CHAPTER 2

LITERATURE REVIEW

2.1

Polymer Composite
Composite materials may be considered as materials made of two or more components

and consisting of two or more phases in solid state. The importance of polymer composite [9]
originates largely because such low-density materials can have unusual high elastic constants and
tensile strength. For the most part, the tensile properties have been adequately dealt with by
using the theory of elasticity. With new demands for materials to survive in a severe environment
of high temperature, compression, and shear rate, deformation from elasticity to viscoelasticity
and to plasticity becomes important as the loading and environmental conditions vary. [13]
A typical composite material is a system of material combines together (mixed or
bonded) to generate a material that beyond the properties of materials. Generally, composite
material is composed of reinforcement (fibers, particles, flakes, and/or tillers) embedded in a
matrix (polymers, metals, or ceramics). The matrix holds the reinforcement to form the desired
shape While the reinforcement improves the overall mechanical properties of the matrix. When
designed properly, the new combined material exhibits better strength than would each
individual material. Figure 2.1 below show classification of composite [15].

ceramic

Composite

polymer
bio fiber petroleum based

metal
natural
fibrous
synthetic fiber

bio fiber - bia

plastic(PLA)
green composite

particulated
laminated

Figure 2.1: Composite hierarchy chart

2.2

Polymer matrix composite (PMC)

Polymer matrix composite (PMC) is made up from two or more materials which are

matrix and reinforcement. A reinforcing phase could be in fiber, sheet or particulate form. While
matrix phase is, reinforcing is embedded [19]. In this project, the polymer will be the matrix
phase in the thermoset material that give high performance composite than thermoplastic
material. Combining these two different materials are to improve mechanical properties of the
polyurethane. This polyurethane will be improved thermal and mechanical properties by adding
silica in the formulation because the characteristic of polyurethane is flexible. [17] Previous
study, silica particles were widely introduced into a polymer to improve heat resistance,
mechanical and electrical properties of polymer materials. [21].
Composites can be classified into roughly three or four types according to the filler as
shown in Figure 2.2 common composite materials can be classified short and long fiber
composites, which is the filler material has a length to diameter ratio such as fiber glass filler for
short fiber composite and carbon fiber, aramid liber (Kevlar) for long type composite. For
particulate composite the filler materials are roughly round, this type of composite would be the

(a)

(b)

(d)

(c)

(e)

Figure 2.2: (a) Random fiber (short fiber), (b) Continuous fiber (long fiber), (c)
Particulate composites, (d) Flake composites, (e) Filler composites [21]

unreinforced concrete where the cement is the matrix and the sand serves as the filler. Flake
composites have a higher theoretical modulus of elasticity than fiber reinforced composites. They
are relatively cheaper to produce and be handled in small quantities. The filler composites result
of addition of filler materials to plastic matrices to replace a portion of the matrix, enhance or
change the properties of the composites. The fillers also enhance strength and reduce weight.

2.3

Polyurethane Foam
Polyurethane foams (PUFs) have been commercially used in wide variety of applications

since the 1940s. These foams surround us in todays society, playing an important role in many
industries and our daily lives. Especially rigid polyurethane foam is one of the most important
thermal insulating materials used today for construction and for sole insulation in electric
appliances like refrigerators, and freezers. [1] Polyurethane foams generally consist of a solid
polymer matrix and a gaseous phase formed by blowing agents. In some cases, more than one
solid components are added in the solid phase as fillers or extenders.
Polyurethanes are copolymers produced from polyester and/or polyethers blocks with low
molecular weight, covalently bonded with a urethane group (-NH-CO-O-) [27]. A urethane
linkage is produced by reacting an isocyanate group, (-N=C=O) with a hydroxyl (alcohol) group,
(-OH). Polyurethanes based on 4, 4-diphenylmethane diisocyanate (MDI) and polyester are
normally used in protective coating, foams, adhesives as well as biomedical materials, especially
when durability is the main desired properties [7].
Foaming of polymeric materials is carried out by mechanical, chemical, or physical
means. The most widely used method involves dispersing a gas throughout a fluid polymer phase
and stabilizing the resultant foam. In most systems, foams are allowed to expand before
stabilizing the system. [2], [3] The kinetic rate of forming polyurethane foam is increased by a
catalyst or by raising temperature. [2] The kinetic rate affects the cell morphology of
polyurethane foam samples. In addition, the kinetic rate is the important factor in the
manufacture of polyurethane foam. [1], [4] For design of a polyurethane foam, information of
the kinetic rate and its effect on the properties of the polyurethane foam are necessary.
Thermal conductivity is the most important property for thermal insulating materials. The
thermal conductivity of closed-cell foams depends mainly on the total gas content and the
thermal conductivity of entrapped blowing gas inside the closed cells. In addition, the structure

and structural stability of the foams also affect the thermal conductivity of foams. Polyurethane
foams are formed by either physical blowing agents or chemical blowing agents. Physical
blowing agent such as cyclopentane and hydrofluorocarbon expand polyurethane (PU) by
vaporization, and this reaction is endothermic. [2], [3] On the contrary, chemical blowing agents
such as water expand polyurethane by carbon dioxide generated by the reaction between the
blowing agent and isocyanate, and this reaction is exothermic. [2], [3].
Polyurethane foams perform well in the most areas of low-temperature insulations.
Products with density ranging from approximately 30200 kg m3 with stand temperatures
down to 196 C [5]. Polyurethane foam is usually synthesized by the reaction of diisocyanate
with polyol. In general, blowing agent, catalyst and surfactant are also employed to regulate the
properties and morphology of the cell structures. Biomass resource such as agricultural residues
are renewable natural polymers and easily obtainable. In recent years, effective utilization of
biomass resources has paid growing attention right from the starting to seek a substitute for
petroleum and environmental protection [6].

2.3.1

Palm Oil Based Polyol

A polyol is an alcohol with more than two reactive hydroxyl groups per
molecule, as shown in Figure 2.3. About 90% of polyol used in making of PU
foam are polyether with terminal hydroxyl groups [11]. Most of commercial
diisocyanate and polyols in industry are derived from petroleum which is rapidly
diminishing natural resources [8].

Figure 2.3: Polyethylene Glycol [8]

The structure, molecular weights and functional groups of the polyols play
vital roles in shaping the properties of the final PU foam. These factors determine
degree of crosslinking formed when synthesized with the diisocyanate. The
degree of crosslinking formed give main effect on stiffness of the PU foam which
will convey to rigid foam that needs a stiff polymer network and so high degree of
crosslinking [11]. The polyols can be synthesized li-om the renewable resources
such as oil, fats and starch. The polyols have been investigated the option of
converting vegetables oils into polyols for producing PU foams. The manufacture
of polyols from epoxidized palm oil was started by Malaysian Palm Oil Board
(MPOB) in late 1980s. The polyols derived from refined- blanched- deodorized
(RBD) palm oil to fabricate rigid PU foam. Density of the PU foam obtained is
approximately 200 kg/m3 with compressive strength greater than 1 MPa. The
semi-rigid and rigid PU foams are able to be produced from the palm oil based
polyols which afterward used as insulators and wall and ceiling-panels [8].
Additionally, palm oil is the cheapest among the ones currently produced
vegetable oils and had the largest contribution of the total production in 2010.
Palm and palm kernel oils production was recorded at 53.6 million tonnes per
year. 37% of the global vegetable oil market [26]. Palm oil-based polyols can be
synthesized using different methods [28,29] said that polyols are usually obtained
by transesteritication with the use of various agents such as diethanolamine
(DEA). The polyol from palm oil can be obtain by using the method, which is
involve the epoxidation of double bonds followed by oxirane ring opening by
various agents. In Figure 2.4 multimodal GPC character is shown. There are two
major fractions in the GPC chromatogram of the palm oil polyol. The dominant
peak corresponds to the hydroxyl derivative of triglyceride with average
functionality of chromatogram is 2.5. The second broad peak in GPC (minor

peak) corresponds to dimers and trimers and is related to both with variations in
fatty acid substituent and oligomerization of a small fraction of palm oil polyol
during the modification. Table 2.1 shows the characteristic of palm oil based
polyol [29].

Figure 2.4: GPC chromatogram of palm oil based polyol

Table 2.1: Characteristic of palm oil based polyol

In the last few years, several works have been aimed at the use of such
polyols for the preparation of flexible foams [22, 25]. These polyols have a
hydroxyl number in the range 70130 mg KOH/g [23]. Using the glycols in the
second step of this method it is possible to obtain palm oil-based polyols with
primary and secondary hydroxyl groups. Another advantage of this method is the
use of whole molecules of triglycerides in the preparation of polyol, thereby the
resulting products are characterized by a high content of renewable raw materials.
The content of hydroxyl groups in the oil polyols can be designed by choosing
appropriate conditions of the epoxidation reaction [16]. The application of
different alcohols as ring-opening agents and chain extenders allows affecting the
content of soft segments in PUR foams [24].

2.3.2

lsocyanate
In the synthesized of PU foam, the common used isocyanates are toluene
diisocyanate (TDI), methylene diphenyl diisocyanate (MDI) and their modified
products. MDI is mainly used in the production of rigid PU foams which is
employed in sandwich panel application [11]. Figure 2.4 shown the chemical

structure of 4, 4-diphenylmethane diisocyanate (MDI) used in the production of

polyurethane foam in this project.

Figure 2.4: 4, 4-diphenylmethane diisocyanate (MDI) [11]

In order to produce PU foam, the synthesized of polyols and diisocyanate
should be in presence of blowing agent to generate nucleating gas bubbles
accompanied by the generation of C02 in the polymerizing or gelling of the
mixture. The polyurethane foam formation reaction basically consists of the
urethane reaction (gelling). The normally used blowing agent for the PU foam
synthesized is water with the addition of additives that play a main role. These
include catalyst, crosslinking agents, chain extending agents, surfactant, coloring
materials, fillers and flame retardants [11].
There are many other complex reactions which occur during the formation
of polyurethane foam. The hydrogen bonding effect was concerned with the
blowing activity. That is to say, by the hydrogen bonding between water and
amine catalyst, the water is present in the vicinity of an isocyanate group that is
activated by tertiary amine [10]. During polyurethane synthesis, the reaction
speed, crosslink density and properties of polyurethane are directly related with
hydroxyl numbers of the used polyol. The aromatic groups propose the rigid
segments in the PU foams, which is favorable to compressive strength. Zou et. al
[12] found that by varying the [NCO]/ [OH] ratio, PU foam properties could be
accustomed for various end uses [10].

Among polymer foams, the use of rigid polyurethane foam has structure is
rising as they can absorb higher energy particularly in the event of impact.
Furthermore, the polyurethane foam can be tailored to attain the properties needed
for the applications. For example, the polyurethane with closed cell structure can
absorb additional energy than the open cell structure. [10].

2.4

Filler
2.4.1

Charcoal
Charcoal can be produced almost anywhere in the world. Wood is the
material most often used to produce charcoal; one of many causes for the rapid
rate of global deforestation.[17] 17 Wunder, Sven. "Deforestation and the Uses of
Wood in the Ecuadorian Andes." Mountain Research and Development 16, No. 4
(1996): 367. Instead of trees, many agricultural waste byproducts are used to
replace wood as the carbon source.
Charcoal, the blackish residue consisting of impure carbon obtained by
removing the volatile constituents of animal and vegetable substances; wood
gives origin to wood-charcoal; sugar to sugar-charcoal; bone to bone-charcoal
(which, however, mainly consists of calcium phosphate); while coal gives coke
and gas-carbon. The first part of the word charcoal is of obscure origin. The
independent use of char, meaning to scorch, to reduce to carbon, is
comparatively recent, and must have been taken from charcoal, which is quite
early. [14] Carbon based biomaterials have attracted intensive attention because of
their nanoscale dimensions, large surface area and good acceptance by the
biological environment [18].
EXTRACTION OF COCONUT SHELL CHARCOAL:
The Process used for extraction of Coconut shell charcoal are as follows:

Cutting: First the Coconut is cut down from the tree and dried for
somedays.

Ripping: Then the Cover is ripped out such that the shell can be

visible properly.
Burning: The Coconut shell is burnt in open air for around 3-4
hours and then product is incinerated in furnace at 8000C for 6
hours then only we can obtain Coconut shell charcoal.

PROPERTIES OF COCONUT SHELL CHARCOAL:

2.4.2

High Strength property than other fillers due to its hardness and low

specific weight.
It shows high modulus Property.
High lignin Content as it has high resistance to different weather and

therefore suitable material for construction of road.

It shows good durability and abrasion resistance Characteristics.
It has low Cellulose Content. [30]

Carbon Black
Carbon blacks are very important fillers, especially in the rubber industry.
A brief description of their preparation and properties follows. [20] Carbon blacks
are, essentially, soot produced by incomplete combustion of volatile organic
materials, generally oil and gas, and have been made and used as pigments for
centuries. Their ready availability, fine particle size and compatibility with
organic materials made them obvious candidates for use as fillers when polymer
development began. Indeed they are the most widely used filler for elastomer
applications, having developed with this technology. They have achieved their
strong position because they are chemically inert, have a relatively low cost and
are easy to prepare in the fine sizes and shapes required. Most importantly, they
naturally possess a surface that is able to form acceptably strong attachments to
elastomer molecules, without the need for expensive coupling agent treatments.

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