Exploration On Industrial Production and Thermo-Chemical

2nd Conference on Chemical Engineering and Advanced Materials (CEAM)
VIRTUAL FORUM
Naples 2010
Section: P: Conventional Materials and Related processing (P5)
Exploration on industrial production and thermo-chemical

properties of Egyptian rice straw cellulose pulps
Raafat M. Issa1, Morsi M. Abou-Sekkina1, Abdalla M. Khedr1, Alam El-Deen M. Bastawisy2

and Wael A. El-Helece3*
Abstract – Cellulose from rice straw obtained at low sodium hydroxide

solution concentration with high quality was used to obtain different
cellulose derivatives through xanthation. Cellulose was then treated with
carbon disulfide in the presence of sodium hydroxide. The viscose obtained
was characterized with both chemical and instrumental analyses namely; IR
spectra, TGA and DTA analysis as well as SEM (scanning electron
microscopy)..
Keywords: Cellulose, Xanthation, IR spectra, TGA, DTA and SEM analyses.
numerous hydroxyl groups, and increase the
1. Introduction hydrophobicity. Introducing ester and ether groups
Production of cellulose from Egyptian rice separates the cellulose chains almost completely
straw could be attained through many methods that the fiber structure is either altered or destroyed.
known generally for the extraction of cellulose The solubility of a cellulose derivative in a solvent
from its sources [1] and especially from rice straw or in water depends on the type of substituents, the
[2]. In this study, cellulose was obtained using the degree of substitution and the molecular weight.
semi-chemical method (treatment of mechanically These cellulose derivatives are grouped according
divided rice straw with sodium hydroxide). The to the processes and chemical substituents [8-11].
produced cellulose was described using IR analysis The technology of the synthesis of viscose
[3, 4]. Cellulose can not be dissolved in water. from raw materials has certain problems [13, 14]
Introducing hydrophilic groups along the chain of connected with low rate of the process and
cellulose cleaves the hydrogen bonds and renders impossibility of preparation of a product with high
its derivatives soluble in conventional solvents, homogeneity on some qualitative indices. This is
widening its applications to, for example, functional due to low reactivity and mass-diffusion of rice
cellulose ethers and esters [3-7]. straw cellulose during the treatment with aqueous
Commercial cellulose derivatives are either solution of sodium hydroxide. It has been
ethers or esters that are soluble in water or organic established, as a result of experiments that, with the
solvents. The three free hydroxyl groups in the use of raw materials mixtures for complete
AGUs react with various functional substitution treatment of rice straw, the arising problems studied
groups. The resultant subsistents therefore disturb must be solved.
the inter- and intra-molecular hydrogen bonds in

cellulose, reduce the hydrophilic character of the
Copyright © 2009 Praise Worthy Prize S.r.l. - All rights reserved 2nd Conference on Chemical Engineering and Advanced
Materials (CEAM)
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In the present research work, the experiments 2.1.4. Effect of cooking temperature on the yield of
pulp
for preparation of laboratory parts of cellulose
10 g samples from rice straw were treated
pulps from rice straw were carried out. The
with 100 ml 10 % NaOH solutions for 2 hrs. at
obtained samples were allowed for IR spectra, TGA
different degrees (40, 60, 80 and 100 oC).
and DTA analysis as well as chemical analysis
(permanganate number determinations) for
comparison between xanthated and original 2.1.5. Effect of the nature of rice straw on the pulp
yield
samples. Scanning electron microscopy (SEM) was
also employed for micro-structural studies.
with 100 ml of 10 % NaOH solutions for 2 hrs. at
boiling point, length of samples used were the
2. Experimental
whole plant (80-120 cm length), 20 cm, 10 cm, 5
2.1 Cooking conditions cm and mechanically divided plant (less than 1 cm).
In these tests, samples from rice straw were

treated with NaOH solutions of different 2.2. Bleaching
concentrations for different time periods at different The pulps produced by NaOH pulping are
temperatures. pale to intense yellow in color and requires

bleaching to reach acceptable brightness. The
2.1.1. Effect of sodium hydroxide concentration brightness of bleached pulp depends on the
bleaching sequences and conditions. So in this
Sodium hydroxide acts as a solublizing agent
study the pulp were treated with sodium bisulphate
for both silica and lignin found in raw materials. 10
solution (4 % and 8 %), and with sodium hydroxide
gm samples were boiled with 100 ml NaOH
solution (4 %) then with hydrogen peroxide
solution of certain concentrations (4 %, 6 %, 8 %,
solution (4 %) [14].
10 % and 12 %) for 2 hours.
2.3. Xanthation
2.1.2. Effect of time at optimum alkalinity
0.5 g of pulp was exactly weighted, placed in
10 g samples were leached with 100 ml of 10
a wide mouth bottle of 150 ml capacity, 100 ml of
% NaOH solutions and were boiled for different
water was added to the pulp and it was allowed to
time periods (1, 2, 3 and 4 hours).
swell in the closed bottle for at least one hour. 50
ml of NaOH solution (280.6/g/L), and 3.5 ml of
2.1.3. Effect of weight / volume ratio
carbon disulphide were added in this sequence, then
the bottle was stoppered. The glass stopper must be
with 10 % NaOH solutions while boiling for 2 hrs.
fixed on the bottle as quickly as possible; the bottle
in different weight per volume ratios 1/5, 1/10, 1/20
was then shaken for 15 minutes and allowed to
and 1/50 (w/v).
rotate in the thermostat at room temperature for 6
hrs.
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2.4. Permanganate number [15] from room temperature up to 1000 oC using 10

o
It is a method of expressing bleachability of C/min heating rate under nitrogen as atmosphere.
pulp. It is determined by the number of mls of 0.1N The differential thermal analysis (DTA) was
KMnO4 consumed by one gram of moisture free performed on 990 Du-Pont differential thermal
pulp under certain specific conditions of time, analyzer of 1200 °C cell using Al2O3 as a reference.
temperature and acidity. Required volume of 0.1N The surface of rice straw and pulp from rice straw
KMnO4 (20 – 40 ml depending upon the rawness samples imaged with the (SEM) scanning electron
of the pulp) were paced in one beaker, an equal microscopy type, JEOL JEM-850 operating at 35
amount of 4N H2SO4 is placed into another beaker kV employed in the Central laboratory, National
and enough water combined with H2SO4, so that, Research Centre, Cairo, Egypt. Samples are
in the final reaction mixture of the permanganate investigated as it is without any change in their
solution will be 1/300 N. When the reagent is physical form.
ready, the pulp specimen is added to the reaction
beaker, followed by addition of sulfuric acid and 3. Results and Discussion
then by addition of permanganate. After exactly 5
minutes at 25 oC an excess of KI is added to stop 3.1. Analysis of raw materials and obtained
cellulose pulp
the reaction. The residual KMnO4 in the mixture
Three samples from rice straw collected
released an equivalent weight of iodine from the
from different places from El-Delta region, Egypt
iodide salt solution. The liberated iodine is then
were subjected for the analysis to determine fibrous
titrated against stander sodium thiosulphate
part of rice straw for each sample. The American
solution [15]. The volume of permanganate
Tappi standards were used in most of the chemical
consumed by the pulp is then calculated. The
analyses of the raw materials and pulps involved in
permanganate number is obtained by dividing the
this work [16]. The results obtained for different
number of mls of 0.1N KMnO4 consumed by the
samples included in this study indicate that the
moisture free weight of the test specimen;
moisture content varies from 10 into12 % and the
25 - V
permengana te number = presence of 10-12 % of water soluble matters
W
whereas the ash content was found to vary from 12-
where V is the number of milliliters of 0.1 N
16 %. The percentage of α-celluloses increases
Na2S2O3 consumed in the titration, W is the weight
from 29 % in raw material into 90 % in the
of moisture free pulp and 25 is the number of mls
obtained pulp.
of 0.1 N KMnO4.
2. Effect of cooking conditions

4. Equipments
The results for different experiments
IR absorption spectra were recorded as KBr
described in the experimental part for this factor,
discs within the 4000-200 cm-1 range on a Perkin
reveals that cooking mechanically divided rice
Elmer 1430 infrared spectrophotometer. The
straw in 10 % NaOH solution for 2 hrs with boiling
thermal gravimetric analysis (TGA) was carried out
and 1/50 (w/v) ratio are the best pulping condition.
on a Shimadzu TG 50 thermogravimetric analyzer
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3. Infrared spectrophotometric study of cellulose hydroxide solution. The group of bands within
obtained from high yield soda rice straw pulps
the 1400-1200 cm-1 becomes sharper with rise
Issa et al. [3, 4], in an article on the silylation
of either NaOH concentration or cooking
of cellulose gave a collective assignment for the
temperature. The intensity of most bands
infrared absorption spectra of the different kinds of
decreases in the same direction while the peaks
cellulose and tabulated the main important bands of
at 1630-1370 cm-1 tend to be sharp and display
each kind. This table is actually very beneficial for
a slight increase in peak intensity. The bands
obtaining the assignments of IR bands of cellulose
within the 1200-900 cm-1 region tend to be less
materials. Hence it is considered to be of great help
broad in the spectra of the pulps, yet the most
for assigning the IR spectra of rice straw pulps
obvious change in this region is the appearance
obtained under different conditions of cooking the
of some sharp peaks near 1100 cm-1. These
rice straw with sodium hydroxide solutions. The
changes recall more or less those observed with
band assignments given by previous authors in
mercerization of cellulose and can be similarly
many studies were helpful in obtaining the correct
accounted for [18].
assignments for the various bands in the IR
TABLE 1
absorption spectra of rice straw pulp samples
obtained under different cooking conditions [17]. ASSIGNMENTS OF BANDS IN THE IR SPECTRUM OF RICE STRAW
PULP
The data obtained are collected in table 1. In this
Wave Wave
point of our study we would discuss the number Assignment number Assignment
(cm-1) (cm-1)
assignments of the bands in the IR spectra of
δCH in pyran
3600 υOH free 1475
Egyptian rice straw and the changes in the infrared ring
spectra which take place during the pulping and υOH (w) H- δCH2 in pyran
3560 1460
bond ring
xanthation processes. On comparing the spectrum
υOH (m) H- δCH2 internal
3450 1450
of the obtained pulp samples under different bond deform.
conditions of treatment and xanthated cellulose δOH3 and R-O-

3380 υOH (s) H-bond 1435
Ar ether
samples (Figs. 1-3) the following can be pointed
δCH2 external
3250 υOH (s) H-bond 1385
out: deform.
a- The broad δOH band at 1600 cm-1 tends to be 3100

υCH asym.
1340
δCH2 external
aromatic deform.
less broad in the spectra of the pulps, υCH asym.
3050 1285 δOH phenolic
meanwhile the band envelopes becomes more aromatic
υCH asym. δCH2 external

symmetrical. This is due to the dissolution of 2980 1270
aliphatic deform.
light celluloses especially α-cellulose in the υCH asym. δCH2 external
2960 1255
cooking medium. The bands due to the aliphatic deform.
υCH sym.
stretching vibrations of the CH-groups tend to 2900
aliphatic
1235 δOH carboxylic
be sharper in the spectra of the pulps with the υCH sym.

2880 1185 υC-OH phenolic
aliphatic
loss of absorption on the higher frequency side
C=O acetyl δCH aromatic
where the bands due to aromatic CH-groups 1750
linkage
1165
and C-O-C
appear. These changes reflect the dissolution of C=O β-keto υC-OH
1730 1140
structure carboxylic
lignin materials on cooking with sodium
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C=O β-keto
1675 1115 δCH aromatic
structure
δOH (water
1630 1065 δCH aromatic
molecules)
C=C aromatic
1610 1040 Lignin band
ring
C=C aromatic C-O cellulose

1595 800
ring
C=C aromatic
1530
ring
Fig. 2 IR absorption spectra of bleached pulp samples

-1
b- The strong band at 1735 cm , assigned to the
stretching vibration of the C=O group of the
acetyl residue from polyurinoid of the
hemicelluloses, displays an obvious decrease in
intensity when rice straw is cooked. The
decrease of C=O band intensity and its
vanishing in the spectra of the pulps is due to
the hydrolytic rupture of the acetyl linkage
between lignin and hemicellulose during the Fig. 3 IR absorption spectra of xanthated cellulose samples
pulping of rice straw with NaOH.
By complete removing of lignin and
c- The bands at 1595-1600 cm-1, which correspond
to the skeletal vibrations of the aromatic rings hemicelluloses dissolvable pulp is formed that is
of the lignin part, show a gradual decrease on used for manufacturing of cellulose derivatives,
such as, cellulose xanthate. In this work for
increasing the cooking time or with rise of
derivatization of rice straw xanthation reaction was
temperature and or alkali concentration. The
drop in the intensity of this band denotes that used in which the ONa groups of cellulose were
the lignin content of the pulps decreased during converted to O=C(S)SNa groups respectively. By
this conversion some hydrogen bonds between
cooking with various degrees depending on the
cellulose chains are broken. The characteristic
prevailing experimental conditions.
absorption bands of phenyl ring of the benzyl group
appear at 1700-2000 cm-1 region. The C=O to the
C=S occurs due to xanthation in addition to that the
C=O band itself which is more sharp and boarder
for sample (b), this my be due to bleaching with
H2O2 as had been stated above which break some
hydrogen bonds and freed more positions to be
xanthated.
Fig. 1 IR absorption spectra of soda treated rice straw samples
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4. TGA studies of cellulose pulp samples 57.790 and 57.731 % of the total sample weight for
The whole rice straw starts to degrade I, II, III and IV.
o TABLE 2
thermally at about 50 C. Between about 300 and
TGA ANALYSIS FOR CELLULOSE SAMPLES
375 oC, the majority of the carbohydrate polymers
Band Weight loss (%)
thermally decomposed and only lignin remains. The
Temperature Sample Sample Sample
Sample I
hemicellulose components start to decompose at range II III IV
about 225 oC and are almost completely degraded 35-100 oC 11.80 14.98 6.12 7.51
by 325 oC. The cellulose polymer is more stable to 300-325 oC 30.35 35.58 57.79 52.73
o
thermal degradation until about 370 C, whereas 470-1000 oC 25.62 21.79 22.89 28.24
o
lignin starts to decompose at about 400 C [19]. Total weight
67.95 75.72 83.44 89.69
loss
Remained ash 32.05 24.28 16.56 10.30
I II
IV
III
Fig. 4 The TGA of

sample I; rice straw pulped in sodium hydroxide solution (8%)
for 1hr.,
sample II; rice straw pulped in sodium hydroxide solution (8%) Fig. 5 The TGA of xanthated pulp.
for 2hrs.,
sample III; rice straw pulped in sodium hydroxide solution (10
%) for 2hrs., The third stages from above 470 ºC to 1000
sample IV; rice straw pulped in sodium hydroxide solution (10
%) for 2hrs. and bleached with sodium bisulphate (5 %) for 1 hr. ºC represent weight loss 25.619, 21.785, 22.891 and
Fig. 4 and Table 4 show that there are three 28.24 % which are due to the complete oxidation of
different thermal loss stages. The first stages started the remaining organic matter. Fig.5 represents TGA
at 25 ºC and ended at 96.10, 30.39, 39.18, and and DTG thermographs of two samples of
38.62 ºC representing weight loss of 11.801, xanthated cellulose. There are two stages for both
14.979, 6.123 and 7.505 % which can be attributed samples representing total weight losses 84.48 %
to the removal of moisture content from samples I, and 84.28 % respectively. These two steps
II, III and IV respectively. The second stages at correspond to the thermal degradation of the
304.13, 253.45, 324.53, and 312.26 ºC, are organic part of the sample. The remaining residue is
suggested to be due to the thermal oxidation of the about 15.5 %.
carbon content, its ratio reached, 30.35, 35.582,
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5. Differential thermal analysis (DTA) studies of assigned to oxidation of carbon content and
cellulose pulp samples
complete oxidation of that carbon.
In Fig. 6, there is an endothermic peak at 90
o
C which can be due to loss of moisture content,
6. SEM investigation [20]
and there are two exothermic peaks at 350 and 470
SEM is powerful and good technique to
o
C which are due to oxidation reactions of cellulose
image the fibers in micrometer scale. The physical
pulp, which is composed mainly from carbon,
trends like the removal of fines and fillers, or the
hydrogen and oxygen which oxidizes both carbon
different nature of hardwood and softwood fibers
and hydrogen and this oxidation is an exothermic
can be visualized with SEM. Surface scanning with
reaction.
the electron microscope was used to compare
between the obtained cellulose pulp samples [21].
The supermolecular structure of the blank
(mechanically divided rice straw), treated with
sodium hydroxide, sodium sulphite and H2O2
bleached samples as well as xanthated cellulose
samples were studied by electron microscopy (Fig.
8). In case of the thermally treated samples the
fibrils bundles become similar and there is a
gradual degree in voids between cellulosic fibers as
a result of dehydration, taking place during the heat
treatment (aging) and the pulp crystallinity
Fig. 6 The DTA thermograph of cellulose sample prepared from increases during this process. When the samples
rice straw by pulping in soda (10 %) for 2hrs.
were treated with different concentrations of alkali,
the fibers tended to agglomerate gradually into
small and large bundles (Fig.8).
Fig. 8 indicates that many bundles
aggregations show the decrease of voids between
them which confirms the increase in the degree of
polymerization and crystallinity. On increasing the
time of pulping and increasing alkali concentration,
the degradation products become more pronounced
with large spaces between them as in case of 10 %
alkali treated pulps, the appearances are most likely
tiny degraded products which have been removed
Fig. 7 The DTA thermograph of xanthated cellulose sample. during the fracture of the pulp surface. Fibers of the
bleached cellulose samples are more arranged and
Fig. 7 displays an endothermic peak at 74 ºC
the crystallinity increased due to the loss of fine
which represents content loss, and there are two
(soluble low molecular cellulose and lignin
exothermic peaks at 346 and 470 ºC which are
products). Evidence of surface roughness can be
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seen using SEM. In addition, porosity and pore size key factors in the production of pulps and
on the fiber surface was found to increase with xanthates. However, the cellulose pulps obtained
increasing treatment with sodium bisulphate and from rice straw are decisive factor for the
hydrogen peroxide. For xanthated pulp samples, the preparation of xanthates. From the results obtained
inhomogeneity of the pulp can be observed. The by different measurements in this work we can
diameter of fibrils becomes heterogeneous. The conclude that, the method used in this work is a
void of the fibrils was randomly distributed. The good way to use this undesired waste to obtain a
aggregated micro fibrils are also randomly very important products in our life (cellulose pulp
distributed. The inhomogenity will lead to the for different uses).
inhomogeneous xanthation reaction in the total
fibrils. The inhomogeneous xanthation will lead to 5. References
poor solubilities of synthesized xanthates. [1] Tappi Committee, Tappi, Atlanta, GA, USA (1999).
[2] R. M. Issa, M. M. Abou-Sekkina, A. E. Bastawisy, A.
M. Khedr and W. A. El-Helece, (Environ. Sci. Ind. J.,
4, 2009, pp.360-366).
[3] R. M. Issa and S. M. Saad, , (Proc. Pak. Acad. Sci.,
15, 1978, pp, 37-42).
[4] S. M. Saad, R. M. Issa, and M. S. Fahmy,
(Holzforschung, 34, 1980, pp, 218-222).
[5] Alternative Agricultural Research and
Commercialization Corporation (AARC)
Information, http://www.usda.gov/aarc, U. S. A.
(1997).
[6] British Columbia Pellet Fuel Manufacturers
Association, http://www.pellet.org/welcome (1997).
[7] California Air Resources Board and California
Department of Food and Agriculture, Progress
Report on the Phase Down of Rice Straw Burning in
the Sacramento Valley Air Basin (1997).
[8] Clean Fuels Development Coalition and American
Bioenergy Association. Ethanol in the 21st Century,
April (1998).
[9] Fibre Crete International,
http://www.fibrecrete.com/index.html (1997).
Fig. 8 SEM of rice straw pulp samples [10] L.Y. Mwaikambo and N. P. Ansell, (Appl. Polym.
Sci. J., 84, 2002, pp, 2222-2230).
[11] P. Stenius, (Tappi J., 3, 2000, pp, 97-99).
4. Conclusion [12] M. M. Abdullaeva, Abstract of dissertation.
Tashkent, IKHFP (Russian), 1993.
Egyptian rice straw can provide high quality [13] J.Gustafsson, and L. Peltonen, , (J. Polym., 44, 2003,
pp, 661-667).
cellulose pulps and was found to be suitable for [14] A. M. Nada, H. El-Saied, M. H. Fadl, and M. Nassar,
(Polym. Degrad. Stab. J., 43, 1994, pp, 55-60).
synthesizing high molecular weight xanthates. The [15] Y. Fahmy, A. E. El-Ashmawy, and S. El-Kalyoubi,
(Celluo. Chem. Techn. J., 13,(1979, pp, 673-680).
xanthates, which were synthesized in an ordinary [16] Tappi Committee, Tappi, http://www.tappi.org,
apparatus, had sufficient and different properties to Atlanta, GA, USA, (1999).
[17] S. M. Saad, R. M. Issa, N. E. Metwally,
compare plant species, process parameters of (Holzforschung, 34, 1980, pp, 98-103).
[18] J. Gassan and A. Bledzki, (Appl. Polym. Sci. J., 82,
pulping and bleaching. Therefore, this method is 2001, pp,1417-1423).
[19] L. A. Lucia, M. M. Goodell, F. S. Chakar, and A. J.
appropriate for evaluating whether certain plants Ragauskas, Institute of paper science and technology
(IPST), Atlanta, Georgia 874, 2000.
could be used to produce xanthated cellulose. Thus, [20] A.Tutus, and H. Eroglu, , (Appita J., 56, 2003,
pp,111-117).
it is feasible and appropriate to produce xanthates [21] H. El-Saied, A. M. Nada, (Polym. Degr. Stab., 40,
1993, pp,287-294).
from rice straw. The pulping conditions were the
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1
Chemistry Department, Faculty of Science, Tanta University, Tanta – Egypt.
2
Chemistry Department, Faculty of Engineering, Tanta University, Tanta – Egypt.
*3
Chemistry Department, Faculty of Science, Gazan University, Gazan – KSA.
Vitae
wael abdalla elhelece
e-mail : wael_elhelece@yahoo.com
Education:
B.Sc. in Chemistry, May 1997, Tanta University
M.Sc. in Inorganic Chemistry, April, 2003, Faculty of Science, Tanta University,
Egypt.
Ph. D. in Inorganic Chemistry, May, 2010, Faculty of Science, Tanta University, Egypt
Occupation:
Lecturer cooperator faculty of engineering, Tanta university, Egypt from 1999 to 2002.
Lecturer faculty of science, Gazan university, KSA, from 2003 to the present.
Main research interests
Environmental science branch of inorganic chemistry, how we can use agricultural wastes and
residues in order to be economical products.
Materials (CEAM)

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2nd Conference on Chemical Engineering and Advanced Materials (CEAM)

Exploration on industrial production and thermo-chemical

Raafat M. Issa1, Morsi M. Abou-Sekkina1, Abdalla M. Khedr1, Alam El-Deen M. Bastawisy2

Abstract – Cellulose from rice straw obtained at low sodium hydroxide

Keywords: Cellulose, Xanthation, IR spectra, TGA, DTA and SEM analyses.

numerous hydroxyl groups, and increase the

1. Introduction hydrophobicity. Introducing ester and ether groups

groups. The resultant subsistents therefore disturb must be solved.

the inter- and intra-molecular hydrogen bonds in

In these tests, samples from rice straw were

temperatures. pale to intense yellow in color and requires

2.4. Permanganate number [15] from room temperature up to 1000 oC using 10

2. Effect of cooking conditions

conditions of treatment and xanthated cellulose δOH3 and R-O-

a- The broad δOH band at 1600 cm-1 tends to be 3100

υCH asym. δCH2 external

be sharper in the spectra of the pulps with the υCH sym.

C=C aromatic C-O cellulose

Fig. 2 IR absorption spectra of bleached pulp samples

Fig. 1 IR absorption spectra of soda treated rice straw samples

Fig. 4 The TGA of

suggested to be due to the thermal oxidation of the about 15.5 %.

carbon content, its ratio reached, 30.35, 35.582,

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