Accepted Manuscript

Title: Microcrystalline cellulose: isolation, characterization

and bio-composites application − A review

Author: Djalal Trache M. Hazwan Hussin Caryn Tan Hui

Chuin Sumiyyah Sabar M.R. Nurul Fazita Owolabi F.A.
Taiwo T.M. Hassan M.K.Mohamad Haafiz

PII: S0141-8130(16)31016-9
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2016.09.056
Reference: BIOMAC 6523

To appear in: International Journal of Biological Macromolecules

Received date: 27-7-2016

Revised date: 30-8-2016
Accepted date: 15-9-2016

Please cite this article as: Djalal Trache, M.Hazwan Hussin, Caryn Tan Hui Chuin,
Sumiyyah Sabar, M.R.Nurul Fazita, Owolabi F.A.Taiwo, T.M.Hassan, M.K.Mohamad
Haafiz, Microcrystalline cellulose: isolation, characterization and bio-composites
application − A review, International Journal of Biological Macromolecules
http://dx.doi.org/10.1016/j.ijbiomac.2016.09.056

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 Microcrystalline cellulose: isolation, characterization and bio-composites
application – A review
Djalal Trachea,*, M. Hazwan Hussinb, Caryn Tan Hui Chuinb, Sumiyyah Sabarc, M.R. Nurul Fazitad,
Owolabi F.A. Taiwod,e, T.M. Hassanc, M.K. Mohamad Haafizd
a
UER Chimie Appliquée, Ecole Militaire Polytechnique, BP 17, Bordj El-Bahri, Algiers, Algeria.

b
Lignocellulosic Research Group, School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden,
Penang, Malaysia.
c
School of Distance Education, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia.
d
School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia.
e
Federal Institute of Industrial Research, Oshodi, Nigeria.

*
Corresponding author. Address: UER Chimie Appliquée, Ecole Militaire Polytechnique, P.O Box 17, Bordj El-
Bahri, Algiers, Algeria. Tel: +213 661808275, Fax: +213 21863204
E-mail Address: [email protected]

1 
 
Graphical abstract

2 
 
Highlights

 This work provides an up-to date review on methods for isolation and characterization
of microcrystalline cellulose (MCC).
 Interest for MCC is exponentially increasing.
 New sources, new isolation processes, new treatments induce new types of MCC
materials for industrialization.
 Opportunities of MCC-based composite polymers for the future are presented and
discussed.

Abstract:

Considering its widespread usage in various fields, such as food, pharmaceutical, medical,

cosmetic and polymer composites industries, microcrystalline cellulose (MCC) is becoming

impellent due to increasing demand of alternatives to non-renewable and scarce fossil

materials. Although it still suffers from some drawbacks, MCC has recently gained more

interest owing to its renewability, non-toxicity, economic value, biodegradability, high

mechanical properties, high surface area and biocompatibility. New sources, new isolation

processes, and new treatments are currently under development to satisfy the increasing

demand of producing new types of MCC-based materials on an industrial scale. Therefore,

this review assembles the current knowledge on the isolation of MCC from different sources

using various procedures, its characterization, and its application in bio-composites.

Challenges and future opportunities of MCC-based composites are discussed as well as

obstacles remaining for their extensive uses.

Keywords: Microcrystalline cellulose, Isolation, Characterization, Bio-composite

   

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1. Introduction

Different kinds of materials play a prominent role in the modern civilization. Among

others, polymer-based materials are usually used in various industries related to chemical

equipment, electrical and electronics equipment, automotive, spacecraft, medical, energy

storage in batteries and supercapacitors [1-4]. These polymeric materials have superseded and

substituted the utilization of the traditional ones such as ceramics, glasses and metals in

several fields due to their low cost, availability, low weight, chemical inertness, strength, and

ease of processing [5, 6]. These polymers allow the broad development of various types of

materials such as plastics, elastomers, artificial fibers, and composites. However, the

depletion of fossil resources coupled with the increase in environmental awareness and health

concerns are acting synergistically in providing the impetus for emerging products and

materials that satisfy the environmental concerns and independence of petrochemical

resources [2, 3, 7, 8]. Consequently, the principles of sustainability, eco-efficiency, industrial

ecology, green chemistry and engineering are being introduced into the development of next

generation products, materials, and processes.

During the past two decades, more attention was being given in the usage of bio-based

materials that can prevent the widespread dependence on fossil fuels [1, 4, 9-13].

Environmental friendly shelter is expected to enhance considerably; it necessitates the seeking

of some new alternatives for sustainability by exploring the widely available natural

resources. Thus, there exists a growing interest in bio-composites research to reduce the

amounts of synthetic petroleum-based composites since most petroleum-based polymeric

composites are non-biodegradable. It often takes many years, even centuries, for nature to

degrade these materials. Bio-based polymer composites are of particular interest. The

improvement in mechanical features of bio-composites is a key prerequisite to enhance the

potential of their uses in several applications. Recently, the tailoring of physicochemical and

4 
 
mechanical properties of such composites has been proven to be dependent on their intrinsic

characteristics, the spatial arrangement of phases and interface behavior [1, 6, 9, 14-16]. They

can be constituted by biopolymer matrix embedded with fibers whose origins can be found

either as natural minerals or as renewable plant raw materials. Advantages of natural fibers

over artificial ones like aramid, carbon, and glass, are as follows: renewability,

biodegradability, low cost, low density and good mechanical properties.

Mankind has employed cellulose for thousands of years as an important material for

hosing and clothing. In contrast with the uses of natural cellulose, the application of this

biopolymer as a chemical feedstock started just 170 years ago with the discovery of the first

cellulose derivative by Braconnot [4, 17], but subsequently developed into a production

volume of more than 5 million tons per year during this century . As reported by Berglund

[18], Boldizar et al. were the first to show that cellulose could be used as a reinforcement for a

polymeric material [19]. A prominent class of cellulosic reinforcing agent is microcrystalline

cellulose [7, 20-24]. MCC has been widely used especially in cosmetic, food, suspension

stabilizer, defense and medical industries.

Microcrystalline cellulose bio-composites are now emerging as a realistic alternative to

other polymeric composites [20, 21, 23, 25-30]. Ecofriendly bio-composites have the potential

to be new products of the current century and partial remediation of several environmental

problems. Engineered bio-composites using MCC reinforcement are currently being

developed to meet the diverse needs for eco-friendly and economical commodity products

with high performance, durability and fully sustainable technology. The next generation of

bio-composites requires the manufacture of products and materials that far exceed current

expectations. Whether it is for automotive, medicine, building, marine, or aerospace, such

materials must possess advanced performances, lower cost, reliable and adaptable properties.

5 
 
 Due to their eco-friendly benefits, MCC products are now easily found throughout the

life cycle (Fig. 1). The isolation of MCC fibers and their application in composite materials

have drawn much attention due to their high mechanical strength and stiffness combined with

renewability, biodegradability and low weight, as it is evidenced by the increasing number of

scientific reports published in the last two decades. This is due to a number of unique

characteristics and properties of MCC which include renewability, non-toxicity,

biodegradability, high mechanical properties, large surface area, low density,

biocompatibility, etc. Fig.2 reveals that such investigations on MCC are on the rise with an

increasing number of scientifically published articles on MCC-based composites. However,

the number of articles is still modest with respect to publications dealing with other organic

and inorganic fillers. The limited application of MCC fibers to date may be partly due to their

separation processes from natural sources and the inherent incompatibility and dispersibity

between the hydrophilic and highly polar cellulose fibers and the hydrophobic and non-polar

polymer matrix [20, 21, 23, 26, 28-30].

Compared to other natural polysaccharide polymers, MCC also suffers some drawbacks

that are desired for some applications, such as, poor wettability, moisture absorption,

incompatibility with most polymeric matrices and limitation in processing temperature. Thus,

various solutions have been suggested in literature in overcoming these disadvantages [20, 21,

25-27, 29, 31]. However, no comprehensive review is available yet regarding the different

methods used to isolate MCC particles and their application in bio-composites. This present

review article revises and discusses the different procedures employed to extract MCC from

different sources, as well as the production of MCC-based composites and their current

applications.

6 
 
2. Cellulose

Cellulose, the ubiquitous renewable natural biopolymer on Earth, is considered to be

one of the most important organic compounds produced in the biosphere. It is biosynthesized

by a number of living organisms ranging from lower to higher plants, sea animals, bacteria

and fungi [3, 4, 14, 32-35]. It is regarded as an inexhaustible source of feedstock for the

increasing demand for biocompatible and environmental friendly materials and products,

since it is regularly regenerated by nature in relatively short periods of time where the annual

fabrication is estimated to be over 7.5 x 1010 tons [14, 36, 37]. A number of reviews and

books have been already been published which reports the state of knowledge of this

fascinating polymer. Therefore only some important details are presented to avoid duplication

and the cellulose present in nature is graphically illustrated in Fig. 3 [1, 4, 14, 33, 35-39].

Cellulose can be effectively obtained from a top-down approach, in which wood, cotton,

annual plant or other agricultural residue can be used to produce a desired size of cellulose, or

from a bottom-up approach, where cellulose is biosynthesized from glucose using bacteria

(eg. Acetobacter Xylinam). The amounts and the properties of cellulose depend on the

extraction process, the origin and the lifetime of the natural source. Commonly, these sources

are composed of cellulose, hemicellulose, lignin, extractives and trace elements. In their cell

walls, the spirally oriented cellulose plays the role of reinforcements in the soft hemicellulose

and lignin matrix. An effective removal process of hemicellulose, lignin and other impurities

generates pure cellulose. As it is well known, cellulose is tasteless, hydrophobic, odorless,

chiral, renewable and biodegradable. It is insoluble in water and in most organic solvents,

which leads to a limitation in its reactivity and processability for utilization.

This biopolymer has gained a remarkable place in the annals of polymers. As early as

1839, the French Chemist Anselme Payen coined the name “cellulose” for a white powder

that he isolated from plant tissue [36, 37, 40, 41]. The chemical structure of cellulose was

7 
 
determined later, in 1920, by Hermann Staudinger [40, 42]. Nowadays, its outstanding

hierarchical structure no longer holds any secret; cellulose is a linear carbohydrate polymer

with long chains of β-(1→4)-linked D-anhydroglucopyranose moieties repeating units (Fig.4).

Since cellulose is made up of sugar monomers, it is called a polysaccharide. The size of

cellulose molecules is commonly conveyed as degree of polymerization (DP), which states

size in terms of the number of anhydroglucose units per cellulose chain. In nature, the DP of

cellulose chains ranges from 100 for MCC to 15,000 for native cotton in relation to their

isolation method [35, 38].

Each monomeric unit in the cellulose chain contains three carbons which are attached to

the hydroxyl groups: a primary C-6 atom in the methylol group (–CH2OH) and two secondary

carbons (C-2 and C-3) of the anhydroglucose unit [43]. The ability of these OH groups to

form hydrogen bonds plays an important role in controlling the physicochemical properties

and also directing the ultrastructure of cellulose. The cellulosic chains (20–300) are bundled

together to generate micro-fibrils, which are jointly grouped to form cellulose fibers. Each

polymeric chain is asymmetric, possessing two different end-units: a reducing and a non-

reducing end. The reducing end has carbonyl functionality, whereas the non-reducing end

features a supplementary OH group in position C-4. Hydrogen bonds within a cellulose chain

hinder the free rotation of the rings along their linked-glycosidic bonds, resulting in the

stiffening of the chain. However, the interchain hydrogen bonds and the van der Waals

interactions lead to the ordered (crystalline) or the disordered regions (amorphous) of the

cellulose structure. This biopolymer exists in different polymorphs, differing in unit cell

dimensions, in geometry, in chain orientation and polarity [35, 38, 44]. In nature, cellulose is

established in the crystalline form, cellulose I, which consists of a mixture of cellulose Iα

(triclinic structure) and Iβ (monoclinic structure). It can be transformed irreversibly into the

thermodynamically most stable cellulose II polymorph using a mercerization process (e.g.

8 
 
treatment with concentrated sodium hydroxide solution) or precipitated (regenerated) from

solution. Four other crystal polymorphs of cellulose (IIII, IIIII, IVI and IV), in addition to

cellulose I and cellulose II, can be produced by different treatments. Within the framework of

this review, only native cellulose I is considered. This semicrystalline fibrillar structure is the

main source of MCC and is responsible for the mechanical properties due to its high modulus

and crystallinity.

2.1. Microcrystalline cellulose

MCC is a naturally occurring substance obtained from purified and partially

depolymerized cellulose. It is conventionally prepared by treating alpha cellulose with an

excessive amount of mineral acids. The microfibrils which make up the alpha cellulose

consist of paracrystalline and crystalline phases at nanometer range. The paracrystalline area

is an amorphous mass of cellulose chains whereas the crystalline regions comprise tight

bundles of microcrystals in a rigid linear arrangement. The crystalline regions are called

cellulose crystallites and they are formed by cellulose chains due to van der Waals

interactions and hydrogen bonding. The diameter of these crystallites is of the same order as

the diameter of the cellulose microfibrils [45]. The amorphous phase is readily hydrolyzed

when subjected to acid hydrolysis. This results in shorter and more crystalline fragments, i.e.

MCC. Consequently, the degree of polymerization of the cellulose chain is reduced with

almost no weight loss.

Interestingly, the discovery of MCC commenced from a failed experiment [46]. The

authors tried to employ a Waring Blender to break up hydrolyzed cellulose to smaller

particles in water. They thought the sharp blades of the Waring Blender would sliver off very

small fragments of the agglomerated microcrystals in the hydrolyzed cellulose, and the

obtained microcrystalline fragments would settle out of water. Instead, they obtained a stable

colloidal suspension, which is known commercially as Avicel [5]. MCC was first

9 
 
commercialized in 1962 under the name Avicel®, which is marketed by FMC Corporation.

Since then, an exponential number of researchers have focused their work on such material.

Industrial scale MCC is manufactured through hydrolysis of cotton and wood cellulose using

dilute mineral acids. MCC is characterized by a high degree of crystallinity, and the values

typically range between 55% and 80% [24].

MCC can be dried to a pure, fine-particle form for powdered grade or co-processed with

a water-soluble polymer to deliver a colloidal form (Fig. 5). It possesses the merits of

cellulose. It has a high potential to be used in several areas such as pharmaceutical, cosmetic,

food and polymer composites industries. In the powder form, it is employed, for instance as a

binder and filler in food, medical tablets, and particularly as reinforcement agent in the

development of polymer composites. In the colloidal form, MCC is utilized as a suspension

stabilizer, a water retainer, a viscosity regulator, and emulsifier in different pastes and creams.

Features like lightness, stiffness, strength, fibrous nature, non-toxicity, water insolubility,

crystallinity, biodegradability and renewability make MCC more attractive to be used in

miscellaneous industrial fields [7, 20-23, 47-50].

2.1.1. Microcrystalline cellulose sources

MCC is currently produced from a number of different cellulosic sources. Wood and

cotton are obviously the main industrial sources of cellulosic fibers, and are thus the most

important feedstock employed in the manufacture of MCC [45, 48, 51-53]. However,

competition among many areas such as furniture, pulp and paper industries, building products,

as well as the combustion of wood for energy and the employment of cotton for textile

industry, renders them challenging to provide all sectors with the required quantities of wood

and cotton at a suitable price. Besides that, wood and cotton are not available in many regions,

thus tuning its options to non-woody cellulose. Therefore, interest in other sources such as

herbaceous plants, grass, aquatic plants, agricultural crops and their by-products has

10 
 
extensively stimulated considerable interest. These non-woody plants usually comprise less

lignin than wood. Therefore, bleaching methods are less chemical and energy demanding.

The extraction of MCC from different sources is relevant since it dictates the overall

performance of MCC. It can be produced from any material that is high in cellulose. In

literature, we find that diverse sources are already being used to produce MCC. For example,

it can be extracted from groundnut shell, cereal straw [54, 55], bagasse and corn cob [56],

bamboo [57], sugar beet pulp [58], luffa cylindrical [53], orange mesocarps [59], jute [60],

rice and bean hulls [61], hemp stalks and rice husks [62], newsprint [52], oil palm biomass

[24], fodder grass [63], wastepaper [64], filter paper [65] and cotton waste [66]. Esparto grass

[67] and soybean hulls [47] have also been investigated as potential sources of MCC.

Bacterial cellulose (e.g. Gluconacetobacter xylinus) has been used as the starting material for

research on MCC production as well [68, 69]. Microcrystalline cellulose obtained from

various types of cellulose sources of miscellaneous provenance using various extraction

methods and conditions commonly differ in molecular weight, particle size, crystallinity,

surface area, moisture content, porous structure, etc.

2.1.2. Microcrystalline cellulose isolations techniques

The amount of cellulose in different natural sources can vary depending on the species

and age of the plant. In nature, lignocellulosic is a bio-composite which results from a

combination between nanoscale domains of cellulose, hemicellulose, lignin and extractives.

Table 1 shows the chemical composition of some common natural sources. From

technological point of view, lignin content evaluation is an important parameter to well

optimize the pretreatment process required to isolate a pure cellulose pulp. Indeed, lignin is

considered the hardest chemical compound to be eliminated from lignocellulosic materials.

However, there are various methods for the extraction of cellulose from plants using

chemical, physical, biological and combined processes [32, 70, 71]. These processes have

11 
 
often been employed as a pretreatment to facilitate the hydrolysis procedure for the

production of MCC.

The hydrolysis treatment is generally followed by neutralization, washing and drying

processes. Currently, the common manufacturing process is performed by spray-drying the

neutralized aqueous slurry obtained from the hydrolysis of cellulose procedure [72]. The main

commercial grades are achieved by controlling the drying steps to well manage the particle

size distribution, the moisture content, binding ability, etc. Other drying methods may be

applied such as freeze-drying, fluidized bed, microwaves and classical oven drying followed

by mechanical grinding to recover the MCC particles [24, 67, 73].

Fig. 5 displays the different steps which are usually followed to produce MCC from its

feedstock using different procedures. For lignocellulosic materials, it involves firstly the

removal of lignin, hemicellulose, etc. and isolation of cellulosic fibers. Secondly, a controlled

hydrolysis treatment (generally acid hydrolysis) to remove the paracrystalline regions of the

cellulose polymer; and finally, post-treatments were performed to recover the final MCC

product. However, some authors had published methods using only one main step as it will be

explained later in the paper.

It is well known that the morphology, physicochemical properties and mechanical

characteristics of MCC exhibit variations according to the origin of the raw material and the

extraction process. Currently, MCC is a material available in the market with more than 60

years of history and the price of MCC (≈$4/kg), which is comparable to or less than some

other engineering should be fillers (glass or aramid) [74]. Over half a century later, MCC is

produced worldwide by more than 10 companies [48]. Several methods such as acid and

alkali hydrolysis,  steam explosion,  extrusion and radiation-enzymatic have been employed to

isolate highly purified MCC from plant cell walls. This section, therefore, describes in detail

the production of MCC processes based on the aforementioned techniques, including their

12 
 
advantages and disadvantages, as well as some important issues regarding the methods used

for the isolation processes.

2.1.2.1. Acid hydrolysis

Regarding the isolation of crystalline cellulosic region, in the form of MCC, a common

process widely used is based on acid hydrolysis because it requires shorter reaction time than

other processes. MCC can be produced by a continuous process rather than a batch-type

process and it uses limited amount of acid and produces small particles. Ranby [75],

considered as the pioneer in the cellulose hydrolysis process, produced stable suspensions of

colloidal-sized cellulose crystals by sulfuric acid hydrolysis of wood and cotton cellulose in

the early 1950s. The preparation of cellulose in microcrystalline form was first described in

several papers by Batistta and Smith of the American Viscose Corporation [46]. They had

isolated MCC fibers by controlled acid hydrolysis of cellulosic fibers to a level-off degree of

polymerization (LODP). The principle of their method was to pass dilute cellulosic pulp-

water suspension through a mechanical homogenizer, in which small fragments of the

agglomerated microcrystals were finally obtained.

Broadly, cellulose microfibrils are composed of crystalline regions and disordered or

paracrystalline domains located at the surface and along their main axis. Upon contact with

acidic solutions, the paracrystalline or amorphous regions are preferentially cleaved; whereas

the crystalline domains that have a higher resistance to acid attack remain essentially intact.

Fig. 6 illustrates the preferential action of the amorphous regions of cellulose microfibrils,

resulting in MCC fibers. It is worth mentioning that the diameter of these MCC fibers (which

usually varies from around 30 nm to 20 μm in diameter and up to hundred microns in length)

is widely determined by their source and the isolation process.

Numerous researchers had investigated the influence of processing conditions on the

physicochemical, thermal and mechanical properties. The temperature and time of hydrolysis

13 
 
procedure, nature and concentration of acid as well as the fiber-to-acid ratio play the

important roles in the particle size, morphology, crystallinity, thermal stability and

mechanical properties of MCC [61, 76, 77]. The acid hydrolysis processes with HCl and

H2SO4 from various cellulosic sources to produce MCC are tabulated in Table 2.

El-Sakhawy and Hassan isolated MCC from agricultural residues using HCl or H2SO4

and explored the effect of acid on the properties of the produced MCC [76]. They

demonstrated that the kind of acid used had no effect on both the crystallinity and crystallite

size. The dynamic laser light scattering particle size analyzer revealed that the nature of the

acid can affect the particle size of MCC depending on the natural sources used. Once the

hydrolysis is performed by H2SO4, the thermal analysis of bagasse-MCC exhibited good

thermal stability. In another work, based on the hydrolysis method with 1–2.5 M HCl at 105

°C, Leppänen et al. produced MCC from cotton, flux and various wood species (hardwood

and softwood) using different pulping processes (kraft and sulfite) [45]. They indicated that

the MCC obtained had very similar nanostructures. The method of producing MCC from

bacterial cellulose was reported by De Oliveira et al. [69]. They used sulfuric acid at a reflux

system under constant stirring. The obtained degree of polymerization (DP) of MCC was 205

and the particles size was between 70–90 μm. Haafiz et al. produced MCC from oil palm

empty fruit bunch [24]. They isolated MCC using an acid hydrolysis method based on original

procedures described by Battista [46]. The hydrolyzed MCC demonstrated a compact

morphological structure and a rough surface with 87% crystallinity. Trache et al. achieved the

desired MCC fibers by applying an HCl hydrolysis method using esparto grass fibers as raw

material [67]. The resultant MCC was transformed into fine powder by grinding. The authors

described that the DP of MCC was 318 and the crystallinity index was 81%.

Besides simple hydrolysis methods, other procedures were also explored to produce

MCC. Schaible and Sherwood reported the preparation of MCC from unbleached kraft pulp

14 
 
using one-step hydrolysis and bleaching process using a sufficient amount of active oxygen in

an acidic environment [78]. In their method, the pulp of southern pine was hydrolyzed

respectively with 2 N HCl and [2 N H2SO4 + 0.2 M ozone] at boiling temperature for 60

minutes; the product was filtered out and washed with hot water, then freeze-dried. The

authors mentioned that this method allows the preparation of MCC from a variety of pulp

grades and it can eliminate the need to perform multiple steps with respect to hydrolysis and

bleaching to achieve a satisfactory product. Such a method would ideally perform these two

processes in a one-step and would offer a high grade MCC product.

On the other hand, the isolation of MCC from different natural sources using the acid

hydrolysis method continues to progress in various research laboratories to further develop

and process MCC into functional and high-value added products. However, some drawbacks

such as the cost, amount of reagents, corrosivity hazards, and effluent treatment required to be

remediated eventually avoid the water pollution problems.

2.1.2.2. Alkali hydrolysis

Alkali treatment is the most commonly used method for delignification of

lignocellulosic materials [1, 5, 79]. This treatment is applied to disrupt the lignin structure and

to allow the separation of the structural linkages between lignin and carbohydrates. Therefore,

in order to overcome some problems caused by the use of acid hydrolysis process, some

authors utilized the alkali treatment to produce MCC. Trusovs mixed a cellulose source

material with an alkaline solution [79]. Once the material is completely swollen, hydrogen

peroxide was added to the mixing suspension to depolymerize the cellulose thereby reducing

viscosity. Finally, the solution was filtered, neutralized, washed and dried. The author

demonstrated that this process presented several advantages. This method does not involve

high temperature/high pressure applications and it leads to MCC in an economically efficient

manner utilizing readily available chemicals and cellulose source materials. Few years later,

15 
 
Nguyen reported the use of this alkali process jointly with an acidic treatment [80]. He

disclosed that this method employs less alkali and acid than previous processes and it is a

simple, economical and environmentally friendly process. However, it is important to note

that the employment of this process needs to be carefully controlled to avoid undesirable

cellulose degradation so that intact MCC can be isolated.

2.1.2.3. Steam explosion

The steam explosion treatment process has been and has always been widely

investigated as a promising mechanical pulping method [70, 81, 82]. It offers many attractive

features compared to other technologies: lower capital investment, lower environmental

impact, fewer hazardous process chemicals and conditions and more potential for energy

efficiency, etc. This process was invented by Mason in 1927 as a process to produce fibers for

board production. It was used for the first time by DeLong to produce MCC [83]. In his

experiment, he treated the lignocellulose raw material in steam in two steps, with the steam-

treated lignocellulose from the first step being extracted to recover a low degree of

polymerization cellulose which is then impregnated with strong mineral acid to obtain MCC

during the second steam treatment. Ha and Landi patented a very interesting process using an

only one-step steam explosion treatment process without the need for conventional acid

hydrolysis as a supplement to steam treatment [82]. In this case, MCC was obtained by a

process of introducing a cellulose source material into a pressurized reactor; subjecting the

cellulosic material to a steam explosion treatment under controlled conditions. Some authors

reported that the steam explosion allows the breakdown of lignocellulosic material

components by steam heating, shearing forces owing to the expansion of the moisture and

hydrolysis of glycosidic bonds by an organic acid formed during the process [81].

2.1.2.4. Extrusion

16 
 
 Extrusion technology is a short-duration, high-temperature hydrolysis method with the

advantages of high flexibility and nonexistence of effluents [47]. Very few investigations

have been reported concerning the production of MCC by extrusion methods. Extrusion

processing can provide a continuous reactor environment with a combination of thermo-

mechanical and chemical treatments for the cellulosic feedstock [84]. Therefore, this

technology could be applied to the extraction of cellulose from lignocellulosic materials,

utilizing a process with lower moisture content. Hanna et al. produced MCC particles by

reactive extrusion [58]. The raw material was fed through an extruder, which consisted of a

screw and a barrel, in the presence of a basic aqueous solution so as to break down the

lignocellulosic complex into lignin, hemicellulose and cellulose. The lignin and hemicellulose

were extracted and the residual cellulose underwent acid hydrolysis to form microcrystalline

cellulose. It was disclosed that this method can provide a quicker process in an efficient

manner and it does not require any mechanical grinding to produce small particles of MCC.

In another paper, Merci et al. reported the use of a simple procedure based on reactive

extrusion to produce MCC from soybean hulls [47]. The method was based on a two-step

extrusion process. The soybean hull was first extruded with sodium hydroxide, followed by

second extrusion with sulfuric acid. These authors revealed that the MCC manufactured by

this method composed of short and rod-shaped fibers, with a cellulose content of 83.79% and

a crystallinity index of 70%. This method was previously scaled up by Hanna et al. and they

reported that the reactive extrusion procedure is an environmental friendly process. However,

the application of this process to produce MCC has received little attention from the scientific

community.

2.1.2.5. Radiation-enzymatic

Finally, MCC can be also produced by a radiation-enzymatic process, but only few

fundamental investigations were dedicated to this procedure. Stupinska et al. utilized a

17 
 
bleached dissolving pulp isolated from mountain spruce using an environmental friendly,

effective two-step radiation-enzymatic depolymerization process [85]. In this method, the

irradiation of cellulose pulp was accomplished by employing an electron beam. The sample,

which was swollen in a chemical solution and washed, was subjected to the action of

enzymes. After washing and filtration, the MCC obtained was dried up at ambient

atmosphere. These authors demonstrated that the MCC obtained was characterized by a

degree of polymerization of 150 and a crystallinity index of 64%. However, as far as we

know, the enzymatic processes to produce MCC are more expensive to be economically

feasible for applications in practical use in one hand, and on the other hand they create MCC

products having lower crystallinity [58, 61].

3. Hydrolysis mechanisms for microcrystalline cellulose isolation

Mechanism is a detailed process of reaction that depicts chemical substances

transforming into another substances. It provides us a better understanding on the behavior of

atoms involved in the reaction process. During the transformation, some bonds or linkages are

broken and new ones are formed. Thus, this reaction mechanism may involve small series of

by-products such as atoms, molecules, electrons, free radicals, and electrons between

substances.

Cellulose contains β-1,4-glycosidic bonds which bind the D-anhydroglucopyranose

units into a long chain. Cellulose breaks down into glucose and reducing sugars

(oligosaccharides) without any enormous formation of dehydration products, for instance

levulinic acid as well as 5-hydroxymethylfurfural [86]. When cellulose is dissolved in acidic

solution such as HCl, cellulose becomes solubilized in the reaction medium. The H+ moves

towards the β-glycosidic bond while the Cl- weakens the glycosidic bond to facilitate

hydrolysis. When the glycosidic linkage breaks, the H-bonded structure of cellulose begins to

open. From this reaction, glucose and reducing sugar are produced with equal or higher yield

18 
 
[87]. Hydronium ions (H3O+) will be formed by protonation from the acid during glucose

degradation and hydrolysis of cellulose [88].

Kinetics show the in-depth reaction mechanism form as it deals with rates during the

chemical reactions [89]. Regarding kinetics, the hydrolysis of cellulose involved the

degradation of glucose and it was assumed to be pseudo-homogenous first order because of

the concentration of H3O+ which was initially reported by Saeman [90], and the reaction

below was adapted from Mosier et al. [88]:

Khyd Kdeg
C G HMF H2O LA FA

where C = cellulose, G = glucose, HMF = hydroxymethylfurfural, LA = levulinic acid, FA =

formic acid, khyd = kinetic constant of cellulose hydrolysis, and kdeg = kinetic constant of

glucose degradation.

From Fig. 7, the protonation of the glycosidic oxygen took place in pathway I whereas the

protonation of pyranic oxygen took place in pathway II. A partial protonation from both

oxygen atoms occurred during the conformational restriction of cellulosic chain along the

glycosidic bond. During acid hydrolysis, the formation of a carbocation via a unimolecular

step was one of the crucial steps as it could be either cycle in pathway I or pathway II formed

from the mechanism. Cyclic carbonation, where the hydrogen and hydroxyl groups were

omitted for clarity also occurred throughout the mechanism which changes the

tetrahydropyran ring [86].

The first scientific knowledge for acid hydrolysis of cellulose with sulfuric acid was

known as the Scholler process, which was discovered in the 1920s, while the Berglus process

referred to the usage of hydrochloric acid in the hydrolysis of cellulose [86]. Li and Zhao

reported that phosphoric acid was less effective for acid hydrolysis while nitric acid and

hydrochloric acid had similar behaviors towards sulfuric acid without pretreatment [87].

Strong acid had the potential in the protonation of glycosidic oxygen because of its lower pKa

19 
 
value compared to weak acid as glycosidic oxygen was a weak base [86, 88]. For a better acid

hydrolysis process, the strength of acidity portrayed a significant role.

4. Characterization of microcrystalline cellulose

In order to study the structure and properties of MCC various complementary techniques

have been employed by many researchers. Such analyses include FTIR, CP/MAS 13C NMR,

GPC, thermal analysis and electron microscopy techniques.

4.1. Fourier transform infrared spectroscopy (FTIR)

Infrared spectroscopy is a particularly powerful and reliable technique which is sensitive

and rapid as well as inexpensive that is used to study polymers [91]. Fourier transform

infrared spectroscopy is a measurement of the intensity and wavelength of the absorption of

IR radiation by a sample. In this modern era, Fourier transform infrared spectroscopy has

been used more in depth by monitoring the chemical structure and functional groups of

lignocellulosic compounds [67, 91, 92]. For instance, various applications for biological,

biochemical, and food industries are widely used in the mid-region at 4000-400 cm-1 where

the band absorption involves transitions between vibrational energy states and rotational

substrates of the molecule [91].

A broad absorption band will be observed at 3400–3500 cm-1 or 3000-3600 cm-1 in the

FTIR spectra, which indicates the presence of –OH stretching vibrations from α-cellulose

when the chemical structure of MCC is analyzed from different biomass such as rice hulls,

bean hulls, Alfa fibers, jute, cotton silver, oil palm empty fruit bunch, fodder grass, banana

fiber waste, groundnut shells, and corn cob [23, 52, 60, 61, 63, 93-97]. For example in Alfa

fibers [67], the peak located at 1512 cm-1 shows the presence of lignin. However, the alkaline

treatment breaks the glycosidic bond between lignin and other carbohydrate fractions, which

results in disruption of the lignin structure in cellulose (Alfa-C). Thus, the presence of more

crystalline order in the microcrystalline cellulose samples (from Alfa-MCC and C-MCC) can

20 
 
be observed at the peak from 2901 - 2905 cm-1. Absorption of water by cellulose displays an

absorption peak at 1639 cm-1 in Alfa-MCC while MCC in cotton silver, jute, rice hulls, and

bean hulls shows the water absorption peak at 1640 and 1645 cm-1 in oil palm empty fruit

bunch [23, 60, 67, 96, 98]. The occurrence of the absorption of water molecules is due to the

strong interaction between cellulose and water as well as the presence of small amounts of

hemicellulose [98, 99].

The absorption bands present at 1425 cm-1, 1430 cm-1, 1432 cm-1 and 1436 cm-1 are due

to intermolecular hydrogen attraction at C6 of the aromatic ring group which increase in the

microcrystalline cellulose sample in rice hulls, bean hulls, oil palm empty fruit bunch, and

Alfa-fibers, respectively [23, 61, 67, 96]. Various studies also revealed that the band between

1157 - 1164 cm-1 corresponds to –C-O-C- stretching of β-1,4-glycosidic linkage [24, 60, 61,

91, 92, 100-102]. C-H vibration of cellulose which corresponds to the β-glycosidic linkage

occurs at 895 - 901 cm-1 [23, 93, 94, 100].

4.2. Solid-state cross-polarization 13C nuclear magnetic resonance (CP/MAS 13C NMR)

Nuclear magnetic resonance (NMR) spectroscopy is used to measure the absorption of

radiofrequency radiation by atomic nuclei together with a nonzero spins in a strong magnetic

field [103]. NMR is a non-destructive method which is able to investigate the structural

behavior under solid phase and solution phase. Differentiation between molecules with

different mobility is allowed using this technique as it is sensitive in dynamics. Pulping

industries utilize NMR to study the final products from pulping processes as detailed

compositional information on the molecular structure of samples such as cellulose and lignin

can be obtained [104].

The peaks of carbon cellulose C1, C4, and C6 appear at the region between 60-105

ppm, which are around δ 102-108 ppm, δ 80-92 ppm, and δ 57-67 ppm, respectively. These

peaks are broad and overlap one another in the NMR spectrum as reported by several reviews

21 
 
[67, 105-107]. The peaks of carbon cellulose C2, C3, and C5 also appear within the region of

60-105 ppm in the spectrum, that is between 72-79 ppm [107]. The appearance of these peaks

within the spectrum of cellulose correspond to the accessible para-crystalline and amorphous

cellulose, as well as inaccessible fibril surfaces [105]. Sharper resonance at δ 86-92 ppm

results from the presence of C4 carbons in the crystalline regions as well as para-crystalline

domain, which is most commonly found in loblolly pine cellulose and MCC from bagasse,

Alfa fiber and cottonwood while the presence of the amorphous region corresponds to the

broad up-field resonance at 80-86 ppm. Thus, C4 carbons have both relative areas of

crystalline and amorphous resonance [67, 105-107].

4.3. Gel permeation chromatography (GPC)

Gel permeation chromatography is a technique that provides detailed information about

molecular weight distribution and relative molecular weight of the cellulose polymers [108].

Molecular weight of the cellulose polymer can be characterized by two types which are

number-average molecular weight (Mn) and weight-average molecular weight, (Mw). Apart

from that, polydispersity index (PDI) (Mw/Mn) is also important during the GPC analysis and

the separation relies on the size of the cellulose polymers.

Naturally occurring cellulose has a degree of polymerization of about 10 000, which

corresponds to a molecular weight of about 2 000 000 g mol-1. Depending on the method of

isolation, cellulose polymer appears to have an average degree of polymerization of 300–3000

and consequently has an average molecular weight of 50 000–500 000 g mol-1. During

hydrolysis process, due to chain breakage, the molecular weight of MCC decreases compared

to that of the original cellulose and this decrease ranges between 30 000 and 50 000 g mol-1.

The degree of polymerization is typically less than 400 [48]. The determination of the degree

of polymerization of cellulose is limited almost to two methods: viscometry and Gel

permeation chromatography. This latter is reputed to be an efficient technique with high

22 
 
reproducibility. This GPC method is usually used to characterize the derived cellulose

samples such as nitrocellulose or cellulose tricarbanilate [67].

During the derivation of cellulose sample, cellulose tricarbanilate (CTC) is obtained by

using phenyl isocyanate and tetrahydrofuran (THF), which act as an eluting agent in the GPC

system [67, 105, 109]. The possible number-average (DPn) and weight-average (DPw) are

calculated by dividing Mn and Mw by 519 which is the weight corresponded to the monomer

of CTC. Depolymerization of cellulose after acid treatment through the cleavage of glycosidic

linkage causes a decrease in the molecular weight (Table 3) of cellulose to MCC[67].

4.4. Thermal analysis

Both thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)

are commonly used to investigate the thermal and degradation properties of cellulose sample

[94, 110]. Generally, the TGA curves of MCC show two degradation stages, which indicate

the weight loss of the sample. The first stage corresponds to the removal of water within the

cellulose at the region between 60-140 °C. The second stage concerns the dehydration,

decarboxylation, depolymerization and decomposition of glycosyl units in cellulose followed

by the char residue formation in the range of 250-450 °C (Table 4). DSC analysis of MCC

indicates the presence of a common endothermic peak, which corresponds to the main

decomposition due to the volatilization of cellulose to levoglucosan and charring [67].

Compared to cellulose, MCC necessitates high energy to be degraded because of the high

degree of molecular ordering. The presence of crystalline region in MCC results in higher

residual weight which is due to the higher amount of crystalline domains in MCC which are

intrinsically flame resistant [67]. According to Adel et al. [98], the degradation of cellulose

contributes to the evolution of volatile compounds while the degradation of lignin

corresponds to thermal degradation properties. In view of the above discussion, it is deduced

23 
 
that MCC exhibits interesting thermal stability and it is a prominent candidate in the

manufacture of biocomposites, food stabilizers and pharmaceutical compounds.

4.5. X-ray diffraction (XRD)

X-ray diffraction (XRD) is commonly used to analyze the identity of crystalline solids

based on their atomic-scale structure of materials [103, 111]. Apart from that, XRD is a

versatile technique that provides in-depth information regarding the chemical composition

and crystallographic structure of the materials. X-rays have wavelengths (λ) in systematic

order of a few angstroms which is same as the interatomic distances which causes diffraction

to occur in crystalline solids [103]. The diffraction pattern displays numerous sharp spots

known as Bragg diffraction peaks [111]. Crystallinity index can be calculated from the height

ratio between intensity of crystalline peak and total intensity of non-crystalline peak using the

equation below as reported by Segal et al. [112]:

I 200  I am (1)
CrI 
I 200

where, CrI is crystallinity index, I200 is maximum intensity of the peak, and Iam is intensity of

diffraction of the non-crystalline material

High degree crystallinity index is obtained for acid hydrolyzed fibers and the average

size of the hydrolyzed fibers is approximately 25 nm [113]. The crystallite sizes are calculated

using the Scherrer equation as follows [114]:

k
L (2)
 cos

where, L is the size of the crystallite (nm), k is the Scherrer constant (0.94), λ is the X-ray

wavelength (0.15418nm), β is the full width half maximum of lattice plane reflection in

radian, and θ is the corresponding Bragg angle (reflection angle)

24 
 
 Various studies demonstrated that crystallinity index and sizes of microcrystalline

cellulose showed the highest value compared to cellulose when tested under X-ray diffraction

(XRD) with different lignocellulosic biomass (Table 5) [24, 52, 61, 67, 80, 93, 94, 115, 116].

This higher crystallinity in MCC is caused by removal of amorphous regions of cellulose by

hydrolysis process which prompts hydrolytic cleavage of glycosidic bonds and leads to

rearrangement of cellulose molecules [24, 98, 117, 118]. When the crystallinity size and index

increase, the toughness of cellulose structure exhibits better tensile strength towards fiber

[117]. This higher tensile strength is expected to increase the mechanical properties of

composite materials [99]. On the other hand, according to Kumar et al. [119], major amount

of lignin was eliminated during alkaline treatment which was then used for cellulose

extraction while the residual quantity of amorphous lignin was removed during acid

hydrolysis of MCC.

4.6. Electron microscopy analysis

High resolution of surface morphology of sample is widely examined using scanning

electron microscope (SEM). The image formed is in a three-dimensional structure and thus it

is useful for analysis of the sample. SEM consists of a shadow-relief effect of both secondary

and backscattered electron contrast, and is able to scan bulky images better with a greater

view, as well as produce a good image of the 3D structure of the sample [103, 120]. On the

other hand, transmission electron microscopy (TEM) is a powerful and unique nanoscale

imaging technique which uses an even higher resolution to construct the sample’s structure

[121]. It can control the size distribution and surface morphology of the sample, but the

analyzing process is time-consuming. By comparing SEM with TEM, SEM has the advantage

of scanning larger amount of sample once at higher magnification and greater resolution

[103].

25 
 
 There is not much difference in the MCC surface morphology as compared with several

types of sources such as MCC from Alfa fiber, rice hulls, bean hulls, bagasse, cotton silver,

jute, rice straw, cotton straw, and oil palm empty fruit brunch, as well as commercial MCC as

shown in Table 6 [52, 61, 67, 76, 96]. It seems that when the cellulose sample underwent

hydrolysis treatment, the surface morphology of MCC changed in terms of size and level of

smoothness. Before the treatment, cellulose exhibited an irregular shape in fibrils, rough

surface area, and was often aggregated as reported by Hemsri et al. [122]. According to

Trache et al. [67] and Adel et al. [98], the average diameter of commercial MCC obtained was

higher compared to that of other MCC from lignocellulose biomass.

Fewer researchers had used TEM to examine the surface morphology of MCC. The

MCC extracted from oil palm empty fruit bunch revealed that MCC particles have the

tendency to agglomerate, thus forming larger particles in the micron range, while the MCC

extracted from cotton silver showed fibrous shape [52, 96].

5. Microcrystalline cellulose based composite polymers

The growing global interest to produce green materials in the recent past that can reduce

continual environmental problems caused by non-biodegradable synthetic polymer wastes has

resulted in the development of composite materials using biodegradable polymers [123].

Polymer bio-composites filled with MCC is a relatively new research area with respect to

conventionally-filled polymers and these bio-composites possess several unique properties

such as high strength and stiffness combined with high surface area, unique morphology, low

density, biodegradability and renewability. However, for reinforcement applications, MCC

particles present some shortcomings, such as moisture absorption, poor wettability,

incompatibility with most polymeric matrices and limitation of processing temperature [20,

21, 26, 31]. For instance, cellulosic materials start to degrade near 220 °C, thus restricting the

type of matrix that can be used in association with cellulosic fillers [67].

26 
 
 The potential of MCC in various sectors of research and application is promising and

attracting increasing investments. There has been an increased interest in research and product

development of composite materials from petroleum-based polymers like polypropylene and

polyethylene reinforced with natural fibers. These composite materials are used extensively in

automotive applications, building materials, and household products [124]. This approach of

replacing petroleum-based materials by sustainable renewable resources aims to reduce the

negative ecological effects on the environment of polymeric materials. Based on these

perspectives, bio-based polymers are considered potential replacement to oil-based sources.

Among the factors contributing to this preference include, their numerous ecological

benefits and diversified raw materials [125]. Extensive research progress report has been

made in the last two decades on the production of biodegradable composites with biomaterials

at a reduced cost while maintaining the original properties of the bio-composite [126]. MCC

is viewed as a readily available baseline reinforcement [20, 21, 23, 25, 26, 28-30]. The

application of MCC as a reinforcing agent with excellent properties has attracted increasing

attention and interest in the past two decades due to its potential advantages such as

renewability, biodegradability and high surface area for bonding. Current global research in

bio-composite materials technology is geared towards replacing the current pure polymers or

glass fiber composites with lignocellulosic biomass fibers and natural fiber reinforced

polymer composites to create low cost, high performance, and low weight composite

materials [127]. In addition, these researches have led to bio-composite products with low

cost and ease of disposal.

To obtain better interaction between the matrix and reinforcement, materials that

provide large surface area are considered [128]. Application of such materials leads to better

mechanical properties, heat resistance and dimensional stability [129, 130]. Such cellulosic

reinforcement for polymers is obtainable in microcrystalline cellulose (MCC), where the

27 
 
amorphous regions have been removed by hydrolysis process. Wood pulp has been the major

source of MCC, but research findings have confirmed the application of vegetative plants and

lignocellulosic biomass suitable for the preparation of MCC that is expected to disintegrate

into cellulose whiskers after a complete hydrolysis The major use of reinforcing filler is

important to enhance its mechanical properties and materials from biomass and it has been of

great interest because of their renewable nature, biocompatibility, and low energy

consumption for its production [131].

The high specific surface area of MCC compared to other conventional cellulose fibers

is an added advantage of MCC. MCC has generated much attention and interest in both

academic and industrial fields. Besides that, MCC also exhibits a unique capacity to improve

the morphology, thermal and mechanical properties of the composite [20, 21, 23, 25, 26, 28-

30, 132-134]. Its average microfibril aspect ratio and fibrillar structure control the

reinforcement effects. MCC forms a stable gel in water, and this is a major reason for its use.

Among the challenges of MCC is that it is difficult to disintegrate once it is dried. This

development is attributed to the presence of hydrogen bonds that cause strong adhesion

between the individual microfibrils. MCC-based composites are expected to contribute

favorably to the mechanical behavior of most polymer bio-composites due to their short

microfibrils and crystalline nature.

It is of some interest to study bio-composite based on MCC, since even short

microfibrils are expected to contribute favorably to the mechanical behavior of most polymer

composites. Impressive mechanical properties and reinforcing capability, abundance, low

weight, and biodegradability make them ideal candidates for the processing of polymer

nanocomposites [135, 136]. MCC have been reported to possess a Young’s modulus of

150 GPa and a surface area of several hundred [137], and they have the potential to

significantly reinforce polymers at low filler loadings.

28 
 
 6. Current applications of microcrystalline cellulose

The microcrystalline cellulose (MCC) is an important ingredient in pharmaceutical (as

binders, adsorbents, flowability), food (as stabilizers, anti-caking agents, fat substitutes and

emulsifiers), beverage (as gelling agents, stabilizers, anti-caking agents and suspending

agents) cosmetic (as fat substitutes, thickeners, binders) and other industries (as binders) [20,

21, 39, 47, 48]. Among the unique properties are its chemical inactivity and hygroscopicity.

Furthermore, the absence of toxicity and high sorption has made MCC possible to be applied

in various industries [138]. The higher thermal stability of MCC over natural fiber has

attracted its acceptability in the manufacture of bio-composites. Another advantage of MCC

over lignocellulosic fillers is the stability of aqueous suspensions of cellulose microcrystals

[136].

Recently, successful preparation of MCC composite with other polymeric matrices has

been reported. Among the bio-composites with MCC are starch [98], chitosan [139],

poly(lactic acid) [23, 26], poly (3-hydroxybutyrate) [140] and poly(vinyl alcohol) [21]. The

use of MCC in polymer bio-composite formulations compared to conventional

microcomposites based on synthetic non-biodegradable materials is still limited. The

limitations in lignocellulosic-based schemes are the difficulties in achieving acceptable

dispersion levels of the filler within the polymeric matrix. In the interim, a palliative measure

in the use of latex in an aqueous suspension of the polymer to form a matrix has been reported

[135]. Besides that, owing to the emergence of new applications of bio-composites, extensive

research is currently being carried out by many research laboratories and companies with

MCC fiber and polymers to develop parts of miscellaneous sectors such as construction, food,

pharmaceutics, medical, automotive industries, packaging and smart materials.

29 
 
7. Concluding remarks

In this review, a comprehensive state-of-art of several aspects of MCC, that is important

for further understanding of this biopolymer, is described. Here, we mainly focus on the MCC

isolation procedures and its characterization. Different approaches including pretreatment

techniques and hydrolysis methods are discussed in the preparation of MCC from different

sources. Several properties of this renewable material are considered, such as chemical

composition, molecular weight, crystallinity, morphology and thermal properties. Owing to its

interesting characteristics, various uses continue to be developed by scientists all around the

world. With regards to MCC-based composites applications, we only report and discuss

several selected examples since the number of polymers used and their applications in various

fields increase continuously.

However, more research should be performed, which focuses on efficient MCC

isolation procedures, treatments and drying. Furthermore, to date, the engineering properties

and MCC-based composites performances are still being developed. In order to satisfy the

criteria of employing MCC for widespread use with higher efficiency, more effort and

developments are required to expand the use of MCC for science and technology.

Acknowledgements

Authors wish to thanks their parental institutes (Universiti Sains Malaysia through USM Short
Term Grant–304/PKIMIA/6313216 and 304/PTEKIND/6313194) for providing the necessary
facility to accomplish this work.

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List of Figures

Fig.1 Life cycle of microcrystalline cellulose-based polymer bio-composites.

Fig. 2 Illustration of the annual number of scientific publications since 1983, using the search
terms “microcrystalline cellulose and composite”. Data analysis completed using
Scopus search system on 19 August, 2016.

Fig. 3 Structural levels of organization of cellulose from the source to the molecule.

Fig. 4 Molecular structure of cellulose showing the numbering of carbon atoms, the reducing
end with a hemiacetal, and the non-reducing end with a free hydroxyl at C4.

Fig. 5 Scheme of the common steps needed to produce MCC from cellulose source materials.

Fig. 6 Schematic diagram of microcrystalline cellulose separation during acid hydrolysis.

Fig. 7 Mechanism of acid hydrolysis of glycosidic bonds [141, 142].

 

43 
 
  

Fig.1

44 
 
  

Fig.2

45 
 
  

Fig.3

46 
 
  

Fig.4

47 
 
 

Fig.5

48 
 
  

Fig.6

49 
 
 O
H3 O
O
O H
O O
O
(1)
Pathway I

H3O
(1) (2)

O
O H H
O O O
O O
OH O
O
H H

(2) (3) H3O

H2 O
Pathway II
OH

OH OH
O (3) O

O O
H2O H3O
 

Fig. 7

50 
 
 Table 1 Chemical composition of cellulose-containing materials.

Source Composition (wt.%) Reference

Cellulose Hemicellulose Lignin
Cotton 93 3 – [143] (Averous and Le Digabel,
2006)
Cotton stalks 75.1 19.3 0.94 [76] (El-Sakhawy and Hassan,
2007)
Softwood 40–44 25–29 25–31 [2] (Abdul Khalil et al., 2012)
Hardwood 43–47 25–35 16–24 [2] (Abdul Khalil et al., 2012)
Jute 61–71 14–20 12–13 [144]Alvarez et al., 2006
Flax fiber 72.1 13.9 4.8 [145] (Bochek et al., 2003)
Flax straw 47.2 7.8 31.6 [145] (Bochek et al., 2003)
Esparto grass 44.6 22.7 21.5 [67] (Trache et al., 2014)
Oil palm fiber 40.2 32.1 18.7 [146] (Ghaffar and Fan, 2014)
Begasse 77.6 21.4 0.87 [76] (El-Sakhawy and Hassan,
2007)
Hemp 68 15 10 [116] (Pracella et al., 2006)
Pineapple 73.4 7.1 10.5 [147] (Abdul Khalil et al., 2007)
Rice hulls 30.98 32.68 16.21 [61] Adel et al., 2011
Bean hulls 51.87 26.50 10.42 [61] Adel et al., 2011
Corn cobs 43.2 31.8 14.6 [146] (Ghaffar and Fan, 2014)
Ramie 68.6–76.2 13.1–16.7 0.6–0.7 [148] (Goda et al., 2006)
Abaca fiber 60.4 20.8 12.4 [146] (Ghaffar and Fan, 2014)
Coconut 32–43 0.15–0.25 40–45 [149] (Rosa et al., 2009)
Sisal 65 12 9.9 [150] (Joseph et al., 2003)
Banana 63–64 19 5 [70] (Pandey et al, 2015)
Kenaf 44–72 19 9–19 [1] (Kalia et al., 2011)
Curaua 73.6 9.9 7.5 [151] (Caraschi and Leato, 2000)
 

51 
 
Table 2 Different acid hydrolysis procedures to produce MCC from various sources.

Source Process References

Cotton stalks HCl, H2SO4 hydrolysis [76] (El-Sakhawy and Hassan,
2007)
Flax straw HCl hydrolysis Bochek et al., 2003
Bagasse HCl, H2SO4 hydrolysis [76] (El-Sakhawy and Hassan,
2007)
Rice hulls HCl, H2SO4 hydrolysis [61] (Adel et al., 2011) 

Bean hulls HCl, H2SO4 hydrolysis [61] (Adel et al., 2011) 

Esparto grass HCl hydrolysis [67] (Trache et al., 2014)

Oil palm fiber HCl hydrolysis [24] (Haafiz et al., 2013a)
Wood HCl hydrolysis [45] (Leppänen et al., 2009)
Kenaf HCl hydrolysis [68] (Keshk and Abu Haija,
2011)
Bacterial cellulose HCl hydrolysis [68] (Keshk and Abu Haija,
2011)
Fodder grass HCl hydrolysis [63] (Kalita et al., 2013)
orange mesocarp HCl hydrolysis [59] (Ejikeme, 2008)
Waste paper H2SO4 hydrolysis [64] (Okwonna, 2013)
Filter paper H2SO4 hydrolysis [65] (Ahmadi et al., 2015)
Newsprint H2SO4 hydrolysis [52] (Das et al., 2010)
Bacterial cellulose H2SO4 hydrolysis [69] (de Oliveira et al., 2011)
Jute H2SO4 hydrolysis [60] (Jahan et al., 2011)
 

52 
 
 Table 3 GPC analyses for the cellulose and microcrystalline cellulose samples.

Mn Mw
Sample DPI DPn DPw References
(RSD%) (RSD%)

Avicel PH- [109] (Hubbell and

N/A N/A N/A 60 294
101 MCC Ragauskas, 2010)

Alfa-C 78,215 (10) 438,004 (9) 5.59 150 844 [67] (Trache et al., 2014) 

Alfa-MCC 40,208 (8) 164,853 (6) 4.10 77 318 [67] (Trache et al., 2014) 

C-MCC 39179 (7) 152,798 (8) 3.89 75 294 [67] (Trache et al., 2014) 

Where Mn = number-average molecular weight; Mw = weight-average molecular weight; DPI

= polydispersity index (Mw/Mn); DPn = number-average degree of polymerization; DPw =
weight–average degree of polymerization
 

53 
 
Table 4 Comparison of thermal properties using TGA and DSC from different biomass.

TGA analysis
DSC
Onset Degradation Residual weight loss DTG peak
Samples analysis References
(°C) Temperature (°C) at 400 °C (%) temperature DTGmax
Tm (°C)
T10 T50 (°C)
B-MCC 251 285 320 22 320 N/A [76] (El-Sakhawy and Hassan,
2007)
RS-MCC 250 320 330 22 335 N/A [76] (El-Sakhawy and Hassan,
2007)
CS-MCC 270 260 325 28 320 N/A [76] (El-Sakhawy and Hassan,
2007)
J-MCC 250 280 475 61 280 N/A [52] (Das et al., 2010)
CS*- 285 340 475 57 340 N/A [52] (Das et al., 2010)
MCC
BW-MCC 230 290 350 18 N/A N/A [95] (Elanthikkal et al., 2010)
RH-MCC 223 270 290 23 283 N/A [61] (Adel et al., 2011)
BH-MCC 230 260 285 25 281 N/A [61] (Adel et al., 2011)
CC-MCC 270 280 340 22 N/A 335 [94] (Azubuike and Okhamafe,
2012a)
GS-MCC 260 275 320 20 N/A 320 [93] (Azubuike and Okhamafe,
2012b)
OPEFB- 275 293 327 20 326 N/A [23, 96] (Haafiz et al., 2013b,
MCC 2014)
FG-MCC 286 300 360 30 N/A N/A [63] (Kalita et al., 2013)
Alfa- 322 330 360 20 351 349 [67] (Trache et al., 2014)
MCC
C-MCC 258 310 333 19 332 N/A [100] (Karim et al., 2014)
Where C-MCC means (commercial MCC); OPEFB-MCC means (oil palm empty fruit brunch-MCC); RH-MCC means (rice hulls-MCC); BH-
MCC means (bean hulls-MCC); B-MCC means (bagasse-MCC); RS-MCC means (rice straw-MCC); CS-MCC means (cotton stalk-MCC); CC-
MCC means (corn cob-MCC) and GS-MCC means (groundnut shell-MCC); J-MCC means (jute-MCC); CS*-MCC means (cotton silver-MCC);
BW-MCC means (banana waste-MCC); FG-MCC means (fodder grass-MCC).

54 
 
Table 5 XRD analysis for crystallinity index (CrI) and crystallite size (L) of microcrystalline
cellulose (MCC) from different biomass.

Samples Reflection at 2θ (°) CrI (%) L (nm) References

B-MCC 18, 26 76 4.42 [76] (El-Sakhawy and Hassan,
2007)
RS-MCC 18, 26 78 3.97 [76] (El-Sakhawy and Hassan,
2007)
CS-MCC 18, 26 77 5.31 [76] (El-Sakhawy and Hassan,
2007)
C-MCC 18, 26 78 5.52 [76] (El-Sakhawy and Hassan,
2007)
J-MCC 13.17, 21.31 83 N/A [52] (Das et al., 2010)
CS*-MCC 3.51, 22.65 80 N/A [52] (Das et al., 2010)
RH-MCC 18, 26 87 5.77 [61] (Adel et al., 2011)
BH-MCC 18, 26 90 9.07 [61] (Adel et al., 2011)
C-MCC 18, 26 85 7.94 [61] (Adel et al., 2011)
J*-MCC 22 74 N/A [60] (Jahan et al., 2011)
CL-MCC 15.2, 22.6 77 N/A [152] (Terinte et al., 2011)
CC-MCC 12.5, 20.4 73 N/A [94] (Azubuike and Okhamafe,
2012a)
GS-MCC 15.0, 16.6, 22.4 74 N/A [93] (Azubuike and Okhamafe,
2012b)
OPEFB-MCC 19, 22.6 87 N/A [23] (Haafiz et al., 2013b) 

C-MCC 19, 22.6 79 N/A [23] (Haafiz et al., 2013b) 

FG-MCC 20.35, 22.3 80 N/A [63] (Kalita et al., 2013)

Alfa-MCC 15.2, 16.8, 22.6 73 5.02 [67] (Trache et al., 2014) 

C-MCC 15.2, 16.8, 22.6 81 5.25 [67] (Trache et al., 2014) 

Where C-MCC means (commercial MCC); OPEFB-MCC means (oil palm empty fruit
brunch-MCC); RH-MCC means (rice hulls-MCC); BH-MCC means (bean hulls-MCC); B-
MCC means (bagasse-MCC); RS-MCC means (rice straw-MCC); CS-MCC means (cotton
stalk-MCC); CL-MCC means (cotton linters-MCC); FG-MCC means (fodder grass-MCC); J-
MCC means (jute-MCC); CC-MCC means (corn cob-MCC); GS-MCC means (groundnut
shell-MCC); CS*-MCC means (cotton silver-MCC); J*-MCC means (jute-MCC).

55 
 
Table 6 SEM analysis for surface morphology of microcrystalline cellulose (MCC) from
different biomass.

Samples Surface Morphology References

B-MCC Shortening of fiber, rod-shaped like structure [76] (El-Sakhawy and Hassan,
2007)
CS-MCC Shortening of fiber, rod-shaped like structure, [76] (El-Sakhawy and Hassan,
large amount of pith 2007)
RS-MCC Shortening of fiber, rod-shaped like structure [76] (El-Sakhawy and Hassan,
2007)
CS*-MCC Structure agglomerate, flat, ribbon-like structure [52] (Das et al., 2010)
J*-MCC Structure agglomerate, flat, small rigid rod-like [52] (Das et al., 2010)
structure
BW-MCC Shortening of fibrous structure, smooth surface [95] (Elanthikkal et al., 2010)
J-MCC Well defined fibrous structure [60] (Jahan et al., 2011)
BH-MCC Shortening of fiber strands, uniform size, long [61] (Adel et al., 2011)
cylindrical-shaped and network structure
RH-MCC Shortening of fiber strands, rod-shaped and [61] (Adel et al., 2011)
network structure
FG-MCC Arranged rod-like shape [63] (Kalita et al., 2013)
OPEFB-MCC Irregular fibril shaped, aggregated, rough surface [23] (Haafiz et al., 2013b)
Alfa-MCC Short fibers strand, rough surface [67] (Trache et al., 2014) 

C-MCC Distinct crystalline shape [67] (Trache et al., 2014) 

Where C-MCC means (commercial MCC); OPEFB-MCC means (oil palm empty fruit
brunch-MCC); RH-MCC means (rice hulls-MCC); BH-MCC means (bean hulls-MCC); B-
MCC means (bagasse-MCC); RS-MCC means (rice straw-MCC); CS-MCC means (cotton
stalk-MCC); FG-MCC means (fodder grass-MCC); J-MCC means (jute-MCC); CS*-MCC
means (cotton silver-MCC); J*-MCC means (jute-MCC); BW-MCC means (banana waste-
MCC).
 

56