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Teknologi Pengolahan
Selulosa (STK 5356)

Structure and Properties

of Cellulose

Iryanti F. Nata
ifnata@ulm.ac.id
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1. Introduction
1.1. Molecular structure
• The cellulose molecule is a linear polymer of D-anhydroglucopyra
nose units linked together by b-1,4-glucosidic bonds (Figure 1.1).
In other words, it is a -1,4-D-glucan (polyglucose). The pyranose
rings are in the energetically favorable C1 chair conformation.
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1. Introduction ULM

Two attached oxygen atoms at C1, hydroxyl substituents at C2 and C3, o

ne attached oxygen atom at C4, and one hydroxymethyl group at C5. Th
e positions 1 and 4 are involved in the inter-unit linkage. O1 is the oxyg
en atom of the glycosidic bond, O5 that of the ring, O2 and O3 those of
the secondary alcohols and O6 that of the primary alcohol. C1 is an acet
al centre along the whole chain except for the right-hand end where it is
a hemiacetal centre with inherent reducing properties. Thus cellulose, as
all 1,4-linked glucans, has one reducing end containing an unsubstituted
hemiacetal, and one non-reducing end containing an additional hydroxyl
group at C4.
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1. Introduction
There are two major crystalline arrangements of cellulose, each being defined
by its unit cell parameters.

These polymorphs are called cellulose I and II. Almost all native celluloses
consist of cellulose I. Celluloses that have been either dissolved and precipitated
(regeneration) or treated with a concentrated alkaline solution and washed
with water (mercerization) consist of cellulose II. The transformation from
cellulose I to cellulose II is irreversible.

Cellulose materials have degrees of polymerization (DPs) that depend on

source and treatment. Cellulose DPs range from 100-300 for cellulose powder
(cellulose obtained from cellulose pulp by milling and fractionation), to 20 000
for cotton secondary wall and even to ~44 000 for Valonia.
In general, native celluloses have DP values higher than regenerated celluloses
(DP 200-500). In practice, purification procedures reduce the high values to
~2500.
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2. Supramolecular structure
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2.1 Crystallinity of cellulose materials

The first X-ray diffraction patterns of native cellulose were taken in 1913.
These patterns brought the first scientific demonstration of the existence of
highly ordered, crystalline regions. The intra- and intermolecular hydrogen bondi
ng system as well as the chemical composition and conformation of cellulose ch
ains are responsible for their tendency to form highly ordered, crystalline domai
ns.
The Bragg reflections from native and man-made celluloses appear broad and
diffuse compared to those from well-developed single crystals. This observation
is typical of semicrystalline polymers. In theory, the broadening of the reflection
peaks may result from small crystallite size or a high concentration of lattice
defects or the presence of an amorphous phase. The relative amount of crystalli
ne polymer in native cellulose varies widely with the source of the sample, as sh
own by the difference in sharpness of the X-ray diagrams (Figure 3.1).
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2. Supramolecular structure
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2.1 Crystallinity of cellulose materials

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2. Supramolecular structure
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2.1 Crystallinity of cellulose materials

Native celluloses have usually a higher crystallinity than man-made celluloses
(Ta b le 3.2). Degrees of crystallinity can reach very high values, particularl
y inValonia algae and in animal tunicates.
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2. Supramolecular structure
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2.2 Crystal Polymorphs

All native celluloses consist of cellulose I. The unique crystalline lattice for almost
all native celluloses was suggested from their similar X-ray diffraction patterns.
This common pattern comes from a structure that is referred to as cellulose I.
However, with the development of new investigation techniques, it has appeared
that cellulose I is actually a composite of two crystalline allomorphs, labeled I a
nd I. It has been shown that the I phasem is metastable and can be converted
Into the thermodynamically more stable I phase by annealing.
Celluloses that have been either dissolved and precipitated (regeneration), or
treated with a concentrated alkaline swelling agent (~20 %) and washed with
water (mercerization) consist of cellulose II. Cellulose II is thermodynamically
more stable than cellulose I, therefore the transformation from cellulose I
to cellulose II is irreversible.
Cellulose III is formed by swelling cellulose I or II with amines or liquid
ammonia, and subsequently removing the swelling agent anhydrously. It is a
fairly stable polymorph with subclasses IIII and IIIII depending on whether the
starting material was cellulose I or II. It should be noted that cellulose IIIII
is more and more hypothetical as nothing definite is known about it.
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2. Supramolecular structure
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2.2 Crystal Polymorphs

Cellulose IV is classically formed by annealing cellulose III in glycerol. It has
subclasses IVI and IVII depending on whether the starting material is cellulose
IIII or IIIII. It is generally accepted that cellulose IVI is a disordered form of
cellulose I. This could explain the reported occurrence of this form in some
plants. Crystals of cellulose IVII can be prepared from solution.

2.3 Cellulose I
This unique crystalline lattice for all native celluloses was suggested from the
similarity of their X-ray diffraction patterns. In their model, the unit cell was
monoclinic (a = 7.9 Å, b = 8.35 Å, c = 10.3 Å, g = 96°) with two antiparallel
cellobiose units, one at the origin (corner) and one at the center of the cell,
oriented along the chain axis (Figure 3.4).
The alternating glucose units in the chains were rotated through 180°, assuming
that the two chains (the origin chain and the center chain) of the cell were loc
ated on two independent two-fold screw axes with cellobiose as a true
repeating unit or asymmetric unit.
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2.3 Cellulose I
Furthermore, the two cellobiose segments were staggered by a quarter of the
c axis (2.5 Å). In terms of lattice symmetry, the two chains of the cell were or a
nized in a P21 space group (P = primitive lattice; 21 = two-fold screw axis), re
quiring adjacent glucose units in the same chain to be identical.
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2.3 Cellulose I
In 1984, Attala and VanderHart [17, 18] concluded
from solid-state C NMR
investigations that cellulose I was a system consisti
ng of two distinct crystal phases, I and I. The re
lative amount of each depends on the native cel
lulose source. Algal and bacterial celluloses are ric
h in I , whereas celluloses from higher plants an
d tunicates are rich in I. This biphasic character
is in line with the observed difference in the diffra
ction patterns and infrared spectra.
It was shown that the I phase is metastable and
can be converted into the thermodynamically
more stable I phase by annealing in diluted
aqueous NaOH or various organic solvents.
2.4 Cellulose II Program Studi S1 Teknik Kimia
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Celluloses that have been either dissolved and precipitated (regeneration) or

treated with a concentrated alkaline solution (~20 %) and washed with water
(mercerization) consist of cellulose II. Cellulose II is thermodynamically more
stable than cellulose I. Therefore, transformation from cellulose I into cellulos
e II is irreversible.
The statistical antiparallelism of cellulose microfibrils has been proven in a
crosssection ofValonia cell wall. This was deduced from electron diffraction
analysis of Valonia cell walls. [32, 34] It was further clearly demonstrated by d
ark-field microscopy, when the polarity of each microfibril was clearly identifie
d. In agreement with this statistical model, the interdigitation mechanism lea
ding to mercerization, proposed by Sarko et al. [36], becomes realistic.
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2.5 Cellulose III an IV ULM

In 2004, Wada et al. [46] determined the crystal and molecular structure as
well as the hydrogen-bonding system in cellulose IIII from synchrotron X-ray
and neutron fiber diffraction. The resulting structure, which confirms the prece
ding, has a one-chain monoclinic unit cell with an asymmetric unit containi
ng only one glucose residue, and with the hydroxymethyl group in the gt
conformation. The positions of hydrogen atoms involved in hydrogenbonding
were determined from neutron diffraction data collected from hydrogenated
and deuterated samples.
The hydrogen-bonding system appears well defined without disorder. A bifurc
ated hydrogen bond links a donating O3H to a ring O5 (major) and an O6 (mi
nor) of an adjacent residue in the same chain.
Two hydrogen bonds are present between neighboring chains, perpendicular t
o the chain axis. Regarding the structure of cellulose IIII, he use of
high pressure/high temperature deuterated and hydrogenated ammonia was
determinant to obtain high quality data sets.
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2.5 Cellulose III an IV ULM
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2. 5 Cellulose III an IV ULM
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2.6. Summary of Crystal Structure

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3. Morphological Structure
The morphological structure of cellulose is intended to describe the organization
of crystals into microfibrils, layers (or lamellae), cell walls, fibers, tissues or other
cellulose morphologies. Whereas native cellulose occurs generally as fibers,
regenerated cellulose is manufactured as fibers, films or other products with a
morphology differing largely from that of native cellulose.

Native cellulose from higher plants, algae, fungi, bacteria, amoebae and tunicate
s is synthesized by the coordinated action of enzymatic polymerization
associated with crystallization into nascent cellulose microfibrils. [62] This mecha
nism allows the generation of highly extended chains that can crystallize into mi
crofibrils including two crystalline phases, cellulose I and I. The icrofibrils are
then assembled to form higher order structures such as layers, cell walls and fib
ers. In some plants, such as cotton, the microfibrils organize into macrofibrils 60
-300 nm wide, which are then organized into fibers. [28] Cotton and wood pulp
originate from single plant cells, whereas bast fibers obtained from the stems of
certain plants (e.g. ramie, hemp, flax and jute) come from bundles of individual
fiber cells.
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3.1 Microfibrils
The microfibrils are ~2 to 50 nm across depending on the synthesizing
organism (Table 3.22) and their lengths can reach several µm
Therefore, they are examples of bionanofibers. Algae such as Micrasterias and
Valonia, and tunicates such as Halocynthia synthesize relatively large microfibril
s. In Micrasterias, the microfibrils occur in crisscrossed bands consisting of a nu
mber of parallel ribbon-like microfibrils.
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3.2 Plant Cell Wall

The walls of plant cells are generally thicker, stronger and more rigid than the e
xtracellular matrix produced by nimal cells. In evolving relatively rigid walls, whic
h vary from 0.1 µm to many micrometers in thickness, early plant cells adopted
a sedentary life-style that has persisted in all current plants.
The composition of the cell wall depends on the cell type.
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3.3 Representative Example

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4. Properties
4. 1. Mechanical Properties
Several modes of deformation can occur within cellulose fibers. [6] The ordered re
gions will show the typical elastic deformations of a crystalline solid, with a high
modulus. It is now well accepted that estimates of the crystal modulus of cellulose
I are in the range of 130-145 GPa.
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4. Properties
4. 2. Physical Properties
Cellulose is a semicrystalline polymer. It is non-melting and not thermoplastic.
Thermal degradation starts at ~180 °C. Up to this temperature, the amorphous
regions of cellulose are in the glassy state, without large-scale molecular motion,
and mechanical properties are maintained. Amorphous cellulose is plasticized
by water as illustrated by cellulose sponges which are rigid when dry and supple
when wet.
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4. Properties
4. 3. Environmental Properties
Cellulose is biodegradable and non-toxic to living organisms. Its biodegradation
is an essential step in the carbon cycle, which ensures the carbon balance in
the biosphere.
The enzymes that hydrolyze the b-1,4 linkages in cellulose are called cellulases
They are produced by many microorganisms such as bacteria and fungi, but also
by plants and some invertebrate animals. Traditionally, cellulases have been divid
ed into two groups, endoglucanases and exoglucanases (or cellobiohydrolases
), according to their respective capacity
to cleave the b-1,4-glucosidic bond either internally or at one of the ends of
the cellulose chain. In addition, the hydrolytic enzymes b-1,4-glucosidases are
capable of cleaving cellobiose into glucose.
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4. Properties
4. 3. Environmental Properties
Cellulose is biodegradable and non-toxic to living organisms. Its biodegradation
is an essential step in the carbon cycle, which ensures the carbon balance in
the biosphere.
The enzymes that hydrolyze the b-1,4 linkages in cellulose are called cellulases
They are produced by many microorganisms such as bacteria and fungi, but also
by plants and some invertebrate animals. Traditionally, cellulases have been divid
ed into two groups, endoglucanases and exoglucanases (or cellobiohydrolases
), according to their respective capacity
to cleave the b-1,4-glucosidic bond either internally or at one of the ends of
the cellulose chain. In addition, the hydrolytic enzymes b-1,4-glucosidases are
capable of cleaving cellobiose into glucose.