or biological agents are used to break down or remove
oil, Controlled burning is also used to reduce the amount of oil in water, but it
can only be done in low wind and can cause air pollution, Dispersants ,
sorbent materials, Electrospun nanofibrous Membranes and Cross-Flow
Filtration (154-158).

1.10.1.1 Oil Spill Cleanup Via Absorption

Absorbent materials are attractive for some applications because of the
possibility of collection and complete removal of the oil from the oil spill site.
The important characteristics of good absorbent materials include
hydrophobicity and oleophilicity, high uptake capacity, high rate of uptake,
retention over time, oil recovery from absorbents, and the reusability of the
26
Introducion Chapter one

absorbents . Over the past two decades, the sorbents used for oil sorption
mainly included natural materials, inorganic mineral products, and organic
synthetic fibers such as PP, which was conventionally used in oil spill
cleanup because of their oleophilic–hydrophobic properties, high oil–water
selectivity, and low density(157-160).

1.10.1.2 Oil Spill Cleanup Via Electrospun Nanofibrous

Membranes

Cross-flow filtration using membrane technology is highly efficient spatially

in the fields of engineering and environmental protection. Recently, much
attention is given to the fabrication of extremely efficient nanofibrous
filtration membranes with advantages of high filtration efficiency due to very
high surface area to volume ratios and resulting high surface cohesion, as well
as the possibility of recycling electrospun membranes. For oil–water
separation, major focus has been shown toward the fabrication of
superhydrophobic and superhydrophilic membranes depending upon the type
of medium to be separated. In this section, we will focus on different
nanofibrousmembranes with varying wetting properties used for oil–water
cross-flow filtration for oil spill cleanup (155,161,162).
1 .12.1.3 Oil Spill Cleanup Via Dispersants
Dispersants are mixtures of surfactants that significantly reduce the interfacial
tension between crude oil and water, thereby facilitating the creation of small
oil droplets with low energy input provided naturally by wave actions and
wind shear (163). The entrainment of the surface slick into the water column is
necessary for mitigating the impact of oil on the shores and aquatic fauna .
Another objective of using dispersants is to enhance the mixing of oil in the
water column and its exposure to the benthic biota for degradation by natural
means.Corexit 9500A is one of the most commonly used dispersants in
theUnited States for marine oil spill remediation(163-165).

27
Introducion Chapter one

Figure (1-6) How dispersants work. (1) Oil and water do not mix. (2)
Dispersants are applied to the surface of the oil ®lm and surfactants
di.use to the oil/water interface where they align themselves. (3) The
interfacial tension is reduced and oil is dispersed as tiny droplets.

1.11 Literature Survey

Most studies dealing with oil spill clean up by using different technique .
Yanyan Gong et al(152), a review of oil, dispersed oil and sediment interactions
in the aquatic environment: Influence on the fate, transport and remediation of
oil spills. This review critically summarizes what is understood to date about
the interactions between oil, oil dispersant sandsediments, their roles in
developing oil spill countermeasures, and how these interactions may change
(155)
in deep water environments. A.F. Avila et al , This paper reports the
development of super hydrophobic Nano composite systems which are also
oleophilic. As hydrophobicity is based on low energy surface and surface
roughness, the electro spinning technique was selected as the manufacturing
technique. N,N di methyl formamide (DMF) was employed as the polystyrene
(156)
(PS) solvent. P. Venkataraman et al , in this work attachment of a
hydrophobically modified Biopolymer at the Oil−Water interface in the
28
Introducion Chapter one

(157)
treatment of Oil spills. X. Zhou et al , facile fabrication of super
hydrophobic sponge with selective absorption and collection of oil from
water, a simple vapor-phase deposition process has been developed to
fabricate a super hydrophobic and super oleophilic sponge using ordinary
commercial polyurethane sponges. X. Sun et al(158), used the acetylation of
rice straw with acetic anhydride at 100 and 120 °C for 1-4 h with four tertiary
amine catalysts (pyridine, 4-dimethylaminopyridine, N-methylpyrrolidine,
and N-methylpyrrolidinone) or without catalyst in a solvent-free system was
undertaken, and the extent of acetylation was Measured by weight percent
gain, which increased with the extent of reaction time and temperature and the
amounts of catalyst used. S. Banerjee et al (160) , in this work Treatment of oil
spill by sorption technique using fatty acid grafted sawdust, the efficacy of
surface modification of sawdust by fatty acids (oleic acid, stearic acid and
decanoic acid) and vegetable oils (castor oil or mustard oil) is demonstrated.
Sorption of seawater contaminated with crude oil and also weathered oil was
greatly enhanced by the surface modification. H. Zhu et al(161), evaluation of
electro spun polyvinyl chloride/polystyrene fibers as sorbent materials for oil
spill cleanup. J. Lin et al (162), the development of oil sorbents with high
sorption capacity, low cost, scalable fabrication, and high selectivity is of
great significance for water environmental protection, especially for oil
spillage on seawater. In this work, we report nonporous polystyrene (PS)
fibers prepared via a one-step electro spinning process used as oil sorbents for
oil spill cleanup.

M. Zheng et al (163), in this work used a chemical dispersant, Corexit-9500, to

disperse the crude oil in the Gulf of Mexico to limit shoreline contamination
problems. Nevertheless, portions of this oil/Corexit mixture reached the
shoreline and still remain in various Gulf shore environments. The use of
Corexit itself has become a significant concern since its impacts on human
health and environment is unclear.

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Introducion Chapter one

1.12 The Aims of the Study

The present study aim for many points can be summarized as follow below:

1- The use of waste polymer as raw materials in the reaction instead of using
pure chemicals.

2- Reducing pollution that results from the accumulation of waste polymers.

3-Synthesis amino compounds from PET-bottle waste.

4-Modification of PS-food dishes waste by different technique.

5-Characterization the synthetic compounds by different technique.

6-Using new compounds those were prepared in the different applications

such as :

a- Oil spill clean up

b- Corrosion inhibiter by using two technique; Tafel Plots and EIS Impedance

30