PREPARATION AND CHARACTERIZATION OF CARBON FIBER NANO-COMPOSITE BY

ELECTROSPINNING METHOD INFLUENCED BY CONCENTRATION OF ACTIVATED

CARBON, VOLTAGE AND COLLECTOR

MUHAMMAD ARIFF ASRAF BIN ZAINAL

PROGRAM KIMIA INDUSTRI

SEKOLAH SAINS DAN TEKNOLOGI
UNIVERSITI MALAYSIA SABAH

2011

Chapter 1

Introduction

1.1

Research Background

Activated carbon is an amorphous solid that has an extremely large surface area and
pore volume. These properties along with high degree of surface reactivity, porosity
and thermal stability make it an excellent form of adsorbent. Since it was discovered
a century ago, various materials have been used to synthesize this unique
compound. The raw material used includes bones, coconut shell (Daud et al., 2004),
peat, woods, fruit stones and nut shells (Lua & Yang, 2000).

Polyacrylonitrile (PAN) exhibits good mechanical properties and has been

widely used as separation membrane materials. However, due to some inherent
disadvantages,

such

as

brittleness,

relatively

low

hydrophilicity

and

poor

biocompatibility, modifications on PAN or PAN-based membranes must be made to

meet the requirements of the increasingly extended applications (Wan et al., 2006).

1.2

Application of Activated Carbon

Activated carbon is known to have commercial value mainly as adsorbent. Because of

its porous surface, activated carbons are able to absorb unwanted molecules from a
medium such as heavy metals, dyes, and dangerous inorganic and organic
compound. The application of activated carbon as absorbent can further be divided
into two categories which are the liquid-phase application and the gas-phase
application.

The liquid phase application involves the application of activated carbon in a

liquid-phase medium such as waste water treatment (Dinesh et al., 2006), portable
water treatment (Muhamed et al., 2004), oil and sugar purification (Kawashima et

al., 2009), groundwater remediation (Wang et al., 2003) and food related application
(Raquel et al., 2010)

While gas phase application involves application of activated carbon in gas

phase medium such as air purification, solvent vapour recovery (Yun et al., 2000),
emission control (Giorgos et al., 2006) and gas filters. Besides that, activated carbons
are also used in chemical processes as catalyst support. Recently, activated carbon
has also been used on the electronic field to make double layer capacitor (Wang et

al., 2010)

The application is now broaden with the intense research on composite and
polymers. Polyacrilonitrile (PAN) is widely used as the basic of a polymer composite
(Wan et al., 2006). It is used to produce various kinds of applications which range
from clothing to pharmaceuticals. PAN is also known to have some disadvantages
that made the application of PAN alone inconvenient. The application of activated
carbon in this polymer will produce a composite with improved properties compared
to PAN alone.

1.3

Scope of Study
This study will concentrate on the application of activated carbon in polymer
composite. Activated carbon is used as additive in the preparation of carbon
fiber nano-composite while polyacrylonitrile (PAN) is used as the base
polymer for the fiber nano-composite. Solution of PAN and dimetyl formide
(DMF) is prepared by heating and stirring of the mixture at 70oC for six hours.
The solution is then added with two different concentration of activated
carbon before being heated for another hour. Carbon fiber nano-composite is
obtained from the solution using electro-spinning process. Parameters
involved during the process are concentration of activated carbon, voltage
supply and collectors condition. The concentration of activated carbon used
are 2 wt% and 5 wt%, the voltage supply used are 15kV and 20kV and the
collectors condition are alternate between dry and wet. The distance from
the tip of the syringe and the flow rate of the syringe pump on the other hand
is kept constant. The fiber collected from the electro-spinning will be
characterize using Differential Scanning Calorimetry (DSC) and Fourier
Transform Infra Red (FT-IR) machine.

1.4

Objectives

The objective of the study are:

a)

To prepare polyacrylonitrile (PAN) carbon fiber nano-composite reinforced

with activated carbon using electro-spinning method and

b)

To characterize the properties of the carbon fiber nao-composite using

Diffrential Scanning Calorimeter (DSC) and Fourier Transform Infra Red (FTIR) machine and

c)

To study the different parameters in the preparation of carbon fiber nanocomposite such as concentration of activated carbon, voltage supply and
collection method.

Chapter 2

Literature Review

2.1

History of activated carbon

Activated carbon or activated coal is a porous material with an extraordinary

excellent surface property which enables it to be a superior adsorbent and catalytic
support (Khalili et al., 2002). The structure of activated carbon is best described as a
twisted network of defective carbon layer planes, cross-linked by aliphatic bridging
groups as shown in Figure 2.1 (McEnany et al., 2004). The race for modern industrial
production of activated carbon was established in 1900-1901 to replace bone chars in
the sugar refining process. In 1900, two very important processes in the
development and manufacturing of activated carbon was founded and patented. Not
very long after that, the first commercial product was produced in Europe.

The precursors at that time are mainly wood which was called Eponite, year
1909, peat which was called Norit, year 1913 and by product of papermaking
process. During World War 1, further developments were achieved. Granular
activated carbon was synthesized from coconut shells in response to the demand of
protective gas mask. Following the war, large-scale commercial use of activated
carbon was extended to refining of beet sugar and corn syrup and to purification.

1940, the termination of the supply of coconut char from the Philippines and India
during World War II forced the development of granular activated carbon products
from coal. More recent innovations in the manufacture and use of activated carbon
products have been driven by the need to recycle resources and to prevent
environmental pollution.

Figure 2.1 Chemical structure of activated carbon

2.2

Physical and Chemical properties

According to McEnany et al (2004), the structure of activated carbon is best

described as a twisted network of defective carbon layer planes, cross linked by
aliphatic bridging group. Under X-ray diffraction, activated carbon reveals that it is
non graphitic. It remains amorphous because of the randomly cross linked network
that inhibits reordering of the structure.

The International Union of Pure and Applied Chemistry or IUPAC classes the
pore sizes of the activated carbon in three categories as shown in the cross section
view of activated carbon particle. Table 2.1 shows the types of pores that can be
found on activated carbon particles and its pore width range. Micropores has pores
6

with width less than 2nm, mesopores has pores with width from 2-50nm and
macropores has pores with width of 50nm. The surface area on the other hand is
determined by the application of the Brunauer-Emmet-Teller or BET model of
physical adsorbtion which uses nitrogen as the adsoptive. Commercially produced
activated carbon has specific surface area in the range of 500-2000 m2/g to 35005000 m2/g.

For the microporous activated carbon, the actual effective surface areas are
often smaller if not far smaller because the effective adsorbtion of nitrogen does not
follow the BET model. This results in the extremely high values for surface area.
These properties and dimensions of the activated carbon often depend on the
precursor and the parameters used during the manufacturing process. Picture 2.1
shows the surface structure of activated carbon generated by SEM. The development
of carbon materials with controlled micro- and mesoporosity is of paramount
importance in order to achieve a high adsorption capacity together with fast
adsorption kinetics for processes involving large molecules (Jurez et al., 2009)

Besides the physical characteristics stated above, the surface chemistry plays
an equal role for the effectiveness in chosen application. The interaction of the free
radicals on the carbon surface with atoms such as oxygen and nitrogen in the
precursor and atmosphere forms functional groups. These functional groups render
the surface of the activated carbon thus influencing its adsorbative properties.
Although activated carbon is known to exhibit a low affinity for water, the functional
groups on it can, making the carbon surface to be more hydrophilic (Salame et al.,
2003).

Other than surface area, pore size distribution and surface chemistry, other
important properties of activated carbon especially commercialized activated carbon
includes pore volume, particle size distribution, apparent density, particle density,
abrasion resistance, hardness and ash content. An example of commercial activated
carbon properties is given in table 2.2.
7

Table 2.1 Pore types and width range in nanometres

Pore types

Pore Width Range

Micropores

< 2nm

Mesopores

2-50nm

Macropores

>50nm

Figure 2.2 Cross section view of activated carbon particle

Picture 2.1 SEM image of the surface of activated carbon

Table 2.2 Properties of three types of activated carbon

Property

Particle size, US
Mesh
Apparent density,
g/cm3
Particle density,
g/cm3
Hardness number,
Abrasion number
Ash content, %
BET surface area,
m2/g
Total pore volume,
cm3/g
Heat capacity,
J/(g.K)d

2.3

Gas phase carbon

Calgon Coal Norit Peat
Westvaco
wood
12x30
3.8mm
10x27

Calgon
Coal
8x30

Liquid phase carbon

Norit Peat
Westvaco
wood
64%
65-85%

>0.48

0.43

0.27

0.52

0.46

0.34-0.37

0.80

0.50

0.80

>90

99

>75

1050-1150

6
1100-1200

1750

900-1000

6
750

3-5
1400-1800

0.8

0.9

1.2

0.85

2.2-2.5

1.05

1.05

Economic value of activated carbon

World demand for activated carbon is forecast to expand 9.9 percent per year
through 2014 to 1.7 million metric tons. As for 2010, world demand has reached 1.2
million metric tons. Most of the activated carbons are marketed to the mature
markets in North America, Western Europe and Japan. Besides the mature market,
Asia and Middle East region has increased its share of the global activated carbon
market as most of the nations in the regions are experiencing rapid economic growth
(Boyce, 2006)

In the developed and developing countries, the strongest growth prospects

for activated carbons are in pharmaceutical and medical sectors besides industry use
and environmental. Developing countries market are more to environment such as
wastewater treatment application. Other environment application such as hazardous

waste remediation and flue gas treatment continues to boost in demand of activated
carbon worldwide. The manufactures of activated carbon are mainly from America,
China and Japan.

2.4

Preparation of activated carbon

The synthesis of activated carbon involves two steps which are preparation of
precursor and activation. The activation processes are then divided into two
methods, thermal or physical activation and chemical activation.

2.4.1 Precursors
Activated carbon requires material with high content of carbon in it. Activated carbon
was originally synthesized from bone chars for the refining process of sugar around
1900-1901. After that, various raw materials have been used to produce this unique
structured material. The materials used includes bark, beat sugar sludge, coal, coffee
beans, coconut shell, lignite, lignin, nut shells, olive stones, wood, rice hulls, rubber
waste, petroleum coke, graphite, municipal waste, molasses, news paper, oil shake,
leather waste, lampblack, refinery waste, jute stick, fruit pits, corn cobs, cottonseed
hulls, carbohydrates, bagasse, palm tree cobs and wheat straw. The preparation of
precursor is fairly simple. The raw material being used will be grinded and sieved
before advancing to activation. More precursors to activated carbon are being
developed and most of them are mainly from organic waste as the awareness to
environment is rising (Mohan et al., 2006). Some of the commonly used raw
materials for the precursors of activated carbons are wood, coconut shell, coal and
petroleum coke.

a. Woods
The wood based activated carbon has high porosity and purity. Majority is
being used in the water and wastewater treatment, decolourization and

10

vapour phase injection systems (Celis et al., 2008). Table 2.3 shows the
properties for the common wood based activated carbon produced.

Table 2.3 properties of a commercial wood based activated carbon

Product unit descriptions

Product Range available

Mesh Size (US sieve)

Passing 100 (99%)

Passing 200 (95%)
Passing 300 (90%)

Surface area (minimum)

1000 m2/g

Moisture

10%

Iron content

0.07-0.1%

Chlorine content

0.1%

b. Coconut shells
Coconut shells have been used as a precursor to activated carbon since the
World War I to produce face mask. Since then, it has been a favourite
precursor among the manufacturer. Coconut shells contain high halocellulose
content and low on lignin. The high content of halocellulose results in a hard
carbon (Daud et al., 2004). This means it can maintain its shape during
carbonization process making it easy to handle. Coconut shells activated
carbon have been used in various application such as gas storage (Azevedo et

al., 2007), and other liquid phase and gas phase application. Table 2.4 shows
the properties of a commercial granular coconut shell activated carbon.

11

Table 2.4 properties of a commercial coconut shell based activated carbon

Product unit descriptions

Product range available

Mesh size (US sieve)

4x8 / 6x12 / 8x16 / 8x30 / 12x40 /

20x50

Surface area (minimum)

850-1350 m2/g

Apparent density

0.40-0.54 g/cc

Hardness (minimum)

95-99%

Ash content (maximum)

5%

Moisture content (maximum)

5%

c. Coal
Coal based activated carbon originates from coal that has undergone steam
activation process to create its activated carbon form. Coal based carbon has
mainly meso-pores and macro-pores and due to its unique distribution of
pores diameter, coal based activated carbon are very popular in the gas
phase

purification,

potable

water

purification

industries,

wastewater

purification industries and aquarium/pond water purification industries. Table

2.5 shows the properties for the commercial coal based activated carbon.

Table 2.5 properties of a commercial coal based activated carbon

Product unit descriptions

Product range available

Mesh size (US sieve)

4x6/4x8/4x10/5x7/6x12/8x16/8x20/8x30/
10x30/10x40/12x40/20x50

Surface area (minimum)

Apparent density

0.35 - 0.60 g/cc

Hardness (minimum)

80 / 85 / 90 / 95%

Ash content (maximum)

8/9/10/11/12/13/14/15/16/17/18%

Moisture content (maximum)

2-5%

12

d. Palm kernel shell

As a leading palm oil producer of the world, Malaysia produces a tremendous
amount of palm kernel shell as a by-product of the edible oil industries. For
the past decades, research conduction by various universities concludes that
palm kernel shell produces good quality activated carbon (Jumarial et al.,
2004). Palm kernel shells have a higher lignin and lower halocellulose content
as compared to its direct rival which is the coconut shell. This means that the
carbon produced are softer compared to coconut shell carbon. For pore
volume, it is known that palm kernel shell produces activated carbon in the
micropore and mesopore range (Daud et al., 2003) which means palm kernel
activated carbon can be used in both gas phase application and liquid phase
application. Picture 2.3 shows a cross section of a palm fruit showing its hard
kernel shell or mesocarp.

Picture 2.2 Cross section of a palm fruit showing the hard shell or mesocarp

13

2.4.2 Activation Process

The word activated suggests that the physical and chemical properties of the carbon
are enhanced by chemical and physical treatment. During the activation process, less
organized loosely bound carbonaceous material in the material are removed. This
clears the spaces between elementary crystalline. The clear spaces together with the
fissure within and parallel to the graphite planes constitute to the porous structure of
activated carbon. The activation processes are normally divided into two categories;
physical or thermal activation and chemical activation. The basic differences between
physical and chemical activation is the number of stages required for activation and
the activation temperature. Chemical activation occurs in one step while physical
activation employs two steps, carbonization and activation. Physical activation
requires temperatures between 8001000 C are higher than those of chemical
activation which only require temperature in the range of 200800 C

(Mohan et

al., 2006

a. Physical or thermal activation

Physical activation involves the carbonization of the precursor at high
temperature (400-600oC). The carbonization process eliminates any form of
volatile matter that may exist forming a carbon skeleton possessing a latent
pore structure. It is then normally followed by partial gasification using mild
oxidizing agent such as carbon dioxide, steam or fuel at 800-1000 oC that
greatly increases the pore volume and surface area of the sample. This is the
step where the porosity and the high surface area are achieved (Dinesh et al.,
2006).

Figure 2.3 shows the process and steps of thermal activation of bituminous
coal taken from Study of Chemical Process by Kirk et al., 2004. Bituminous
coal is pulverized and passed to a briquette press. Binders may be added at
this stage before compression of the coal into briquettes. The briquetted coal
is then crushed and passed through a screen, from which the on size material
14

passes to an oxidizing kiln. Here, the coking properties of the coal particles
are destroyed by oxidation at moderate temperatures in air. The oxidized coal
is then devolatilized in a second rotary kiln at higher temperatures under
steam.

To comply with environmental pollution regulations, the kiln off gases

containing dust and volatile matter pass through an incinerator before
discharge to the atmosphere. The devolatilized coal particles are transported
to a direct-fired multihearth furnace where they are activated by holding the
temperature of the furnace at about 1000oC. Product quality is maintained by
controlling coal feed rate and bed temperature. As before, dust particles in
the furnace off-gas are combusted in an afterburner before discharge of the
gas to the atmosphere. Finally, the granular product is screened to provide
the desired particle size. A typical yield of activated carbon is about 3035%
by weight based on the raw coal.
Physical activation process is widely adopted industrially for commercial
production owing to the simplicity of process and the ability to produce
activated carbons with well developed micro porosity and desirable physical
characteristics such as the good physical strength (Yang et al., 2010)

Figure 2.3 Thermal activation process of bituminous coal

15

b. Chemical activation
Chemical activation on the other hand uses chemicals as the name suggests
developing the porosity. Inorganic additives, metallic chlorides, phosphoric
acid, and potassium hydroxide are impregnated into the precursor before the
carbonization process. Carbons with well-developed meso- and microporous
structure can be produced by ZnCl2 incorporation. KOH activation successfully
increased active carbon surface area and pore volume. Ammonium salts,
borates, calcium oxide, ferric and ferrous compound, manganese dioxide,
nickel salts, hydrochloric acid, nitric acid and sulphuric acid have also been
used for activation. Unlike physical activation, chemical activation requires
less temperature which is around 200-800 oC (Dinesh et al., 2006).

Figure 2.4 shows the steps in chemical activation from The Study of Chemical
Process by Kirket al., 2004. In the first step, sawdust is impregnated with
concentrated phosphoric acid and fed to a rotary kiln, where it is dried,
carbonized, and activated at a moderate temperature. To comply with
environmental pollution regulations, the kiln off-gases are treated before
discharge to the atmosphere. The char is washed with water to remove the
acid from the carbon, and the carbon is separated from the slurry. The filtrate
is then passed to an acid recovery unit. Some manufacturing plants do not
recycle all the acid but use a part of it to manufacture fertilizer in an allied
plant. If necessary, the pH of the activated carbon is adjusted, and the
product is dried. The dry product is screened and classified into the size range
required for specific granular carbon applications.

Chemical activation offers several advantages which include single step

activation, low activation temperatures, low activation time, higher yields and
better porous structure. However the process involves a complex recovery
and recycle of the activating agent, which generates liquid discharge that
demands effluent treatment (Yang et al., 2010).

16

Figure 2.4 Chemical activation of wood

2.5

Application of activated carbon

Nowadays, activated carbon has been widely used as adsorbent and the purification
and separation of gas and liquid stream. Recent studies have also shown that
activated carbon can be used successfully in solvent recovery, gas refining, and air
purification, exhaust desulfurization and deodorization processes (Yun et al., 2000).
Application of these carbons has been considered a major unit operation in the
chemical and petrochemical industries. In addition to serving as an adsorbent, highporosity carbons have recently been used in the manufacture of high-performance
double-layer capacitors (Wang et al., 2010).

Activated carbon are normally produced and classified as granular, powdered,

shaped and pelletized products. Granular activated carbons are produced directly
from its granular precursor such as crushed coal while powdered activated carbons
are obtained by grinding the granular activated carbon products. Shaped and
pelletized activated carbons are the same thing as shaped activated carbon is
produced as cylindrical pellets by extrusion of the precursor with binders. The
different classification enables activated carbon to be applied to various applications
that needs specific requirement. Picture 2.2 shows the different physical
characteristic of the activated carbon.
17

Picture 2.3 Classification of activated carbon

2.5.1 Liquid Phase Application

Application of activated carbon in the liquid phase related industry accounts for
approximately 82% of the total activated carbon. They include portable water (Cheng

et al., 2010), industrial and municipal wastewater (Mohan et al., 2006)., sweetener
decolourization, groundwater, household uses, food and beverages (Raquel et al.,
2010), mining, pharmaceutical (Rivera et al., 2009) and chemical processing. The
difference between activated carbon for liquid phase application is their pore volumes
which are higher in the macropore and mesopore range. This characteristic allows
the liquid to diffuse more rapidly into the meso and macropores. The form of liquid
phase activated carbon used depends strongly on its application. Granular and
shaped carbons are usually applied when there is a continuous flow through deep
bed involved and when a large carbon buffer is needed in order to withstand
variations in adsorbtion variations (Joana et al., 2007).

Powdered carbons on the other hand are preferred when a wider range of
impurity removal is required. This can be attained by batch application of powdered
activated carbon with controlled dose until the degree of purification desired is
achieved.

18

a. Potable Water Treatment

Treatment for drinking water accounts for about 30% of the total activated
carbon used in liquid-phase application. Most of the common water sources
are often contaminated by bacteria, viruses, pesticide residue, halogenated
materials, organic compound, heavy metals such as zinc, lead and copper and
vegetation decay product (Muhamed et al., 2004). Although most of the
contaminants can be removed by filtration and normal disinfection, some toxic
compound may still be there. Treatment by activated carbon removes these
toxic materials from the water making it safe for consumption at a low price
compared to other complex/ hybrid filtration system. For portable water
treatment, activated carbon that is normally used is the granular type.
Recent studies by Kim et al, (2005) combines powdered activated carbon with
microfiltration system to enhance the result of treatment. By using this hybrid
method to purify portable water from rivers containing secondary effluent, the
removal rates were increased to almost 100 percent. Another research
focuses on the removal of arsenic from portable water. Arsenic is a toxic
material that can be highly harmful to living organisms. It can cause various
dangerous deceases including skin, kidney, lung and bladder cancer.
Treatment with granular activated carbon impregnated with iron removes
arsenic from portable and drinking water effectively (Cheng et al., 2010)

b. Industrial water Treatment

Wastewater from industries has always had a large potential to cause water
pollution. Unlike the domestic waste, it is sometimes very difficult to
generalize wastewater from the industries as it varies from plant to plant.
Wastewater contains suspended solids, toxic organic material, inorganic
contaminants and hazardous microorganisms. The conventional methods for
removing these impurities are expensive to build, maintain and operate.
These contaminants must be removed before the water can be rereleased to
the environment. Granular and shaped carbon removes this contaminants
efficiently especially the residual toxic waste (Mohan et al., 2006)

19

Hybrid technology in the filtration filed has shown significant result recently.
Taraj Mohammadi et al. (2004) showed that when activated carbon is coupled
with ultra-filtration unit to produce a hybrid ultra-filtration, the results
obtained are more promising with more advantages. Conventional system can
sometimes be difficult to control and operate. The hybrid technology
developed on other hand is more operator friendly as it is easier to control
and operate. The hybrid system is also more efficient compared to the
conventional result.

c. Groundwater Remediation
Groundwater contamination has been recognised since the early 80s.
Pollution of groundwater with nitrate is an increasing problem. Water
contaminated with this substance causes various diseases (Wang et al.,
2003). There are basically two ways for treating groundwater. The first one is
the conventional method using granular, powdered and shaped carbon. The
second method uses air stripping to transfer the volatile compounds from
water to air. The compound can be recovered by passing the contaminant air
through a bed of activated carbon (Bayer et al., 2005)

d. Decolourization of commercial sweetener

Activated carbons are originally used for one sole purpose which is purification
of corn syrup and sugar. It is the sweetener industries that jumpstarts the
activated carbon research race. The sugars produced from sugar canes are
normally brown in colour because of the impurities content. By applying
activated carbon, the sugar or sweetener is decolorized producing white
product. Besides normal sugar, high fructose corn sweeteners are also
produced in the same manner. The activated carbon eliminates undesirable
taste and odour in the compound. (Kuhn et al., 2010)

20

e. Foods
Activated carbons are one of the used in the food purification process. In the
production of alcoholic beverages for instance, activated carbon is used to
remove the haze causing compound from beer, taste and odour from vodka
and fusel oil from whiskey. Edible oil such as animal fat and vegetable oils
uses activated carbon to eliminate contaminants (Kawashima et al., 2009).
While feed water for soft drink production is often treated with carbon in
order to capture the undesirable taste and odour compounds and also to
remove free chlorine radical that got through the disinfection treatment.

2.5.2 Gas phase Application

Gas-phase applications of activated carbon include separation, gas storage, and

catalysis. Although only 20% of activated carbon production is used for gas-phase
applications, these products are generally more expensive than liquid-phase carbons
and account for about 40% of the total dollar value of shipments. Most of the
activated carbon used in gas-phase applications is granular or shaped. Gas phase
applications account for 18% of total activated carbon. They include air purification,
42%; automotive emission control, 21%; solvent vapour recovery, 14%; cigarette
filters medium, 2% and miscellaneous, 21%. Separation processes comprise the
main gas-phase applications of activated carbon. These usually exploit the
differences in the adsorptive behaviour of gases and vapours on activated carbon on
the basis of molecular weight and size. For example, organic molecules with a
molecular weight greater than about 40 are readily removed from air by activated
carbon. (Guo et al., 2000)

a. Emission control
Petroleum based fuel has always caused emission that are dangerous to
human and living things. These emission that escape from vents in
21

automotive fuels system can be controlled with proper method (Ho et al.,
2008). One of the methods used is absorption by activated carbon (Giorgos et

al., 2006). Fuel vapours vented when the fuel tank or engine are heated are
captured in a canister containing 0.5 to 2 L of activated carbon. Regeneration
of the carbon is then accomplished by using intake manifold vacuum to draw
air through the canister. The air carries desorbed vapour into the engine
where it is burned during normal operation. Typically, the adsorption vessels
contain around 15 m3 of activated carbon and are regenerated by application
of a vacuum. Regeneration for the condition is normally quite mild. The most
suitable type of pore size would be the mesopores (Kirk et al., 2004)

b. Solvent vapour recovery

Activated carbon with micropores has a very strong adsorbtion forces. These
forces enable the activated carbon to capture small vapour molecules such as
acetone. Larger and heavier vapour molecules such as cyclohexanone and
cumene adsorbed better by mesopores activated carbon. Because of these
interesting properties, activated carbon is used to prevent the release of
organic compounds that are harmful into the atmosphere which are often
used as solvent in the industries. Application of activated carbon gave a huge
impact in the industries as the solvent adsorbed by activated carbon are able
to be recovered to its usable stage (Yun et al., 2000).

c. Cigarette filter medium

Cigarette smoke has been known to contain various chemicals that are
harmful to ones health. These colloidal particles and vapours of chemical
compound can somehow be removed without affecting the taste of the
tobacco. One of the promising methods for removing these undesired
compounds is the incorporation of activated carbon into the picture (Sasaki et

al., 2008). The reason behind this is because activated carbon adsorbs
volatile compounds effectively in the smoke and from other source.
22

d. Miscellaneous
Besides the application stated above, application in the gas phase also
includes

adsorbtion

of

radionuclides,

protection

against

atmospheric

contaminants, gas storage, and catalyst support and process stream

separation. Radionuclides that escape during nuclear reaction in nuclear
power plant such as xenon and krypton are able to be contained by activated
carbon.

2.5.3 Nanocomposites

Composite materials were developed in order to enhance the properties of a material.

A nano-composite material applies when the enhancer used is in nano-scale such as
granulated activated carbon and carbon nanotubes (Fiedler et al., 2006). There are
various compounds that can be turn into a composite, one of the compounds that
have been intensely studied over the years is polymer such as epoxy,
polyacrilonitrile, and resin. When a polymer such as polyacrilonitrile (PAN) is mixed
with a compound such as granulated activated carbon, a nano-composite is form.

As explained earlier, activated carbon possesses unique properties such as

thermally stable, adsorptive, porous and affinity to water molecule. When these
properties are reinforced into the polymer, a nano-composite with enhanced
activated carbon properties is produced. There are several precursor materials for
carbon nano-comopsite production such as polyacrylonitrile (PAN), pitch and
cellulose, PAN is the most widely used precursor as it have shown successful result in
many studies (Chae et al., 2009)

The nano-composite form from the PAN and activated carbon can be
prepared by using various methods. Some of the methods include mechanical
alloying, fecile synthesis or co-precipitation and electro-spinning method. Each of the
method produces different form of nano-composite with different application field.
23

Out of all the form of nano-composite developed, carbon fiber has shown to have a
very bright future as commercial product.

Carbon fibers are prepared from a solution of carbon source, polymer and
solvent. The solution is either extruded directly into a coagulation bath or extruded
through an electric field onto a collector (Chae et al., 2009). The later process is also
known as electro-spinning method. Electro-spinning has gained the worlds attention
for its versatility in producing a wide variety of polymeric fibers and also consistently
producing fibers in the submicron range which is very difficult to achieve with other
method (Bhardway & Kundu, 2010).

The fundamentals of electro-spinning dates more than 60 years earlier when

Formalas published a method describing the process (Huang et al., 2003). In the
process, polymer filament was produced by introducing a polymer solution into an
electric field between two oppositely charged electrodes. One electrode was placed
into the solution while the other was placed on the collector. The polymer solution
was then ejected through a metal spinnerets and collected on the collector (Huang et

al., 2003)

24

Figure 2.5 Electro-spinning apparatus setup

Figure 2.5 shows the typical apparatus setup for electro-spinning process.
During the electro-spinning process, the electrostatic force from the electric field
created is more than the surface tension of the viscoelastic region of the polymer.
This results in the dispersion of the polymer onto the collector creating fine
nanofibers (Fenot et al., 2003).

Like any other process, electro-spinning process is affected by various

parameters. Besides the polymer used, other parameters that affect the properties of
the carbon fiber nano-composite includes the solvent, the concentration of carbon
source, voltage of power supply, the distance between the tip of the syringe and the
collector and collector (Duan et al., 2006). The concentration of the reinforcement for
instance will affect the thermal behaviour, and surface chemistry of the fiber nanocomposite produced. It can also affect the morphologies of the fiber nano-composite.
While the voltage, collector, syringe distance, flow rate of polymer and other

25

parameter might only affect the morphology of the fiber nano-composite prepared.
Good fiber nano-composite can be prepared by the clever manipulation of the
parameters.

26

Chapter 3

Methodology

3.1

Chemicals and Apparatus

The chemicals and apparatus used in this research are shown in the table 3.1 and
table 3.2.

Table 3.1 List of chemicals

Chemical

Brand

Purity

Acetone

QRec

99.5%

Dimethyl formide (DMF)

J.T. Baker

99%

Activated carbon

Sigma aldrich

99%

Nitrogen gas (N2)

MOX

99.999%

Oxygen gas (O2)

MOX

98%

Polyacrylonitrile (PAN)

SIGMA-ALDRICH

27

Table 3.2 List of apparatus

Apparatus

Brand

High voltage power supply

Glassman

Syringe pump

TERUMO

Differential Scanning Calorimetry (DSC)

PerkinElmer

Glass syringe (10,15,20cm)

TERUMO

Trineck flask

Quickfit

Syringe needle

TERUMO

Rotary evaporator

FAVORIT

3.2 Raw Material

Raw material in this study is granulated activated carbon from Norit which was
imported from Sigma Aldrich. The activated carbon is from peat origin that was
steam activated. The detailed information about raw material in this study is shown
in Table 3.3

Table 3.3 The name, purity, brand, diameter and functional group of raw material.
Raw Material
Granulated

Purity
activated 99%

Brand

Size

Sigma Aldrich

3.8nm

carbon (AC)

28

3.3 Reaction

Polyacrylonitrile (PAN) was mixed with dimethyl formide (DMF) solvent before the
activated carbon is added into the solution. The mixture was heated and stirred at
constant temperature in an oil bath until a homogenous solution was formed. The
solution of PAN/AC/DMF was then transferred into a syringe in the syringe pump for
electro-spinning process which was done under the selected parameters. The electrospun fibers was collected and characterized.

3.3.1 Preparation of polyacrilonitrile (PAN)/DMF /AC solution

PAN powder was mixed together with DMF solvent. The ratio of PAN to DMF was
1:10 which means 10.00g PAN was dissolved in 100mL of DMF solvent. The
PAN/DMF mixture was heated and stirred in an oil bath at 70oC (Chae et al., 2009).
A 50mL round bottom flask was used for the mixing of the solution. The heating and
stirring were kept constant for 6 hours before the addition of activated carbon into
the solution. The PAN/DMF solution was then divided into two portions, one for the
addition of 2wt% activated carbon and the other for the addition of 5 wt% activated
carbon. The two solutions were then heated for one hour in the oil bath at 70 oC
before continuing with the electro-spinning process.

3.3.2 Preparation of electro-spun carbon fiber nanocomposite

The electro-spinning apparatus was set up as in figure 3.1. The height from the tip of
the syringe to the collector was set at 15cm. This distance is kept constant for the
whole process. The flow rate of the syringe pump was set to 2mL/min and is also
kept constant for the whole process. The parameters and detail of each samples is
listed in table 3.4.

29

Figure 3.1 Diagram of electro-spinning station

Table 3.4 Summary of the parameters and naming of each sample

Description
Sample

Concentration of AC

Collector

Voltage Supply, kV

AD15KV

2 wt%

Dry

15

AD20KV

2 wt%

Dry

20

AW15KV

2 wt%

Wet

15

AW20KV

2 wt%

Wet

20

BD15KV

5 wt%

Dry

15

BD20KV

5 wt%

Dry

20

BW15KV

5 wt%

Wet

15

BW20KV

5 wt%

Wet

20

30

In the parameter studied, the voltage supplies used were 15kV and 20kV. The
solution with 2 wt% and 5 wt% activated carbon undergoes the electro-spinning with
both voltage supplies. The other parameter studied was the collector. Two collectors
were used in the process, a dry collector and a wet collector. The dry collector uses a
cardboard wrapped with an aluminium foil while the wet collector uses a basin filled
with tap water. The spun collected was dried and kept in plastic container.

3.4 Characterization

The carbon fiber nano-composite produced is characterized using two instruments. A

Differential Scanning Calorimetri (DSC) is used to obtain the samples thermal profile
such as its melting point and heat enthalpies while a Fourier Transform Infra Red
(FT-IR) machine is used to detect the functional group present in the samples.

3.4.1 Differential Scanning Calorimetri (DSC)

Picture 3.1 shows a picture of a DSC machine. DSC reads the thermal profile of a
sample when exposed to a long range of temperature. The thermal profile obtained
can be used to determine a samples melting point, crystallization point, heat
enthalpies and stability. Small amount of product would be placed in the machine
and setting 30 minutes of time with the presence of nitrogen gas. The changes of
samples weight in relation to change in temperature would be observed in a graph
form. The temperature range set is until 4500C (Hohne et al., 1996)

31

Picture 3.1 Perkin Elmer Differential Scanning Calorimetri (DSC)

3.4.2 Fourier Transform Infrared Spectroscopy (FT-IR)

Fourier Transform-Infrared Spectroscopy (FTIR) is an analytical technique used to

identify organic and in some cases inorganic materials by detecting the functional
groupe present in the compound. This technique measures the absorption of infrared
radiation by the sample material versus wavelength. The infrared absorption bands
identify molecular components and structures. When a material is irradiated with
infrared radiation, absorbed IR radiation usually excites molecules into a higher
vibrational state. The wavelength of light absorbed by a particular molecule is a
function of the energy difference between the at-rest and excited vibrational states.
The wavelengths that are absorbed by the sample are characteristic of its molecular
structure.

Picture 3.4 Perkin-Elmer FT-IR

32

3.5

Flow Chart

3.5.1

Preparation of polyacrilonitrile (PAN)/DMF/ activated carbon

solution

10.00g PAN was dissolved in 100mL of DMF

PAN/DMF mixture was heated, stirred at 70oC in an oil bath for 6 hours.

The solution was separated into two portion, one for 2 wt% activated carbon and
one for 5 wt%

The mixture of PAN/DMF/AC were heated and stirred at 70oC in an oil bath for 1
hour

Homogenous solution obtained transferred into a syringe for electro-spinning

process

33

3.5.2 Preparation of carbon fiber nano-composite using electro-spinning

method

Polymer composite solution transferred to syringe

Voltage of 15kV was applied

Flow rate of syringe pump set to 2mL/min

Distance from the tip of syringe to collector was set to 15cm

Electro-spinning process starts

Carbon fiber nano-composite obtained dried and stored

Steps repeated using 20kV of voltage supply

34

CHAPTER 4

RESULTS AND DISCUSSION

In this study, carbon fiber nanocomposite was prepared by electro-spinning method.

Poly-acrylonitrile (PAN) was used as the polymer base with dimethylformide (DMF) as
the solvent. The weight ratio of Poly-acrilonitrile to volume of DMF used was 1:10
while granulated activated carbon was used as the carbon source. The weight
percent of activated carbon used was 2 wt% and 5 wt%. Besides the weight percent
of activated carbon, other parameters include amount of voltage used and collecting
method. The distance from the tip of the needle to the collector and flow rate of the
syringe pump was kept constant for the entire sample.

The properties of the carbon fiber nano-composite prepared were then

characterized using two instruments. A Differential Scanning Calorimeter (DSC) was
used to identify the thermal behavior of the carbon fiber nano-composite prepared
while the functional group present was determined by a FT-IR machine. Table 4.1
shows the list of sample prepared with descriptions and coding.

35

Table 4.1 List of samples with descriptions and coding

Description
Sample

Concentration of AC

Collector

Voltage Supply, KV

AD15KV

2 wt%

Dry

15

AD20KV

2 wt%

Dry

20

AW15KV

2 wt%

Wet

15

AW20KV

2 wt%

Wet

20

BD15KV

5 wt%

Dry

15

BD20KV

5 wt%

Dry

20

BW15KV

5 wt%

Wet

15

BW20KV

5 wt%

Wet

20

4.1

Thermal behavior of carbon fiber nano-composite

The thermal behavior of the fiber produced from the electro-spinning method was
analyzed with a DSC machine. DSC was conducted under the presence of N2 at
atmospheric pressure. Generally PAN will begin to degrade when heated near its
melting point. The endothermic reaction of the degradation of PAN usually tends to
obscure its melting endotherm in the DSC traces; therefore the melting endotherm is
not observed (Ying et al., 2008). Before reviewing the parameters, the activated
carbon, controlled group and one of the samples was compared.

Figure 4.1 shows the thermal profile for activated carbon, electrospun PAN
fiber with DMF as solvent and sample AD20KV while table 4.2 shows the summary
for the thermal profile obtained. PAN fiber produced by electro-spinning method has
a lower melting point than of the powdered form. According to studies conducted by
(Ying et al., 2008), the exothermic reaction of PAN alone ranges between 200 to
350oC.

36

These values might lessen than the original PAN range as the cyclization is
initiated easily at lower temperature in electro-spun fibers, that low cyclization
temperature is mainly due to the improvement in the orientation of molecular chains
in the fibers (Han et al., 2010), where molecular chains were oriented within the
electrospun fibers during the electrospinning process.

Figure 4.1 Thermal profile of activated carbon (Yellow), electrospun PAN fiber with
DMF and (Red) and eletrospun carbon fiber from AD20KV ( Black)

Table 4.2 Summary of the thermal profile of activated carbon, elecrospun PAN fiber
with DMF and sample AD20KV
Sample

Melting point (oC)

Heat enthalpy (J/g)

Activated carbon

PAN + DMF

301.27

-205.2378

AD20KV

309.73

-292.8354

This theory was proved by the thermal profile obtained; the controlled group
which was the PAN with DMF, has a melting point of 300oC, lower than the PAN in
37

powdered form while the activated carbon produces an endothermic peak around
100oC and no exothermic peak. When these two compounds are combined together
in the activated carbon fiber composite, it gives a slightly higher melting point which
was 318oC which was higher than the controlled group than the controlled group.

The thermal profile obtained from DSC for PAN with DMF shows an
exothermic peak at 120oC. This exothermic behavior is the result of crystallization of
the PAN polymer. In this crystalline state, the molecules in the polymer are arranged
in a more ordered manner, the process gives up heat. Next on the curve is a peak at
300oC which represent its melting point. During the melting of the polymer, the
earlier arranged crystalline structure of the molecules began to fall apart and come
out from their ordered arrangement leaving them freely moving. This process uses
heat thus creating an endothermic peak in the DSC curve (M. Naffakh et al., 2011).
The activated carbon curve has no endothermic peak as it has been stabilize during
the activation process.

The thermal profiling data obtained from the DSC for all of the samples are
listed in table 4.1. The entire sample shows an endothermic peak in their curve with
weak exothermic peak in some of the samples. The temperature for the melting point
ranges from 304oC to 334oC. This thermal behavior differences are due to the
parameters incorporated in the procedure which are the concentration of activated
carbon used, voltage supply and collector condition. The effect of each parameter on
the thermal behavior of each sample is discussed by comparing the samples.

38

Table 4.3 Thermal profiles for all the samples and controlled groups
Sample

Melting point (oC)

Heat enthalpy (J/g)

PAN + DMF

301.27

-205.2378

AD15KV

334.87

-322.9976

AD20KV

309.73

-292.8354

AW15KV

316.14

-300.0930

AW20KV

304.39

-419.8985

BD15KV

303.41

-343.5365

BD20KV

316.65

-246.9860

BW15KV

316.57

-223.9124

BW20KV

318.31

-263.7909

4.1.1 Concentration of activated carbon

The first parameter that will be evaluated is the weight percent of the
activated carbon used. Figure 4.2 and table 4.4 shows the thermal profile for the first
batch, which was the one prepared with 2 wt% of activated carbon; the melting
point of the four samples ranges from as low as 304.39oC to as high as 334.00oC.
The incorporation of activated carbon in the composite resulted in a higher melting
point than the controlled group, PAN and DMF.

There are also noticeable exothermic peaks at the beginning of the heating
process for all the four samples, which are around 70oC; this may be attributed by
the presence of water in the sample which was evaporated at that particular
temperature. This exothermic peak normally appears around 0oC but in this case, the
heating process was started at around 25.0oC, so the exothermic shifts to a slightly
higher temperature (M. Naffakh et al., 2011). The shift may also be contributed by
the presence of impurities either in the water present or in the sample itself. Besides
39

the ability to shift the baseline, impurities can also act as plasticizers and disrupts the
transition temperature of the fiber composite prepared.

After the melting peak, a weak exothermic signal can be seen in all of the
samples with 2wt% activated carbon. This is caused by the baseline shift which
happens as a result of changes in the sample weight, heating rate or the specific
heat of the sample (M. Naffakh et al., 2011) A change in specific heat might occur as
the sample has gone through melting transition while the weight of the sample often
changes after the decomposition of the sample.

Figure 4.2 Thermal profile sample AD15KV (red line), AD20KV (blue line), AW15KV
(black line), AW20KV (yellow line)

40

Table 4.4 Thermal profile of carbon fiber nanocomposite prepared with 2 wt%
activated carbon
Sample

Melting point (oC)

Heat enthalpy (J/g)

AD15KV

334.87

-322.9976

AD20KV

309.73

-292.8354

AW15KV

316.14

-300.0930

AW20KV

304.39

-419.8985

The second batch was prepared with 5 wt% of activated carbon. Figure 4.3
and table 4.5 shows the thermal profile for the carbon fiber nanocomposite prepared
with 5 wt% activated carbon. The melting point of the carbon fiber prepared varies
from 303.41oC to 318.31oC. Similar to the fiber with 2 wt% activated carbon, fiber
with 5 wt% activated carbon also shows the exothermic peak created by the
presence of impurities such as water. The exothermic peak was expected as the
samples was not stored in a dry and air tight environment. Besides, other impurities
can also be the cause of the exothermic peak as the electro-spun fibers were not
treated before the analysis took place. The treatment was not carried out because
the process was difficult to set up besides the unavailability of some apparatus. The
temperature regimes for the two concentration of activated carbon are also different.
The fibers prepared with 2 wt% activated carbon in average have a higher initial
temperature, which caused a broader temperature regime and greater heat energies.

In comparison to the electro-spun fibers prepared with 5 wt% activated

carbon, the main peak in average displays higher temperature in the initial state and
broader regime but with smaller heat energies. This results indicate that the fiber
prepared with the higher concentration of activated carbon has relatively high
thermal stability than the one prepared with 2wt% activated carbon which was
expected because of the properties of the activated carbon used. The differences is
due to the cross linking which favors the higher concentration activated carbon which
limit the segment mobility in amorphous area and reduce the cyclization in the
molecule, giving it a better thermal stability (Han et al., 2007)
41

Figure 4.3 Thermal profile sample BD15KV (red line), BD20KV (blue line), BW15KV
(black line), BW20KV (yellow line)

Table 4.5 Thermal profile of carbon fiber nanocomposite prepared with 5 wt%
activated carbon
Sample

Melting point (oC)

Heat enthalpy (J/g)

BD15KV

303.41

-343.5365

BD20KV

316.65

-246.9860

BW15KV

316.57

-223.9124

BW20KV

318.31

-263.7909

The best sample from each concentration was then compared with activated
carbon and PAN fiber with DMF solvent. Figure 4.4 and table 4.6 show the thermal
profile of activated carbon, PAN fiber, AD20KV and BD20KV. The sample prepared
with dry collector with 20KV power supply was chosen because the sample shows
better thermal stability than the other sample. The thermal stability was measured by

42

the melting point and the heat enthalpies of the sample, higher melting point and
lower heat enthalpies results in improved thermal stability.

Based on figure 4.4, the PAN fiber prepared with DMF has a melting point of
301.27oC with an enthalpy of -205.2378 J/g. The improved nano-composite fibers on
the other hand has higher melting point than the controlled group. This indicates that
the addition of activated carbon into the PAN fiber nano-composite successfully
improved the melting point of the compound. The heat enthalpies of samples
increased slightly than the controlled group. BD20KV has a higher heat enthalpy
compared to the AD20KV sample, thus giving the BD20KV better thermal stability
than AD20KV.

Figure 4.4 Thermal profile of activated carbon (Blue), PAN fiber (Red), AD20KV
(Black) and BD20KV (Green)

43

Table 4.6 Thermal profile of activated carbon, PAN fiber, AD20KV and BD20KV
Sample

Melting point (oC)

Heat enthalpy (J/g)

PAN + DMF

301.27

-205.2378

AD20KV

309.73

-292.8354

BD20KV

316.65

-246.9860

4.1.2 Voltage

The second parameter is the voltage used which are 15KV and 20KV for creating the
electric field in the electro-spinning method. The differences between the two voltage
used affects mainly the melting point and the heat energies of the fiber. In the 2
wt% activated carbon fiber for instance, the fiber prepared by using 20KV as the
power supply produces lower temperature regime than the 15KV. The heat enthalpy
is also lower in the 20KV fiber.

Figure 4.5 Thermal profile of activated carbon (Black), PAN fiber (Red), BD20KV
(Blue), BD15KV (Green)

44

Table 4.7 Thermal profile of activated carbon, PAN with DMF fiber, BD15KV and
BD20KV
Sample

Melting point (oC)

Heat enthalpy (J/g)

PAN + DMF

301.27

-205.2378

BD15KV

303.41

-343.5365

BD20KV

316.65

-246.9860

From the concentration of activated carbon used, it is known that 5 wt%

activated carbon produce carbon fiber nano-composite with better thermal properties
than 2 wt% activated carbon. So, only the carbon fiber nano-composite prepared
with 5 wt% activated carbon with voltage 15KV and 20KV will be compared with the
activated carbon and controlled group.

The carbon fiber prepared with 15KV shows a melting point of 303.41oC with
a heat enthalpy of -343.5365 J/g while the carbon fiber prepared with 20KV produces
a melting point of 316.65oC with a heat enthalpy of -246.9860 J/g. Both sample
shows higher melting point than the controlled group but sample BD20KV proves to
be far superior to the controlled group and BD15KV.

Greater voltage also causes greater stretching of the solution as the result of
the greater columbic forces in the jet which affects the reduction of fiber diameter
and evaporation of solvent from the fiber (Bhardwaj & Kundu, 2010). The heat
enthalpy for BD20KV are also smaller than sample BD15KV, this means that it has a
better thermal stability. Besides that, the applied voltage does not really affect the
thermal properties of the fiber produced. The effect of voltage can mainly be seen in
the fiber morphology and physical characteristics such as its diameter, presence of
beads and etc.

45

4.1.3 Collection method

The collection methods used in this study are wet and dry collector. The dry collector
incorporate a piece of cardboard wrapped with aluminum foil while the wet collector
uses a basin filled with tap water. Theoretically, wet collector will produce a more
better fiber composite as the electrons from tap water help attracts the positively
charged fibers but it appears to be quite an unconventional method as the fibers
tend to fall into the water and agglomerate and produce wet fibers.

Figure 4.6 Thermal profile of activated carbon (Black), PAN fiber (Red),

BD20KV

(Blue) and BW20KV (Green)

Table 4.8 Thermal profile of activated carbon, Pan fiber, BD20KV and BW20KV
Sample

Melting point (oC)

Heat enthalpy (J/g)

PAN + DMF

301.27

-205.2378

BW20KV

318.31

-263.7909

BD20KV

316.65

-246.9860

46

Figure 4.6 shows the thermal profile of activated carbon, PAN fiber, BW20KV
and BD20KV while table 4.8 show the summary of the thermal profile obtained.
These two samples were chosen for comparisons because the previous parameters
which are concentrations of activated carbon and voltage supply concludes that the
carbon fiber produced with 5 wt% activated carbon 20kV power supply has the most
outstanding thermal properties among the other samples.

Sample BW20KV shows the highest melting point among the three fibers but
it also shows a high heat enthalpy. BD20KV on the other hand has a lower melting
point than sample BW20KV but with a smaller heat enthalpy. Small heat enthalpy
results in better thermal stability of the carbon fiber nano-composite. The differences
are relatively low as the collectors condition affects mainly the morphology of the
carbon fiber nano-composite produced.

Besides the thermal profile, it was found that the carbon fiber collected with
wet collector tends to agglomerate the PAN, activated carbon and DMF solution, thus
producing beads. The dry collector on the other hand produces fine fibers with no
beads. As mentioned earlier, the wet collector should produce better result as the
positively charged solution is attracted to the negative charge of the water molecules
but the result show the opposite. This is due to the pH of the solution which are
around which is more basic than normal. The pH of the solution was in the 7.6 to 7.6
range. Basic solution is attracted to positively charged compound; in this case it is
the aluminum foil used.

47

4.2

Study of functional group of carbon fiber nano-composite

The significance of this study is to identify the functional group present in the carbon
fiber nano-composite. The chemical structure and properties of the fiber prepared
was analyzed with a FT-IR machine which provides useful information regarding its
functional group content. The entire fiber sample was prepared by the same solvent
and activated carbon, so they all have the same chemical structure which includes
the functional group. Instead of comparing the spectra of all the samples, only one
sample, controlled group and activated carbon spectra were compared. Based on the
thermal behavior of the fiber, it is known that the fiber composite containing
activated carbon have a higher thermal resistance than the controlled group. The
thermal resistance may also be attributed by the combination of functional group
present in the sample.

Figure 4.7 is an FT-IR spectra obtained from the activated carbon fiber
composite with 5 wt% activated carbon in dry condition. As can be seen, the signals
are quite weak but most of the important functional groups can be identified. For
instance, the C=N stretch vibration from the polyacrylonitrile used can be seen at
around 2200 cm-1.There are also some overlapping peaks at 1800 to 1100 cm-1 which
indicates the presence of conjugated C=C, C=N, C=O, C-O and OH group which
results from the combination of the PAN and activated carbon. This overlapping peak
proves that the combination of these two compounds was close to successful. The
major functional groups for AD20KV had to be estimated as the signal is very low.
Table 4.9 shows the major peaks present in the spectra and their wavelength.

48

Figure 4.7 FT-IR spectra of (a) PAN fiber, (b) AD20KV, and (c) BD20KV

Table 4.9 Summary of the functional groups and their frequencies

Functional groups

Frequencies (cm-1)
Controlled group

BD20KV

AD20KV

(PAN+DMF)
O-H

3430

3450

3400

C=O

1726

1730

1700

C-O

1255

1230

1250

2245

2250

2250

49

CHAPTER 5

CONCLUSION

An activated carbon fiber composite was prepared by electro-spinning method where

two concentration of activated carbon were used, 2 wt% and 5wt%. Other
parameters include voltage used for the electric field and collection methods which
are wet and dry while the syringe flow rate and distance from the tip of the needle to
the collector was kept constant for the whole experiment. From the thermal analysis
conducted with DSC machine, the fiber composite produced was found to have
higher melting point than the PAN DMF group. Comparison of the sample prepared
with the three parameters found that the fiber composite with 5wt% activated
carbon has higher thermal stability than the fiber composite with 2wt% activated
carbon. The differences in thermal stability are due to the cross linking which favors
the higher concentration activated carbon which limit the segment mobility in
amorphous area and reduce the cyclization in the molecule. As for the voltage and
collection method, these parameters did not affect the thermal behavior and
functional group of the fiber composite much. The effects are more pronounce in the
morphology of the fiber composite produced. Higher voltage produced a more fine
fiber composite than the lower 15KV. Wet collection method proves to be
inconvenience as wet fibers was produced. The wet collection method also makes the
polymer solution agglomerate faster resulting in bead formation on the fibers. The

50

study of functional group proves that the composite was successfully produced with
the presence of overlapping functional groups.

51

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APPENDIX

Picture of the electro-spun carbon fiber nano-composite.

Top left: AD15KV, AD20KV, AW15KV, AW20KV
Bottom left: BD15KV, BD20KV, BW15KV, BW20KV

57

Picture of electrospun carbon fiber nano-composite collected with dry (left) and wet
collector (right) with 20kV and 5 wt% activated carbon

58