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The crystal structure of chitin and chitosan

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DOI: 10.1134/S0965545X06020039

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ISSN 0965-545X, Polymer Science, Ser. A, 2006, Vol. 48, No. 2, pp. 116–123. © Pleiades Publishing, Inc., 2006
Original Russian Text © E.L. Mogilevskaya, T.A. Akopova, A.N. Zelenetskii, A.N. Ozerin, 2006, published in Vysokomolekulyarnye Soedineniya, Ser. A, 2006, Vol. 48, No. 2,
pp. 216–226.
STRUCTURE,
PROPERTIES

The Crystal Structure of Chitin and Chitosan1

E. L. Mogilevskaya2, T. A. Akopova, A. N. Zelenetskii, and A. N. Ozerin
Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences,
ul. Profsoyuznaya 70, Moscow, 117393 Russia
Received March 31, 2005;
Revised Manuscript Received August 4, 2005

Abstract—Roentgenographic studies are performed to investigate the structural changes in chitin under pres-
sure and shear during its solid-state processing using a twin-screw extruder and Bridgman anvils. The structure
of chitosan synthesized by the solid-phase method is studied. Deformation under the conditions of dry extrusion
grinding at room temperature reduces the crystallinity of the original chitin. Addition of water restores the crys-
tallinity of the material up to the value characteristic of the original chitin. Extrusion processing of chitin at
room temperature with addition of water virtually preserves the crystallinity and degree of ordering of the chitin
crystal lattice, the same as ordinary dry grinding at an elevated (180°C) temperature. The maximum degree of
amorphization of chitin is attained by its processing on Bridgman anvils. Solid-state synthesis of chitosan from
chitin leads to a product with a more amorphous structure in comparison with chitosan produced by the suspen-
sion method.
DOI: 10.1134/S0965545X06020039

Chitin and chitosan (deacetylated derivative of
chitin) belong to the class of polysaccharides, one of
the groups of natural macromolecules. Chitin is no less
widespread than cellulose and performs various func-
tions in tissues of live organisms. Its natural sources are
shells of Crustacea, exo skeletons of mollusks and
insects, and some types of mushrooms.
The high interest in studies of these polymers is
explained by the need to solve both general problems
concerning rational utilization of rich natural biore-
sources and, in particular, specific problems of their use
for production of biodegradable (degradable by micro-
organisms existing in the environment) materials with
various possible practical applications [1–6]. However,
the mechanisms of structural and chemical conversions
in chitin and chitosan under various conditions of their
physicochemical processing have not yet been studied
in most cases.
The results of [7–13], obtained using various meth-
ods of polymer structure investigations (IR spectros-
copy, NMR, X-ray scattering, microscopy, sorption
techniques, etc.), showed that chitin, just as cellulose, is
characterized by an ordered fibrillar structure, a devel-
oped system of intra- and intermolecular hydrogen
bonds, a high degree of crystallinity, and polymor-
phism. Chitin is a stiff-chain infusible polymer, insolu-
ble in commonly available solvents, and thus has
reduced reactivity under the conditions of heteroge-
neous modification. To use its potentially wide capacity
for chemical modification and to produce materials
1 Thiswork was supported by the Russian Foundation for Basic
Research, project no. 04-03-32765.
2 E-mail:
eugenia_l_m@mail.ru
with valuable properties, chitin should be subjected to
preliminary activation, which accelerates the corre-
sponding reactions. The activation process is usually
performed via swelling, inclusion, or partial degrada-
tion and may be implemented in various ways [6]. Most
of these approaches are characterized by common
drawbacks, such as the use of a large excess of aggres-
sive reagents, significant duration and multistage nature
of the processes, and the need to dispose of waste-
waters.
An example of an alternative process that reduces
the consumption of water and low-molecular-mass
reagents is plastic deformation under pressure and
shear. It leads to dispersion of chitin, increases the spe-
cific surface area of its particles, and causes chemical
conversions and degradation of the polymer [14]. A
pilot method of chitin modification, which implements
this approach via synthesis in the solid aggregation
state using a twin-screw extruder, is described
in [15−17]. Note that comminution of the material per
se is only one of the results of extrusion processing,
along with accumulation of structural defects, forma-
tion of free radicals and excited electron states, molec-
ular-level mixing, and other physicochemical transfor-
mations [18]. Further, however, we will use the term
grinding to briefly denote the process of plastic defor-
mation caused by pressure and shear, while taking all
its specific features into account.
The distinguishing characteristic of chitosan thus
produced is its high degree of deacetylation along with
a comparatively low content of crystalline regions. This
feature makes it attractive for a number of actual prac-
tical applications, e.g., in pharmacy and biotechnology.
Note that the low crystallinity of chitosan synthesized

116
 THE CRYSTAL STRUCTURE OF CHITIN AND CHITOSAN
in the solid aggregation state is a rather surprising
result. The chemical structure of chitosan, just as in the
case of the initial chitin, was expected to lead to the for-
mation of highly ordered supermolecular structures
with a large amount of intra- and intermolecular hydro-
gen bonds and a high degree of crystallinity.
The aim of this study is to perform comparative
analysis of structural transformations that take place
during the processing of solid-state chitin in an extruder
and to study the structure of chitosan produced by
solid-state synthesis.
OBJECTS AND METHODS
The materials were processed in a pilot twin-screw
extruder (Berstorff) with a screw diameter of D =
40 mm and controlled zone heating.
For preparation of reference samples, we processed
them on Bridgman anvils (pressure of 1 GPa, anvil rota-
tion angle of 250°).
As the starting material in this study, we used
α-chitin isolated from Far East crab shells (Kombio,
Vladivostok, Russia).
The materials under investigation were original
chitin (sample C-1) and chitin subjected to simple (dry)
grinding at room temperature (C-2, C-3) and at 180°C
(C-5), the temperature at which the chitin deacetylation
reaction is usually performed. To study the effect of
water on the specificity of physicochemical conver-
sions in chitin, we considered samples C-6 and C-7,
which were produced by grinding chitin with simulta-
neous addition of different amounts of water, and also
sample C-4, which was produced after addition of
water to ground chitin and subsequent drying. For com-
parative study, we also prepared a chitin sample (C-8)
amorphized on a Bridgman anvil. In all these cases,
chitin was ground at room temperature unless other-
wise specified.
Chitosan, produced by deacetylation of the original
chitin [16], was represented by an extrusion mixture,
which is the product of the reaction occurring during
intergrinding of chitin and alkali (for NaOH, the
chitin : alkali molar ratio was 1 : 5 and the weight ratio
was 1 : 1) at 180°C.
The studied chitosan samples included chitosan iso-
lated by dialysis (washing with water up to neutral reac-
tion) of the extrusion mixture (sample CT-1) and repre-
cipitated forms of chitosan (CT-2, CT-4) with the insol-
uble fraction removed. For comparison, we also studied
sample CT-3 produced by a method traditional for
present-day industry: deacetylation in an alkali solution
under laboratory conditions [19]. Just as in the series of
chitin samples, chitosan amorphized on a Bridgman
anvil (CT-5) was also studied for comparison.
POLYMER SCIENCE Series A Vol. 48 No. 2 2006
117
The MM of all studied chitosan samples, deter-
mined according to [20], was 6 × 104. The degree of
deacetylation of all chitosan samples was DD = 90–
[ NH 2 ]
92%. The DD value was calculated as DD = --------------- ×
N sum
100%, where the content of nitrogen [Nsum] was found
by chemical element analysis and the content of pri-
mary amino groups [NH2] was found by van Slyke
deamination.
As the main method of polymer structure investiga-
tion in this study, we used wide-angle X-ray diffraction
(WAXD).
The diffractograms were recorded for a rotating
sample in the transmission mode in the range of scatter-
ing angles 2θ = 5°–100° on a D8 diffractometer
(Bruker) with a Ge monochromator crystal on a pri-
mary beam (CuKα radiation, wavelength λ =
0.1542 nm). The test samples were represented by pow-
ders placed in a specimen holder with windows of thin
amorphous PET.
Primary processing of the diffractograms was per-
formed with allowance for the inherent scattering of the
cell and correction for absorption and polarization of
radiation [21].
To perform comparative quantitative analysis, all
diffractograms were brought to normalized absolute
scattering units (scattering by an “averaged atom” of
the chitin or chitosan unit or reaction mixture). This
procedure included the following stages:
(1) Calculation of the effective scattering factor of
the averaged atom according to the formula
∑
2
Ni f i
f eff = 〈 f eff 〉 = ------------------- ,
2 2
(1)
∑
Ni
where 〈 f eff 〉 is expressed in the so-called electron units
2
Ie , which represent the energy scattered by a free elec-
tron inside a unit spatial angle, and Ni and fi are the
number of atoms of the ith sort and their atom scatter-
ing factor [22] in the stoichiometric formula of the
polymer unit, respectively.
(2) Calculation of the incoherent part of the aver-
aged-atom scattering.
(3) Multiplication by the normalization constant
(for passing to absolute scattering units).
Passing to absolute scattering units made it possible
to proceed from experimental scattering intensity
curves (which depend on the number of atoms in the
sample) to the total scattering intensity per averaged
atom of the elementary polymer unit, expressed in elec-
tron scattering units. This is necessary for comparative
measurements.
118 MOGILEVSKAYA et al.
2
– ks
To determine the crystallinity of chitin and chitosan exp , where k + kT + kI + kII , into the formula for the
samples in this study, we used a well-substantiated intensity of the crystalline fraction. The kT, kI , and kII
method developed by Ruland [21, 23–25]. Its specific values correspond to thermal oscillations about the
feature is the possibility of simultaneous consideration equilibrium position and to defects of the first and sec-
of distortions in the crystal lattice of the polymer during ond kind, respectively, thus covering all types of possi-
calculations of its degree of crystallinity. However, the ble deviations of atoms from their ideal positions in the
use of this method involves certain difficulties: the scat- crystal lattice. The larger the k value, the higher the
tering curve is to be determined within a fairly wide degree of disorder in the crystal lattice.
range of scattering angles 2θ, and the calculations are
time-consuming. As a rule, this technique was earlier Using the mean-square scattering factor of an aver-
aged atom 〈 f eff 〉 from Eq. (1), one can write the equa-
2
used for synthetic polymers (PE, PA, PP) [21, 23],
whereas examples of its application to natural or artifi- tion for determining the degree of crystallinity with
cial polymers (cellulose and its derivatives) are very allowance for factor D in the form
rare [26].
∞ ∞
If I(s) is the intensity of coherent scattering from the
∫ s I ds ∫ s 〈 f eff〉 ds
2 2 2
sample at the point of reciprocal space with vector s, c
2 sin θ
where |s| = -------------- , and Ic(s) is the intensity at the same 0 0
-.
x c = ----------------------------------------------- (4)
λ ∞ ∞

∫ s I ds ∫ s 〈 f eff〉 D ds
2 2 2
point due to the crystalline phase, the integrated scatter-
ing intensities over the entire reciprocal space are deter- 0 0
mined by the relationships
∞ ∞
Formula (4) is applicable under the following condi-
tions: random orientation of structural elements inside
∫ I ( s ) dn ∫
= 4π s I ( s ) ds ,
2
s (2) the sample, three-dimensional nature of ordering in the
0 0 crystalline regions, justified replacement of infinite
limits of integration by finite ones corresponding to a
∞ ∞ certain range of scattering angles, possibility of precise
∫ I ( s ) dn ∫
= 4π s I c ( s ) ds .
2
c s (3) and reproducible discrimination of crystal peaks
(which is equivalent to the requirement [21, 27] that the
0 0
size of the crystalline regions is not below 3–5 nm), and
The I(s) and Ic(s) values pertain to scattering inten- knowledge of factor D.
sities per unit spatial angle ω at distance s from the Figure 1 shows the general pattern of the scattering
coordinate origin in the reciprocal space: curve in absolute units for one of the studied chitin
4π
samples (C-2).
1
4π ∫
I ( s ) = ------ I ( s ) dw . The hatched region in Fig. 1 corresponds to incoher-
ent scattering. The region between the smooth line con-
0
necting the minima and the hatched part corresponds to
In the first approximation, the degree of crystallinity diffuse scattering.
of a two-phase semicrystalline system (the volume frac- Using Ruland’s method, one can simultaneously
tion of the crystal phase) is described by the formula determine the k, D, xc values and the integration range
∞ [s0, sp] that ensure fulfillment of the condition

∫ s I ( s ) ds
2
c ∞ ∞

∫ s I ds ∫ s 〈 f eff〉 ds
0 2 2 2
∞
-.
x c = ------------------------ c

∫ s I ( s ) ds
2 0 0
x c = -----------------------------------------------
∞ ∞
-

∫ s I ds ∫ s 〈 f eff〉 D ds
0 2 2 2

The xc value thus determined will be an underesti- 0 0

(5)
mate because part of the X-ray radiation scattered by sp
crystalline regions contributes to the background dif-
∫ s I ds
2
c
fuse scattering rather than to the intensity of crystal
- K ( s 0, s p, D, 〈 f eff〉 ) = const.
0 2
peaks. This result is due to atom oscillations about the = -----------------
sp
equilibrium positions and to lattice imperfections.
∫ s I ds
2
As is shown in [24], this effect can be taken into
account by introducing the disorder parameter D = s0

POLYMER SCIENCE Series A Vol. 48 No. 2 2006

 THE CRYSTAL STRUCTURE OF CHITIN AND CHITOSAN 119

The error in the determination of the xc value from
X-ray data, estimated for the objects of this research,
amounted to ±5%.
The structure of the crystalline regions in the studied
polymers was described within Hosemann’s paracrys-
talline model [28–30], whose main theses are thor-
oughly considered and analyzed in monograph [31].
The use of the paracrystalline model made it possible to
determine the values of such structural parameters as
crystallite dimensions (the size of the coherent X-ray
scattering region), the paracrystalline distortion factor,
and also the type of macromolecule ordering (crystal-
line or “liquid”) in the condensed phase corresponding
to the recorded scattering pattern.
RESULTS AND DISCUSSION
Chitin
The unit cell of chitin has the space symmetry
group P212121 with the parameters a = 0.469 nm
(interchain distance), b = 1.913 nm, and c = 1.043 nm
(along the chain) [32, 33]. The table lists the interpla-
nar spacings corresponding to the most intense peaks.
The peaks recorded on the experimental diffracto-
grams (Fig. 2) were attributed in accordance with the
data in the table. The calculated degrees of crystallin-
ity xc and disorder parameters k of the studied chitin
samples are listed below.

Sample C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8

xc 0.82 0.57 0.61 0.79 0.79 0.71 0.67 0.13

k 6 4 5 6 6 6 6 4

Our results make it possible to monitor the structural
transformations during solid-state processing of chitin.
The maximum amorphization (maximum decrease
in the degree of crystallinity) of the original chitin C-1
is attained in its processing on Bridgman anvils (sam-
ple C-8).
Extrusion processing of the original chitin also
reduces its total degree of crystallinity (samples C-2
and C-3) but to a lesser extent than in the case of Bridg-
man anvils. At the same time, the crystalline phase pre-
served after grinding in this case is characterized by
higher ordering in comparison with the initial sample.
Addition of water after grinding (sample C-4)
restores the original structure of the material, and the
values of the crystallinity parameters obtained for the
case of chitin grinding in combination with water (sam-
ples C-6 and C-7) enable one to conclude that water
acts as a plasticizer in this case. Hence, the crystallinity

s2I(s), arb. units

0.1 0.3 0.5

s × 10, nm–1
Fig. 1. Diffractogram of chitin sample C-2. The hatched region corresponds to incoherent scattering. The region
between the smooth line joining the maxima and the hatched part corresponds to diffuse scattering.

POLYMER SCIENCE Series A Vol. 48 No. 2 2006

120 MOGILEVSKAYA et al.

Crystallographic characteristics of chitin and chitosan

Angular position Angular position
Interplanar spacing Interplanar spacing
Plane hkl of maximum scalc × 10–1, of maximum sobs × 10–1,
dcalc × 10, nm dobs × 10, nm
nm–1 nm–1
Chitin
020 0.105 9.542 0.105 9.52
021 0.144 6.940 0.144 6.94
002 (012) 0.198 5.056 0.199 5.03
110 0.218 4.595 0.216 4.63
101 (041, 111) 0.235 4.257 0.232 4.31
032 0.252 3.970 0.250 4.00
130 0.266 3.761 0.261 3.83
013 (003) 0.298 3.358 0.294 3.40
210 (200, 220) 0.433 2.311 0.432 2.31
Chitosan
020 0.118 8.49 0.118 8.49
200 0.223 4.48 0.221 4.52
201 0.243 4.12 0.241 4.14
230 0.284 3.52 0.283 3.53
142 0.325 3.08 0.324 3.08
143 0.390 2.56 0.390 2.57
Note: The data in the first three columns are taken from [31, 32] for chitin and from [33, 34] for chitosan. The data in the last two columns
are determined in this study for C-1, C-2, and CT-1.

of chitin decreases to a minor extent and the disorder
factor of the crystalline phase is preserved.
Simple grinding at an elevated temperature (sample
C-5) has virtually no effect on the structure of the crys-
talline phase of the initial chitin.
Calculating the corresponding structural parameters
of the paracrystalline model [28–31] of the crystalline
phase structure, we showed that scattering from all
chitin samples except for the amorphized one is due to
scattering from the condensed phase with long-range
crystalline order rather than the short-range “liquid-
type” nature of ordering.
Within the framework of the same model, we deter-
mined the dimensions of the crystalline regions of
chitin in different crystallographic directions with
allowance for the paracrystalline distortion factor. For
example, depending on the sample processing method,
the crystallite size in direction b of the crystallographic
cell (along the planes of glucopyran rings) changed
from 14 to 16 nm. This crystallite size is attained if
approximately 15 polysaccharide chains are packed in
the relevant direction. In direction a (perpendicular to
the macromolecule layer), this value amounts to
11−12 nm, corresponding to packing of about 25 layers.
The most significant changes for different types of
chitin processing were observed in crystallographic
direction Ò (the longitudinal size of the crystallites),
which varied in the 27–32 nm range, corresponding to
the segment length (~60 units) of the polysaccharide
macromolecule. As a result of grinding, the longitudi-
nal size of the crystallites decreased. After addition of
water, owing to the recrystallization process, the value
of this parameter became the highest among the studied
series of samples.
As is known, reliable determination of the crystallite
dimensions and paracrystalline distortion factor in the
crystal lattice according to X-ray data requires that the
diffractogram of the sample should contain several
orders of reflections from some set of planes in the
crystal lattice of the material. Unfortunately, the dif-
fractograms of the studied chitin samples, like those in
Fig. 2, mostly enabled us to distinguish only the peaks
corresponding to the first orders of reflections. For this
reason, the above dimensions of chitin crystallites are
actually just estimates of their minimum values.
Chitosan
The unit cell parameters of chitosan (ê212121) are
a = 0.895, b = 1.698, and c = 1.034 nm [34, 35]. As was

POLYMER SCIENCE Series A Vol. 48 No. 2 2006

 THE CRYSTAL STRUCTURE OF CHITIN AND CHITOSAN 121

I(θ), el. units

80
013
1
110 2
60

020

40

101

20 021 002

10 30 50
2θ, deg

Fig. 2. Diffractograms of chitin samples (1) C-1 and (2) C-2.

noted in [36], chitosan is hydrated in its usual form and
there is one water molecule per unit of the polysaccha-
ride. However, this conclusion requires additional cor-
roboration.
The interplanar spacings corresponding to the more
intense peaks of chitosan are listed in the table.
The reaction mixture obtained via solid-state syn-
thesis contains not only the target product (chitosan)
but also the residual reagents. Chitosan in the form of a
suspension was isolated from the reaction mixture by
dialysis after neutralization of the alkali contained in
the mixture down to pH 8–9. Reprecipitation of the
resultant product shows that the suspension isolated by
dialysis contains an insoluble fraction in an amount up
to 10 wt %. The diffractogram of the insoluble fraction,
as well as the degree of crystallinity (0.81) and crystal-
line phase disorder factor (k = 6) calculated for it,
turned out to be the same as for the initial chitin.
Thus, a minor part of the initial chitin is not involved
in the deacetylation reaction during solid-state synthe-
sis under the experimental conditions used in this study.
By virtue of this feature, the parameter values char-
acterizing the crystallinity of chitosan CT-1 (diffracto-
metric curve 1 in Fig. 3), produced by solid-state
deacetylation and purified only by dialysis (which, in
fact, was a mixture of chitosan and residual chitin),
could have been overestimated owing to the presence of
a certain residual amount of unreacted high-crystallin-
ity chitin in the isolated chitosan. To eliminate the influ-
ence of this factor, as is customary in X-ray phase anal-
ysis of materials, scattering caused by pure chitin was
subtracted from the diffractogram of the mixture; as a
result, it became possible to compare the chitosan sam-
ples CT-1 and CT-3, produced by solid-phase and sus-
pension methods (curves 2 and 3, respectively).
The calculated crystallinities and disorder factors of
the crystalline phase of the studied chitosan samples are
tabulated below.

Chitosan sample CT-1 CT-1* CT-2 CT-3 CT-4 CT-5

xc 0.39 0.22–0.25 0.26 0.38 0.30 0.10

k 5 2–3 4 4 5 3
* Values obtained after subtracting scattering from residual chitin.

POLYMER SCIENCE Series A Vol. 48 No. 2 2006

122 MOGILEVSKAYA et al.
I(θ), el. units
200
80
201
60
020
40
20
10
Fig. 3. Diffractograms of chitosan samples (1) CT-1, (2) CT-1 after subtraction of scattering from 10% residual chitin,
and (3) CT-3. For more convenient representation, the diffractograms are shifted in relation to each other along the
ordinate axis.
The calculated degree of crystallinity for chitosan
sample CT-3, which was produced by the traditional
suspension method, is about 40%, whereas the corre-
sponding value for sample CT-1, produced by solid-
state synthesis, is about 25% (after subtraction of scat-
tering from the residual chitin). Since both samples had
equal degrees of deacetylation, one can conclude that
solid-state synthesis makes it possible to obtain a prod-
uct with a more amorphous structure in comparison
with chitosan produced by the traditional suspension
method (at a comparable level of conversion of aceta-
mide groups into amino groups). The simplest explana-
tion for the aforementioned difference in the degree of
crystallinity consists in different patterns of the distri-
bution of residual acetamide groups in macromolecules
of the two polysaccharides under comparison. How-
ever, to confirm this explanation, additional research
beyond the scope of this study is needed.
Chitosan sample CT-4, which was produced by
reprecipitation from formic acid, had a somewhat
higher degree of crystallinity than CT-1 (after purifica-
tion by dialysis) and CT-2 (reprecipitated from HCl).
However, the ordering of crystalline regions in sample
CT-4 is further from perfect than CT-1 and CT-2. This
result illustrates the relationship, depending on the
method of chitosan synthesis and processing, between
the calculated crystallinity parameters and the change
in the nature of the ordering of chitosan molecules.
1
2
3
30 50
2θ, deg
It was found that scattering from all chitosan sam-
ples except for the amorphized one, just as in the case
of chitin, actually represents scattering from the con-
densed phase with long-range crystalline ordering
rather than the short-range liquid-type one.
To estimate the dimensions of crystalline regions of
chitosan in different crystallographic directions and the
corresponding values of the paracrystalline distortion
factor, we used the X-ray data obtained for chitosan
CT-1.
The calculated crystallite sizes in chitosan turned
out to be much smaller than in chitin. The crystallite
dimensions along crystallographic directions a, b, and
c were 6, 4–5, and 3–4 nm, respectively. This size cor-
responds to an “average” crystallite consisting of
13−14 layers, where each layer is formed by four to six
chains with six to eight units in each chain. Since the
diffraction pattern of chitosan samples provides insuffi-
cient information, these dimensions of crystallites are
only estimates corresponding to the minimum values,
just as in the case of chitin.
Thus, this study considers X-ray investigations of
structural transformations that take place in chitin as a
result of its processing in a twin-screw extruder and the
structure of chitosan produced by solid-state synthesis.
Deformation under the action of shear and stress in
the absence of water at room temperature is shown to
reduce the crystallinity of the initial chitin. However,
POLYMER SCIENCE Series A Vol. 48 No. 2 2006
 THE CRYSTAL STRUCTURE OF CHITIN AND CHITOSAN
subsequent addition of water restores the degree of
crystallinity so that it becomes equal to the value char-
acteristic for the initial chitin. Extrusion processing of
chitin at room temperature with the addition of water
has virtually no effect on the crystallinity and degree of
ordering of the chitin crystal lattice, a result which is
similar to that obtained for simple dry grinding at an
elevated (180°C) temperature. The maximum degree of
chitin amorphization is attained during its processing
on Bridgman anvils.
Solid-state synthesis using a twin-screw extruder is
shown to yield a more amorphous product in compari-
son with chitosan produced by the traditional suspen-
sion method (at a comparable level of acetamide group
conversion into amino groups). The degree of crystal-
linity and the disorder factor of the chitosan crystal lat-
tice are found to depend on the method of chitosan syn-
thesis or processing.
The dimensions of both chitin and chitosan crystal-
lites after solid-state treatment agree with the values
obtained for the original chitin and for chitosan synthe-
sized by the traditional suspension method. At the same
time, the crystalline phases of these samples seem to be
formed under different conditions. This result agrees
with the general theory of mechanochemistry [18]. Pro-
cessing of chitin and synthesis of chitosan in the solid
state are accompanied not only by dispersion of the
crystalline phase at the macroscopic level. In addition,
the mechanically activated materials demonstrate the
formation of labile nanoscale structures; inside these
structures, dislocationless mass transfer ensures defor-
mation-induced molecular-level mixing, which is suffi-
cient, in particular, for the solid-state deacetylation
reaction with a quantitative yield.
The results of this study are important for optimiza-
tion of chitin modification processes and for making
various products and materials based on modified chitin
and chitosan.
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(1983).
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