CHAPTER II

LITERATURE REVIEW

This chapter examines the conceptual and research literature relevant to the study's

objectives. The concepts and ideas related to this study were explained in detail for better

understanding.

Conceptual Literature

Aerogel

Mitrofanov et al. (2017) defined aerogel as a special material with a variety of

potential applications. The three most significant characteristics of an aerogel are its

high specific surface area, low density, and high porosity, and possess great thermal

stability. These qualities make aerogel a perfect material for thermal insulation.

According to Meti et al. (2022), aerogels can be made with a broad variety of

chemical compositions and structural characteristics, making them useful for a variety of

applications such as medication delivery, thermal insulation, sensing, aerospace,

medicinal, CO2 collection, and environmental remediation.

Aerogels are made by draining the liquid out of gels without changing the

structure of the network. Because the methods for turning gels into aerogels—such as

CPD or freeze-drying [FD]—are fairly developed, the key to synthesis is developing wet

gels, or more precisely, managing the gelation process (Jiang et al., 2021). Depending

on their intended application, aerogels are available in a range of sizes and forms.

Based on appearance, there are three different varieties of aerogel: film, powder, and

monolith. Depending on the process of production, it is referred to as hydrogel, cryogel,

xerogel, or aerogel. Aerogel is classified as microporous (2 nm), mesoporous (2–50 nm),

 and mixed porous (2–50 nm) based on its various microstructures. Classification based

on chemical composition appears to be significantly more beneficial in analyzing and

comprehending the features of aerogels [22]. Based on their chemical structure,

aerogels are classified into three groups: composite, inorganic, and organic. Metallic

alkoxide or metal salts are examples of inorganic precursor materials used to create

inorganic aerogels (Moheman et al., 2021).

1. Application of an Aerogel

1.1. Thermal Insulator

Thermal insulation materials, which can be composed of one or more

materials, are selected to minimize heat transfer across a medium. The

importance of insulating materials drives energy engineers to improve the

thermal properties of thermal insulation materials in order to achieve greater

thermal resistance. Materials that are fibrous, cellular, and granular are

frequently utilized as insulation in structures. The temperature of both indoor and

outdoor areas, thermal conductivity, thermal mass, cost, and other

considerations are taken into account when choosing a thermal insulation

material. (Alawadhi, 2015)

1.2. Acoustic Insulation

Aerogels make it possible to combine good acoustic qualities with

efficient heat insulation. The density, pore formation, and manner of material

preparation all have a major impact on the acoustic insulation and absorption

properties of aerogel. As a result, the sound waves' amplitude and speed are

reduced, which accelerates their dispersion and slows them down. As a result,

aerogels might become appropriate materials for acoustic insulation. (Khan et al.,

2024)

1.3. Biomedical Engineering

 Aerogels based on silica, polymers, and hybrids are particularly relevant

for biomedical and pharmaceutical applications since they all demonstrate

exceptional permeability, biocompatibility, biodegradability, and the ability to

replicate organic structures. Numerous biological uses exist for aerogels, such as

drug delivery, biosensing, wound healing, regenerative medicine, implanted

devices, and diagnostic tools. (Khan et al., 2024)

2. Classification of an Aerogel

2.1. Organic

Organic aerogels have been around for as long as any other type of aerogel; in

fact, the first aerogel Samuel Kistler is thought to have developed was a jelly aerogel

(which is composed of the organic heteropolysaccharide pectin). Kistler also made

gelatin aerogel and rubbers, which are both made of organic polymers.

An organic aerogel is essentially any aerogel with a structure made mostly of

organic polymers. Organic aerogels, in contrast to inorganic aerogels like silica and

metal oxide aerogels, have radically distinct characteristics. They are less delicate and

friable than inorganic aerogels, squishing instead when compressed. The phrase

"organic aerogel" can apply to a variety of distinct types of aerogels, each with unique

features derived from the polymer that forms the framework of the aerogel.

Organic aerogels can be made from resorcinol formaldehyde, phenol

formaldehyde, melamine formaldehyde, cresol formaldehyde, phenol furfuryl alcohol,

polyacrylamides, polyacrylonitrile, polyacrylates, polyisocyanurate, polyfurfuryl alcohol,

polyimides, polystyrenes, polyurethanes, polyvinyl alcohol dialdehyde, epoxies, agar

agar, agarose, and many others.

Organic aerogels have existed since the first aerogels were manufactured, but

they were mostly ignored until the 1980s, when scientists at Lawrence Livermore

National Laboratory began manufacturing organic aerogels made of phenolic resins. Dr.
 Rick Pekala and Dr. Joe Satcher, who created the first resorcinol-formaldehyde polymer

aerogels, did the majority of the work (or RF aerogels for short). Aerogels made of the

same substance as "Bakelite" plastic. RF aerogels come in a variety of colors and

densities, ranging from bright orange to deep red to black, and are translucent to

opaque.Organic aerogels with a low density (0.020 g cm-3) are squishy and irreversibly

squishy, akin to green floral potting foam. Organic aerogels with a high density (>0.5 g

cm-3) can be incredibly tough to squeeze, almost like a car seat cushion.

2.2. Inorganic

Moheman et al. (2021b) asserted that inorganic precursor materials, such

as metal salts or metallic alkoxide, are the source of inorganic aerogel.

2.3. Composite or Hybrids Aerogel

Ferreira-Gonçalves et al. (2022) stated that hybrid aerogels incorporate

organic and inorganic components into a single structure.

3. Types of an Aerogel

3.1. Cellulose Aerogel

Ferreira-Gonçalves et al. (2022) asserted that natural cellulose polymers

are biodegradable and renewable. In addition to possessing the renewability,

biocompatibility, and biodegradability of cellulose, aerogel made from cellulose

also has a lot of other benefits like high porosity, low density, and a large specific

surface area. As a result, it can be used in a wide range of industries, including

biomedical applications, thermal insulation, adsorption, and oil/water separation.

Three varieties of cellulose aerogels exist: regenerated cellulose aerogels,

aerogels derived from cellulose derivatives, and natural cellulose aerogels

(nanocellulose and bacterial cellulose aerogels).

3.2. Silica Aerogel

 Silica aerogels have a large surface area, are highly porous, lightweight,

and mechanically stiff, and will undoubtedly find use in a variety of industries

ranging from pharmaceutical to semiconductor. Chemical modifications to silica

aerogels can also be made to suit specific applications. Following surface

modification, silica aerogel can contain a wide range of bio-species, including tiny

medication, antigen, and protein molecules. The hunt for uses for silica aerogel in

biotechnology is a popular research topic. Surface functionalization of silica

aerogels for biomolecule transport can be separated into two categories. The first

technique relies on basic electrostatic contact to bind bio-species non-covalently.

3.3. Carbon Aerogel

Carbon aerogels are made by pyrolyzing phenol-furfural or resorcinol-

formaldehyde gels to create monolithic, three-dimensional, mesoporous networks

of carbon nanoparticles. The density of the material is determined by the degree

of dilution of the solid components in the gel mixture, while the concentration of

the catalyst regulates the sizes of the final particles. Supercritical fluid extraction

is typically used to dry the aerogel precursors; in the absence of this method, the

thermally dried products are referred to as xerogels. In an argon flow, ethanol

can be transformed into "solid smoke" at 1100 °C. Because there are fewer grain

boundaries between the particles, carbon aerogels have a high surface area,

extreme blackness, low density, and good electrical conductivity. They can also

be handled without the need for binding chemicals to create electrode materials

(Kurzweil, 2009).

3.4. Metal Aerogel

Jiang et al. (2021) stated that the beginnings of metal aerogels (MAs) can

be traced back to 2009, when resorcinol-formaldehyde (RF)/iron oxide (FeOx)

composite aerogels were melted to create iron (Fe) aerogels. Similarly, colloidal
 nanoparticles (NPs) were used to assemble noble metal aerogels, such as gold

[Au], silver [Ag], and platinum [Pt]. Due to the remarkable application potential of

Metal Aerogel (MAs), especially in electrocatalysis, can be attributed to their

unique plasmonic properties and 3D conductive pathways. Over the past ten

years, a number of approaches have been developed to broaden the chemical

composition even further. These include metalloids (silicon [Si]), noble metals

(palladium [Pd], ruthenium [Ru], rhodium [Rh], and osmium [Os]), and the diverse

single-metallic transition metals (iron [Fe], nickel [Ni], cobalt [Co], tin [Sn], copper

[Cu], titanium [Ti], and tantalum [Ta]).

4. Properties of an Aerogel

4.1. Density

A material's density is defined as its mass per unit volume. Materials'

densities are determined by a number of factors, including the microstructure's

porosity, atomic weight and size, and packing density.

4.2. Particle Size

The Particle Size Distribution (PSD) is a fundamental property of granular

materials, including aggregates and soils, that greatly influences the mechanical

and hydraulic properties of geomaterials. Thus, among the most crucial tests for

geomaterials are the PSD test (also known as the gradation test), which can also

be performed using a laser-based particle analyzer, a hydrometer, or a sieve

analysis (Liu et al., 2019).

4.3. Porosity

Issaadi et al. (2018) stated that the measurement of porosity is crucial for

characterizing the microstructures of materials. It is equivalent to the fluid-holding

capacity of the interstices relative to the material's overall volume. The pore

system, which is made up of small-diameter channels and networks of

 communicating or non-communicating pores, can be divided into various porosity

classes. The term "residual porosity" or "closed porosity" describes the portion of

the pore system that is made up of occluded pores that are cut off from the

outside world and the other pore spaces. Although this kind of porosity affects

the material strength, it is not a factor in the mass transfer phenomenon.

Additionally, the porosity that accounts for the volume of accessible or connected

pores is known as the "effective" or "open" porosity, which is formed by the

communicating pores. By taking into account the pore size distribution, the

description of the pore system can be improved.

4.4. Thermal Stability

According to (Polymer Composites With Functionalized Nanoparticles,

n.d.), the term "thermal stability" refers to a polymer's capacity to withstand heat

and retain certain characteristics, like strength, toughness, or elasticity, at a

specific temperature. Typically, thermogravimetric analysis (TGA) and Differential

Scanning Calorimetry (DSC) is used to assess the heat stability of polymers.

5. Methods/ Synthesis

5.1. Freeze Drying

Nowak and Jakubczyk (2020) stated that the term freeze-drying,

sometimes referred to as lyophilization, is a low-pressure method of sublimating

water in the form of ice to remove it from a material.

Aerogels are produced by sublimating the solvent under vacuum during

the freeze-drying process, which changes the solvent from a liquid state to a

solid state. This is regarded as an affordable and environmentally friendly drying

technique. Aerogel performance enhancement and structural control greatly

depend on the optimization of the freeze-drying process. Solvent heat transfer

and state transition—which can be further broken down into liquid cooling stage,
 phase transition stage, and solid cooling stage—occur during the freezing phase

of the freeze-drying process.

5.2. Ambient Pressure Drying

Maleki (2016) stated that an approach that shows promise, easy to use,

safe, and allows gels to be dried in ambient temperature is ambient pressure

drying. This method may work well for large-scale industrial manufacturing.

However, in order to prevent additional condensations in nearby surface

functioning after being compressed by capillary pressures, the gel's pore walls'

surface needs to be chemically treated with some non-polar groups. In addition,

to avoid the capillary stresses that the pore walls experience, the pore-filling

solvent needs to be replaced with a hydrocarbon or a solvent with lower surface

tension.

Ambient Pressure Drying (APD) is typically performed in two steps: first,

the OH groups are silylated by replacing the solvent with a water-free solvent and

a silylating chemical. Three phases comprise the process of evaporation at

ambient pressure: a warming phase; a first drying phase during which capillary

forces propel water to the exterior; and a second drying phase dominated by

diffusive vapour transport, which permits liquid to gently escape to the outside.

(Buratti & Moretti, 2013)

5.3. Supercritical Drying

According to Subrahmanyam et al. (2023), a process known as

supercritical drying is used to separate a solid component from a material by

replacing its liquid with a gas while preserving the substance's fragile

nanostructured pore network.

One of two techniques can be used for Supercritical Drying (SCD): light

temperature supercritical drying (HTSCD), which involves heating an autoclave

 partially filled with aged gel to a temperature and pressure above critical, then

depressurizing it isothermally and cooling it to room temperature at ambient

pressure. Similar to HTSCD, low temperature supercritical drying (LTSCD) is a

three-step process that involves placing the aged gel in an autoclave, filling it

with CO2 at 4–10 °C and 100 bar to replace the solvent in the pores, heating it to

40 °C while maintaining 100 bar, isothermally depressurizing it, and then cooling

it at room temperature at ambient pressure. (Buratti & Moretti, 2013)

6. Problem Encounter

The challenges for aerogel application that require discussion include high costs,

low mechanical strength, fragile texture, fire safety of aerogel products, and

environmental issues in aerogel production, among others. Aerogel insulation materials

are more costly and challenging to install than several traditional insulation options due

to their high production costs and poor tensile strength.

Agricultural Wastes

The term "agricultural waste" refers to undesirable trash generated as a result of

agricultural activity (i.e., manure, oil, silage plastics, fertilizer, pesticides and herbicides; wastes

from farms, poultry houses and slaughterhouses; veterinary medicines, or horticultural plastics).

1. Coconut Husk

The coconut husks are the shell's exterior covering. They constitute the majority

of garbage in the Philippines. They are composed of 10% bristle fiber, 20% mattress

fiber, and 70% coir, shorts, or trash.

 Figure 1: Image of Coconut Husk.

Source: Barrett, A., 2019

Table 1. Physical Properties of Coconut Husk

PHYSICAL PROPERTIES
Color Brown
Length 50mm
Tensile Strength 1.5-3.1 MPa
Oil Absorption 9.87%.
Water Absorption 1.54%

Source: Tondo M. 2023

1.1. Benefit

The outer shell of coconut fruit or coconut husk is used to make a variety

of key products in the current consumer market. It is used in the production of

coco husk chips, coco peat, coir fiber, and coco crush. It is the world's best

natural organic growing medium. The husk is used for potting plants and flowers.
 It is a soil raw material used in greenhouse production. Coconut husk can help

plants grow faster and absorb nutrients more effectively. It enriches the soil for

the plants by decaying swiftly.

Coconut husk is also utilized as a biofuel, as well as a source of charcoal.

Coconut husks are used to make carpets and home furnishings.

1.2. Production

The Philippines is regarded as the world's second largest producer of

coconut. One-third of the country's population is employed in the industry. In

2015, the country had 338 million coconut-bearing trees that produced an

average of 15.3 billion nuts each year.

The Philippines' Davao Region is the leading coconut producer,

accounting for 14.4 percent of the country's total coconut production in 2018. The

manufacturing of coconut goods generates a significant amount of waste in the

form of coconut husks. Around 85 percent of the husks from the nearly 50 billion

coconuts grown annually are tossed as trash, giving fuel to the fire that is global

pollution.

1.3. Elemental Composition

Table 2. Elemental Composition of Coconut Husk

CHEMICAL PROPERTIES
Silica 11-90%
Hemicellulose 17.74%
Ash 5.67%
Cellulose 26.60%
Lignin 41.18%

Source: Zarib, N. A., et al. (2020)

 The amount of SiO2 in coconut husk ash (CHA) varies between 8 and 11

percent and can reach up to 90 percent after chemical treatment. Because

coconut husk contains a significant amount of lignin and cellulose, it has a high

calorific value of 18.62MJ/kg. According to Zarib, N. A., et al. (2020), coconut

husks are made up of cellulose, lignin, pyroligneous acid, gas, charcoal, tar,

tannin, and potassium.

2. Cogon Grass

Cogon grass (Imperata cylindrica), also known as Japanese blood grass or blady

grass, "talahib" in Tagalog and "palat" in Kapampangan, is a common sight in the

Philippines. This grass, which has stiff stalks and saw-toothed leaves, quickly takes over

any area. Cogongrass is regarded as one of the world's 10 most annoying and

problematic weedy species. It is a tenacious grass that is tough to eradicate. It is a

perennial grass that grows in temperate and tropical areas of the Old World. Cogon

grass is a major weed in South Africa and Australia's agricultural regions, and it is

considered an invasive species in many areas outside of its natural habitat. The plant is

extensively used for erosion control and certain varieties are planted as ornamentals.
 Figure 2: Image of Cogon Grass

Source : Virginia Invasive Species, n.d.

Table 3. Physical Properties of Cogon Grass

PHYSICAL PROPERTIES
Color Green
Length 0.6–3 m (2–10 feet)
Tensile Strength 38.61 MPa
Oil Absorption 37.5%
Water Absorption 1.54% per 45 min

Source: Britannica (n.d.)

Cogon grass grows to a height of 0.6–3 meters (2–10 feet) and has roots that

can reach a length of more than one meter (3.3 feet). The long leaves have a sharp

point at the end and are covered in silica crystals. The upper leaf surface is often hairy at

the base, and the leaf margins are sharply toothed. The little wind-pollinated blooms are

borne in a narrow cluster with many long silky hairs on each spikelet.

2.1. Utilization
 Cogon grass is a traditional medicine that is used to treat nephritis, fever,

hypertension, dyspnea, epitaxy, as a hepatoprotector, and to reduce cholesterol

and blood glucose levels.

2.2. Elemental Composition

Cogon grass contains cellulose (37.13%), hemicellulose (27.13%) and

the lignin (5.67%). (Kassim,2015)

Table 4. Elemental Composition of Cogon Grass

CHEMICAL PROPERTIES
Cellulose 37.13%
Hemicellulose 27.13%
Ash 8.24%
Silica 2.9%
Lignin 5.67%

Source: Kassim (2015)

Research Literature

Based on the study by Silviana, S., et al. (2022) entitled, Synthesis of Silica-Cellulose

Aerogel Derived from Bagasse through Impregnation and Ambient Pressure Drying Methods as

Thermal Insulator, silica aerogel impregnated with cellulose aerogel can produce a material

with better characteristics than cellulose aerogel alone. The product created by silica

impregnation will have a noticeable improvement in transparency, as well as enhanced surface

area, flexibility, mechanical strength, and thermal conductivity. By using sustainable and

renewable resources, a low-energy manufacturing method, and the least amount of waste

production feasible, this development demonstrates the attempt to make thermal insulators that

are more ecologically friendly. With this process, silica-cellulose aerogel with exceptional

qualities will be produced, enabling the development of novel environmentally friendly material

technology.

The study by Dang, Y.T., et al. (2022), stated that coconut fibers (CFs), a byproduct of

the coconut industry, are successfully created to create a promising and cost-effective aerogel

for addressing environmental issues like color pollution or oil spillage. Coconut fibers (CFs) are

processed using the alkali-urea method and economically freeze-dried to create bio-based

aerogel. The environmentally friendly recycled aerogel has a high porosity (94.2–96.7%), a

Young's modulus of up to 176.6 kPa, and an ultra-low density (0.038–0.067 g/cm 3). It was

successfully manufactured using green solvents along with recovering used chemicals and

byproducts. A significant adsorption capacity of up to 46.9 mg/g for crystal violet (CV) with an

initial concentration of 200 ppm is also demonstrated by the aerogels as-fabricated.

Based on the study conducted by Norul, A. M. Z. and Syamim, S. S. (2022), agriculture

wastes, particularly ash containing silica, are excellent sources of silica for the synthesis of

synthetic amorphous silica. Coconut husk ash (CHA) was used as a raw material in this study to
generate silica. Coconut husk was burned in a controlled atmosphere inside a furnace at 900

°C. The produced ashes were subjected to two independent chemical processes in order to

remove silica. In the acid treatment, 5N H2SO4 was utilized, whereas in the alkali treatment,

2.5N NaOH was used followed by titration of 5N H2SO4. Fourier-transform infrared

spectroscopy (FTIR) was used to characterize the manufactured products. The FTIR analysis of

coconut husk ash revealed that the content of SiO2 increased following both chemical

treatments, particularly after the alkali treatment. The silica recovered from acid treatment

ranged from 25% to 68%, whereas alkali treatment yielded 76%.

The study conducted by Chen (2022) entitled “Effect of Silica Aerogel on Thermal

Insulation and Acoustic Absorption of Geopolymer Foam Composites: The Role of Aerogel

Particle Size” stated that the greater particle sizes in aerogels prove advantageous for acoustic

absorption and thermal insulation, whereas smaller particles exhibit diminished effectiveness in

terms of insulation properties.

Cogon grass (Imperata cylindrica), known as "talahib" in Tagalog and "palat" in

Kapampangan, is a pervasive and resilient grass in the Philippines. Recognized globally as one

of the top 10 troublesome weed species, it dominates with stiff stalks and saw-toothed leaves,

growing 0.6–3 meters tall. Its practical applications include roofing material and raw material for

various products.Cogon grass is used as roofing materials for nipa hut, handmade paper,

boxes, frames, notebooks, etc. (Pena, 2021). Designated as an "invasive species" by the

Philippine government, cogon grass disrupts agriculture with its rapid seed generation and

powerful root structure, choking valuable plants (PBworks, n.d.).

Chen, Y. X., et. al. (2021) said that in order to produce a silica-cellulose composite

aerogel, a silica aerogel synthesized from olivine silica rather than standard tetraethoxysilane or
water glass is used in a simple one-pot synthesis technique. Using the sol-gel technique and

freeze drying, silica aerogel nanoparticles are produced inside cellulose nanofibrils.

The group of Husain, F. M. (2021), stated that aerogels are a distinct family of materials

with remarkable features such as low bulk density, high porosity, heat resistance, very high

specific surface area, low dielectric constant, and low refractive index. Synthetic polymer-based

aerogels are unsuitable for application due to their low biodegradability, toxic precursors, and

hazardous breakdown products. The emphasis has shifted to the production of aerogels from

biological materials. Bio-aerogels have been created using polysaccharides, proteins, and

polymers produced from biomass. Aerogel biological synthesis is beneficial since these

materials are biodegradable, biocompatible, plentiful in nature, and contain no harmful

components, making them an excellent contender for a variety of biomedical and environmental

applications.

Sago pith cellulose nanofibril (SPCNF) aerogel was effectively made from sago pith

waste (SPW) in three steps: dewaxing and delignification, ultra-sonication and homogenization,

and freeze drying. Field emission scanning electron microscopy (FE-SEM), Fourier transform

infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA)

were used to analyze the aerogel. The SPCNF aerogel, with a density of 2.1 mg/cm3, was

effective in the removal of methylene blue (MB), with a maximum MB adsorption of 222.2 mg/g

at 20 °C. The adsorption of MB onto the SPCNF aerogel is said to be efficient and to follow a

pseudo-second-order kinetic model, with the adsorption isotherm agreeing with the Langmuir

model. The SPCNF aerogel demonstrated exceptional MB removal efficacies, with 5 mg and 20

mg of SPCNF capable of removing over 90% and almost 99% MB respectively as stated by

Beh, J. H., et al. (2020).

 In the study conducted by Liao et al. (2020), it stated that using a unique solution-freeze-

drying technique, the ultra-low density AlCl3-chitosan composite aerogel was created. After that,

the chitosan template was removed from the AlCl3-chitosan aerogel by carbonization or

calcination, producing ultra-low density Al2O3-based aerogel with good forming ability. Using

this technique, the density of the Al2O3-based aerogels was around 9 mg/cm3. The density of

the aerogels investigated in the present study was observed to be comparatively lower than that

of nanofibrillated cellulose aerogel, as reported by Gupta et al. (2019), which exhibited a density

of 0.0233 g/cm³.

The study was investigated by Swanger, A. and Fesmire, J. E. (2020), entitled

“Cryogenic Flux Capacitor for Advanced Molecular and Energy Storage Applications”. In their

research, liquid oxygen boil-off calorimetry testing was employed to determine the total charging

heat for the aerogel specimen. Furthermore, in the study from Tang, et al. (2019), which is

entitled, “Synthesis of Lightweight, High-strength Biomass-derived Composite Aerogels with

Low Thermal Conductivities”. In their study, a water-absorption test was conducted to determine

the water absorption capacity of the composite aerogels.

Based on the study conducted by Lakatos, Á., et. al. (2019) entitled, Effects of the heat

treatment in the properties of fibrous aerogel thermal insulation, which focused on the thermal

annealing that causes changes in both the thermal performance and the material structure of

the aerogel blanket. The specific heat capacity was evaluated using differential scanning

calorimetry (DSC) with sapphire as the calibrant in accordance with DIN 51007. DSC was

performed with Mettler Toledo DSC 822e (Greifensee, Switzerland) equipment. The studies

were carried out in an air environment with a flow rate of 50 mL/min at temperatures ranging

from 25 °C to 300 °C. The heating rate was 10 °C/min, and the isothermal regime (5 minutes)

was used before and after linear heating. The sample mass was approximately 9 mg, and

aluminum crucibles (volume of 40 mm3) with covers were utilized.

 In the study of Abiaziem et al. (2019) entitled “Preparation and Characterisation of

Cellulose Nanocrystal from Sugarcane Peels by XRD, SEM, and CP/MAS 13 C NMR”, the

advantages of achieving a heightened crystallinity index exceeding 70% include a significant

enhancement in resistance to bacteria, as well as improved chemical and thermal stability.

Furthermore, the crystallinity of the cellulose nanocrystals can range between 50% to 90%.

According to Gopi et al. (2018) conducted a study titled “Applications of Cellulose

nanofibrils in drug delivery”, the study stated that one of the most renowned and practical

characteristics of aerogel is its extraordinary lightweight nature. It usually exhibits a density

ranging from 0.0011 to 0.5 g/cm³, with an average around 0.020 g/cm³.

According to Long, L.-Y., Weng, Y.-X., & Wang, Y.-Z. (2018), silica aerogels are

extraordinary substances with exceptional physiochemical characteristics, including high

surface area and porosity, low density, and heat conductivity. They do, however, exhibit several

drawbacks, such as poor dimensional stability at high temperatures (over 600 °C) and limited

mechanical strength. Although these aerogels are often utilized as thermal insulators, several of

their features need to be enhanced for high temperature conditions. Meanwhile, cellulose

aerogels offer outstanding qualities including low density, high porosity, and a high specific

surface area in addition to the cellulose’s ecologically beneficial renewability, biocompatibility,

and biodegradability. In addition to numerous other uses, cellulose aerogels are particularly well

suited for the adsorption and separation of biomedical and thermal insulation components.

Regarding the development and modification of cellulose aerogels, there are still certain

problems. The price of nanocellulose and bacterial cellulose is expensive, and during the drying

process, nanocellulose is prone to self-agglomeration. Additionally, while creating regenerated

cellulose aerogels, it is challenging to recover cellulose solvents and the solvent exchange

procedure is sometimes quite time-consuming. Second, certain ways of modifying cellulose

aerogels, such modifying them with a silane coupling agent, are intricate and expensive.
 The group of Anuar, M. F. (2018) conducted a study that states waste coconut husk was

investigated as a potential raw material for silica synthesis. Coconut husk was burnt in a

controlled setting inside an electrical furnace at temperatures of 500, 600, and 700 degrees

Celsius. To recover the largest proportion of silica from these ashes, two distinct chemical

processes were used. The amount of SiO2 in coconut husk ash (CHA) fluctuates between 8 and

11% and increases up to 90% following chemical treatment, according to XRF studies.

According to the XRD spectrum, the silica produced was crystalline after acid treatment but

amorphous following alkali treatment. The CHA morphology was reported to have rod-like

structure on FESEM images but changed to irregular forms and began to agglomerate together

following the chemical treatments. The EDX results correspond well with the XRF data since the

same elements were found in both analyses. CHA can be used as an alternative source of high

pure silica, which has a strong potential in optoelectronic applications. For extraction, the

coconut husk acquired from local markets was cleaned and dried in an electrical oven at 120 °C

to eliminate the majority of the contaminants and moisture. To avoid further pollutants and

moisture from the surrounding environment, the fibers of coconut husk were removed from the

outer layer of the coconut and placed in a drying box. To obtain CHA, clean coconut fibers were

put in an alumina crucible and heated for 2 hours at temperatures of 500, 600, and 700 °C in an

electrical furnace at a continuous heating rate of 10 °C/min. Meanwhile, for acid treatment, in a

beaker, 20 mL of 5 N sulphuric acid was mixed with CHA. The solution was heated to 50 °C and

constantly swirled for 1 hour with a hotplate magnetic stirrer. The solution was filtered after the

leaching process, and the residue was washed many times with distilled water to eliminate the

excess acid content in the ash. The ash residue was oven dried for 2 hours at 70 °C to produce

white powdered silica. On the other hand, for alkali treatment, after dissolving the silica in CHA

in 20 mL of 2.5 N NaOH, the solution was heated at 100 °C for 1 hour with continual stirring to

generate sodium silicate. The solution was filtered using Whatman No. 41 ashless filter paper.

The filtrate was allowed to cool before being properly titrated with 5 N of H2SO4 while stirring
constantly. When the pH fell below 10, silica gel began to precipitate. The resultant wet white

precipitate was washed several times with deionized water and filtered to eliminate excess

sulphate impurities. To get amorphous silica, the white precipitate was dried in an electrical

oven.

According to the study by Das et al. (2018), cellulose fibers were successfully extracted

from Musa sapientum and subjected to different treatments. Then, the obtained cellulose

materials were characterized for better understanding their structure. The XRD spectra

contained peaks at 2θ ~14.9°, 16.7°, 22.6° and 34.9°, corresponding to the (1 0), (110), (200)

and (004) crystallographic planes, respectively. This study stated the level of crystallinity of

cellulose derived from BFR (52.24%), BFS (62.94%), BFB (71.54%), and BFA (83.33%).

Feng, J., et al. (2016), cited that silica-cellulose aerogels were successfully created

using recycled cellulose fibers and methoxytrimethylsilane silica precursor. The thermal

conductivity was 0.04 W/mK. Furthermore, the cellulose component of silica-cellulose aerogels

demonstrated a 25°C improvement in thermal degradation temperature over cellulose aerogels.

The sound absorption coefficients of silica cellulose aerogels with a thickness of 10 mm were

higher than those cellulose aerogels and commercial polystyrene foams. This study describes a

facile approach for producing silica cellulose aerogels with industrial dimensions for thermal and

acoustic insulation applications.

Derived from coconut exteriors, the versatile coconut husk is a vital resource with

diverse applications. Beyond being the foundation for potting material crucial for plant growth, it

serves as an eco-friendly solution in greenhouse production. Recognized for its nutrient-

absorbing capability, rapid decomposition, and soil-enriching qualities, the husk varies in

grades, demanding quality evaluation. Its utility extends to biofuel, charcoal production, and as a

material for manufacturing household items. Despite the Philippines' substantial coconut
production of 14.69 billion nuts annually, the underutilization of husks, often discarded as farm

trash, signifies untapped potential in contrast to the modest projected use of 334 tons per day

(PCA, 2015).

The study by Kow, K. W. (2014), stated that silica aerogel has a high potential for usage

as a thermal insulator due to its exceptionally low thermal conductivity. Furthermore, pure silica

aerogel absorbs less infrared radiation at three to eight μm, resulting in an increase in thermal

conductivity at high temperatures. Carbon is widely employed as an opacifier in silica aerogel to

absorb radiation and hence reduce aerogel thermal conductivity. However, a separate carbon

supply is necessary for aerogel opacification. Bamboo leaves and cogon grass, for example,

contain both silica and carbon. They may supply both sources for the production of carbon-

opacified silica aerogel (COSA). The utilization of biomass in the synthesis of COSA may

decrease not only the cost of costly materials, but also agricultural waste. The secondary

gelation approach was used to effectively construct composite aerogel beads with

pomegranate-like structure made of hydrophobic silica aerogel powder, PVA and agarose. The

concentration of PVA solution was critical to the integrity of the silica aerogel skeleton, and a

concentration of 4wt% to 8wt% maintained outstanding integrity. The difference in wettability

between the composite aerogel beads interior and exteriors aided in preserving the superiority

of aerogel materials while boosting the hydrophilicity of the composite aerogel beads exteriors.

The composite aerogel beads' unusual wettability boosted the adhesive qualities of water-based

thermal insulation coating with composite aerogel beads (WTICC) by about 110 KPa when

compared to water-based thermal insulation coating with native hydrophobic silica aerogel

powder (WTICN). Furthermore, as compared to silica aerogel beads, the compressive fracture

force of the composite aerogel beads was substantially higher. As a result of the superior

adhesive characteristics and great toughness, the WTICC has good mechanical properties.

Furthermore, WTICC performed much better in terms of thermal insulation than pure putty
blocks of the same thickness. This pomegranate-like structure broadened aerogel’s applicability

in thermal insulation and energy saving in buildings.

The study conducted by Demilecamps, A., et al. (2014) states that, cellulose-silica

composite aerogels were created using a “one-pot” method in which aqueous solutions of 60%

cellulose-8% NaOH and 40% sodium silicate were combined, coagulated, and dried in

supercritical CO2. At various temperatures and concentrations, cellulose and sodium silicate

solutions were combined and the mixture characteristics were evaluated using dynamic

rheology.

According to the study by Jian, L., et al. (2014) entitled, Fabrication of cellulose aerogel

from wheat straw with strong absorptive capacity, it deals with a moderate solvent solution

comprising NaOH/PEGto dissolve the cellulose isolated from the wheat straw. The cellulose

aerogel was successfully created by a combination regeneration procedure and freeze drying.

The resulting cellulose hydrogel samples were freeze-dried for 48 hours at -30 °C.

According to Lin, Y. S. and Lee, W. C. (2011), the commercial cellulase Accellerase

1500 and Ethanol Red dry yeast were used to optimize the simultaneous saccharification and

fermentation (SSF) of alkaline pretreated cogon grass to ethanol. Cogon grass was processed

with 10% (wt) NaOH for 24 hours at room temperature, resulting in an increase in cellulose

percentage from 38.5% to 60.5%. Each SSF of alkali-pretreated cogon grass was performed

with 1g/L of dry yeast loading at pH 5.0 and 150 rpm shaking. Pre-cut-air-dried cogon grass

sticks of ca. 2cm in length. Cogon grass sticks were pretreated with 10% (wt) NaOH in a solid-

to-liquid ratio of 1:20(w/v) at room temperature for one day before being rinsed with tap water

until the pH reached neutral. The prepared cogon grass was kept in sealed plastic bags at 4 °C.

The dried weight of pretreatment cogon grass was determined by drying it in a vacuum oven at

105 °C for 3 hours. A Hitachi-S2400 SEM-EDX microscope was used to capture scanning
electron microscopy (SEM) micrographs of cross-sections of cogon grass before and after

pretreatment.

According to the study led by Fan, A., et al. (2020), regarding the developed crosslinked

polyimide aerogels with silicon dioxide nanoparticles, essential for achieving high thermal

insulation performance and mechanical durability in thermal insulation materials. It was revealed

that the material showcases favorable thermal insulation characteristics across an extensive

temperature range spanning from 20 °C to 300 °C.

Synthesis

With the above mentioned literature there is a need to conduct studies on the evaluation

of aerogels that will help in heat reduction. With this, the researchers want to conduct a study

about the evaluation of cellulose-silica based aerogel from cogon grass and coconut husk as a

thermal insulating material. The following paragraphs show the similarities and differences of

the past studies on the present study of the researchers.

First, research carried out by Norul, A. M. Z. and Syamim, S. S. (2022) titled “The

Preparation and Characterization of Silica from Coconut Husk” involved subjecting coconut husk

to acid treatment. The present researchers used the same pretreatment method used in this

study for extracting silica from coconut husk.

Furthermore, the study conducted by Chen (2022) about the effect of silica aerogel from

geopolymer foam composites on thermal insulation and acoustic absorption, particularly

focusing on the particle size of an aerogel. This study shares similarities with the current study

as both assess the efficacy of utilizing aerogel as a thermal insulating material. The present

researchers specifically examined the particle size of the cellulose-silica based aerogel, given

its demonstrated advantages in terms of insulation properties.

 Dang, Y. T., et al. (2022), highlighted that coconut fibers can be effectively utilized to

produce a promising and cost-efficient aerogel aimed at addressing environmental concerns

such as color pollution or oil spillage. The fibers are processed through the alkali-urea method

and then economically freeze dried to produce bio-based aerogels. These aerogels were

employed for oil spill remediation, whereas the current study focuses on their application as

thermal insulation. This study shares similarities with the present research as both utilize

coconut husks to produce aerogel, and both employ freeze drying methods to create bio-based

aerogel. However, they differ in the pretreatment method, with Dang using alkali-urea method

while the current study employs acid treatment.

The group of Chen, Y. X., et al. (2021) conducted a study about one-pot synthesis of

monolithic silica-cellulose aerogel, utilizing a sustainable sodium silicate precursor, employed

methodologies such as sol-gel method, one-pot synthesis, and freeze drying method in

incorporating cellulose and silica which has the same approach as the present study. However,

these studies differ in the materials utilized wherein Chen’s study employed olivine silica, while

the present study extracted silica from coconut husk using acid treatment. Similar to the study

conducted by the group of Liao (2020) who also used a freeze drying method to generate

aluminum chloride based aerogel.

In addition to that, Husain, F. M., and others (2021) said that aerogels represent a

distinct category of materials with remarkable characteristics including low bulk density, high

porosity, heat resistance, very high specific surface area, low dielectric constant, and low

refractive index. Consequently, the present researchers employed density, particle size,

porosity, and thermal stability to evaluate the properties of the aerogel, enabling them to

ascertain whether the produced samples meet the criteria for classification as aerogels.
 Also, the research study conducted by Beh, J. H., et al. (2020), entitled “Cellulose

Nanofibril-Based Aerogel Derived from Sago Pith Waste and its Application on Methylene Blue

Removal,” utilized an Agilent Cary 640 Fourier-Transform Infrared (FTIR) Spectrometer to

identify the main functional groups in sago pith waste and sago pith cellulose nanofibril. The

morphologies of the sago pith cellulose nanofibril aerogel were investigated and characterized

using a Hitachi SU8020 Field Emission Scanning Electron Microscope. Additionally,

Thermogravimetric Analysis was conducted using a Perkin Elmer TGA4000 thermogravimetric

analyzer to assess the thermal stability of the aerogel. Similarly, the present study employed

Thermogravimetric Analysis to evaluate the thermal stability of the produced cellulose-silica

based aerogel. However, the present researchers utilized Scanning Electron Microscopy and

Energy Dispersive X-ray Spectroscopy to determine the elemental composition of the pretreated

coconut husk as well as X-ray Diffraction Analysis to determine the presence of cellulose in the

pretreated cogon grass.

The research conducted by Silviana, S., et al. (2020), entitled, “Synthesis of Silica-

Cellulose Aerogel Derived from Bagasse through Impregnation and Ambient Pressure Drying

Method as Thermal Insulator,” explored the utilization of silica and cellulose aerogel to produce

a material with greater qualities. This research shares similarities with the present study, as both

involve the incorporation of cellulose and silica to develop cellulose-silica based aerogels, which

are utilized for thermal insulation purposes. However, the past study used Bagasse as the raw

material, while the present study used cogon grass and coconut husk as sources of cellulose

and silica. Additionally, Silviana’s study utilized ambient pressure drying, while the current study

used freeze drying.

The study conducted by Thai et al. (2020) is similar to the present study since both of

the produced aerogels will be used as thermal insulation. But the studies differ because the past

study used sugarcane bagasse to make biodegradable aerogel while the present researchers
will use cogon grass and coconut husk. Also, the produced aerogel from the past study can be

used in oil clean up in the marine environment. Besides, the past study used polyvinyl alcohol

(PVA) binder while the current study uses a sol-gel method followed by freeze drying to

generate aerogel. On the other hand, in order to generate aerogel, the current study will be

using a sol-gel process by adding NaOH to extract cellulose from cogon grass while in an

attempt to extract the silica from coconut husk, acid treatment will be used. Then, the extracted

cellulose and silica will be mixed together using the process called one-pot synthesis. After that,

freeze frying will be used to remove all the excess moisture.

The application used in this study was adapted from Swanger, A. and Fesmire, J. E.

(2020), entitled “Cryogenic Flux Capacitor for Advanced Molecular and Energy Storage

Applications”. In their research, liquid oxygen boil-off calorimetry testing was employed to

determine the total charging heat for the aerogel specimen. Meanwhile, in this study, the

researchers utilized boiling water and maintaining its temperature at 100 °C which is positioned

beneath the sample, exposing it to the steam for 20 minutes. Through this, the researchers

were able to identify the temperature that the samples absorbed.

The application used in this study was derived from Tang, et al. (2019), which is entitled,

“Synthesis of Lightweight, High-strength Biomass-derived Composite Aerogels with Low

Thermal Conductivities”. In their study, a water-absorption test was conducted to determine the

water absorption capacity of the composite aerogels. On the other hand, in this study, the

approach involved immersing the samples in water for 30 minutes and measuring their weight to

determine the extent of water absorption by the samples.

Furthermore, the study conducted by a group of Lakatos, Á. (2019) entitled, Effects of

the heat treatment in the properties of fibrous aerogel thermal insulation, was modified in the

current study specifically the use of differential scanning calorimetry. This method will be used
to determine the thermal transitions of an aerogel. This will be done by using the temperature

range of 25 °C up to 300 °C in an air environment with a flow rate of 50mL/min. The heating rate

was 10 °C/min, and the isothermal regime (5 minutes) was used before and after linear heating

The study by Feng, J., et al. (2016) is similar to the present study in a way that both

studies use cellulose and silica to produce aerogel. It differs because the created aerogel from

past study was used as acoustic insulation while the current study mainly focuses on thermal

insulation. Aside from thermal conductivity, other tests and procedures will be conducted.

Moreover, the study conducted by Jiao, Y., et al. (2014) is different from the current

study since they used bamboo fiber. Also, their study focused on the carbon fiber type of

aerogel, whereas the current researchers will use cogon grass and coconut husk as their

primary materials in making aerogel and they will be using cellulose-silica based aerogel.

Furthermore, the current study will use one-pot synthesis in order to synthesize cellulose

and silica which is adapted from the study of Demilecamps, A, et. al. (2014) entitled Cellulose-

silica composite aerogels from “one-pot” synthesis. As the previous study used the proportion of

60:40, the current study will use the proportion of 70:30, 50:50, 30:70 in one-pot synthesis in

order to test the effectiveness of the aerogel.

Besides, the study by Jian, L., et. al. (2014) entitled, Fabrication of cellulose aerogel

from wheat straw with strong absorptive capacity, was adapted in the present study which is

through the use of freeze drying method. The synthesized cellulose and silica will be freeze

dried at -30 °C for 48 hours.

In the study of Abiaziem, et al. (2019), entitled “Preparation and Characterization of

Cellulose Nanocrystal from Sugarcane Peels by VRD, SEM and CP/MAS 13 C NMR”, achieving

a crystallinity index exceeding 70% offers notable advantages, including heightened resistance

to bacteria and improved chemical and thermal stability. Additionally, the crystallinity of the
cellulose nanocrystals can vary between 50% to 90%, similar to the present study, where the

crystallinity index reached 86.39%, indicating promising and favorable thermal stability.

Additionally, in the study entitled “Applications of Cellulose Nanofibrils in Drug Delivery”

by Gopi, et al. (2018), stated that one of the most prominent and useful features of aerogel is its

exceptional lightweight nature. Typically, aerogels demonstrate a density ranging from 0.0011 to

0.5 g/cm3, with an average around 0.020 g/cm3. This research served as the reference for

determining acceptable density values to classify a material as an aerogel in the present study.

According to Long et al. (2018), silica aerogels possess remarkable physiochemical

attributes such as high surface area and porosity, low density, and heat conductivity.

Nevertheless, they are prone to certain drawbacks like poor dimensional stability at elevated

temperatures and limited mechanical strength. In contrast, cellulose aerogels offer exceptional

qualities including low density, high porosity, and a substantial specific surface area, alongside

the environmentally beneficial renewability, biocompatibility, and biodegradability of cellulose.

Besides numerous other applications, cellulose aerogels are particularly suitable for adsorption

and separation in biomedical and thermal insulation applications. With these properties, the

present researchers proposed the idea of incorporating cellulose and silica.

Anuar et al. (2018) conducted research exploring the utilization of waste coconut husk

as a potential source for silica synthesis. Coconut husk underwent controlled burning in an

electric furnace at temperatures of 500, 600, and 700 degrees Celsius. For acid treatment, 20

mL of 5 N sulphuric acid was combined with the charred husk ash (CHA) in a beaker. The

solution was heated to 50°C and continuously stirred for 1 hour using a hotplate magnetic

stirrer. After the leaching process, the solution was filtered, and the residue was washed

multiple times with distilled water to remove excess acid content. The ash residue was then

oven-dried at 70°C for 2 hours to obtain white powdered silica. The present researchers
adopted the pretreatment and acid treatment methods described in this study for extracting

silica from coconut husk.

In the research conducted by Das et al. (2018), cellulose fibers were successfully

isolated from Musa sapientum and subjected to various treatments. Subsequently, the extracted

cellulose materials underwent characterization to gain insight into their structure. The XRD

spectra exhibited peaks at 2θ ~14.9°, 16.7°, 22.6°, and 34.9°, corresponding to the (1 0), (110),

(200), and (004) crystallographic planes, respectively. This investigation reported the level of

crystallinity of cellulose derived from BFR (52.24%), BFS (62.94%), BFB (71.54%), and BFA

(83.33%). Similarly, in this study, the researchers utilized XRD analysis to identify the presence

of cellulose in cogon grass.

Also, according to Feng et al. (2016), silica-cellulose aerogels were successfully

fabricated using recycled cellulose fibers and methoxytrimethylsilane silica precursor. These

aerogels exhibited a thermal conductivity of 0.04 W/mK. Additionally, the cellulose component in

silica-cellulose aerogels showed a 25°C enhancement in thermal degradation temperature

compared to cellulose aerogels alone. Similar to the current study, it is evident that cellulose-

silica based aerogels displayed higher thermal stability compared to pure cellulose aerogels.

Furthermore, both types of aerogels were utilized for thermal insulation applications.

Although the Philippines boasts a significant coconut production of 14.69 billion nuts

annually, the neglect of coconut husks, typically discarded as agricultural waste, indicates

untapped potential, especially when compared to the relatively modest projected usage of 334

tons per day as reported by PCA (2015). In light of this, the current researchers opted to utilize

coconut husks as raw material, both to reduce coconut waste and due to its abundance as a

source of silica.
 Additionally, the study by Kow, K. W. (2014), stated that silica aerogel has a high

potential for usage as a thermal insulator due to its remarkably low thermal conductivity.

Furthermore, pure silica aerogel absorbs less infrared radiation at three to eight μm, which

contributes to an increase in thermal conductivity at high temperatures. Meanwhile, in the

present study both aerogels were used for thermal insulations.

Besides, according to Lin, Y. S. and Lee, W. C. (2011), the commercial cellulase

Accellerase 1500 and Ethanol Red dry yeast were used to optimize the simultaneous

saccharification and fermentation (SSF) of alkaline pretreated cogon grass to ethanol. Cogon

grass was processed with 10% (wt) NaOH for 24 hours at room temperature, resulting in an

increase in cellulose percentage from 38.5% to 60.5%. The current researchers utilized the

pretreatment and alkali treatment methods described in this study for extraction of cellulose

from cogon grass.

In the study conducted by Fan, A., et al. (2020), regarding the developed crosslinked

polyimide aerogels with silicon dioxide nanoparticles, essential for achieving high thermal

insulation performance and mechanical durability in thermal insulation materials. It was

demonstrated that the material exhibited favorable thermal insulation properties over a wide

temperature range extending from 20°C to 300°C.This study served as the basis for

establishing acceptable and favorable values for the thermal stability of aerogels in the present

research. The current study revealed that the thermal stability of the produced aerogels falls

within the specified range.