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Industrial Crops and Products 47 (2013) 1–12

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Industrial Crops and Products


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Sugar cane plant fibres: Separation and characterisation


Lynne Wong Sak Hoi a,b , Bice S. Martincigh a,∗
a
School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
b
Mauritius Sugar Industry Research Institute, Reduit, Mauritius

a r t i c l e i n f o a b s t r a c t

Article history: Sugar cane is a potential source of large amounts of natural fibres which has not yet been adequately
Received 2 November 2012 exploited. A simple physical method was devised to separate the fibres and the fines/pith from var-
Received in revised form 9 February 2013 ious locations in the plant to yield nine components. The yield of fibres obtained was greatest from
Accepted 11 February 2013
the leaves. The fibre/pith ratios of four cane varieties investigated indicated good millability. All the
components, except stalk pith, were morphologically similar and FTIR spectroscopy confirmed the ligno-
Keywords:
cellulosic nature of the material. The four components that arise from the cane, namely, rind fibre, rind
Sugar cane
fines, stalk fibre and stalk pith, showed clear trends in the crystallinity index, combustion temperatures,
Fibre
Pith
amount of residue after pyrolysis, percentage carbon content and gross calorific value. The fibres from
Crystallinity the leaves and tops did not exhibit clear trends. The information gleaned from this study can be used to
Value addition select appropriate end-uses for these different fibres.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction According to Van Dillewijn (1952), the structure of cane stalk


can be roughly divided into two parts: an outer peripheral region
Sugar cane is the world’s largest crop and is grown in more than or rind, and an inner soft pith section, which differ mainly in the
100 countries (White et al., 2011). Although it is primarily grown relative concentrations of juice-containing cells (parenchyma) and
for the production of sugar, current focus on sustainable energy fibrovascular bundles. The rind has a strong outer cuticle often cov-
and sound environmental practices have led to the realisation that ered with a layer of wax, which prevents evaporation of water
lignocellulosic biomass such as that derived from sugar cane can from the inner cells and gives them protection against mechanical
form the basis of a biorefinery with a wide range of possible prod- injuries and attack by micro-organisms. The term “rind” normally
ucts (Moncada et al., 2012). The recent drop in the worldwide price refers to the relatively thin external layer of the stalk, but it is some-
of sugar in 2012 has also spurred an increased interest in other uses times also taken as the adjacent layer of dense tissue in which there
of the sugar cane plant. is a high concentration of vascular bundles and relatively few juice
Because the sugar cane plant is a perennial C4 grass it is a highly cells. By virtue of its high fibre content, this is the strongest portion
efficient converter of solar radiation into biomass, more so than of the plant and it gives the stalk much of its characteristic strength
wheat or maize. The composition of sugar cane depends very much and rigidity.
on the cane variety, the region and the climatic conditions under The juice-containing parenchyma cells are thin-walled and con-
which it is grown, the degree of maturity of the cane, and so on. tribute only a small part of the total fibre in the cane. On the other
Sugar cane is composed mainly of sucrose, fibre and water, usu- hand, the vascular bundles contain many small thick-walled cells
ally in the proportions of about 12%, 15% and 70%, respectively which surround the large vessels and sieve tubes. The vessels carry
(Anon., 2007), in Mauritius. The remaining constituents are other water from the roots and the sieve tubes conduct sugary juices from
sugars (glucose and fructose), inorganic materials, nitrogenous sub- the leaves. High tensile strength in the vascular bundles appears to
stances, gums, waxes and organic acids (Chen and Chou, 1993). impart good milling quality to the cane variety.
The sugar cane plant can be divided into three parts: roots, stalk After the sugar-containing juice has been extracted from the
and leaves, the composition of which was reported by Brown and cane stalk by either tandem milling or diffusion, the remaining
Blouin (1907) and is shown in Table 1. It can be seen that the main dry fibre (known as bagasse) is left. It consists mainly of cel-
part of the sugar cane plant from which sugar can be extracted is lulose, hemicellulose and lignin (Paturau, 1989). Cellulose is a
the stalk. glucopolysaccharide having the general formula (C6 H10 O5 )n and it
is the main constituent of vegetable tissue. It rarely occurs in nature
in the pure state but is generally intimately mixed with lignin,
∗ Corresponding author. Tel.: +27 31 2601394; fax: +27 31 2603091. hemicellulose, gums, tannins, fats, colouring matter, etc. It forms
E-mail address: martinci@ukzn.ac.za (B.S. Martincigh). chains of up to approximately 10,000 glucose units arranged in

0926-6690/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2013.02.017
2 L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12

Table 1 2. Experimental
Composition of different parts of cane (Brown and Blouin, 1907).

Percentage composition Stalks Roots Leaves 2.1. Materials


Water 74.96 68.79 74.38
Ash 0.64 1.87 2.23 The cane samples tested in this work were all grown under
Fats and wax 0.38 0.54 0.69 the same conditions in the North of Mauritius in an area called
Nitrogenous matter 0.58 1.59 1.70 Nouvelle Industrie. Four Mauritian cane varieties: R 579, R 570, M
Fibre
1557/70 and M 1400/86, each aged 52, 44 and 36 weeks were cho-
Crude cellulose 4.86 9.58 9.18
Pentosans 3.04 7.04 5.49 sen. The samples used for fibre extraction consisted of four cane
Ligneous bodies 2.14 4.25 4.13 stalks including cane tops each from each of three replicates with
Sugars, etc. 13.40 6.34 2.21 all their attached dry and green leaves. The materials were removed
“randomly” from the experimental rows of maturity testing trials
established by the Plant Physiology Department of the Mauritius
microfibrils held together by hydrogen bonds. These bonds impart Sugar Industry Research Institute (MSIRI).
high tensile strength to cellulose and make it insoluble in most
solvents. Hemicellulose is a polysaccharide consisting of a number 2.2. Equipment for fibre extraction
of different sugar units, but xylose is the most predominant sugar
present. It is amorphous in nature and has a random structure with A heavy duty universal model 264 Jeffco cutter-grinder with
branching in the polymer chains. Lignin is an amorphous, com- a 7500 W, three-phase motor, was used to pre-treat peeled cane
plex phenolic polymer cross-linked to hemicellulose. It provides stalk, rind, dry leaves and green leaves prior to fibre extraction in
mechanical strength for plants, and because of its hydrophobic a Jeffco wet disintegrator. The Jeffco wet disintegrator used was a
nature prevents the absorption of water through the cell walls. Model 292 with a water-jacketed 7 L-bowl and a standard 50 Hz
Paturau (1989) identified two important types of fibrous residue AC motor of 2250 W, three phase, 2880 rpm and 415 V. The bowl
occurring in bagasse: (a) the tough, hard-walled, cylindrical cells of unit could be easily lowered or raised for sample disintegration
the rind and vascular tissues (true fibre); and (b) the soft, thin- and tilted for sample unloading. Up to four blades could be fitted at
walled, irregularly shaped parenchymatous cells of the inner stalk right angles to each other on the central vertical spindle which can
tissue (pith). The vessel segments, also associated with the vascular be rotated at high speed to disintegrate the cane sample. A Pinette
bundles, are often, but not always, considered as a pith fraction. Emidecau press was used to press out liquid from fibre cake pre-
According to Paturau (1989), the true fibre and the pith have pared from sugar cane components. A Schmidt and Haensch DUR
almost the same chemical composition but their structures differ W2 sugar refractometer was used to measure the refractive index
widely. The true fibres have a fairly high ratio of length-to-diameter of the washings and the results were displayed as dissolved solids
(approximately 70), and a relatively high coefficient of expansion (g) in 100 g solution (Brix). The Brix readings of the washings from
and contraction upon wetting and subsequent drying. This results the fibre cake were required to ensure no residual Brix remained
in close bonding of one fibre with another and accounts for the in the extracted fibre. A selection of three sieves with openings of
strength, cohesiveness and ability to become matted when sub- 2 mm, 1.18 mm and 38 ␮m was assembled on top of each other.
jected to pulping processes. The pith cells are of irregular size and The top two sieves served to retain the fibre and the bottom sieve
shape, with a length-to-diameter ratio of about 5. They are char- of 38 ␮m, the pith. Because of the large number of samples required
acterised by their absorption properties. They do not adhere and to be dried in this study, a large capacity industrial oven equipped
so tend to weaken any pulp in which they are incorporated and, with a thermostat was used.
further, prevent its rapid drying. However, they can absorb many
times their mass of liquid. 2.3. Method of fibre extraction from the sugar cane plant
Currently sugar factories use this bagasse by-product almost
entirely as fuel for their boilers and some countries are using or When the three replicates (each consisting of four stalks) of
investigating the use of bagasse for cogeneration of electricity. the four varieties aged 52 weeks were delivered at the laboratory,
However, in countries like Brazil there is an excess supply and for each sample, the number of dry leaves and green leaves were
stock-piling is a problem (Ramajo-Escalera et al., 2006; White et al., noted, separated from the stalks and weighed. The cane tops (that
2011). This bagasse is a very promising feedstock for energy, mate- is, the growing point region or the immature apical internodes),
rials and chemicals. after being detached from the stalks at the point where they nat-
Bagasse composition is highly variable. This has been exacer- urally broke off from the stalks, were weighed. All the nodes were
bated by the advent of green cane harvesting, because cane supplied removed, weighed and discarded (this was done because the nodes
to mills now contains increased amounts of extraneous material. could not be separated into homogeneous fibres and proved diffi-
This extraneous matter includes green and dry (that is, brown, cult to disintegrate). The rind was peeled off longitudinally from
senescing leaves) cane leaves, cane tops and other non-cane mate- the stalk. The masses of the rind and peeled stalk were determined.
rial. The extraction of fibres starting first with the tops, followed by
There is therefore an increased interest in the fibre component green leaves, peeled stalk, rind and dry leaves, could be completed
of sugar cane, that is, both bagasse and sugar cane leaves, and a within one week. All the samples were separated into fibre and
need for better knowledge of its chemical and physical properties. pith/fines, dried and sealed in plastic bags pending dry sieving at a
This will assist in determining the end-uses of these fibres. This later stage.
work consequently focussed on separating the fibres from the sugar The optimum conditions for fibre extraction from the various
cane stalk and leaves and characterising these component parts by components of the sugar cane plant depend on the type of sample
elemental analysis, bomb calorimetry, Fourier transform infrared processed; the sample mass used and the disintegrating time vary,
spectroscopy (FTIR), X-ray diffraction, thermogravimetric analysis as detailed in the following section.
(TGA), differential scanning calorimetry (DSC) and scanning elec-
tron microscopy (SEM). To the best of our knowledge this is the 2.3.1. Cane stalk
first time that fibres from all parts of the sugar cane plant have The peeled cane stalks were cut longitudinally into thin sticks
been separated and characterised. (about 6–8 pieces depending on the diameter of the stalk), and put
L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12 3

through a Jeffco cutter-grinder. About 500 g of the sample was then


placed in a Jeffco wet disintegrator, followed by 4 dm3 of water. The
disintegrator was operated at 8000 rpm for 30 s. The fibres were
then inspected to see whether they were well separated and soft;
if not, the disintegration was continued until good separation was
obtained. After all the cutter-ground stalks had been processed in
this manner, the resulting fibres and pith were washed free from
gummy matter and rinsed under tap water, using a 38 ␮m sieve to
catch the sample. Retting of the sample was then effected overnight
in a bucket of water. After which, the sample was washed free from
sucrose and tested for residual Brix. The Brix readings of the wash-
ings were required to be less than 0.01 when 150 cm3 of distilled
water was added to 16 g of the moist pressed fibre-cake sample.
To separate pith from fibre, a sieve assembly was mounted with
a 2 mm, 1.18 mm and 38 ␮m sieve in order on top of each other. A
handful of fibre and pith mixture was put onto the top sieve, and
running tap water was used to wash the pith into the bottom sieve.
Separation of pith from the fibre in the sample was thus effected.
The separated fibre was hand-pressed and placed in a metal tray
for drying in an oven at 65 ◦ C to constant mass. The separated pith
was also dried in the same way.
The dried fibre samples sometimes still contained some pith,
and dry sieving by using a 1.18 mm sieve mounted on top of a
receiver was used to ensure complete separation.

2.3.2. Rind, dry leaves and green leaves


These samples were treated in the same way as cane stalk. Pre-
treatment in a Jeffco cutter-grinder was necessary. In the case of
rind, dry leaves and green leaves, sample masses of 300, 100 and
300 g were treated in the Jeffco wet disintegrator for disintegration
times of 75, 60 and 30 s, respectively.

2.3.3. Cane tops


After the cane tops were detached from the stalks at the point
where they naturally broke off the stalks, they were cut into 10 cm
lengths and into thin strips lengthwise; pre-treatment in a Jeffco
cutter-grinder was therefore not necessary. The top sample was
then treated as for the cane stalk; a sample mass of 400 g was
disintegrated for 60 s in the Jeffco wet disintegrator.
The three replicates (four stalks each) of the four varieties aged
44 weeks were treated in the same manner the following week, and
those aged 36 weeks the week thereafter.
Some relevant fibre extraction processes from the sugar cane
plant are illustrated in Fig. 1.

2.4. Characterisation of the sugar cane component parts

The fibres extracted were investigated by elemental analysis,


bomb calorimetry, FTIR, attenuated total reflectance spectroscopy
(ATR), X-ray diffraction, TGA, DSC and SEM, in order to observe any
structural and morphological differences.

2.4.1. Elemental analysis


The elemental analysis of the nine components of R 570 of 52
weeks age was performed on a ThermoScientific Flash 2000 instru- Fig. 1. Fibre extraction process from sugar cane stalks and leaves. (a) Removal of
ment. Prior to analysis the fibres were dried to ensure the absence cane nodes. (b) Removal of green leaves. (c) Green leaf sample before and after
cutter-grinding. (d) Washing of green leaf sample after cutter-grinding and retting.
of any residual moisture. This was done by first drying the fibres for (e) Green leaf cake washed free from Brix (top) and three fractions after wet-sieving.
2 h in an air-oven at 65 ◦ C, followed by 16 h overnight in a vacuum (f) Dry leaf sample before and after cutter-grinding. (g) Dry leaf cake washed free
oven at 65 ◦ C and 900 mbar. from Brix (top) and three fractions after wet-sieving. (h) Cane top sample cut into
10-cm lengths and then in thin strips before being treated in a wet disintegrator.
(i) Cane stalk with rind (top), with rind removed and cut into thin sticks (left) and
2.4.2. Bomb calorimetry
rind (right). (j) Stalk sample before and after cutter-grinding. (k) Stalk cake washed
The gross calorific value of the extracted fibres was measured free from Brix (top) and three fractions after wet-sieving. (l) Rind sample before and
with a Parr model 1241 adiabatic oxygen bomb calorimeter. Sam- after cutter-grinding. (m) Rind cake washed free from Brix (top) and three fractions
ples of the four cane varieties R 579, R 570, M 1557/70 and M after wet-sieving.
1400/86 (52 weeks old) were analysed. The nodes were rejected
and the combined rind fibre and fines, as well as stalk fibre, stalk
4 L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12

pith and dry leaf, were examined. The fibres were dried at 105 ◦ C 3.1. Dry mass % cane extracted from sugar cane component parts
for 3 h before analysis. Each sample, when required, was removed
from the oven, pressed into a pellet and burnt in the adiabatic The dry mass % cane extracted as rind, stalk fibre and stalk pith
oxygen bomb calorimeter. Benzoic acid was used to calibrate the was calculated and the average results for the samples of the three
calorimeter. ages are presented in Table 2. Since the nodes had been excluded
from fibre extraction, the mass of cane was taken to be the mass
2.4.3. Fourier transform infrared spectroscopy of stalk plus rind only. In the analysis of variance, the three fac-
For the infrared technique, samples of stalk fibre and pith of the tors considered were variety, age and part of plant (three levels:
four different cane varieties aged 36, 44 and 52 weeks, and the fibres rind, stalk fibre and stalk pith). Variety (p = 0.017) and part of plant
extracted from the top, rind, dry leaf and green leaf of the same four (p < 0.001) are significant, but not age. In pairwise comparisons, all
cane varieties aged 52 weeks, were examined. The measurements pairwise differences between parts of the plant are significant. The
were performed on a Nicolet FTIR spectrophotometer. The samples means are: 1.341 (stalk fibre), 2.018 (stalk pith) and 4.982 (rind).
were dried and pressed with KBr into discs for analysis. Additional Thus, the lowest dry mass extracted was from the hard fibre of
measurements were made on the nine cane component parts of R the stalk, followed by stalk pith and rind. In the case of rind the
570 aged 52 weeks with a Perkin Elmer Spectrum 100 Universal percentage fibre extracted decreased with age for all the varieties.
ATR spectrometer. This instrument has a diamond crystal. On the other hand, for stalk fibre this percentage increased with
age (except for R 570). There are no significant pairwise differences
2.4.4. X-ray diffraction between varieties, the means of which are: 2.381 (R 579), 2.816 (M
The cellulose crystallinity of the material from R 570 aged 52 1400/86), 2.955 (M 1557/70) and 2.969 (R 570).
weeks was determined by X-ray diffraction. X-ray data were col-
lected with a Rigaku Miniflex 600 diffractometer with Ni-filtered 3.2. Fibre/pith ratios in cane component parts and in cane
Cu-K␣ radiation. Samples were scanned from 2 of 10◦ to 30◦ with
a step size of 0.02◦ . The crystallinity index (CI) was calculated by Bernhardt (1998), in characterising the particle properties of
the Segal et al. (1959) method where bagasse, suggested that it was not only the mean fibre length
obtained by sieving with an assembly of sieves of differing aper-
I0 0 2 − Iam
CI = × 100 tures that was important; it was also important to determine the
I0 0 2
“coarse-to-fine” ratio of bagasse. This ratio he defined as the mass of
Here I0 0 2 is the diffraction intensity of the peak at about 22.5◦ and particles retained by the sieves with apertures of 2 mm and higher,
Iam is the intensity of the baseline at about 18◦ . divided by the mass of particles that pass through the 0.85 mm
sieve.
2.4.5. Thermal analysis In this work it was found much simpler to separate the fibres
The thermogravimetric experiments were performed on a TA into two fractions, namely, one that is retained by a 1.18 mm sieve
Q600 instrument. Approximately 10 mg of sample was heated from and one that passes through it. The former is referred to as fibre and
ambient temperature to 700 ◦ C at a heating rate of 10 ◦ C/min, under the latter as fines in the case of dry leaf, green leaf, top and rind,
a nitrogen flow of 50 mL/min. DSC was performed on a Shimadzu and as pith in the case of stalk.
DSC-60 using about 5 mg sample in an aluminium pan heated from Results of the fibre/fines ratios of dry leaf, green leaf, top, rind
room temperature to 600 ◦ C at a rate of 10 ◦ C/min. Fibres of the nine and stalk in the four cane varieties at three ages are given in Table 3.
cane component parts extracted from the R 570 sugar cane plant In the analysis of variance, the factors are variety, age and part of
aged 52 weeks were examined. plant (five levels: dry leaf, green leaf, top, rind and stalk). Part of
plant and age are significant (p < 0.001), but not variety. The means
2.4.6. Scanning electron microscopy by part of plant show only one non-significant difference (dry leaf
For the scanning electron microscopy, samples were mounted and rind). They are as follows, with means having a superscript
on an aluminium stub by using double-sided carbon tape, the spec- in common not being significantly different: 0.571a (stalk), 1.402b
imens were then sputter-coated with gold in a Polaron coating (dry leaf), 1.784b (rind), 2.360c (green leaf) and 3.890d (top). Thus it
unit, and viewed in a Leo 1450 scanning electron microscope at can be seen that, irrespective of the cane variety and age, stalk has
10 kV. Fibres derived from cane variety R 570 aged 52 weeks were the lowest fibre/pith value, followed by dry leaf, rind, green leaf and
examined. top. There were no significant pairwise differences between ages,
the means of which are: 1.664 (36 weeks), 2.001 (44 weeks) and
2.5. Statistical analyses 2.339 (52 weeks).
By combining the mass of fibre or pith in both rind and stalk, and
The software used for the statistical analyses was the widely expressing the hard fibre, pith and total fibre as % cane, some mean-
used free statistical computing environment R (R Development ingful results, including the fibre/pith ratio in cane, were obtained
Core Team, 2011). In particular, the routines aov and pairwise.t.test and are presented in Table 4 for the four cane varieties of three ages.
were used to perform analyses of variance and pairwise compar- The changes in these parameters due to the presence of extraneous
isons, the latter with level 0.01 and method = BH, i.e. with the matter, namely dry leaf, green leaf and tops were also calculated
Benjamini–Hochberg adjustment for multiple testing. In all cases and appear in Table 4. This was done because, as was mentioned
variety has four levels (R 579, R 570, M 1557/70 and M 1400/86) earlier, cane stalks are commonly delivered with extraneous mat-
and age has three (36, 44 and 52 weeks). ter to the mills. Again, since the nodes had been excluded from the
fibre extraction, the mass of cane was taken to be the mass of stalk
3. Results and discussion plus rind only. For all varieties and ages, green leaves appear to
affect the fibre/pith ratio the most as indicated by the statistical
The greatest percentage of fibre extracted was from the dry analysis.
leaves, followed by green leaves, tops and cane stalks (rind, pith In the analysis of variance of the fibre/pith ratio, the factors are
and fibre). This is in keeping with the composition of these plant variety, age and type of extraneous matter (four levels: none, dry
parts as indicated in Table 1, where fibres form 18% of the leaves leaf, green leaf and tops). Variety and type of extraneous matter are
and 10% of the stalk. significant (p < 0.001), but not age. For pairwise comparisons the
L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12 5

Table 2
Average dry mass % cane extracted from sugar cane components of four cane varieties and three ages.

Age (weeks) 52 44 36

Sample Rind Stalk fibre Stalk pith Rind Stalk fibre Stalk pith Rind Stalk fibre Stalk pith

R 579 3.60 1.69 1.92 3.80 1.29 2.04 4.13 1.22 1.74
R 570 4.28 1.36 1.73 5.89 1.60 1.92 6.65 1.17 2.11
M 1557/70 4.94 1.62 2.08 5.72 1.34 2.13 5.97 0.92 1.87
M 1400/86 4.80 1.50 2.24 4.98 1.34 2.38 5.02 1.03 2.05

Table 3
Average fibre/fines ratio in cane components of four cane varieties and three ages.

Age (weeks) 52 44 36

Sample Dry leaf Green leaf Top Rind Stalk Dry leaf Green leaf Top Rind Stalk Dry leaf Green leaf Top Rind Stalk

R 579 1.38 2.08 5.43 2.18 0.63 1.13 2.46 3.57 1.91 0.63 1.42 2.47 2.25 2.23 0.55
R 570 1.40 2.08 6.34 1.55 0.69 1.16 2.42 3.35 2.04 0.66 1.72 2.36 2.37 1.53 0.55
M 1557/70 1.31 2.38 5.90 1.91 0.64 0.89 2.30 2.56 1.74 0.55 2.14 2.38 2.31 1.70 0.45
M 1400/86 1.34 2.64 6.90 1.65 0.55 1.04 2.31 3.04 1.39 0.52 1.91 2.44 2.66 1.57 0.45

means by variety are as follows, with means having a superscript the cane reached maturity (9 months) more hard fibre was present
in common not being significantly different: 1.150a (M 1400/86), in the stalks giving approximately equal amounts of hard fibre and
1.276ab (M 1557/70), 1.290b (R 570) and 1.303b (R 579). The means pith. This fibre/pith ratio of approximately one remained constant
by extraneous matter type are: 1.112a (none), 1.198a (dry leaf), for the duration of the season.
1.277a (tops) and 1.432b (green leaf). From Table 4 for the four cane varieties, the pith % cane increases
in all cases (except R 570) as the cane matures from 36 to 44 weeks,
3.2.1. Effect of cane age on fibre and pith contents of cane but decreases from 36 to 52 weeks. However, there is no indication
As the cane matures, the hard fibre % cane is expected to of an increase of hard fibre % cane with age in any of the four cane
increase, as is the total fibre % cane. varieties. In fact, the value found for the total fibre % cane was on
Moodley (1991) tested two cane varieties aged 6 months and the low side. This can be attributed to the fact that the samples
19 months. With one variety, the fibre/pith ratio did not vary to a examined had had the nodes eliminated, and some probably had
large extent; it was 2.22 and 2.27 for the 6-month and 19-month some stalk and rind removed in the process as in the case of cane
samples respectively, whereas for the other, it was 2.94 and 3.45 aged 52 weeks. However, R 570, M 1557/70 and M 1400/86 did
respectively. show an increase in hard fibre % cane from 36 weeks to 44 weeks.
Snow (1974) investigated the seasonal variations in the ratio of In spite of this shortcoming, the fibre/pith value in cane calculated
hard fibre to pith within a cane variety at regular monthly intervals can still be considered as reliable since both Moodley (1991) and
for 7–12-month old cane. Young or immature cane had more pith Snow (1974) had found that fibre/pith ratio remained more or less
than hard fibre with a fibre/pith ratio of about 0.58 at 7 months. As constant.

Table 4
Average effect of extraneous matter on fibre/pith ratio in four cane varieties and three ages.

R 579 R 570 M 1557/70 M 1400/86

Age (weeks) 52 44 36 52 44 36 52 44 36 52 44 36

Initial
Mass of cane/g 4740 4540 2827 4020 4487 4020 5087 3897 2747 4653 4397 3340
Hard fibre % cane 3.80 4.04 4.14 3.68 5.71 5.51 4.46 5.09 4.89 4.24 4.39 4.31
Pith % cane 3.18 3.60 3.46 3.51 4.42 5.10 3.77 4.62 4.41 4.03 4.78 4.44
Total fibre % cane 6.98 7.64 7.61 7.19 10.13 10.61 8.22 9.71 9.30 8.27 9.17 8.75
Fibre/pith ratio 1.21 1.12 1.20 1.08 1.30 1.08 1.20 1.11 1.11 1.06 0.92 0.97
Dry leaf
Mass added/g 207 583 253 253 533 323 230 553 193 287 547 290
% gross cane 4.49 11.80 8.08 6.09 10.60 7.67 4.43 12.45 6.55 5.75 10.99 8.23
Hard fibre % cane 5.34 6.11 6.76 5.58 7.41 8.36 5.73 6.41 7.26 6.04 6.30 7.57
Pith % cane 4.24 5.41 5.24 4.78 5.96 6.63 4.71 6.26 5.38 5.28 6.52 5.99
Total fibre % cane 9.59 11.52 12.00 10.36 13.37 14.98 10.44 12.67 12.64 11.33 12.83 13.55
Fibre/pith ratio 1.27 1.13 1.29 1.18 1.25 1.26 1.22 1.02 1.35 1.15 0.97 1.27
Green leaf
Mass added/g 720 880 583 840 897 1010 980 853 757 663 800 777
% gross cane 13.86 16.85 17.12 17.47 16.97 20.81 17.51 18.10 21.51 12.04 15.43 19.07
Hard fibre % cane 5.48 5.87 6.23 5.76 7.38 8.18 6.67 6.97 7.39 5.92 6.36 7.06
Pith % cane 3.81 4.03 4.01 4.24 4.78 5.67 4.39 5.00 4.97 4.40 5.18 5.07
Total fibre % cane 9.28 9.90 10.24 10.00 12.16 13.85 11.06 11.96 12.36 10.32 11.54 12.13
Fibre/pith ratio 1.45 1.45 1.55 1.37 1.56 1.44 1.53 1.40 1.49 1.34 1.23 1.40
Tops
Mass added/g 603 450 300 680 570 413 660 433 370 460 527 387
% gross cane 12.27 9.47 9.57 14.78 11.60 9.76 12.61 10.10 11.90 9.23 10.70 10.45
Hard fibre % cane 4.01 4.45 4.77 4.00 6.18 6.22 4.97 5.45 5.66 4.84 5.03 5.22
Pith % cane 2.91 3.48 3.65 3.10 4.25 5.28 3.48 4.49 4.62 3.80 4.63 4.64
Total fibre % cane 6.92 7.93 8.42 7.09 10.43 11.50 8.45 9.94 10.28 8.64 9.66 9.86
Fibre/pith ratio 1.39 1.28 1.30 1.32 1.46 1.18 1.46 1.22 1.23 1.28 1.09 1.13
6 L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12

Table 5
Elemental analysis of fibres from sugar cane plant.

Component C H O Sum General formula Cx Hy Oz Relative ratio

(C + H + O) x y z C/Sum H/Sum O/Sum

Stalk fibre 46.080 5.691 46.125 97.896 1.000 1.472 0.751 0.471 0.058 0.471
Stalk pith 44.388 5.880 48.328 98.596 1.000 1.579 0.817 0.453 0.060 0.494
Rind fibre 46.774 5.857 45.689 98.320 1.000 1.492 0.733 0.478 0.060 0.467
Rind fines 46.474 5.925 45.399 97.798 1.000 1.519 0.733 0.475 0.061 0.464
Top fibre 41.498 5.005 46.729 93.232 1.000 1.437 0.845 0.424 0.051 0.477
Green leaf fibre 39.115 2.973 45.049 87.137 1.000 0.906 0.865 0.400 0.030 0.460
Green leaf fines 37.391 1.865 45.173 84.429 1.000 0.594 0.907 0.382 0.019 0.461
Dry leaf fibre 45.202 5.788 47.350 98.340 1.000 1.526 0.786 0.462 0.059 0.484
Dry leaf fines 44.631 5.114 44.766 94.511 1.000 1.365 0.753 0.456 0.052 0.457
Cellulose 44.46 6.17 49.37 (C6 H10 O5 )n
Pentosan (xylan) 45.47 6.06 48.47 (C5 H8 O4 )n
Lignin 64.80 6.34 28.86 C9 H8.83 O2.37 (OCH)0.96
Sugar cane bagassea 45.50 5.60 45.20
a
Bilba et al. (2007).

3.2.2. Effect of cane variety on fibre/pith ratio in cane The elemental composition of the fibres is shown in Table 5.
From Table 4, for the mature cane aged 52 weeks, the fibre/pith In addition, the relative ratios calculated as (element amount/sum
ratios of R 570 and M 1400/86 were close to the expected value amount) and general formulae are given to facilitate comparisons.
of one with values of 1.08 and 1.06 respectively, whereas those The elemental composition and general formulae for the main com-
of R 579 and M 1557/70 were high, at about 1.20. According to ponents of the fibres, namely, cellulose, hemicellulose and lignin,
Snow (1974), cane with a high ratio of hard fibre to pith, e.g. 1.52, are given after Ouensanga (1989). Rind fibres and rind fines showed
causes problems in milling due to the toughness of the stalks entail- the highest carbon content. This reflects the higher lignin content
ing excessive maintenance of the equipment due to stress and mill of the rind since lignin imparts mechanical strength to these outer
chokes induced by bagasse jamming in the radial and juice grooves. fibres of the cane stalk. Green leaf fibre and fines exhibited the
On the other hand, cane varieties with more pith than hard fibre, lowest carbon and hydrogen content. Since this is the growing part
with a fibre/pith ratio of about 0.6, cause an overall slowdown in of the plant, it is likely that this part contains more nitrogen (not
mill operations manifested in occasional reduced grinding rates measured) and hence these lower amounts. The composition of the
due to the soft “mushy” consistency of the macerated material stalk fibres agreed very well with that reported by Bilba et al. (2007)
leading to mill roll slippage or chokes, and high residual mois- for sugar cane bagasse. Stalk pith contained less carbon than stalk
ture content of the bagasse. Varieties with approximately equal fibres. In the case of the other locations, the fines fraction also con-
amounts of hard fibre and pith proved to be the best milling vari- tained marginally less carbon but this was within the experimental
eties. Hence the varieties investigated here should be considered error margin so is not conclusive. The relative ratios (C/Sum) and
good milling varieties if judged on their fibre/pith ratios. (H/Sum) were smaller for top fibre and green leaf fibre and fines,
Snow (1974) tested eight cane varieties of 11-month maturity, whereas for the other components they were similar. The ratio
where the fibre/pith ratio varied from 0.66 to 1.52 and fibre % cane (O/Sum) was virtually constant irrespective of the location of the
(presumably total fibre % cane) ranged from 9.0 to 12.2. Moodley fibre. Ouensanga (1989) observed that between the bottom and the
(1991) tested four different varieties of cane aged 19 months and top of the sugar cane stalk there was a decrease in lignin and pen-
found that although the fibre/pith ratio did vary from 2.00 to 2.86, tosan content, whereas the cellulose content increased up to the
there was not much difference in pith % cane, but that the hard fibre middle of the stalk and then decreased up to the top.
% cane did vary over a wide range from 8.85 to 12.86. Since sugar cane bagasse is widely used as an energy source it
In this study, with the four cane varieties aged 52 weeks, was of interest to determine the amount of energy provided by the
fibre/pith ratio in cane ranged from 1.06 to 1.21, in agreement with various components of the plant. The results of the determination
values found by Snow (1974). Hard fibre % cane varied from 3.68 to of the gross calorific value (GCV) of the various cane components
4.46, pith % cane from 3.18 to 4.03, and total fibre % cane from 6.98 are listed in Table 6. THE GCV is the amount of heat released from
to 8.27. As mentioned earlier, the total fibre % cane values appear a specific quantity of material after it is burnt and the products are
to be low, as do those of hard fibre % cane. cooled back to the pre-combustion temperature. In the analysis of
variance the factors are variety and part of plant (four levels: rind,
stalk fibre, stalk pith and dry leaf). Both variety and part of plant are
3.2.3. Effect of extraneous matter on fibre/pith ratio in cane
significant (p < 0.001). Pairwise comparisons between parts of plant
From the data in Table 4 it can also be seen that all the extrane-
show only one non-significant difference (stalk fibre and rind). The
ous matter (dry leaves, green leaves and tops) added to clean cane
means by part of plant are as follows: 17,512a (stalk pith), 18,268b
increases the fibre/pith ratio (except dry leaf when added to 44
(dry leaf), 19,041c (stalk fibre) and 19,443c (rind). Thus, the rind
week old cane) and hard fibre % cane. Dry and green leaves, in addi-
has the highest gross calorific value, followed by stalk fibre and dry
tion, increase pith % cane and total fibre in cane but not cane tops.
These results are consistent with the adverse effects of extraneous
matter reported by Wong Sak Hoi and Martincigh (2012). Table 6
Gross calorific value of sugar cane components.

Sample Gross calorific value of dried sample/kJ kg−1


3.3. Characterisation of sugar cane component parts
Rind Stalk fibre Stalk pith Dry leaf
A number of techniques were employed to characterise the com- R 579 19,241 19,411 17,927 18,211
ponents separated from the sugar cane plant. These were elemental R 570 19,885 19,302 17,318 19,085
analysis, bomb calorimetry, FTIR, X-ray diffraction, TGA, DSC and M 1557/70 19,203 18,978 17,086 17,734
M 1400/86 19,444 18,472 17,716 18,042
SEM.
Table 7
Peak wavenumbers (in cm−1 ) of the main IR absorption bands and their interpretation including values of crystallinity indices for the nine fibre components of R 570 aged 52 weeks.

Stalk fibre Stalk Rind Rind Top Green leaf Green leaf Dry leaf Dry leaf Cellulose Hemicellulose Lignin Assignmenta
pith fibre fines fibre fibre fines fibre fines

L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12
3334.45 3332.24 3330.49 3335.49 3326.78 3325.78 3329.25 3318.87 3323.3 X O H stretching vibration
2898.77 2895.05 2894.40 2900.06 2917.55 2918.82 2919.29 2918.50 2917.70 X C H stretching vibration
2851.49 2850.81 2850.71 X CH2 symmetric stretching vibration
1727.51 1726.89 1728.52 1727.75 1730.73 1730.75 1729.87 1731.06 1727.89 X X C O stretching vibration
1632.85 1634.03 1631.60 1633.20 1635.62 1633.13 1633.88 1625.03 1632.5 X H O H bending of adsorbed water
1602.82 1604.49 1603.26 1603.90 1604.51 1604.56 1603.57 X C C stretching of aromatic ring
1514.21 1514.83 1509.39 1511.61 1513.59 1513.87 1513.90 1515.22 1511.21 X C C stretching of aromatic ring
1456.59 1455.89 1462.38 1455.89 X X C H bending
1424.76 1427.02 1424.71 1424.93 1427.07 1427.06 1427.45 1428.99 1423.51 X C H bending
1370.93 1370.63 1368.33 1369.35 1370.15 1368.44 1370.07 1367.83 1369.17 X C H bending
1321.82 1319.22 1321.48 1320.85 1317.88 1316.72 1318.08 1317.70 1318.32 X C H bending
1242.93 1245.77 1242.29 1242.49 1244.98 1244.54 1244.74 1239.78 1245.62 X C O C stretching of ether linkage
1159.63 1159.92 1159.59 1160.55 1157.90 1161.51 1160.58 1160.52 1159.74 X C O C, C OH stretching
1102.88
1033.15 1032.50 1029.2 1033.67 1028.97 1032.78 1034.53 1034.65 1031.05 X C OH stretching
897.68 897.97 897.06 897.74 897.79 897.19 897.58 897.03 897.54 X X ␤-Glycosidic linkages of glucose ring in
cellulose
833.05 833.76 833.53 833.35 831.28 833.86 833.49 833.28 831.75 X
718.86
663.66 663.53 661.70 663.23 663.74 Out of plane bending vibration of
intermolecular H-bonded O H groups
and out-of-plane O H bending
560.49 561.68 554.36 558.23 563.76 546.65 558.51 557.27 563.64 Torsional vibration of pyranose ring
523.96 523.12 527.88
460.88
0.7680 0.6863 0.7390 0.8130 0.4267 0.1995 0.7219 0.1818 0.5309 Total crystallinity index (TCI)
0.6111 0.4398 0.8542 0.7178 0.4430 0.2264 0.3706 0.2021 0.4361 Lateral order index (LOI)
50.32 45.62 68.68 55.31 50.91 51.42 46.32 51.91 46.54 Crystallinity index as determined by X-ray diffraction
a
Bilba and Ouensanga (1996), Cherian et al. (2008), Garside and Wyeth (2003), Morán et al. (2008), Mwaikambo and Ansell (2002) and Viera et al. (2007).

7
8 L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12

leaf. Stalk pith has the lowest value. This trend is in keeping with the 2918 and 2850 cm−1 ). This doublet is characteristic of the spectrum
carbon content of the components. Pairwise comparisons between of hemicellulose (Fan et al., 2012). All the infrared absorbance peaks
varieties show no significant differences. The means are: 18,250 (M for the components are listed in Table 7, along with their corre-
1557/70), 18,418 (M 1400/86), 18,697 (R 579) and 18,897 (R 570). sponding assignments as found in the literature and whether they
The stalk fibres of R 579 and R 570 have higher values than those arise from the cellulose, hemicellulose or lignin component. The
of the other two cane varieties. The GCV values obtained here for ATR–FTIR spectra for the components of R 570 aged 52 weeks are
dried rind and stalk fibres are close to the value of 19.25 MJ kg−1 shown in Fig. 2.
reported by Hugot (1986) for dry bagasse. Cellulose crystallinity in the fibres is an important parameter
The sugar cane fibre samples from the various component parts since it affects the thermal stability and the mechanical properties
were analysed by FTIR and ATR–FTIR in order to confirm the of the fibres. It was assessed by both FTIR spectroscopy and X-ray
presence of the main chemical constituents. The resulting spectra diffraction. It must be borne in mind that these crystallinity values
contained essentially the same bands that are typical of ligno- are relative measures and not absolute values.
cellulosic fibres. For all samples the strongest peaks occurred at The relative crystallinity of the fibres was assessed by calcu-
approximately 3327 and 1032 cm−1 . These arise from O H and lating the FTIR indices proposed by Nelson and O’Connor (1964).
C OH stretching vibrations, respectively. The fibres arising from They established the absorption band at 1430 cm−1 as typical of
the cane, namely stalk and rind, showed one absorption peak at crystalline regions, and that at 900 cm−1 as typical of amorphous
approximately 2900 cm−1 . Those fibres arising from the leaves and regions in the polymer (O’Connor et al., 1958). The ratio of the inten-
tops, however, showed a doublet in this region (at approximately sities of these two bands is termed the “lateral order index” (LOI).

Fig. 2. ATR–FTIR spectra of the nine components of R 570 aged 52 weeks: (a) stalk fibre, (b) stalk pith, (c) rind fibre, (d) rind fines, (e) top fibre, (f) green leaf fibre, (g) green
leaf fines, (h) dry leaf fibre, (i) dry leaf fines.
L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12 9

Later they arrived at another crystalline index from the ratio of the The pyrolysis characteristics of the nine components in an inert
bands at 1372 and 2900 cm−1 called the “total crystallinity index” atmosphere of nitrogen are shown in Fig. 3 in the form of TG and
(TCI) (Nelson and O’Connor, 1964). From the values listed in Table 7 DTG curves. All the components showed a small weight loss at
it is apparent that the fibres from the rind are the most crystalline low temperatures (<100 ◦ C). This corresponds to the evaporation
followed by stalk fibres. Those fibres derived from the leaves are of physically adsorbed water. Because of the hygroscopic nature
the least crystalline since they contain more amorphous polymers. of the fibres, the amount of moisture is highly dependent on the
Hemicelluloses and lignin are amorphous polymers, whereas cel- ambient humidity and the manner in which the fibres are han-
lulose contains crystalline and amorphous regions. In sugar cane, dled. The fibres are essentially stable up to a temperature of 200 ◦ C.
cellulose I is the predominant polymorph of cellulose, hence the Thereafter, the thermal stability decreases and pyrolysis occurs.
LOI is an indication of the amount of cellulose I in the fibres (Oh Yang et al. (2007) investigated the individual pyrolysis char-
et al., 2005). A knowledge of the degree of crystallinity of the fibres acteristics of the three main components of biomass, namely,
is important since this controls the degree of reactivity. Most reac- hemicellulose, cellulose and lignin. They found that the max-
tants only penetrate the amorphous regions on the surface (Ciolacu imum weight loss for hemicellulose and cellulose occurred at
et al., 2011). 268 ◦ C and 355 ◦ C respectively. Lignin was difficult to decompose
The crystallinity index as measured by powder X-ray diffraction and did so slowly from ambient temperature to 900 ◦ C with no
is a measure of the amount of crystalline cellulose present in the clear maximum. The solid residue remaining was the highest for
biomass. The CI values listed in Table 7 indicate that rind fibres fol- lignin (45.7 wt.%), followed by hemicellulose (20 wt.%) and cellu-
lowed by rind fines contain the most crystalline cellulose and stalk lose (6.5 wt.%). The DSC thermograms showed that the pyrolysis
pith the least. Therefore, sugar cane, unlike wheat straw (Liu et al., of cellulose at 355 ◦ C was endothermic, but those of hemicellulose
2005), shows a variation in the crystallinity index for different tis- at 275 ◦ C and lignin at 365 ◦ C were exothermic. They accounted
sue types. The CI has also been shown to differ between the stems for this behaviour in terms of the structures of the three compo-
and leaves of sorghum (Reddy and Yang, 2007), which like sugar nents. Hemicellulose consists of saccharides and has a random,
cane, is also a C-4 photosynthetic grass. This may be attributed amorphous and branched structure which is easy to decompose at
to a difference in the content of amorphous components, that is, low temperatures. Cellulose, on the other hand, is a long polymer
hemicellulose and lignin, in the component parts. The CI and LOI of glucose without branches, is ordered and has hydrogen bond-
values for the material derived from the cane (namely, stalk and ing, and is therefore more difficult to decompose. Lignin consists of
rind) are in the same relative order. However, for the rest of the differing aromatic rings with branching and therefore decomposes
fibres there is no coherence between the CI and LOI. As has been over a wide thermal range. The three components therefore do not
observed by other workers (Colom et al., 2003), and as is the case decompose as three independent reactions.
here, there is also no coherence between the TCI and LOI values. As At temperatures above 200 ◦ C the DTG curves in Fig. 3 show two
mentioned by Colom et al. (2003) the band at 2900 cm−1 does not overlapping peaks for the fibres from the stalk and rind whereas, for
arise exclusively from cellulose and it may be that the TCI is not a the fibres from the tops and leaves, two clear maxima are observed.
suitable indicator for multicomponent samples. In fact, Garside and All the curves exhibit tailing at temperatures greater than 400 ◦ C.
Wyeth (2003) have used the absorption at 2900 cm−1 as a measure The first maximum occurs at approximately 300 ◦ C and corresponds
of overall organic content for such multicomponent samples with to the decomposition of hemicellulose and lignin. The second max-
some degree of success. imum at approximately 350 ◦ C arises from the decomposition of

Fig. 3. TG (a) and (b) and DTG (c) and (d) thermograms for the nine components of the sugar cane plant R 570 aged 52 weeks determined in an atmosphere of nitrogen.
10 L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12

Table 8
Thermal analysis results for the fibres from the nine components of R 570 aged 52 weeks.

Component Thermogravimetric analysis in an inert atmosphere of nitrogen Differential scanning calorimetry in an


oxidative atmosphere of air

First-decomposition Second-decomposition Residue at 700 ◦ C/mass % First-combustion Second-combustion


temperature/◦ C temperature/◦ C temperature/◦ C temperature/◦ C

Stalk fibre 317 365.0 9.1 356.38 480.22


Stalk pith 306 363.2 21.4 344.19 444.72
Rind fibre 313 363.8 6.4 356.37 498.87
Rind fines 310.5 367.6 7.1 352.72 492.89
Top fibre 310.5 357.8 14.5 356.38 469.39
Green leaf fibre 302.8 358.1 12.7 352.73 476.68
Green leaf fines 305.2 359.7 14.4 349.89 456.64
Dry leaf fibre 308.2 353.9 18.1 358.19 456.64
Dry leaf fines 309.8 357.5 21.1 352.73 440.22

10
30
30

5 20
Heat/mW

Heat/mW
20
Heat/mW

10
10
0
0 200 400 600 0
0
0 200 400 600
0 200 400 600
-5 -10
-10
Temperature/oC Temperature/oC
Temperature/oC

Stalk fibre Stalk pith Rind fibre

20 30
20
20
Heat/mW

Heat/mW
Heat/mW

10
10
10
0
0 0
0 200 400 600
0 200 400 600 0 200 400 600
-10 -10 -10
Temperature/oC Temperature/oC Temperature/oC

Rind fines Top fibre Dry leaf fibre


30
20
20
20
Heat/mW
Heat/mW
Heat/mW

10
10 10

0 0 0
0 200 400 600 0 200 400 600 0 200 400 600

-10 -10 -10


Temperature/ C o Temperature/oC Temperature/oC

Dry leaf fines Green leaf fibre Green leaf fines


Fig. 4. DSC curves for the nine cane component parts of R 570 aged 52 weeks in an atmosphere of air.
L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12 11

cellulose and lignin. Since lignin decomposes at a very slow rate The DSC thermograms recorded in air are displayed in Fig. 4.
over 100–900 ◦ C a maximum is not clearly visible apart from the They show an endotherm below 100 ◦ C that corresponds to the
tailing in the DTG curves at temperatures greater than 400 ◦ C. It evaporation of moisture from the fibres. There are two exotherms:
has been noted that the two degradation maxima observed here one at approximately 350 ◦ C (range 344–358 ◦ C) and the other
are not always clearly visible (as is the case for the fibres from stalk between 440 and 500 ◦ C (see Table 8). It is known that in air
and rind) (Griffin, 2011). This has been attributed to the presence the pyrolytic temperature is lowered (White et al., 2011). Griffin
of inorganic materials that catalyse the decomposition reactions. (2011) showed that the DTG plots for bagasse in an air environ-
Washing with water has been shown to reduce this mineral con- ment exhibited maxima at 325 and 454 ◦ C. The first was ascribed
tent (Müller-Hagedorn et al., 2003), leading to a separation of the to hemicellulose and cellulose degradation and the second to oxi-
merged peaks (Manya and Arauzo, 2008). The pre-treatment of dation of char and non-volatile material. From our results it appears
the fibres in this work with water in order to separate them has that these are exothermic processes. Ramajo-Escalera et al. (2006)
therefore decreased the mineral content. Table 8 lists the degrada- found that in an oxygen environment the two exotherms occurred
tion temperatures and the amount of residue remaining at 700 ◦ C at 316 and 436 ◦ C, which is consistent with our findings since their
for the various samples. Green leaf fibres showed the lowest first- results are for a more oxidative environment than air.
decomposition temperature and stalk fibres the highest. For the All the scanning electron micrographs showed normal wood tis-
nine components the first-decomposition temperatures fell within sues such as parenchyma and wood fibres, and no difference was
the range 303–317 ◦ C and the second-decomposition temperatures detected in the fibres of dry leaf, green leaf, rind, stalk and top
fell within 354–368 ◦ C. The maximum degradation rates reported (Fig. 5). These components are fibrous, exhibit bundles of microfib-
for bagasse by Griffin (2011) occurred at temperatures of 308 and rils and have a high aspect ratio. Stalk pith (Fig. 5b), however,
358 ◦ C which fall within these ranges. Han and Wu (2004) ana- appears to be different; it is flaky, does not exhibit the fibrous nature
lysed sugar cane rind and reported the temperatures of maximum and has a higher surface area than the other components. The fibres
weight loss for the outer layer of the rind as 368 ◦ C, the middle layer from the fines components (Fig. 5d, g and i) contain some debris
of rind as 373 ◦ C and the inner rind layer as 372 ◦ C. These values are together with shorter aspect ratio fibres.
consistent with the second decomposition temperatures reported Some consistencies are evident from the results of the various
here for rind fibre and rind fines. Rind fibres produced the least characterisation techniques. If one considers the four components
amount of residue (6.4 wt.%) at 700 ◦ C, whereas stalk pith produced that arise from the cane, namely, rind fibre, rind fines, stalk fibre
the most (21.4 wt.%). This is, however, less than the 35% reported and stalk pith, in that order, they are in the same order as the
by Ramajo-Escalera et al. (2006) for sugar cane bagasse. (i) LOI ratio (highest to lowest) which is an indicator of the

Fig. 5. Fibres of the sugar cane components of R 575 aged 52 weeks observed under a scanning electron microscope. (a) Stalk fibre. (b) Stalk pith. (c) Rind fibre. (d) Rind fines.
(e) Top fibre. (f) Dry leaf fibre. (g) Dry leaf fines. (h) Green leaf fibre. (i) Green leaf fines.
12 L. Wong Sak Hoi, B.S. Martincigh / Industrial Crops and Products 47 (2013) 1–12

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