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The crystalline structure of cellulose has for the apparent crystallinity (%) of the
been studied for a long time. It is well mentioned samples from different
known that crystallinity of cellulose can sources to demonstrate the
be measured using quite a number of dissimilarities that can be obtained
methods, X-ray diffraction, solid state using different X-ray methods. For the
13
C CP-MAS NMR, Fourier transform- crystallinity analysis, assumption had to
infrared (FT-IR) spectroscopy and be made that all cotton linters and
13
Raman spectroscopy. The solid state C Avicel PH-101 used in the literature
CP-MAS NMR and FT-IR spectroscopy were of the same quality, even though it
considers contributions from both has been reported that the quality of
crystalline and non-crystalline cellulose both samples can vary between batches
regions resulting in relative values, and production locations. The reported
while the alternative X-ray diffraction crystallinity values of cotton linters were
approach gives more detailed data on between 56-78 %, for microcrystalline
features of crystalline and less on the cellulose (MCC), crystallinity varied
non-crystalline fraction of cellulose. within the range 65-83 % and Avicel
Raman spectroscopy is also used to PH-101 powder gave crystallinity values
study cellulose crystallinity. This paper between 37-93 % dependent on the X-
gives an overview on the crystallinity of ray methods and experimental mode
three cellulose samples, cotton linters, used.
microcrystalline cellulose (cotton linters)
and Avicel powder cellulose (Avicel PH- Keywords: cotton linters, microcrystalline
101) determined by wide angle X-ray cellulose (MCC), Avicel PH-101,
diffraction (WAXD). The study crystallinity, X-ray diffraction, X-ray
compares literature data with our data methods
__________________________________________
Introduction
cellulose I. Comparisons were made with literature MC celluloses from cotton linters
literature data for the apparent crystallinity (literature: 7 in number) were prepared by
(%) of two types of cellulose - cotton mild acid hydrolysis using different
linters (CL), its microcrystalline cellulose concentrations of sulphuric acid (H2SO4)
and for comparison the well-known Avicel or hydrochloric acid (HCl) to prepare the
PH-101 from different sources - to MC cellulose particles. There are several
demonstrate the dissimilarities that can be different grades of the microcrystalline
obtained using different X-ray methods. cellulose powders currently commercially
Data in literature and experimental results available under the brand name Avicel. For
indicated a wide range of numerical values this study, Avicel PH-101 was used. A
are obtained for crystallinity using range of 16 Avicel powder samples all
different X-ray diffraction methods for the called PH-101 are produced by FMC
same sample, although its interpretation is Corporation and Biochemika Fluka, as
still under discussion. reported in literature (Table 1), obtained
from different sources and probably from
Experimental different production trials. The crystalline
structure of cotton linters, MCC from
Materials cotton linters and of Avicel PH-101 are
In the reviewed literature, three different assigned as cellulose I. Table 1 gives
types of cellulose were used: cotton linters, specifications available from the suppliers
microcrystalline cellulose from cotton about the reported cellulose samples, (a)
linters and the commercial Avicel powder cotton linters, (b) its microcrystalline
cellulose. Cotton linters (literature: 8 in cellulose and (c) Avicel PH-101 used
number) were purchased from different throughout the study. Our data on Avicel
sources as shown in Table 1. The reported PH-101 are also included in Table 1, (c).
Table 1. List of native cellulose, (a) cotton linters and MC cellulose samples tested, from (b) cotton linters and
(c) Avicel PH-101.
pattern in a least squares fitting numerical non-crystalline scattering was found at this
procedure to fit the complete X-ray range.
diffractograms including the background Figure 3 illustrates the X-ray diffraction
or diffusive scattering due to non- spectra of a cellulose I sample presenting
crystalline regions. the X-ray method of P. H. Hermans and A.
Weidinger. Evaluation of the diffuse
3. Hermans-Weidinger X-ray diffract- background consists first in background
tion method correction scattered by air which is small
The classical method developed by P. H. and neglected. This portion of background
Hermans and A. Weidinger [10-12] is radiation has to be subtracted in order to
based on a two phase concept and it was obtain a reliable measure of the quantity of
used for the evaluation of crystallinity the non-crystalline fraction. Background
from X-ray intensity measurements. correction is still to be corrected due to
According to P. H. Hermans and A. thermal agitation of the atoms and
Weidinger, a careful attention is given to Compton radiation. The background
the control of samples and of instrumental intensity of well-ordered crystals of
variables, and photographic recording of sucrose was measured and subtracted from
the diffracted beam is employed. that of the cellulose over the range.
Integration was performed by copying the Crystalline peaks were separated from
traces of the photometer curves in diffuse background fraction by
duplicate on transparent paper of known extrapolating smoothly the background
weight per unit surface, cutting the figures curve near a crystalline peak and
out, weighing them and taking the average connecting the two end points of the peak.
value. Denoting the mass of crystalline, The separation of the crystalline I cr and
non-crystalline fractions as Mcr and Mnon-cr non-crystalline I non cr intensities is done
and total mass as M respectively, the
relationships between mass and cellulose usually with the help of appropriate
apparent crystallinity is: software, Shimadzu XRD-6000 version
I cr ( ) d
2.5, Japan [36].
M cr
C 100
M cr M non cr
The Hermans-Weidinger method of
I cr ( ) d knon cr / kcr I non cr ( ) d
determining X-ray crystallinity of cellulose
and the Ruland-Vonk method were found
where C is apparent crystallinity [%] to be identical [49].
defined by P. H. Hermans and A.
Weidinger, kcr and knon-cr are constants
and the integrated intensities of crystalline
Icr and non-crystalline Inon-cr fractions can
be determined from the diffraction patterns
(Figure 2). Using the above equation the
following relationship [39] can be given:
Table 2. Literature values for the apparent crystallinity of (a) cotton linters, (b) MC cellulose from cotton linters
and (c) Avicel PH-101 categorized by the different measurement techniques and experimental modes.