CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

Fiber-reinforced composites have piqued importance due to their numerous superior

properties and applications. The strengthening of fiber in various polymers greatly improves
the mechanical properties of composites, as is well known. Furthermore, advanced research
with two or three polymers/reinforcements or fillers has identified the increasing performance
of composites. However, due to the difficulty in separating their constituents, recycling of
these composites is difficult. Most of these composites are made from petroleum-based
nonrenewable resources. Eco-friendly bio composites must have a lower environmental
impact to replace petroleum-based nonrenewable resource-based composites. In general, bio
composites are made up of one or more phases of natural fiber reinforcement with organic
matrix or biopolymers.

2.2 Composite

A composite is a material made from two or more different materials that, when
combined, are stronger than those individual materials by themselves. Simply stated,
composites are made up of many different components. Composites are materials that are
created by combining two or more natural or artificial elements (with different physical or
chemical properties) to create a substance that is stronger as a composite than as individual
performances. The component materials do not fully merge or lose their distinct identities;
instead, they integrate and contribute their most useful characteristics to maximise the final
product's outcome. Composites are usually created for a specific purpose, such as increased
strength, performance, or longevity.

2.2.1 What are composites made of?

Composites, also known as Fiber-Reinforced Polymer (FRP) composites, are made

from a polymer matrix that is reinforced with an engineered, man-made or natural fiber (like
glass, carbon, or aramid) or other reinforcing material. The matrix protects the fibers from
environmental and external damage and transfers the load between the fibers. The fibers, in
turn, provide strength and stiffness to reinforce the matrix and help it resist cracks and
fractures.
 A. Fiber B. Matrix C. Fiber composite matrix

2.2.2 Natural and synthetic composites

Composites can be natural or synthetic. Wood, a natural composite, is a combination

of cellulose or wood fibers and a substance called lignin. The fibers give wood its strength;
lignin is the matrix or natural glue that binds and stabilizes them. Other composites are
synthetic (man-made). Plywood is a man-made composite that combines natural and synthetic
materials. Thin layers of wood veneer are bonded together with adhesive to form flat sheets
of laminated wood that are stronger than natural wood.

Many terms are used to define FRP composites. Modifiers have been used to identify a
specific fibre such as Glass Fiber Reinforced Polymer (GFRP), Carbon Fiber Reinforced
Polymer (CFRP), and Aramid Fiber Reinforced Polymer (AFRP) (AFRP). Fiber Reinforced
Plastics is another common term. Furthermore, other acronyms have been developed over the
years, and their use has been determined by geographical location or market use. Many
references, for example, mention Fiber Reinforced Composites (FRC), Glass Reinforced
Plastics (GRP), and Polymer Matrix Composites (PMC). Each of the preceding terms refers to
the same thing: FRP composites.
 Figure 1: Classification of natural and synthetic fiber (Lilholt and Lawther, 2002).

2.2.3 History of composite

The invention of cellulose fiber–reinforced phenolic composites in 1908 ushered in the

age of natural fiber composites now known as bio composites. Synthetic glass fiber–
reinforced polyester composites were developed after this and became commonplace in the
1940s. Henry Ford first used biobased green polymers to make auto parts in 1941, when he
made fenders and deck lids out of soy protein–based bioplastic. The use of composite
materials derived from renewable and sustainable resources has emerged as a critical
component of the next generation of industrial practice. Their increased use is being driven by
several factors, including the need for sustainable growth, energy security, a lower carbon
footprint, and effective resource management, while the functional properties of the materials
are being improved at the same time. Innovative sustainable resources, such as biosourced
materials, wastes, coproducts, and recycled materials, can be used as both the matrix and
reinforcement in composites to reduce the use of nonrenewable resources and better utilize
waste streams.
 Canoe builders began experimenting with different materials to make paper laminates
in the late 1800s. They experimented with gluing layers of kraft paper (strong, machine-made
paper made from wood pulp) together with shellac. It was a good idea, but it failed because
the materials available were inadequate. Between 1870 and 1890, the first synthetic (man-
made) resins that could be converted from liquid to solid via a chemical process known as
polymerization were developed. By crosslinking the molecules, these polymer resins are
transformed from a liquid to a solid state. The 1930s signaled the beginning of a new era for
resins and, ultimately, the composites industry. Carleton Ellis patented unsaturated polyester
resins in 1936. They became the primary choice for resins in composites manufacturing due to
their curing or hardening properties. Other high-performance resin systems, such as epoxy
resins, became available by the late 1930s.

The 787 Dreamliner validated composites for high-strength and rigid applications in
the mid-2000s, and the continued advancement of finish technology, such as PVD and
THERMTIAL™, increased the number of applications in the automotive, appliance, and
consumer goods industries. Nowadays, governments, suppliers, and universities are now
funding composites science. These investments help to speed up the pace of innovation.
Specialized businesses, such as aerospace composites firms, will thrive in the industry. Aerial
composite materials and composite sheets for marine use are two applications that continue to
see creative development.

2.3 Biocomposite

Biocomposites are defined as biocompatible and/or eco-friendly composites. They

consist of a large variety of organic and/or inorganic components, such as natural and
synthetic polymers, polysaccharides, proteins, sugars, ceramics, metals, and nanocarbons.
Biocomposites are present in various forms, such as films, membranes, mouldings, coatings,
particles, fibres, and foams. In addition to the studies aimed at improving basic mechanical
properties and functionalities of the materials, a large number of studies have been conducted
to develop eco-friendly composite and/or biomedical materials for use in the fields of sensors,
tissue engineering, implants, and scaffolds.(Haraguchi, 2021)

Fiber-reinforced composites have piqued interest in recent years due to their numerous
superior properties and applications. The strengthening of fibres in various polymers greatly
improves the mechanical properties of composites, as is well known. In general, synthetic
fibres such as glass and carbon fibres are preferred for polymer reinforcement in the aircraft
and automotive industries. Furthermore, advanced research has established the increasing
performance of composites with two or three polymers, reinforcements, or fillers. However,
due to the difficulty of separating the components of these composites, recycling is difficult.
In the other hand, these composites have a negative impact on the atmosphere as they are
disposed of in landfills or burned. The majority of these composites are manufactured from
nonrenewable petroleum-based materials.(Manikandan et al., 2021).

Eco-friendly biocomposites would reduce environmental impact to replace petroleum-

based nonrenewable resource-based composites. In general, biocomposites are made up of
one or more phases of natural fibre reinforcement with organic matrix or biopolymers. These
reinforcements (cotton, hemp, flax, sisal, jute, and kenaf, as well as recycled wood and paper)
and biopolymers (natural biopolymers like gelatin, corn zein, and soy protein, synthetic
biopolymers like poly(lactic acid) (PLA), poly(vinyl alcohol) (PVA), and other microbial
fermentations like microbial polyesters) are sustainable and degradable. (Akampumuza et al.,
2017)(Misra et al., 2011).

Meanwhile, in a different approach, these biocomposites are made from renewable,

recyclable, and sustainable agricultural and forestry feedstocks rather than food or feed, which
can result in a better day-to-day improvement in the environment. The use of bio-based
polymers as a reinforced matrix to shape biocomposites is the in a systematic way. The
dramatic impact on biopolymer-based composites production, which has led to the rapid
growth of biocomposites in the market, can be seen.
2.4 Properties of biocomposite

The most important aspect of selecting materials for different applications is that they
are dependent on their properties. Materials' properties are often influenced by their isotropic
and anisotropic nature. In each operating range, the properties of materials that contribute to
various physical phenomena always behave linearly. The differential constitutive equations
that the property describes can be greatly simplified by modelling them as linear. The related
equations, on the other hand, are often used to calculate the material properties. If we know a
material's original length, we can calculate the gain or loss of that length by measuring the
difference in length. Standardized test methods are the most reliable way to quantify material
properties. Many of these research methods have been registered by their respective user
groups and published by the American Society for Testing and Materials (ASTM).

We noted the most important properties of the renewable biocomposites from several
researchers’ investigations that are listed below: -

I. Physical properties
II. Mechanical properties

The matrix serves to preserve the fibres from environmental degradation and
mechanical damage, but its primary function is to keep them together and pass loads. This
matrix is usually made of a thermoset or thermoplastic resin, but since biocomposite is in
demand, the resin should be made from renewable materials.

2.5 Applications of Bio-Composites in Industrial Products

Natural fibres have become increasingly popular in composites. Bast fibres (jute, flax,
hemp, ramie, and kenaf), leaf fibres (abaca, sisal, and pineapple), seed fibres (coir, cotton, and
kapok), core fibres (kenaf, hemp, and jute), grass and reed fibres (wheat, corn, and rice), and
all other varieties are the six basic types of natural fibres (wood and roots)(Faruk et al., 2012).

2.5.1 Automotive applications

The investigation of the suitability of natural fibre composites has shown more interest
in structural and infrastructure applications where moderate strength, lower cost, and
environmentally friendly properties are required. Figure 2 below shows the interior
components of an E-Class car which are made of various natural fibre composite. In
Germany, the major car manufactures such as Mercedes, Volkswagen, Audi, and Ford use
natural fibre composites for various interior and exterior applications. Figure 3 shows car door
inner trim panels that are precast using mats of 60% natural fibre in a Baypreg® polyurethane
resin (Courtesy of Bayer Polymers)

Figure 2: The interior components made of a natural fibre composite for an E-class car

Figure 3: These modern door inner trim panels are moulded using mats of 60% natural fibre in a Baypreg polyurethane resin
(Courtesy of Bayer Polymers)

The automotive industry has applications that are both difficult for mechanical design
and interesting to the public. Until now, most advances in this field have focused on natural
fibre reinforced synthetic polymers. The main fibres now used for this purpose are bast fibres
such as flax, cotton, jute, and others. Mercedes-Benz and BMW, for example, are leaders in
providing extensive in-house experience as well as applications in their vehicles (door liners,
boot liners, parcel shelves, etc). Natural fibre substrates have also been certified by other
European manufacturers, including Ford and Opel in Germany, and Renault, Peugeot, and
Citroen in France.

2.5.2 Applications in marine environment

Due to their strong mechanical properties and biodegradability, several researchers

discovered that biocomposites have possible marine applications. Because of these
characteristics, biocomposites have emerged as a viable alternative to synthetic fibre-
reinforced composites. In a related study, existing environmental issues such as depletion and
waste management must be factored into sailing yacht design creativity. This leads to the
incorporation of natural fibres into the matrix, resulting in eco-friendly composite materials
that could be used in a variety of applications. DuPont TM developed a Kevlar-based marine
composite that provides an ideal combination of strength, stiffness, and lightweight properties
for a variety of marine applications. This improves the higher speeds that can be reached in
patrol and service boats by rising engine capacity. These composites made with Kevlar be
lighter yet tougher, damage tolerant and perform better under hydrodynamic fatigue loading.

Figure 4: Composite material used in marine applications

2.6 Rice husk

Rice husk is a cellulose-based fibre that can be used in composite panel

manufacturing. Rice husks have not been successfully utilised like other cellulose fibres due
to poor contact between them and the binding materials, which results in weak particle–matrix
adhesion. Rice husk has a rougher outer surface than the inner surface that contains the rice
grain. It has a significant amount of silica in it (20% w/w). On the outer surface of rice husks,
silica occurs in the form of a silicon–cellulose membrane that acts as a natural barrier against
termites and other microorganisms. This component is thought to be the cause of poor
adhesion between accessible functional groups on the surfaces of rice husks and various
matrix binders. The removal of silica and other surface impurities is expected to strengthen
the adhesion of rice husks to binders and, as a result, the composite's properties. Rice husk has
a smooth inner surface that may contain wax and natural fats that provide good protection for
the grain. However, the presence of these impurities on the inner surfaces of rice husks has a
chemical and physical effect on the adhesion properties of rice husks.

Modifications to the surfaces of plant fibres have been made to enhance their
hydrophobicity or adhesion properties. Surface alteration is the process of removing surface
impurities from fibre surfaces by causing physical and chemical changes.

Figure 5: Rice husk

2.6.1 Rice husk product

The rice husk, also called rice hull, is the coating on a seed or grain of rice. It is
formed from hard materials, including silica and lignin, to protect the seed during the growing
season. Each kg of milled white rice results in roughly 0.28 kg of rice husk as a by-product of
rice production during milling.

Figure 6: Paddy grain (left) and its products after husking.

 Rice husk is often used for energy processing, such as combustion and gasification, in
its loose shape. Combustion is the method of converting carbon in the rice husk into CO2 and
heat energy for later use. Direct combustion, which eliminates the need for a heat exchanger
and a proper furnace to produce heat for drying paddy, is one of the most effective uses of this
by-product. The conversion of rice husk to synthesis gas (syngas) in a gasifier reactor with a
regulated amount of air is known as gasification. Syngas can be used as a drying and cooking
fuel, or it can be used to generate electricity in a cogeneration system.

Figure 7: Rice husk loose form

Densification is used to increase the density of materials and their combustion

efficiency in the production of rice husk briquettes and pellets. These densified rice husks are
primarily used as a fossil fuel replacement in industrial boilers.

Figure 8: rice husk briquette

After the rice husk ash has been combusted, the by-product is rice husk ash. The amount of
carbon left in ash is determined by the combustion efficiency (complete or incomplete
combustion). Rice husk ash can be used in a variety of applications, including soil amendment
and cement and steel additives. However, compared to total rice husk output, only a small
percentage is used for this reason.

Figure 9: Rice husk ash

Thermal decomposition of rice husk under a small supply of oxygen (O2) and at
relatively low temperatures (less than 700°C) produces carbonised rice husk. Carbonized
biochar may be used as a soil modification, processing fertiliser, and activated carbon, among
other things.

Figure 10: Carbonized rice husk ash

2.7 Characteristics of rice husk

Rice husk is produced during rice milling and is already dried and stored at the
factory. Uncompressed rice husk has a specific weight of around 100 kg/m3. According to
various research on the rice husk by Beagle (1978), Jeng et al. (2012), and Jenkins, average
properties of rice husk in proximate analysis and ultimate analysis b are shown in Tables 1
and 2, respectively (1998).

Silicon oxide forms the main component of the ash with trace amounts of Al2O3,
Fe2O3, CaO, MgO, K2O, and Na2O. The physical and chemical properties of rice husk ash
are dependent on the components of the combustion process, such as combustion type,
feeding type, temperature, residence time, and availability of oxygen (aerobic or anaerobic).

The characteristics of rice husk compared with other solid fuels can be summarized as
follows:

 Its high silica content causes excessive wear to parts of processing machines, such as
conveyors or grinders, and hampers digestibility in livestock. The content of volatile
matter in the rice husk is higher than in wood and much higher than in coal, whereas
 fixed carbon is much lower than in coal. Ash content in the rice husk is much higher
than in wood and coal, which causes barriers in energy conversion.

 The high content of ash, alkali, and potassium causes agglomeration, fouling, and
melting of the parts of combustors or boilers.

2.8 Utilization of rice husk

Rice husk was long regarded as a waste product of the rice milling process, and it was
often discarded or burned. Rice husk has often been used as an energy source for small
applications, such as brick manufacturing, steam engines and gasifiers used to power rice
mills, and generating heat for rice dryers, due to its ease of collection and low cost. Rice husk
ash is a suitable additive for the steel and concrete industries because of its high silica content.
Rice husk ash is used as a soil conditioner, activated carbon, insulator, and other things to a
lesser extent. Creating electrical power on a small to medium scale up to 5 megawatts has
recently been piloted across Asia. There are some promising methods, but there are also some
limitations that have been shown. Failure was mostly due to feedstock supply issues once the
previously free waste rice husk became a traded commodity, as well as logistics issues and
high costs as transportation distances became too great. Figure 11 shows a schematic of how
rice husks are used.
Figure 11: Options for the use of rice husk.