International Journal of Polymer Analysis and

Characterization

ISSN: 1023-666X (Print) 1563-5341 (Online) Journal homepage: http://www.tandfonline.com/loi/gpac20

Thermal behaviour of Cardanol resin reinforced

20 mm long untreated bagasse fiber composites

A. Balaji, B. Karthikeyan, J. Swaminathan & C. Sundar Raj

To cite this article: A. Balaji, B. Karthikeyan, J. Swaminathan & C. Sundar Raj (2017):
Thermal behaviour of Cardanol resin reinforced 20 mm long untreated bagasse fiber
composites, International Journal of Polymer Analysis and Characterization, DOI:
10.1080/1023666X.2017.1387448

To link to this article: http://dx.doi.org/10.1080/1023666X.2017.1387448

Accepted author version posted online: 13

Oct 2017.

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 Thermal behaviour of Cardanol resin reinforced 20 mm long untreated bagasse
fiber composites

A. Balaji1, B. Karthikeyan2, J. Swaminathan3, C. Sundar Raj1

1
Department of Mechanical Engineering, A.V.C. College of Engineering,
Mayiladuthurai, TamilNadu, India, 2Department of Mechanical Engineering, Faculty of
Engineering and Technology, Annamalai University, Tamil Nadu, India, 3Department of
Chemistry, A.V.C. College of Engineering, Mayiladuthurai, TamilNadu, India
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Received: 8 September 2017; Accepted: 29 September 2017.

CONTACT A. Balaji, E-mail: autpbalaji@rediffmail.com

Abstract

Recently the attention in composite materials reinforced with natural fibers has

significantly increased due to the new environmental legislation as well as consumer

pressure that forced manufacturing industries to search substitutes for the conventional

materials, e.g. glass fibers. In this way, the objective of the paper was to evaluate the

thermal properties of sugarcane bagasse fiber/Cardanol resin composites. Fibers were cut

down to 20 mm length in diagonally. These fibers were mixed with the Cardanol and

epoxy resin, and fabricate in a biocomposites with different compositions like 0, 5, 10, 15

and 20 wt%. The thermal properties were evaluated by Thermal Gravimetric Analysis

(TGA) and Differential Thermogravimetry Analysis (DTA) and also chemical

formulation studied in Fourier Transform Infrared (FT-IR) spectroscopy. The results

showed the improved thermal strength of the composites in comparison to the neat

polymer (0 wt%).

1
 KEYWORDS: Sugarcane bagasse fiber, Cardanol, Thermal properties, Polymer

composites, biocomposites

1. INTRODUCTION

Polymers have replaced a number of conventional materials in a variety of purposes

during the past number of years.[1–3] The responsiveness by using natural fibers as
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balancing materials in polymeric materials are grown to a large extent because of their

renewable and eco-friendly nature. The value added advantages of using polymers in

place of other traditional materials are the cost reduction, ease of processing and

productivity.[4,5] Recently, biofibers have attracted the attention of material scientists

because of the advantages these fibers offer over conventional reinforcement materials.

Also the natural fibers shows some few disadvantages, such as the incompatibility

between fibers and polymer matrix, the propensity to form aggregates during processing

and the poor resistance to moisture, reduce the use of natural fibers as reinforcements in

polymers.[6] On the other hand, there is quite a lot of methods of surface modifications to

get better fibers and polymer matrices compatibility, which can be physical or chemical

according to modification technique to reduce the hydrophilic character. Frequently

adopted treatments are bleaching, silane treatment, use of compatibilizer, plasma

treatment, acetylation, alkali treatment and treatment with other chemicals.[7–8]

Various natural fibers have been used in automobiles, biomedical, aerospace, trucks and

railway cars.[9] Natural fibers for example jute, sisal, bagasse, pineapple, abaca and

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 coir[10] have been studied as reinforcement and filler in composites. Amongst those,

bagasse is as the remains from the removal of juice from the sugarcane and has been used

as a combustible material for energy supply in sugarcane factories, as a pulp raw material

in paper industries and as a reinforcing material for fiber board. However, few studies on

the biodegradable composites reinforced with bagasse fiber have been reported.
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Additionally, thermoset polymers used as a matrix in composites can be also obtained

from natural sources. Among these, the Cardanol thermoset resin (figure. 1) prepared

from cashew nut shell liquid (CNSL) is an important candidate, because cashew nuts are

also produced in the same geographic region.

The great ease of access of cardanol in tropical areas could be the exploited for the

synthesis of thermosetting matrices for composites, taking benefit of its low cost. The

latent applications of such matrices, in competition with polyester, epoxy or vinylester

resins, are related to the process ability and the performances that could be achieved.

The aim of this work is (1) to prepare bagasse fiber (cut 20 mm length); (2) to fabricate

composite materials from thermosetting cardanol–epoxy resin with bagasse fibers as

reinforcement in different weight percentages (0-20 Wt%); (3) to examine the thermal

and mechanical properties of the composite materials.

2. MATERIALS AND METHODS

2.1. Materials

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 The sugarcane bagasse collected from roadside sugarcane juice shop at Chidambaram,

(Cuddalore District, Tamil Nadu, India). Epoxy and HY 951 (hardener) were procured

from Indian scientific solution (Mayiladuthurai, Tamil Nadu India).

2.2. Preparation of Bagasse Fiber

Sugarcane baggase was dried in the sunlight for two days to eliminate moisture content
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from it. Later, the sugarcane baggase was placed in the hot air oven at 90 to 1000 C for

24 hours to eliminate the moisture content entirely. Then, the fibers were cut into 20 mm

length diagonally. Figure 2 shows the photograph of the prepared bagasse fibers.

3. COMPOSITES PREPARATION

The prepared 20 mm length bagasse fibers were mixed with the prepared Cardanol in our

earlier work[11], epoxy resin and HY 951 matrix in a ratio of 3: 8: 1. This combination

was transferred to a mould in dimension of 300 × 300 × 3 mm and was fabricated. After

that the material was taken into the compression moulding machine. By compression

moulding process, under temperature of 110°C and a pressure of 100 kgf, the laminate

was created. The composites were left to cure at 60 to 70°C temperature for 24 hours in

hot air oven. The different weight composition fibers, viz., 0, 5, 10, 15, and 20 wt% were

fabricated. Figure 3 shows the photograph of the developed composites.

3. RESULTS AND DISCUSSION

3.1. Thermal Analysis

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 3.1.1. Thermogravimetric Analysis (TGA)

Thermogravimetry Analysis (TGA) technique was used to analyze the thermal stability of

composites. All the measurements were performed using a TA Instruments NETZSCH

STA 449F3 thermo gravimetric analyzer. Samples weighing 10 mg were placed in a

platinum pan and tests were carried out in a programmed temperature range of 30/20.0

(K/min) /600.
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Figure 4 shows the TGA thermograms of samples 5, 10, 15 and 20 wt% relative to 0

wt%. As depicted in Figure 4, all the samples showed thermal stability up to 50 °C. The

observed thermal stability is quite higher than other Cardanol-based reinforced

biocomposites reported in literature (Berreto et al., 2011).[12] The plateau occurring at

temperatures less than 50°C indicates the lack of any thermodynamic reaction occurring

at those temperature ranges. The slight inflexions of the thermograms in the 50 – 150 °C

shows the removal of physically absorbed water on the samples.

Generally, these category of samples exhibited good thermal stability upto 225°C as

presented in Figure 4. Inflexions attributable to the decomposition of hemicellulose

materials of the various samples were rather lumped together as observed between 150 –

220 °C. This observation could be due to the characteristic nature of the prepared

samples. The hemicellulose components in all samples decomposition were revealed in

the 220 – 310 °C temperature range. It can be seen that the extent of decomposition of the

hemicellulose materials in each sample is largely as a function of the weighed percentage

incorporation of the fiber materials.[13]

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 Finally, the drastic reduction in weight of the samples beyond 310 °C is consistent with

the decomposition of lignin in the materials. Complete decomposition of the combustible

materials in these samples occurred in the 475 °C temperature. As expected, the total

weight loss was generally in the 82 – 88 wt% range depending on the percentage

incorporation of the fiber materials. Among various weight percentages, 15 wt% fiber
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sample showed least overall weight loss. A detailed comparative summary of the

observed weight losses of all samples is presented in Table 1 below [14].

3.1.2. Differential Thermal Analysis (Dta)

A combination of differential thermal analysis (DTA) to thermo-gravimetric analysis

(TGA) was considered to be one of the most powerful thermal analytical techniques. This

could be understood on the basis of minimal sample requirements, simplicity and the

reliance on fundamental parameters (e.g. temperature, time and weight). Thus, the

evaluation of the thermal dynamics of materials is of significant relevance to reinforced

biocomposite applications. In this regard, the DTA of all the cardanol-based reinforced

biocomposites materials were carried out at a heating rate of 20 °C/min up to a maximum

of 700 °C.

DTA thermograms of the 20 mm untreated bagasse reinforced fiber biocomposite

samples of various weight percentages (5, 10, 15, & 20 wt%) were compared to the

sample 0 wt% is shown in Figure. 5. Their corresponding peak positions were carefully

tabulated in Table 2.

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 In Figure 5, well defined peaks were displayed that matches very well with the data

presented in the TGA thermograms showed previously. Slight inflexions observed below

100 °C temperatures indicate weight losses due to moisture or atmospheric humidity.

Thus, these lower temperature endothermic peaks confirm the evaporation of water

molecules in the samples as postulated in the TGA thermograms.

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It can be seen that no peak was observed until up to 220 °C temperatures, providing

supporting evidence on the thermal stability of the samples in that temperature ranges.

Thus, the DTA thermograms independently corroborate the results of the TGA analysis

of the biocomposite materials. Absorption of thermal energy for evaporation of water

molecules within the fiber in the biocomposite matrices caused the formation of two

weak endothermic peaks near 310 and 400 °C. In addition, to the illustrated endothermic

peaks, well-defined exothermic peaks were presented at or about 230, 368 and 500 °C

temperatures. The untreated fiber cellulose and hemicellulose components

decompositions were expressed by the exothermic peaks observed at temperatures around

the 230 °C. The corresponding lignin component degradations could be tentatively

related to exothermic peaks showed in the 368 °C temperature range. The 500 °C

exothermic peak shows the liberation of thermal energy within the cross-linked

molecules in the fiber materials. The noticeable shifts in peak positions could be related

to the unique nature of the each sample.[15,16]

3.1.3 FT-IR Spectroscopy

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 The FT-IR spectra analysis was carried out for the untreated bagasse fiber

composites by Bruker IFS 66 infra-red spectrophotometer, using KBr pellet, in the

infrared region. All the samples were recorded in the region 4000 – 400 cm-1. The

spectral measurements were carried out at Annamalai University, Annamalai Nagar,

India. The FT-IR spectra for the composite of Cardanol, epoxy and bagasse fiber in the of

20 mm length and different percentage composition, viz., 0, 5, 10, 15 and 20 wt% were
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taken and the comparison was shown in figure 6 and Table 3 represents the identity of

chemical groups respectively.[17,18]

3.1.4. Water Absorption Test

The water absorption test was carried out to find out the absorptivity of the composites.

The samples were weighed by weighing balancing to get the mass of the sample before

immersed in water and recorded. Then they were immersed in the beaker contains water

for 24 hours to measure the water absorption by the samples. After 24 hours, they were

taken out from the beaker and weighed again to record the mass water absorption. The

percentage of water absorption was calculated using the expression.[19]

W % = Ww - Wd / Wd 100 % , (1)

where, Ww and Wd were the wet and dry weight of specimens respectively.

From Figure 7, the water absorption of the composites increases with increasing of wt%

bagasse fiber, because reinforcement material bagasse fiber absorb more water than the

matrix material Cardanol - epoxy. This is because the presence of filler material increased

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 holes inside the composite, by this means increasing the water absorption ability of the

composite.

4. CONCLUSION

In the present experimental investigation, Bagasse fiber reinforced Cardanol resin

composites were fabricated. FT-IR, TGA and DTA behaviour of the developed
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composites was analysed. From the above analyses, the following conclusions were

drawn.

• The FT-IR analysis of the laminates shows the existence of inter molecular hydrogen

bonding of the cellulose in baggase fiber and cardanol resin which indicates the strength

of the laminates irrespective of the composition.

• TGA results shows that among various weight percentages of untreated bagasse fiber

composites, bagasse fiber of 15 wt % had the highest thermal stability.

• The DTA study indicates that the increased modulus, together with the positive shift in

tan delta peak position, was attributed to the physical interaction between the polymer

and fibers that restrict the segmental mobility of the polymer chains in the vicinity of the

Bagasse fiber.

• In general, under the current experimental conditions, 15 wt % was are the optimum

bagasse fiber reinforcement for reinforcing cardanol matrix.

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 9. Shibata, M, K. Ozawa, N. Teramoto, R. Yosomiya, and H. Takeishi. (2003).

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11. Balaji, A, B. Karthikeyan, J. Swaminathan, and C. Sundar Raj. (2017). Mechanical

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Poly. 18, 1193-1199.

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sisal fibers treated by alkali solution and their application into cardanol-based

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 Table 1. Weight losses at 100, 250, 500 and 700 °C temperatures.

Weight loss Weight loss Weight loss Total weight loss

Wt%
(%) at 100°C (%) at 250 °C (%) at 500 °C (%) at 700 °C

0 0.07 5.34 80.40 87.77

5 0.91 6.14 78.17 86.87

10 1.92 4.23 80.82 87.55

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15 1.60 8.21 70.44 82.15

20 2.50 9.37 69.96 83.90

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 Table 2. DTA of 20 mm untreated bagasse fiber reinforced biocomposite materials

Wt% Endothermic Peaks (°C) Exothermic Peaks (°C)

0 75.11 300.00 398.03 220.62 365.78 550.01

5 77.62 319. 01 416.42 256.13 365.18 507.12

10 95.44 308.87 369.05 248.27 347.01 483.26

15 99.72 306.57 378.45 259.11 353.92 502.83

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20 96.01 304.19 374.66 237.01 353.70 541.33

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 Table 3. Chemical groups of biocomposites

WAVE NUMBER
S.No FUNCTIONAL GROUPS INDICATIONS
(cm-1)

Presence of inter-

1. 3700 -3300 O-H group vibration molecular hydrogen

bonding.
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2. 2900 CH2 stretching vibration Cardanol resin.

Acidic functional

group of the cellulose

3. 1700 C=O stretching vibration
present in the bagasse

fiber.

Both bagasse and

4. 1500 -1450 C-C stretching vibration
cardanol resin.

Fiber and Cardanol

5. 1250 C-O stretching vibration
resin.

6. 1100 – 1000 C-H stretching vibration Cardanol resin.

6. 800 C-C-C Cardanol resin.

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Figure 1. Structure of Cardanol resin

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Figure 2. Photograph of the prepared 20 mm length bagasse fiber
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Figure 3. Photograph of the developed composites
 Figure. 4 TGA analysis of Untreated 20 mm Length Bagasse fiber composites
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Figure 5 DTA of Untreated 20 mm Bagasse fiber composites
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Figure 6 FT - IR for different composition of composites
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Figure 7 Variation of water absorption with wt % bagasse fiber