Industrial Crops and Products 43 (2013) 496–505

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Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

Formulation of a novel bio-resin from banana sap

V. Paul a , K. Kanny b,∗ , G.G. Redhi a
a
Department of Chemistry, Durban University of Technology, Durban, South Africa
b
Department of Mechanical Engineering, Durban University of Technology, Durban, South Africa

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

Article history: The purpose of this work is to develop and characterise a novel bio-resin made from banana sap (BS)
Received 15 May 2012 for low end applications such as the interior components of motor vehicles. The sap from banana plant
Received in revised form 27 July 2012 (Musa cavendish), that is locally grown in Kwa-Zulu Natal, South Africa, was used as the starting material
Accepted 31 July 2012
for the bio-resin. The BS was characterised using various physical and chemical testing methods. Quali-
tative analysis of BS confirmed the presence of carbohydrates which was quantified by high performance
Keywords:
liquid chromatography. Phenols were identified by gas chromatography–mass spectrometry. BS from
Musa cavendish
the pseudo stem of the plant was added in varying concentrations (30–65 wt.%) to polyester resin. The
Banana sap maleate
Thermal properties
bio-resin was processed for 12–35 h and reacted with styrene, an initiator and a catalyst, and cured at
Mechanical properties room temperature for 24 h and post cured at 80 ◦ C for 3 h. The thermal and mechanical properties of the
Non-petroleum based products resulting product, called a banana sap maleate were evaluated by differential scanning calorimetry, ther-
Banana sap characteristics mogravimetry and dynamic mechanical analysis. It was concluded that adding 50 wt.% BS gave the best
mechanical properties when compared to the control resin which is 100% petroleum-based unsaturated
polyester resin.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction Musa cavendish), is a monocotyledonous annual herbaceous plant,

and has been suggested as a suitable crop for bio-composite appli-
Growing environmental awareness and new rules and regu- cations (Daneel et al., 2003; Reddy and Yang, 2005; Sapuan et al.,
lations (Il’ina and Varlamov, 2004) are forcing scientists to seek 2006). Daneel et al. (2003) conducted a survey of the banana belt of
new and improved ecologically friendly bio-composites. There- Limpopo province, South Africa, which indicated the availability of
fore scientists have since explored the development of engineering sufficient quantities of a Musa cultivar that is suitable for process-
material from natural resources such as soybean, sisal fibre, coir ing of composites. Once the banana fruit is harvested, the plant is
fibre, wood, banana etc. (Cordeiro et al., 2004; Fowler et al., 2008; left to decompose and a large amount of biomass remains because
Elanthikkal et al., 2010; Barreto et al., 2011). The automotive each banana plant that has borne fruit cannot be used for the next
industry benefits from lighter material and recyclable components harvest. These pseudo stems become organic waste and cause envi-
due to improved energy efficiency (Herrera-Estrada et al., 2009). ronmental pollution (Li et al., 2010). Exploitation of waste banana
Consequently there is a need to utilise environmentally friendly plants will be beneficial to the environment and will have prof-
bio-based or “green composites” (O’donnell et al., 2004). Amongst itable economic benefits (De Beer and Sigawa, 2008). Cellulosic
all the natural resources, banana fibre and plant research is rela- fibre obtained from the pseudo stem of the banana plant are exten-
tively new and unexplored. Here in Kwa-Zulu Natal, South Africa, sively used for paper board, tissue paper, clothing, weaving baskets,
there is an abundance of banana plants. The banana plant (genus natural sorbents etc. (Mohapatra et al., 2010). Numerous reports
(Pothan and Thomas, 2003; Savastano Jr. et al., 2004; Zainudin et al.,
2009) have shown the use of banana fibres as reinforcement in var-
ious composites. Banana fibres have also been use as adsorbents
Abbreviations: BS, banana sap; MA, maleic anhydride; PG, propylene glycol;
to remove heavy metals (Low et al., 1995; Noeline et al., 2005;
BSM, banana sap maleate; HPLC, high performance liquid chromatography; GC–MS,
gas chromatography–mass spectroscopy; DSC, differential scanning calorimetry; Anirudhan et al., 2006). An extensive literature search has shown
TG, thermogravimetry; DMA, dynamic mechanical analyser; UV/Vis, ultra vio- that there are no reports of the banana sap from the pseudo stem
let/visible spectroscopy; nm, nanometre; FTIR, Fourier transform infra-red; DCM, being used in the manufacture of a bio-resin and this work investi-
dichloromethane; ASTM, American Society for Testing and Materials. gates the utilisation of the banana sap in the synthesis of a bio-resin.
∗ Corresponding author at: Department of Mechanical Engineering, Steve Biko
Due to limited information available on the chemical composition
Campus, PO Box 1334, Durban 4000, South Africa. Tel.: +27 031 373 2230;
fax: +27 031 373 2139. of the banana sap, this study will address this gap. Bio-resins are
E-mail address: kannyk@dut.ac.za (K. Kanny). formed from many biological sources such as chitosan (Ravi Kumar,

0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2012.07.064
 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505 497

2000) poly lactic acid (Narayanan et al., 2004), soybean oil (Haq Spectrophotometric analysis of total phenols was carried out
et al., 2008), collagen, carbohydrate-derivatives from starch or cel- using a Perkin Elmer UV/vis spectrophotometer. The total pheno-
lulose (Satyanarayana et al., 2009), natural rubber based adhesives lic content of extracts was determined using the Folin–Ciocalteu
(John et al., 2008; Mathew et al., 2010) and natural phenolic adhe- method (Singleton and Rossi Jr., 1965). The extracts were oxidized
sives such as tannin or lignin (Fowler et al., 2008). In this study with Folin–Ciocalteu reagent, and the reaction was neutralised with
banana sap, containing carbohydrates is used in the formulation of sodium carbonate. The absorbance of the resulting blue colour was
a novel bio-resin. measured at 765 nm after 60 min. Gallic acid (GA) was used as
Polyester resins are commercially prepared by a polycondensa- a standard the total phenolic content was expressed as mg GA
tion reaction between a saturated diol and a mixture of unsaturated equivalent/L of extract. The standard curve was prepared using
dibasic acids (John et al., 2008). The cross-linking may be achieved concentrations 50–500 mg/L.
by the use of either polyols or an unsaturated di-carboxylic HPLC analysis was performed using the Waters HPLC unit with
acid as described by (Shaktawat et al., 2008). In this study the a refractive index detector and ultra-violet detector with the Phe-
banana sap which consists of about 90% water was subjected nomenex Rezex H Organic Acid column. The mobile phase was
to an esterification process using maleic anhydride and propy- made of 0.0025M H2 SO4 /H2 O. Chromatograms were recorded and
lene glycol. The removal of water from the sap was subsequently the peaks from the sample were identified by comparison to pure
effected. standards. The peak areas were determined by integration using
Since it was difficult to produce a natural resin with banana sap, the Clarity Software from Delta.
a hybrid resin was formed using a polyester resin. The remain- GC–MS analysis was performed using the Agilent Technolo-
ing organics in the banana sap reacted with the polyester resin. gies 6890 Series GC coupled with an Agilent 5973 Mass Selective
Polyester resins are cost effective and there is a very large market Detector driven by Agilent Chemstation software. The samples
for it in South Africa. The locally available banana sap is compatible were prepared by liquid–liquid extraction using dichloromethane,
with the polyester resin. ethyl acetate and hexane to extract the polar, medium polar and
Polyester resins are used in various applications such as con- non- polar components. All solvents were of GC grade. The organic
struction, transportation and marine applications (Riedel et al., extracts were concentrated by rotavap and analysed by GC–MS.
1999; Baley et al., 2006) and it was for these reasons it was used. The titration method is used to measure the acid number of the
Maleated polypropylene composites showed improved flexural banana sap maleate. The acid number is the measure of carboxylic
properties (Gironès et al., 2011). Reactions of maleic anhydride acid in the polymer. Acid number is defined in ASTM D 1386 as
with polypropylene is of great industrial interest to enhance its the milligrams of potassium hydroxide required to neutralise 1 g
compatibility, adhesion and reactivity to fibres (Saad, 2011). of sample. Viscosity measurements were performed with the Cone
Over the years landfill sites are being strewn with automo- and Plate viscometer. The molecular weight distribution was done
tive interior components that do not biodegrade. This negatively by gel permeation chromatography. During the processing of the
impacts on the carbon footprint. In order to minimise this prob- resin samples were taken every hour and then every half hour to
lem the automotive sector has made a commitment to produce measure acid number, viscosity and molecular weight distribution.
components that do biodegrade (Gerrard and Kandlikar, 2007). Functional groups of the resin were determined by use of a Nico-
Therefore the aim of this study is to produce a bio-based resin let FTIR instrument with Attenuated total reflectance (ATR) in the
system from banana sap that is biodegradable and environmen- range of 400–4000 cm−1 .
tally friendly. Clearly the material system must have comparable Thermal analysis was performed by TA SDT Q600 instrument.
thermal and mechanical properties with the existing system. The DSC and TG analysis of the samples were performed at 40–400 ◦ C,
resin system will be used for low end applications for the interior heating rate of 10 ◦ C/min with a nitrogen flow of 50 mL/min.
of motor vehicles (Patel et al., 2003) such as dashboard supports,
internal door trim, seat back trim etc. 2.3. Bio-resin processing

2. Experimental Maleic anhydride (MA) and propylene glycol (PG) were pro-
cessed at temperatures between 170–240 ◦ C for 12–40 h with
2.1. Materials of synthesis 30–64% BS as per Table 1. The polypropylene maleate with dou-
ble bonds cross-linked with the unsaturated monomer styrene. A
The stem of the banana plant was collected from a banana control sample was also prepared without banana sap.
plantation in Durban, South Africa. The sheets of the plant were The resin blend was processed with cobalt naphthenate as an
separated and crushed with a Pinette Emidecau Hydraulic Press. accelerator and methyl ketone peroxide as an initiator. The resin
The sap was collected and stored in the freezer at −18 ◦ C for further was cast between two moulds that were assembled from two pieces
use. The fibres were washed several times to remove the pith, air of plate glass, each of size 300 mm by 300 mm and 4 mm of thick-
dried and then stored in plastic bags for further use. Chemical tests ness with a polyurethane gasket between the glass plates. The resin
were performed on the banana sap. Maleic anhydride, propylene cured within 24 h and was post cured at 80 ◦ C for 3 h.
glycol, cobalt naphthenate, styrene and methyl ketone peroxide The new bio-resin was called “banana sap maleate” (BSM).
were purchased from Sigma–Aldrich, South Africa. Table 1 shows the differing composition of the banana sap in the
resin.

2.2. Chemical tests

Table 1
Experimentally it was found that banana sap (BS) constitutes Percentage composition of banana sap (BS) in banana sap maleate (BSM).

approximately 97% water. This was confirmed by the Dean and Sample Composition/%
Stark method which removes water continuously that is produced BSM 0 0% BS
during a chemical reaction performed at reflux temperature. Li BSM 1 30% BS
et al. (2010) reported about 96% moisture content in fresh banana BSM 2 47% BS
pseudo stem. The sap was qualitatively analysed for carbohydrates BSM 3 57% BS
BSM 4 64% BS
using the Molish test (a solution of ␣-napthol in 95% ethanol).
 498 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505

0.8 and 2,4 bis 1.1 dimethylethyl phenol. The phenolic compounds
0.7 were confirmed by the UV/vis and GC–MS methods. It is presumed
that these esters and phenolic compounds polymerise within them-
0.6
selves before attaching themselves to the maleate backbone.
Absorbance

0.5 In Fig. 3 it is observed that as the banana sap concentration was

0.4 increased, the colour of the resin darkened as compared to the con-
trol. This could be explained that as the concentration increases the
0.3
amount of oxidative products namely the phenols also increase.
0.2 This could contribute to the increase in the intensity of the colour.
0.1
122 mg/L
0 3.3. The polymerisation process
0 100 200 300 400 500 600
Conc / mg/L Maleic anhydride (di-functional acid) and propylene glycol
(alcohol) were used as the starting materials to form the polypropy-
Fig. 1. Concentration of total phenolic compounds in banana sap using the UV/vis lene maleate. Fig. 4 shows the proposed reaction mechanism of the
spectrophotometer.
polypropylene maleate. The propylene glycol and the maleic acid
react to form the polypropylene maleate. In Fig. 5 the double bond
2.4. Mechanical analysis in the polypropylene maleate breaks and forms radicals that react
with the monomer styrene, to start the crosslinking process. The
Mechanical properties (tensile strength and tensile modulus) condensation reaction is the most appropriate to form the ester
were measured with an SDT Q 800 DMA. The dimensions of the since water from the banana sap is removed in this reaction It is
specimens for the tensile tests were 20 mm length by 12 mm width difficult to understand the mechanism of how the organics from
and 4 mm thickness. the BS attaches itself to the maleate backbone. In Fig. 6 the mecha-
The Barcol hardness was performed by Colman GYZJ 934-1 nism of how one of the esters from the BS (Table 3) attaches itself
hand-held portable hardness tester. The Barcol hardness was mea- to the backbone of the polypropylene is predicted. It is assumed
sured at ten locations on the surface of the specimens. that the esters co-polymerise before they attach to the maleate
backbone. This deduction is based on the resin becoming darker
3. Results and discussion and the mechanical properties improving when compared to the
control sample.
3.1. Chemical tests performed on the banana sap
3.4. Acid number, viscosity and molecular weight measurement
The Molisch test proved positive for the presence of carbohy- of resin
drates. Oxidative browning took place when the banana sap was
exposed to air. Oxidation of natural phenolic compounds in certain During the polymerisation process, propylene glycol and maleic
plants and fruits caused them to turn brown or black. Chemically, anhydride react with banana sap and water is expelled. The acid
the phenolic compounds are oxidized into quinones which rapidly number is used to indicate the remaining level of the reactive mate-
combine into a dark polymer residue (Rice-Evans et al., 1997). rial. Generally a value less than 50 is desirable (Parkyn, 1967).
Fig. 7a shows that with an increase in time, the acid value
3.2. Characterisation decreased from 220 to 24 and the viscosity increased from 0.05
to 110 Pa.S. Fig. 7b illustrates the growth of the polymer chain
The calibration curve from the UV/vis spectral analysis was used with time. The reaction was stopped when the acid value of 24,
to determine the corresponding gallic acid concentration of the viscosity of 110 Pa.S and molecular weight of 2179 was obtained.
samples in gallic acid equivalents (GAE) using units of mg/litre. As Further processing of the resin beyond 14.5 h would have resulted
per Fig. 1 the phenol content of the sap was found to be 122 mg/L.
Oxidation of phenolic compounds can form quinones. When the Table 3
water is removed from the BS during the condensation reaction of Most abundant compounds extracted from BS using polar, non-polar and medium
the maleic anhydride and propylene glycol, it is possible that the polar solvents analysed by GC–MS.

remaining phenolic compounds react with the resin, imparting the DCM extract Dihydro-5-pentyl 2(3H)-furanone
dark brown colour. Hexadecane
The carbohydrates identified by the HPLC analysis as per Fig. 2 6,10,14-Trimethyl 2-pentadecanone,
Dibutyl phthalate
were: sucrose, fructose and glucose. These sugars quantified in
1,2-Benzenedicarboxylic acid, butyl
Table 2, are caramelized during the heating process of the resin. It 2-methylpropyl ester
is assumed that the caramelized sugars could also contribute to the Hexadecanoic acid
dark colours of the resin. However, it has not been ascertained if the Hexane extract 2-Methyl-heptane
sugars actually attach themselves to the backbone of the maleate 3-Methyl-heptane
resin. 1,3-Dimethyl cyclohexane
GC–MS results in Table 3 confirmed the most abundant pres- 2,5-Dimethyl heptane
3-Methyl octane
ence of 1,2 benzenedicarboxylic acid, bis (2-methylpropyl) ester
1,3-Dimethyl benzene
p-Xylene
Table 2 Ethyl acetate extract 1-Ethyl-3-methyl benzene
Concentration of sucrose, fructose and glucose in banana sap. 2,4-Bis(1,1-dimethylethyl phenol
2,6-Bis(1,1-dimethylethyl) phenol
Carbohydrate Original sap/%
2,5-Bis(1,1-dimethylethyl) phenol
Sucrose 0.018 3,5-Bis(1,1-dimethylethyl) phenol
Glucose 0.04 1,2-Benzenedicarboxylic acid,
Fructose 0.04 bis(2-methylpropyl) ester
 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505 499

Fig. 2. HPLC chromatogram of carbohydrates in BS (peak 3 – sucrose, peak 5 – glucose, peak 6 – fructose).

Fig. 3. Image of control sample and samples with varying concentration of BS.

in the resin gelling. From Fig. 7a and b it can be observed that as chain transfer predominates over the acid-glycol esterification
the acid value decreases, the viscosity and the molecular weight reaction. Here the large polymer chains start joining together and
increases. increasing the molecular weight. If at this stage the product is not
The acid value is low and molecular weight is very high which cooled in time the MW would increase too much and the product
should improve the chemical resistance of the polymer when cross- will harden to an irreversible cross-linked polymer which would be
linked. The sudden rise in viscosity and MW at the end is where incompatible with styrene and require strong solvents to dissolve it.

Fig. 4. Reaction mechanism of maleic anhydride and propylene glycol.

500 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505

O (CH 2 ) 3 O C CH CH C O (CH 2 ) 3 O

O O

O (CH 2 ) 3 O C CH CH C O (CH 2 ) 3 O

O O
CH CH 2
+

O (CH 2 ) 3 O C CH CH C O (CH 2 ) 3 O

O CH 2 O

CHPh n
O (CH 2 ) 3 O C CH CH C O (CH 2 ) 3 O

O CH 2 O

CHPh n
O (CH 2 ) 3 O C CH CH C O (CH 2 ) 3 O

O O

Fig. 5. Proposed mechanism of crosslinking of polypropylene maleate with styrene.

1,2-Benzenedicarboxylicacid, 1,2-bis(2-methylpropyl)
O CH3 ester
C O CH2 C CH3 O
H CH3
CH3 C O CH2 C CH3
C O CH2 C CH3 H
O H CH3
C O CH2 C CH3
O H

O (CH2)3 O C CH CH C O (CH2)3 O

O O O CH3
C O CH2C CH3
H
CH3
C O CH2C CH3
O O H
O (CH2)3 O C CH CH C O (CH2)3
O CH2 O

CHPh n
O (CH2)3 O C CH CH C O (CH2)3 O O CH3
O C O CH2C CH3
CH2 O H
CH3
CHPh n C O CH2C CH3
O H
O (CH2)3 O C CH CH C O (CH2)3 O
O CH3
O O C O CH2C CH3
H
CH3
C O CH2C CH3
O H

Fig. 6. Proposed mechanism of the ester from BS with polypropylene.

 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505 501

250 a 120 Table 4

Melting point temperature, H and Tg values of control, BSM1-4.
110.49
200
100 Sample Melting point/◦ C H/J g−1 Tg /◦ C
Acid Value/ mgKOH/g

BSM-0 (0% BS) 373.34 62.73 63.6

80

Viscosity / Pa.s
BSM-1 (30% BS) 374.25 122.5 65.84
150
BSM-2 (47% BS) 375.98 151.2 71.35
60 BSM-3 (57% BS) 376.89 166.4 69.93
100 BSM-4 (64% BS) 377.34 29.71 68.58
40

50
20 3.5. Thermal analysis
24
0 0 Acid Value A comparison of the thermal transitions of the bio-based resins
8 10 12 14 16
Viscosity and the control sample are shown in Fig. 10. The control sample
Time / hours
is labelled as BSM-0 while BSM-1 to BSM-4 represents 30%, 47%,
Molecular weight distribuon

2500 b 57% and 64% of banana sap in the maleate resin. BSM-0, BSM-1,
2000
2179 BSM-2 and BSM-3 shows the glass transition (Tg ) between 63 ◦ C
and 69 ◦ C and melting point temperatures (Tmelt ) from 373 ◦ C to
1500 376 ◦ C (Table 4). BSM-4 on the other hand displays a glass tansition
1000 at 68 ◦ C, melting point at 377 ◦ C and crystallisation temperature at
300 ◦ C. BSM-4 exists in both amorphous and crystalline forms.
500
BSM-3 and BSM-4 has a lower Tg value than BSM-2 because
0 they contain of more banana sap than BSM-2, resulting in the sam-
11 12 13 14 15 ple becoming more diluted. This means that there could be some
Time / hours unreactive components in the sap that cannot be esterified and
remain as free plasticizers in the polymer. The control sample has an
Fig. 7. (a) Comparison of acid value and viscosity of the banana sap maleate and (b)
molecular weight distribution of the banana sap maleate.
enthalphy value of 62.73 J g−1 . As the BS concentration is increased
from 30 to 57 wt.%, the change in enthalpy (H) of BSM-1, BSM-2,
BSM-3 was observed to increase from 122 to 166 J g−1 respectively.
However H of BSM-4 (64% BS) decreased to 29.71 J g−1 due to
Fig. 8 shows the FTIR scans of the functional groups of BS, MA the crystallisation temperature at 300 ◦ C. One of the factors affect-
and PG. The carbonyl groups of the MA are depicted at 1855 cm−1 ing the enthalpy of a reaction is the concentration of the reactants
and 1776 cm−1 . The FTIR analysis of the PG and BS are dominated and products. The change in enthalpy depends upon the quantity
by hydroxyl moieties at 3310 and 3320 cm−1 respectively. The peak of reactants used. When the number of moles of MA, PG and BS
at 1628 cm−1 in the BS may be attributed to the presence of ketones increases, the change in enthalpy (H) also increases. As the chain
and 1030 cm−1 may be attributed to C O stretching. The polyester length increases so too does the melting point. In this study, only
chain grows as the acid and the hydroxyl groups combine to form one weight loss or degradation step was shown in Fig. 11 at approx-
ester and water is removed in the polycondensation reaction as imately 371 ◦ C. This is the decomposition step of the polymers.
seen in Fig. 9 during the processing at 2 h, 12, 13 and 13.5 h. As the
resin was processed and the water from the BS was removed, the 3.6. Mechanical properties
O H band at 3400 cm−1 slowly disappears. The carbonyl stretch at
1709 and 1716 cm−1 gradually becoming more pronounced as the 3.6.1. Dynamic and static stiffness
esters are formed. The peak at 1640 cm−1 gradually disappears as The stress–strain behaviour of these resins are shown in Fig. 12.
the C C stretch breaks. BSM 1–4 showed a greater stiffness than the control sample. By

Fig. 8. Comparison of FTIR of starting materials of the resin namely banana sap, maleic anhydride and propylene glycol.
502 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505

Fig. 9. FTIR scans of the banana sap maleate resin during the processing at 2, 12, 13 and 13.5 h.

Fig. 10. DSC curves of BSM-0 (control) and BSM-1, BSM-2, BSM-3 and BSM-4 (sample weight 10 mg, heating rate 10 ◦ C/min, and nitrogen atmosphere).

Fig. 11. TG curves of BSM-0 (control) and BSM-1, BSM-2, BSM-3 and BSM-4 (sample weight 10 mg, heating rate 10 ◦ C/min, and nitrogen atmosphere).
 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505 503

CONTROL
30.000
BSM1
BSM2
25.000 BSM2
BSM3

BSM1 BSM4
20.000
Stress / MPa

BSM3
CONTROL
15.000 BSM4

10.000

5.000

0.000 Fig. 14. Comparison of stiffness of control sample with BSM1, BSM2, BSM3 and
0.000 5.000 10.000 15.000 BSM4.
Strain / %

Fig. 12. Stress–strain curves of CONTROL sample compared to BSM1, BSM2, BSM3
and BSM4.

adding varying quantities of BS, the resin has imparted some inter-
esting mechanical properties. The control sample, containing no BS,
has an elongation at break value of 9.2% and can be classified as a
strong and tough polymer. BSM 1, 2 and 3 undergo stress at 20, 23
and 19 MPa respectively but BSM 4 has a strain value of 12 MPa.
BSM 1, 2 and 3 can be classified as strong but not tough resins. BSM
4 is more brittle than the other resins.
Due to the reduced crosslink density caused by reduced maleate
content, BSM 4 with 64% BS had a lower value. By incrementally
increasing the quantity of the BS we are also reducing the maleate
content and thus have less saturation available for crosslinking
with styrene. This may result in the styrene crosslinking with Fig. 15. Flexural stress–strain curve of control sample and BSM1, BSM2, BSM3 and
itself and also residual styrene left in the cured resin with reduces BSM4.

the mechanical properties of the resin making it brittle. We can

also deduce that during the process of forming the resin vary-
ing amounts of the organics from the BS will react with maleate. Table 5 it can be seen that by adding 57% of the BS to the control
Although there is less saturation for crosslinking, we have shown there is a 200% increase in stiffness. This implies that the organics
that the esters from the BS will also crosslink on the maleate back- in the BS contributed to the increase in the stiffness.
bone. Fig. 15 shows the 3 point flexural test was done according to
Fig. 13 shows that the tensile strength of the polymer increased ASTM D790 method. Under static load BSM 1, 2 and 3 required
with 47% BS and then decreased with 57% BS and increases again at 270 N, 160 N, 90 N respectively to extend the sample when com-
64% BS. The strength represents the ultimate load of stress which pared to the control sample that broke at 40 N. BSM 4, however did
the material can withstand before it fails by fracture or excessive not follow the trend. This sample had the most amount of banana
deformation. As the polymer chain grows and the molecular weight sap which consequently leads to the reduced maleate concentra-
distribution increases the strength of the polymer also increases. tion and saturation for crosslinking with styrene. The brittle nature
The resin with 47% BS (BSM4) has an ultimate strength of 25 MPa of this sample resulted in the sample breaking at a load of 50 N.
and from Table 5 it can be seen there is 108% increase in tensile The dynamic flexural modulus is shown in Fig. 16. The elastic
strength with 47% BS. (Young’s) modulus is used as a measure of the rigidity of the mate-
Fig. 14 shows that dynamic stiffness of the resin. The stiffness rial. From Table 5 it can be seen that by adding 57% of the BS to the
represents the resistance to deformation it can be concluded that control there is a 190% increase in flexural modulus.
57% of the BS added to the maleate is the optimum amount. From

Fig. 13. Comparison of the tensile strength of CONTROL sample and BSM1, BSM2, Fig. 16. Comparison of flexural modulus of control sample with BSM1, BSM2, BSM3
BSM3 and BSM4. and BSM4.
504 V. Paul et al. / Industrial Crops and Products 43 (2013) 496–505

Table 5
Comparison of mechanical properties of banana sap maleate with the control sample. The percentage difference between the sample and control is given in parenthesis.

Property Control BSM1 BSM2 BSM3 BSM4

Dynamic stiffness (GPa) 0.4 0.62 (55%) 0.79 (98%) 1.20 (200%) 0.64 (60%)
Static strength (MPa) 12 12.6 (5%) 27 (125%) 21.7 (81%) 25 (108%)
Flexural modulus (MPa) 870 1571 (81%) 1677 (93%) 2528 (190%) 1727 (98%)
Tensile stress–strain 16.5 21 (27%) 23 (39%) 19.0 (18%) 12.6 (<1%)

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