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Der Pharmacia Lettre, 2012, 4 (4):1162-1168

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ISSN 0975-5071
USA CODEN: DPLEB4

Development of banana/glass short hybrid fiber reinforced nanochitosan

polymer composities
Mubashirunnisa, A 1, Vijayalakshmi.K 2, Gomathi.T2, Sudha P.N 2*
1
Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India
2
PG & Research Department of Chemistry,DKM College for Women,Vellore, Tamilnadu, India,
_________________________________________________________________________________________

ABSTRACT

Natural fiber reinforced composites have attracted the attention of research community mainly because they are
turning out to be an alternative solution to the ever depleting petroleum sources. Various natural fibres such as jute,
sisal, palm, coir and banana are used as reinforcements. In this paper, banana fibres and glass fibers have been
used as reinforcement. The aim of this present study was to develop a polymer made up of banana/glass fiber
reinforced nanochitosan composites. The nanochitosan was prepared using polyphosphoric acid and composites of
nanochitosan were prepared with short fibers of banana and glass in the presence of crosslinking agent
glutaraldehyde. The prepared glass and banana fiber reinforced nanocomposites were characterized using different
analytical tools such as FT-IR, XRD, TGA and DSC. The FT-IR studies reveal the formation of nanocomposites. The
observed results of TGA and DSC show that the addition of glutaraldehyde along with the nanosized chitosan has
increased the thermal stability.The XRD results indicate the change in crystallinity of nanocomposites.

Keywords: Banana fiber, glass fiber, nanocomposites, characterisation.

_________________________________________________________________________________________

INTRODUCTION

Lignocellulosic biomass is the most abundant material in the world. Much work is done in the application of natural
fibre as reinforcement in polymer composites [1]. There is a growing interest in the use of natural fibers as
reinforcing components for both thermoplastic and thermoset matrices, because of the ideal benefits offered by
natural fibers such as convenient renewability, biodegradability, and environmentally friendliness [2]. A great
interest towards the development of composite materials reinforced with natural fibers has emerged in the last
decade [3-5]. According to the Food and Agricultural Organization (FAO), each year farmers harvest around 35
million tons of natural fibers from a wide range of plants and animals. The term natural fibers is used to designate
numerous kinds of fibers that are naturally produced by plants, animals and minerals [6]. The natural fibers such as
sisal, coir, jute, ramie, pineapple leaf, and kenaf have the potential to be used as reinforcement materials in
composites.

The growing interest in lignocellulosic fibres is mainly due to their economical production with few requirements
for equipment and low specific weight, which results in a higher specific strength and stiffness when compared to
synthetic fibers. The inherent polar and hydrophilic nature of lignocellulosic fibres and the non-polar characteristics
of most thermoplastics results in compounding difficulties leading to non-uniform dispersion of fibres within the

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matrix which impairs the efficiency of the composite. This is a major disadvantage of natural fibre reinforced
composites.

Another problem is that the processing temperature of composites is restricted to 200C as vegetable fibres undergo
degradation at higher temperatures; this restricts the choice of matrix material [7]. Another setback is the high
moisture absorption of natural fibres leading to swelling and presence of voids at the interface, which results in poor
mechanical properties and reduces dimensional stability of composites. It is quite clear that the advantages outweigh
the disadvantages and most of the shortcomings have remedial measures in the form of chemical treatment [8].

In India, banana is abundantly cultivated. Banana fiber can be obtained easily from the plants which are rendered as
waste after the fruits have ripened. So banana fiber can be explored as a potential reinforcement. Banana fiber, a
ligno-cellulosic fiber, obtained from the pseudo-stem of banana plant (Musa sepientum), is a bast fiber with
relatively good mechanical properties. Banana fiber possesses good specific strength properties comparable to those
of conventional materials like glass fibers [9-11]. Furthermore, this materials has a lower density than glass fiber
[12]. However banana fibers are associated with some challenges including high moisture uptake low thermal
stability and low bonding with polymers.

The glass fiber is blended with a thermoplastic fiber as a route to a perform material that could be easily shaped and
molded into its final form without the need for a resin. Such composites are desirable because of their high strength,
low cost and good fatigue resistance. Additionally glass fibers have good impact strength, good chemical and
corrosion resistance, good electrical resistance, low dielectric constant and good dimensional stability. In the present
study banana and glass fiber reinforced nanochitosan polymer composites were prepared and its mechanical strength
was tested.

MATERIALS AND METHODS

Materials
Chitosan was kind gift from Indian Sea Foods, Cochin, Kerala. Banana Fibers was purchased from Vibrant Nature,
Chennai, India and Glass Fibers was obtained from Placon Agencies, Chennai. All the chemicals used in the present
work were of analytical grade.

Preparation of nanochitosan
Nanochitosan was prepared by sol-gel method using polyphosphoric acid. About 15g of chitosan was dissolved in 3
litres of conductivity water containing 60 ml of 2% v/v acetic acid .The above solution was stirred well for 45
minutes. Then to the above prepared chitosan solution, 12 gms of sodium hexametaphosphate dissolved in 1600 ml
of conductivity water was added dropwise. A milky coloured emulsion like appearance was obtained. This solution
was then allowed to settle as suspension by adding conductivity water in excess for 24 hours. After this process is
over, the supersaturated solution was then decanted.

Preparation of fiber composites

The banana and glass fibers were cut into very small pieces of approximately 0.25 cm length to be used as dust
fibers and three cm length for using as short fibers. The nanochitosan was dispersed in minimum amount of water.
The above dispersed nanochitosan solution and the fibers was then mixed and blended in different proportions. The
binary composites of nanochitosan were prepared with banana and glass fiber in the two different forms using short
and dust fiber of glass and banana in the ratio 30:1 and 30:2 in the presence of crosslinking agent glutaraldehyde.
This mixture was then stirred for 30 minutes using the high speed mixer Remi motor (200 rpm, 30 min) which was
then stored overnight. It was then poured into the petridishes and allowed to dry.

Glass fiber nanochitosan composites:

a. Short fiber: b. Dust fiber:
NC+GF(30:1) NC+GF(30:1)
NC+GF(30:2) NC+GF(30:2)

Banana fiber nanochitosan composites:

a. Short fiber: b. Dust fiber:
NC+BF(30:1) NC+BF(30:1)
NC+BF(30:2) NC+BF(30:2)

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FTIR Studies of blends.
FT-IR Measurements were performed with the fiber composites using Thermo Nicolet AVATAR 330
spectrophotometer in 4000 400cm-1 wavenumber range using KBr pellet method.

TGA
Thermogravimetric analysis of the nanocomposite fibers (cut into small flakes) was conducted on a SDT Q600 V8.0
Build 95 instrument in the temperature range of 50o to 800oC at the heating rate of 20K/min.

X Ray Diffraction Studies

Xray diffraction (XRD) studies of fiber nanocomposites was performed with the X-ray powder diffractometer
(XRD SHIMADZU XD D1) using a Ni filtered Cu K Xray radiation source. Banana fiber in the form of
short non woven fibers (3mm) was used in this work.

RESULTS AND DISCUSSION

FT-IR Spectroscopy
Figure-1 shows the FT-IR spectra of pure nanochitosan. The IR spectra of nanochitosan (Figure 1) shows prominent
peak at 3385.92 cm-1 corresponding to OH stretching of axial OH group, -NH stretching. Peak obtained at
2908.57cm-1 corresponds to the aliphatic CH asymmetric stretching. Certain peaks observed at 1635.20cm-1, 897
cm-1 corresponds to NH bending and C-C stretching. The FT IR spectra of NC+GF (30:1) (figure 2) shows
prominent peak at 3436.08 cm-1 corresponding to OH stretching of axial OH group, -NH stretching. Peak at
2926.20cm-1 corresponds to the aliphatic CH stretching. The peak at 1632.98cm-1 corresponds to NH bending and
the peaks at 614cm-1 corresponds to out of plane bending. A similar type of results was observed in the case of
NC+GF (30:2) nanocomposite (Figure-3). The FT-IR spectral details of NC+GF (30:1) (dust fiber) and NC+GF
(30:2)(dust fiber) was represented in the figure-(4)-(5).The FT-IR spectra of NC+GF (dust fiber) (30:1) shows
prominent peak at various wave number values such as 3454.10 cm-1 , 2925.03cm-1, 776.59cm-1,476.82 and 416.70
cm-1.These observed peaks indicate the presence of intermolecular hydrogen bonded OH stretching, aliphatic CH
asymmetric stretching, NH bending and C-C bending.
100 MC
831.32
897.95

90
500.31
2908.57

667.71
618.67
1431.02

80
1324.83
1635.20

1376.80

70
1163.38
1113.24

60
1058.87
3385.92
%T

50

40

30

20

10

0
3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm-1)

Figure-1 KR7
98
98 98 96
95
4 0 2. 70 42 3 . 74

96 96 94
771. 85
849.47
771.83

4 8 5 . 95
488.65
89 8.50

47 2.56

86 0. 0 4

92
475. 93
861. 22
579. 79

94 94 90
860.39

90
714.63
608.39
62 4.73

624. 74

66 7. 1 6
669.88
669.45

92
2856.59

1229.47

6 2 0 . 30

92
88
17 44.43

85
40 3.72

29 1 9 .1 0

90
667. 58

86
2923.61

90
2919.11
1160.38
14 66.47
29 24.33

1160.94
1160.92

11 60 . 8 1

88 84
88 80
82
1110.52
1111 .15
1628 .21

86
1111.68

1 6 1 6 .5 7

1 1 11 .2 4

86
1060.31

%T
10 59.25

80
%T
1383.07
%T

75
%T

84
1604.87

1059.84

84 78
10 59 . 5 3
1627.14

82
82 70 76
13 80 .7 8
13 82.73

1381.51

80 74
34 27 . 0 6

80
78 65 72
3426.79

78 70
76
76 60 68
74
3436 .08

66
3428.14

74 72
55 64
72 70 62
70 68 50 60
3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm-1) Wavenumbers (cm-1) Wavenumbers (cm-1) Wavenumbers (cm-1)

Figure-2 Figure-3 Figure-4 Figure-5

Figure-6-9 shows the FT-IR spectra of NC+BF (30:1), NC+BF (30:2), NC+BF (30:1) (dust fiber) and NC+BF
(30:2) (dust fiber) respectively. The FT-IR spectra of nanochitosan banana fiber composites prepared in different
ratios shows prominent peak at 3446.01 cm-1 corresponding to OH stretching of axial OH group. The peak obtained
at 2925.31cm-1 was attributed to the aliphatic CH stretching. Certain peaks observed at 1089.81 cm-1 corresponds
to CO stretching and the peak obtained at 780.01 cm-1 corresponds to N-H bending. On comparing the FT-IR
spectral results of the nanochitosan glass fiber composites and nanochitosan banana fiber composites prepared in
different ratios with pure nanochitosan it was observed that some more additional peaks were observed in the case
of fiber nanocomposites corresponding to the groups present in the glass fiber and banana fiber. In addition to this,
the intensity of the OH bands has also increased when compared to the pure nanochitosan .These FT-IR spectral
results indicate that there are no significant conformational differences between nanochitosan and the composites

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formed. There are no significant differences in the major bands, however there are shift differences in the peak
intensities which indicate changes in the amount or concentration.
KR8
98
95 95
85
96

411. 50
410. 99
902. 59

784.09
94 90

489. 12
90

902.59
857.15
80

489.89
92

403. 33
899.28
85

714.63

551. 18
85 90

669.68

894.42

472.50
788.18
617.21

608.39
673. 77
75
88

575.70
2916.95

624.73
80

1430.58
623.74
80

673. 77
2923.91

668.79

2918.31
86

1315.28

404.77
1433.78

1321.51
1624.67
70

1377.93
75 84 75

1168.18
1382.53

1319.3 7
1431.1 2
1160.90

1628.45
82

1628.20

1110.98

13 78.42

%T
1058.61

%T

2917 .64

1163.0 1
%T
70 65
%T

1590.90

70

1161.89
80

1113.92
1111.60

78

1057.74
65 65
60

1111.61
76
1378.28

74 60
60
1059.62

1060.03
72 55

3445.81

3426.47
3423 .72
55 70 55
3415.64

68 50
50 50
66
64 45
45 45
62
40 60 40 40
3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm-1) Wavenumbers (cm-1) Wavenumbers (cm-1) Wavenumbers (cm-1)

Figure-6 Figure-7 Figure-8 Figure-9

TGA
The TGA thermogram details of NC+GF (short fiber) (30:1), NC+GF (30:2) (short fiber), NC+GF (30:1)(dust fiber),
NC+GF (30:2) (dust fiber) and NC+BF (short fiber) (30:1), NC+BF (30:2) (short fiber), NC+BF (30:1)(dust fiber)
and NC+BF (30:2) (dust fiber) was represented in the Table-1-2 ,Figures-10(a-h).

Table-1
%Weight Loss SAMPLE Decomposition Temperature(C)
10 180
NC+GF(short fiber) (30:1) 20 225
30 278
10 270
NC+GF(short fiber) (30:2) 20 319
30 344
10 218
NC+GF (dust fiber) (30:1) 20 262
30 300
10 190
NC+GF (dust fiber) (30:2) 20 248
30 292

Figure-10 (a) Figure-10(b) Figure-10(c) Figure-10(d)

Table-2

SAMPLE %Weight Loss Decomposition Temperature(C)

10 205
NC+BF(short fiber) (30:1) 20 258
30 355
10 260
NC+BF(short fiber) (30:2) 20 400
30 470
10 284
NC+BF (dust fiber) (30:1) 20 682
30 700
10 105
NC+BF (dust fiber) (30:2) 20 260
30 370

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Figure-10(e) Figure-10(f) Figure-10(g) Figure-10(h)

The initial weight loss obtained in the region of 50100C was mainly due to moisture evaporation and water
adsorbed to the fiber. The degradation of fiber reinforced nanocomposite in the temperature region ranging from
220300 C was mainly attributed to thermal depolymerization of hemicellulose and the cleavage of glycosidic
linkages of cellulose. The broad peak obtained in the region from 200 to 500C was contributed by lignin
components and the degradation of cellulose take place between the temperature ranges from 275C and 400C.

From the results of TGA it was observed that in the case of composites of nanochitosan with glass fibre an increase
in the amount of glass fibre (ratio) increases the thermal degradation, where as in the dust forms it decreases. In case
of the composites of nanochitosan with banana fibre an increase in the amount of banana fibre in short form as well
as dust form increases the degradation temperature. On comparing the results of TGA of glass fiber composites with
banana fiber, it was concluded that the nanochitosan with banana fibre composites have higher thermal stability in
terms of higher degradation temperature than the nanochitosan with glass fibre composites. This was confirmed
from the amount of residue remained at the end of the experiment and the various decomposition temperatures.

DSC
DSC is an analytical tool which helps to understand the thermal behavior of polymers and composites. It helps in
finding glass transition temperature and polymer composites. The glass transition temperature (Tg) is the
temperature at which the material undergoes a structural transition from an amorphous solid state (glassy state) to a
more viscous (rubbery) state. Below Tg, films are rigid and brittle, whereas above it films become flexible and
pliable. Figures:11(a-h) represents the DSC curve of NC+GF (short fiber) (30:1), NC+GF (30:2) (short fiber),
NC+GF (30:1)(dust fiber), NC+GF (30:2) (dust fiber) and NC+BF (short fiber) (30:1), NC+BF (30:2) (short fiber),
NC+BF (30:1)(dust fiber) and NC+BF (30:2) (dust fiber) respectively.

Figure-11(a) Figure-11(b) Figure-11(c) Figure-11(d)

Figure-11(e) Figure-11(f) Figure-11(g) Figure-11(h)

The DSC curve of NC/GF short and the dust forms prepared in the ratio of (30:1, 30:2) shows an endothermic peak
at various temperatures such as 99.9C, 69.1C, 70.3C, and 69.4C respectively, where as for NC/BF the
endothermic peaks are observed at 72.5C, 78.3C, 75.2C and 73.2C respectively. The glass transistion
temperature of the glass fiber reinforced composites was found to be around 130C in case of both short fiber and
dust fiber whereas in the case of banana fiber reinforced composites the glass transistion temperature was found to
be around 135C. On comparing the glass transistion temperature of glass fiber reinforced composites with the

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banana fiber reinforced composites it was concluded that the bananafiber reinforced composites was found to be
highly thermally stable than the glass fiber reinforced composites.

XRD
XRD has been one of the most widely used methods for materials, especially metal and inorganic materials. The
crystalline phases and their relative contents in materials can be quantitatively obtained by the diffraction peak
location, diffraction peak number and relative intensity of XRD pattern. The XRD spectral details of NC+GF (short
fiber) (30:1), NC+GF (30:2) (short fiber), NC+GF (30:1)(dust fiber), NC+GF (30:2) (dust fiber) and NC+BF (short
fiber) (30:1), NC+BF (30:2) (short fiber), NC+BF (30:1)(dust fiber) and NC+BF (30:2) (dust fiber) was represented
in the Table-3,Figures-12(a-h).

Figure-12(a) Figure-12(b) Figure-12(c) Figure-12(d)

44.7104
25.8958

450 V3
36.0525

V1

44.7104
26.3494
35 0 V3
41.6338

400
40.5885

1200 450

39.8391
45.5978

26.3494
350

39.2672
49.5619

400
33.7845

30 0

46.6825

52.4808
1000
35.52

L in(counts)

54.3149

39.8391
23.7855

350

39.2672
300

64.0969
60.0539

68.8893

46.6825
L in(counts)

77.0541
72.9323

52.4808
53.5063

31.5362
25 0

L in(counts)

54.3149
L in (counts)

800 300

64.0969
60.0539
25.9944

68.8893
58.8115

250

77.0541
63.5841

72.9323
70.1318

31.5362
65.9705

78.5333
20.2948

20 0 14.9107 250
74.51

19.1509
600 200
44.0004
30.7276

14.9107
19.1509
200
15 0 150
400
150
10 0 100
200 100
50
50 50
0 0
0 10 20 30 40 50 60 70 80 90 0
0 10 20 30 40 50 60 70 80 90
0 10 20 30 40 50 60 70 80 90
0 10 20 30 40 50 60 70 80 90
2 Th eta 2 theta 2 Theta 2 T h eta

Figure-12(e) Figure-12(f) Figure-12(g) Figure-12(h)

TABLE:3
% OF CRYSTALLINITY
BINARY COMPOSITES COMPOSITION
SHORT FIBER DUST FIBER
NC+GF 30:1 25.2 18.3
NC+GF 30:2 24.6 23.3
NC+BF 30:1 10.9 11.1
NC+BF 30:2 19.9 15.5

X-ray diffraction pattern of polymer contain both sharp as well as diffused bands. Sharp bands correspond to
crystalline orderly regions and diffused bands correspond to amorphous regions [13]. The crystallinity is calculated
by separating intensities due to amorphous and crystalline phase on diffraction phase. Computer aided curve
resolving technique is used to separate crystalline and amorphous phases of diffracted graph. After separation,
Percentage of crystallinity Xc % is measured as ratio of crystalline area to Total area.

Xc% = Ac/Ac+Aa 100.

where
Ac= Area of crystalline phase
Aa= Area of amorphous phase
Xc= Percentage of crystallinity

Small Angle X-ray Scattering (SAXS), Infrared Spectroscopy, can also be used to measure crystallinity [14]. From
the XRD results of table 3 and figures-12(a-h), it was observed that the % degree of crystallinity was found to be
higher in case of short fiber when compared to dust fiber. Moreover the composites made up of glass fiber
reinforced with nanochitosan has more crystallinity in terms of better strength compared to banana composites
reinforced nanochitosan [15, 16]. From the results the dust fiber fiber composite is having more amorphous region
which can be useful for the wastewater remediation. The banana fiber is a low cost, good biosorbent [17], it
efficiency was further improved during the composite formation.

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CONCLUSION

The prepared nanocomposites have been expected to have improved mechanical properties. The FT-IR results of
fiber reinforced nanocomposites show that there were no significant differences in the molecules and the bondings
in the composites when compared to the novel materials such as banana fiber, glass fiber and nanochitosan. From
the XRD results it was concluded that the glass fibre reinforced composites has more crystallinity, showing better
strength and higher dispersion than banana fiber composites. The results of TGA and DSC indicate that the
nanochitosan with banana fibre composites have higher thermal stability in terms of higher degradation temperature
than the nanochitosan with glass fibre composites.

REFERENCES

[1] G. Rajesh Ghosh, Dr. A. Reena , Bh. Rama Krishna , Lakshmipathi Raju, International Journal Of Advanced
Engineering Sciences And Technologies, 2011,Vol No. 4, Issue No. 1, 089 091.
[2] M. Thiruchitrambalam, A. Alavudeen, A. Athijayamani, N. Venkateshwaran, A. Elaya Peruma, Materials
Physics and Mechanics, 2009, 8, 165-173.
[3] M.A. Martins and L.H.C. Mattoso, Journal of applied polymer science, 2003, 91(1),670-677.
[4] S. Mohanty and S.K. Nayak, Journal reinforced plastics and composites, 2004b, 23(18), 2047-2063.
[5] A.B. Thomson, A. Thygesen, V. Bohn, K.V. Neilsen, B. Pallesan and M.S. Jorgensen, Ind crops and products,
2006, 24(3),113-118.
[6] A.K. Bledzki, J. Gassan, Prog. Polym. Sci. , 1999. 24, 221-274.
[7] R. Kozlowski, M. Muzyczek and B. Mieleniak, Journal of Natural Fibres, 2004, 1, 8592.
[8] M. Zimniewska, R. Kozlowski and M. Rawluk, Journal of Natural Fibers, 2004, 1(2), 6981.
[9] S.H. Aziz, and M.P. Ansell, Composites science and technology, 2004, 64:1219-1230.
[10] M. Idicula, S.K. Maholtra, K. Joseph and S. Thomas, Journal of applied polymer science, 2005, 97:2168-2174.
[11] S. Supuan, A. Leenie, M. Harimi and Y. Beng, Materials and design, 2006, 27:689-693.
[12] K.M. Mahon Rao, Composites structure, 2007, 97:288-295.
[13] V.R. Gowariker, N.V. Viswanathan and Jayadev Sreedhar Polymer Science Published by New Age
International (P) Ltd., 1986, p, 173.
[14] V.B. Gupta and V.K. Kothari, Manufactured Fiber Technology Published by Chapman & Hall. 1997, p, 225.
[15] R. Zeng, M. Tu, H.W. Liu, J.H. Zhao, Z.G. Zha, and C.R. Zhou, Carbohydrate Polymers, 2009, 78,107111.
[16] Z. Zong, Y. Kimura, M. Takahashi, and H. Yamane. Polymer, 2000, 41, 899906.
[17] H. Mas Rosemal, Mas Haris1 and Kathiresan Sathasivam, Archives of Applied Science Research, 2010, 2
(5):209-216

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