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Biobased Polystyrene Foam-like Material from

Crosslinked Cassava Starch and Nanocellulose from
Sugarcane Bagasse
Parichat Phaodee, Neungruthai Tangjaroensirirat, and Chularat Sakdaronnarong*

This research aimed to study the effect of lignin, natural rubber latex
(NRL), nanocellulose, and talc on production of biobased foam using
cassava starch as matrix. Comparison study on lignin extraction from
sugarcane bagasse (SCB) for different types of base (KOH and NaOH),
concentration (10 %w/w and 40 %w/w), and temperatures (60 C for 3 h
and 120 C for 1 h) was performed. The most suitable isolation condition
giving the highest yield of lignin and lowest hemicellulose contamination
was 40 %KOH at 120 oC for 1 h. A mechanical method was superior to a
chemical method for cellulose size reduction owing to more appropriate
size distribution and uniformity of nanocellulose. The most favorable
proportion of foam contained 20% nanocellulose, 3% talc, 0.1% NRL,
38.5% water, and 76.9% crosslinked cassava starch. These conditions
resulted in favorable flexural strength, modulus, and percentage of
elongation, analogous to polystyrene foam. An appropriate amount of
added lignin increased the elasticity of biofoam.

Keywords: Biobased foam; Nanocellulose; Lignin additive; Natural rubber latex; Thermal compression
molding; Water drop test; Hydrophobic surface

Contact information: Department of Chemical Engineering, Faculty of Engineering, Mahidol University,

25/25 Putthamonthon 4 Road, Salaya, Putthamonthon, Nakhonpathom, 73170 Thailand;
*Corresponding author: chularat.sak@mahidol.ac.th

INTRODUCTION

Biobased foam from agro-industrial residues has gained much more attention to
replace petroleum-based foam from polystyrene, as the latter requires more than 100 years
to be degraded. Cassava starch, natural rubber latex (NRL), and sugarcane bagasse (SCB),
which are abundant and can be easily found in Thailand, are potential renewable sources
for biobased foam production. Starch can be used as a matrix of foam; however it exhibits
higher water absorption in comparison to petroleum-based polymers. The crosslinking
reaction between starch molecules and crosslinking agents was proposed to improve the
water resistance of starch. Glyoxal was used as one of the crosslinking agents for starch,
and it was reported to improve the internal structure of bio-foam and to yield a more
homogeneous foam (Uslu and Polat 2012). The crosslinking reaction additionally resulted
in increased strength, decreased density, and reduced water absorption of biofoam made of
starch. Cellulose fibers isolated from lignocellulosic biomass were investigated to be used
as reinforcement units. To improve the flexural strength of biofoam, cellulose nanofibers
were added into the starch matrix; such preparation additionally enhanced the modulus of
the materials (Floros et al. 2012; Narkchamnan and Sakdaronnarong 2013). In addition,
poly(vinyl alcohol) matrix reinforced with nanocellulose resulted in increased tensile
modulus and tensile strength of the composite (Floros et al. 2012). Interestingly, from a

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previous study in the authors’ group, a lignin by-product from cellulose isolation
significantly improved the water resistance of starch composite, as indicated by an increase
of contact angle on the surface of foam by water drop test analysis (Narkchamnan and
Sakdaronnarong 2013). Attempts have been made to overcome the brittleness and improve
the porosity of bio-based starch composites. NRL was found to increase the flexibility of
rigid foam (Teixeira et al. 2011). Higher NRL content in biofoam decreased the modulus
and stress to breakage but increased strain to breakage of biofoam (Shey et al. 2006).
Additionally, the effect of nucleating agents such as talc on improving regular porosity was
studied. Composite material produced from wood fiber, talc, and poly(hydroxybutyrate-
co-valerate) by extrusion had good pore distribution with increased talc content (Singh et
al. 2010).
To the best of our knowledge, the present work was the first time that a crosslinking
technique using glutaraldehyde and thermal compression molding technique has been
applied to produce bio-based polystyrene foam-like material. An experimental design by
the Box-Behnken method was performed in order to screen the crucial factors and
determine the most favorable condition to produce biofoam having similar physical and
mechanical properties to polystyrene foam. A study of the influence of nanocellulose, talc,
and NRL on biobased foam formation was carried out. Effects of lignin addition on the
properties of biobased foam were also tested.

EXPERIMENTAL

Materials
Cellulose fibers and lignin were isolated from SCB provided by Kornburi Sugar
factory, Nakornratchasrima, Thailand. Cassava starch was purchased from Pla Mungkorn
Co., Ltd., Thailand. NRL (50% solids) was supplied from Srijaroen Latex, Co., Ltd. in
Nakornsrithammarat province, Thailand. Black liquor from soda pulping process was
contributed from Environment Pulp and Paper, Co., Ltd., Nakornsawan, Thailand.
Accellerase enzyme (Genencor, USA) was supplied from Siam Victory Chemicals, Co.,
Ltd. Glutaraldehyde, talc (Prod. No. 18654, Sigma-Aldrich with the particle size between
10 to 20 m), dioxane, standard lignin (alkali lignin, low sulfonate), and microcrystalline
cellulose and 3,5-dinitrosalicylic acid (DNS) were from Sigma-Aldrich. Other chemicals
e.g. sulfuric acid, hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide,
and sodium acetate, were purchased from Ajax.

Lignin Extraction and Nanocellulose from Sugarcane Bagasse (SCB)

SCB was milled by centrifugal mill, sieved to 20-40 mesh, and then dried at 50 oC
until constant weight before use. For lignin extraction, 30 g SCB was soaked in 300 mL of
alkaline solution by varying types and concentrations of base (10% NaOH, 10% KOH,
40% NaOH and 40% KOH) as well as temperature and time at 120 oC for 1 h and 60 oC for
3 h. Subsequently, solid and liquid parts were separated. To remove the solid lignin from
the liquid part, lignin was precipitated by adding concentrated sulfuric acid until pH 1, and
then the whole solution was centrifuged at 5000 rpm for 5 min. The supernatant solution
was rich in hemicelluloses. Wet lignin slurry was dried at 50 oC under vacuum condition
until constant weight and ground to a fine powder. Solid lignin was analyzed for
hemicellulose contamination and by spectroscopic analysis.

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Solid residue from the lignin extraction, containing mainly cellulose, was washed
with distilled water, and then the pH of pulp was adjusted to the range 4 to 5 by acetic acid.
For the bleaching step, the cellulose pulp was soaked in 11%w/w hydrogen peroxide and
stirred using magnetic stirrer for 24 h. Bleached fibers were then soaked in 10%w/w
hydrochloric acid in an ultrasonicator at 60 oC for 2 h prior to size reduction step. Two size
reduction methods used in this work were by 1) mechanical and 2) chemical means. For
the mechanical size reduction method, bleached fibers were adjusted to neutral pH by
adding distilled water (1: 60 of pulp dry weight: water ratio) then high shear
homogenization (Heidolph, DIAX 900, Germany) was performed at 20,000 rpm for 15
min. For chemical size reduction method, bleached fibers were soaked in 6 M sulfuric acid
at 45 oC for 30 min then washed with distilled water until neutral pH. Never-dried
nanocellulose was determined for the moisture content and used for biofoam
reinforcement. Vacuum-dried nanocellulose at 50 C was used for analyses.

Biobased Foam Production

100 g native cassava starch was added into 0.4% glutaraldehyde solution and stirred
using a magnetic stirrer for 24 h at room temperature. Crosslinked starch was washed three
times using distilled water and then dried at 50 oC before grinding to a fine powder. The
effects of cellulose fibers, talc, NRL, and water proportions were studied for biobased foam
formation. 18 g dry weight of mixture was filled into a stainless steel mold having
dimensions of 6.25 cm  7.5 cm  0.2 mm. Thermal compression molding was performed
at 200 C for 3 min. Response surface methodology using Box-Behnken method was
performed to investigate the proper foam formulation to produce PS-like material.
Experimental data and quadratic models of all responses were statistically analyzed by
ANOVA (Design Expert version 9, www.statease.com). The suitable condition that gave
the foam’s mechanical and physical properties analogous to polystyrene foam was selected
for the study of influence of lignin isolated from sugarcane bagasse on foam’s properties.

Analytical Methods
The yield of lignin and cellulose was determined from the dry weight of isolated
material based on the initial dry weight of SCB. Hemicellulose contamination was
determined by hemicellulase hydrolysis in 15 mL of hydrolysate containing 2 mL of black
liquor, 10 mL of sodium acetate buffer (pH 4.8), and 3 mL of Accellerase enzyme. The
hydrolysis took place at 50 oC for 48 h. Reducing sugar was measured by DNS assay
(Miller 1959). Hemicellulose contamination onto precipitated lignin expressed as reducing
sugar based on dry weight of lignin as shown in Eq. 1.

Reducing sugar (mg mL-1 )×15 mL hydrolysate

Hemicellulose contamination (mg sugar mg lignin-1 )=
lignin (g dry weight)
(1)
UV-Vis spectrophotometry (T60U, PG instrument, China) of isolated lignin
solubilized in dioxane-water solution (lignin: dioxane ratio of 1: 9) was measured between
200 and 600 nm wavelength. Functional groups of lignin were analyzed by FTIR
spectroscopy (Spectrum 2000, Perkin ELMER, USA )at 4000 to 400 cm-1 wave number at
4 cm-1 resolution and 128 numbers of scan for triplicates) when lignin pellet was prepared
at a lignin:KBr ratio of 1:99 by weight. An X-ray diffractometer (XRD) (Bruker, D8-
Discover, Germany) was used for crystallinity analysis of nanocellulose. Crystallinity

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index (CrI) was calculated from the intensity of the 200 peak (I200, 2 = 22.6°) and the
minimum intensity between the peaks at 200 and 110 (Iam, 2=18.7°) by using the empirical
equation, CrI = (I200-Iam)/I200*100 (Segal et al. 1959). Transmission electron microscope
(TEM) analysis (JEM-1230, JEOL, Japan )for mechanical and chemical size reduction
nanocellulose was conducted.
Mechanical properties measurements of biobased foam, namely flexural strength,
modulus, and elongation, were carried out with a Universal Testing Machine (Instron 4467,
USA) using a three-point bending method at 0.5 kN loading cell, 4 mm min-1 crosshead
speed, and 40 mm span. Foam density was calculated from the weight of dried biofoam
(50 C under vacuum for 24 h) divided by the volume of foam having a dimension of 7.5
cm  7.5 cm  2 mm. Light transmission digital microscopy was performed for analysis of
cell distribution of biofoam at 5 magnification. The morphology of the cellulose fibers
was examined using a scanning electron microscope (SEM) (Hitachi S4800, Japan). The
specimens were coated with a thin platinum layer for 15 min in a vacuum in order to
improve the conductivity and prevent electron charging. Images were taken at 5kV. Water
resistance analysis was determined by drop shape instrument (FTA1000, Brand, Canada).
A dynamic change of contact angle between biofoam surface and water drop was calculated
between 1 sec and 60 sec by image analyzer equipped with water drop test apparatus.

RESULTS AND DISCUSSION

Lignin Extraction from Sugarcane Bagasse

Sugarcane bagasse was extracted by alkaline solution for lignin, and the results
showed that when the temperature and base solution were varied, the yield of lignin was
different, as shown in Fig. 1(A). Results of the analysis showed similar levels of lignin
yields (2.6%w/v) from all extraction conditions from 10% NaOH, 40% NaOH, and 40%
KOH at 120 oC for 1 h, as well as 40% NaOH at 60 oC for 3 h. The highest yield of lignin
at 6.3%w/v was isolated from black liquor from the pulp and paper factory. Higher lignin
yield from the factory was obtained compared with lignin yield isolated from SCB because
higher temperature and pressure were applied in the soda pulping process (14% NaOH at
170 C) (Jiménez et al. 1999). It was reported that an increase of lignocellulose treatment
severity, e.g. temperature and catalyst concentration, enhanced lignin yield (Fernández-
Bolaños et al. 1999). However, hemicelluloses contamination within lignin extract seems
to be enhanced when increasing alkaline concentration and temperature.
Hemicellulose has amorphous structure, and the presence of hemicellulose has been
found to increase the moisture absorption of biofilm (Bahcegul et al. 2012). To select a
suitable condition for lignin extraction, not only high lignin yield but also the lowest
hemicellulose contamination were considered. As shown in Fig. 1(B), lignin extracted by
40% KOH at 120 oC for 1 h had less hemicellulose contamination (133.4 mg sugar/g lignin)
than that extracted by 40% NaOH at 120 oC for 1 h (182.6 mg sugar g lignin-1). The highest
hemicellulose contamination was obtained from lignin in black liquor from pulp and paper
factory (205.4 mg sugar g lignin-1). Therefore, 40% KOH at 120 oC for 1 h was the most
suitable condition for lignin extraction because of higher yield of lignin and least
hemicellulose contamination. The result was in accordance with the study of hemicellulose
contamination in extracted lignin by Bahcegul and colleagues (2012), who evaluated the
effect of alkaline pretreatment temperature on a multi-product basis for the co-production

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of glucose and hemicellulose based films from lignocellulosic biomass. They reported that
9.8% hemicellulose recovery from 10% KOH was obtained from lignin extraction at 25 oC
and 18.2% hemicellulose recovery was obtained from lignin extraction at 90 oC. Thus,
higher temperature for lignin extraction provided higher hemicellulose released from
lignocellulosic material.
8
(A)
6.3
6
Lignin yield (%w/v)

4 T 120 oC
2.6 2.6 2.6 2.6
T 60 oC
1.9
2 1.3 1.2
1.1

0
10% NaOH 40% NaOH 10% KOH 40% KOH Pulp&paper factory

250
(B) 219.7
contamination in solid

205.4
extracted lignin (mg

200 182.6
sugar/g lignin)
Hemicellulose

166.3 160.5
151.7
150 139.6 133.4 T 120 oC
114.4
T 60 oC
100

50

0
10% NaOH 40% NaOH 10% KOH 40% KOH Pulp&paper factory

Fig. 1. (A) Yield of isolated lignin at different temperatures, base types, and concentrations, and
(B) hemicellulose contamination in solid extracted lignin

As illustrated in Fig. 2(A), analysis of lignin by UV spectrophotometer showed a

typical peak at a wavelength of 280 nm, which is attributable to non-conjugated phenolic
units, and a peak at wavelength of 315 nm can be assigned to conjugated phenolic units
(Maziero et al. 2012). Figure 2(A) shows that lignin extracted using 10% KOH at 120 oC
for 1 h gave the maximum absorbance at a wavelength of 280 nm and 315 nm. The second
highest spectrum at 280 and 350 nm was from lignin extracted with 40% KOH at 120 oC
for 1 h. Moreover, the absorbance ratio of A280/A315 was higher for lignin extracted from
KOH compared to NaOH extracted lignin. This result indicated that lignin extraction with
KOH led to higher yield of unconjugated lignin than conjugated lignin; thus KOH
extraction yielding small molecules of lignin was more suitable for use as an additive in
biocomposite formation, in accordance with the results from a previous work (Sun et al.
2004). As illustrated in Fig. 2(B), FTIR spectroscopy of isolated lignin typically shows a
peak at 1500 cm-1 (I1500) assigned to aromatic lignin. Peak intensity at 1734 cm-1 (I1734) is
assigned to hemicellulose, peaks at 1373 and 1161 cm-1 (I1373 and I1161) are polysaccharides,
and peak intensity at 900 cm-1 (I900) is attributed to cellulose (Krongtaew et al. 2012). The
FTIR spectrum indicated that the more purified lignin gave a lower percentage of
transmittance or higher absorbance at the peak near 1500 cm-1 (Zeng et al. 2012). The FTIR
spectrum of lignin from pulp and paper factory was similar to the FTIR spectrum of

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extracted lignin from 40% KOH (120 C, 1 h) as well as that of standard lignin.
Nevertheless, the intensity near polysaccharide absorption was different among all
extracted lignin specimens; thus the ratio of lignin to carbohydrate transmittance intensity
was more appropriately considered to indicate hemicellulose contamination in lignin
molecules, as demonstrated in Table 1.

Table 1. Relative Intensity Ratios of FTIR Spectroscopy of Hemicellulase

Enzyme Treated and Untreated Lignin
Enzymatic Sample Relative intensity ratio
treatment Base solution I /I I /I I /I I /I
1510 1734 1510 1373 1510 1161 1510 898
40% NaOH 0.95 1.07 1.31 0.95
40% KOH 0.94 1.13 1.36 1.02
Untreated
Pulp & paper
0.96 1.21 1.54 1.06
factory
40% NaOH 0.85 1.01 1.12 0.90
40% KOH 0.89 1.10 1.28 0.91
Treated
Pulp & paper
0.87 1.09 1.26 0.95
factory
- Standard lignin 0.87 1.02 1.08 0.87

2
1.8 (A)
10 %w/w KOH
1.6
40 %w/w KOH
Absorbance

1.4
10 %w/w NaOH
1.2
40 %w/w NaOH
1
0.8
0.6
0.4
0.2
0
250 300 350 400 450 500 550 600
Wavelength (nm)

110 -1
Hemicellulose at 1734 cm-1 Cellulose at 900 cm
(B)
Aromatic lignin at 1500 cm-1
100

90
10 % w/w KOH
% Transmittance

80 40 % w/w KOH
10 % w/w NaOH
70 40 % w/w NaOH
Std. lignin
60 Polysaccharides
-1
OH gr. at at 1373and 1161 cm
3400 cm-1
50
4000 3500 3000 2500 2000 1500 1000 500
Wave number (cm-1)
Fig. 2. (A) Lignin extracted at 120 C analyzed by UV-vis spectrophotometer, (B) Lignin extracted
at 120 C after treated by hemicellulase enzyme analyzed by FTIR spectroscopy

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In transmittance mode, less intensity of lignin-to-carbohydrate ratio represents
higher lignin content compared with carbohydrate content, thus representing more purified
lignin. From the results, the intensity ratio of extracted lignin after hemicellulase enzyme
treatment was less than untreated lignin, showing that enzymatic treated lignin was more
purified than untreated lignin. The average intensity of extracted lignin from 40% KOH at
120 oC for 1 h had the same value as lignin from pulp and paper factory. Due to similar
FTIR spectra and relative intensity ratios of lignin-to-carbohydrate components, both
extracted lignin from SCB (40% KOH at 120 oC for 1 h) and from the pulp and paper
factory were able to be used as an additive for biofoam production.

Cellulose Isolation and Size Reduction

Delignified SCB from 40% KOH at 120 oC for 1 h and subsequent acid
hydrolysis/H2O2 bleaching yielded 44.8% cellulose. A lower yield of cellulose (37.9%
yield of cellulose) was achieved from 40% NaOH at 120 oC for 1 h and subsequent acid
hydrolysis/H2O2 bleaching. The results were in good agreement with those of Sun and
coworkers, who reported that lignin yield from KOH extraction was higher than that from
NaOH extraction (Sun et al. 2004). It was suggested that KOH was preferential for
hemicellulose removal from sugarcane bagasse, and more than 90% of the original
hemicelluloses were released. This significant solubility of hemicelluloses was probably
due to the hemicelluloses being present to a greater degree on outer fiber surfaces, from
where they could dissolve easily in the alkaline solution. By contrast, cellulose is more
located in the inner parts of the fibres and therefore is not easily dissolved. In the present
study, the findings suggested that the most appropriate extraction condition yielding
highest lignin and cellulose yields was at 40% KOH at 120 oC for 1 h.
After the bleaching step, isolated cellulose from SCB was subjected to size
reduction. Nanocellulose was added in biofoam to increase its mechanical properties. TEM
analysis illustrated morphology and size distribution of nanocellulose fibers for mechanical
(Fig. 3(A) and 3(B)) and chemical methods (Fig. 3(C) and 3(D)).

(A) (B)

(C) (D)

Fig. 3. TEM images for reduce size of cellulose by mechanical method (×80,000 magnification) (A)
cellulose from 40% NaOH at 120 oC extraction for 1 h, and (B) cellulose from 40% KOH at 120 oC
extraction for 1 h. For reducing size of cellulose by chemical method (×100,000 magnification), (C)
cellulose from 40% NaOH at 120 oC extraction for 1 h, and (D) cellulose from 40% KOH at 120 oC
extraction for 1 h

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Both size reduction methods decreased the diameter of cellulose fibers from micro-
scale (data not shown) to nano-scale with the same average diameter ranging from 10 to
20 nm. The average length of the nanocellulose ranged between 200 and 800 nm, which is
the same length (100 to 500 nm) as cellulose whiskers isolated from sugarcane bagasse in
previous work (Teixeira et al. 2011). In the present study, mechanical method was selected
to produce nanocellulose due to superior shape distribution, simplicity of handling, and
less amount of effluent compared with the chemical method.
An XRD diffractogram of isolated nanocellulose indicating crystallinity of
cellulose apparently showed a mixture of polymorphs of cellulose (typical peaks near 2 =
22.6o) (Sun et al. 2004) and amorphous moieties near 2 = 16.8o, as depicted in Fig. 4.
Nanocellulose isolated from 40 %KOH at 120 C for 1 h using the chemical method for
size reduction exhibited a higher typical peak intensity of cellulose (2 = 22.6o) than that
using the mechanical method, as shown in Fig. 4(A) and 4(B). Higher crystallinity of
cellulose was obtained from the chemical size reduction method (69.3 % CrI) relative to
the mechanical size reduction method (66.5 % CrI). Accordingly, analysis of TEM and
XRD results for nanocellulose from different reducing size methods showed that
mechanical method was more suitable than chemical method to use as reinforcement units
in biofoam.

200
210

(A) (B)
190
200
180
190
170
180
160 170
150 160
140 150

130 140
Intensity (cps)

Intensity (cps)

120 130

110 120

100 110

90 100

90
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
0
0
5 10 20 30 40
5 10 20 30 40

2-Theta - Scale 2-Theta - Scale

File: 4,3 40% KOH.raw - Type: 2Th/Th locked - Start: 5.000 ° - End: 40.000 ° - Step: 0.020 ° - Step time: 1.2 s - Temp.: 25 °C (Room) - Time Started: 16 s - 2-Theta: 5.
File: 4,1 40% KOH.raw - Type: 2Th/Th locked - Start: 5.000 ° - End: 40.000 ° - Step: 0.020 ° - Step time: 1.2 s - Temp.: 25 °C (Room) - Time Started: 16 s - 2-Theta: 5.

Fig. 4. X-ray diffractogram of 40 %KOH which reduce size of cellulose by (A) mechanical method,
and (B) chemical method

Production of Biobased Foam

It has been widely known that biobased foam from starch has disadvantages in
terms of high stiffness, high brittleness, low elasticity, and high water absorption. Many
researchers have investigated this issue and found that addition of petroleum-based plastics
e.g. polypropylene (Bagheri 2009), polystyrene (Pushpadass et al. 2010), polyvinyl-
chloride (Viña et al. 2007), as well as plasticizers, e.g. glycerol and sorbital (Das et al.
2011), is able to overcome the aforementioned problems. In the present work, addition of
NRL into biobased foam made of starch matrix was hypothetically applicable, as it
improved the water resistance as well as elasticity of composite, although it could diminish
the biodegradability of the composite (Bouthegourd et al. 2011).

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Effect of NRL on biofoam properties
As shown in Table 2, the ingredients for production of biobased starch foam
included nanocellulose, talc, NRL, and distilled water. The dry weight of the mixture was
calculated based on cassava starch (dry weight). The responses of varying biofoam
compositions were demonstrated as mechanical and physical properties of biofoam
consisting of flexural strength, elongation, modulus, and density. From the results, NRL
gave increasing elongation and flexural strength of biobased foam, as demonstrated in
sample no. 20 and sample no. 23. Addition of 10% NRL increased the percentage of
elongation up to 5.93%, compared with 3.1% elongation when adding 0.1% NRL. An
increase of 91.3% elongation was achieved when adding 10% NRL into biofoam
containing 15% nanocellulose, 5% talc, 38.5% distilled water, and 70% crosslinked
cassava starch (dry weight). The solids in natural rubber latex are comprised mainly of cis-
1,4-polyisoprene (Shey et al. 2006). When this latex cures or dries during thermal
compression molding, an elastic and hydrophobic material is produced. However, before
the latex is cured, it is in an aqueous emulsion, which allows the rubber to be evenly
distributed throughout the batter in the production of thermal compressed starch foams.
Table 2 also shows that the flexural strength was slightly decreased, and a 43.5% decrease
of modulus was obtained when adding 10% NRL compared with 0.1% NRL. The results
agreed with those of Shey and coworkers (2006), who reported that addition of NRL
increased strain by approximately 60% compared with biofoam without rubber latex.
Therefore, enhancement of NRL content increased elasticity of biofoam caused by
polyisoprene in NRL. In other words, at low content of NRL (sample no. 20) the higher
cassava starch loading was used compared with the sample no. 23, and thus more
crystalline regions were introduced compared to the control biofoam. This occurs as a
consequence of the retrogradation process of starch, which realigns the amylose and
amylopectin chains (Mohamed et al. 2008). It has been reported that as the crystalline
region is increased, the NRL composite becomes vulnerable to the formation of cracks and
failure upon stress application. At higher starch loading, the formation of bigger sizes and
numbers of crystal regions contribute to a composite’s failure during mechanical testing.
The formation of starch crystalline regions also decreased NRL composite’s ability to
elongate further (Afiq and Azura 2013). Nevertheless, from the ANOVA of flexural
strength and elongation in Table 3, it was found that talc content also gave significant effect
on these two responses. An increase of NRL content gave significant effect on flexural
strength and elongation enhancement (P<0.05). However, an increase of talc content as
well as interaction between talc and NRL contents additionally augmented flexural strength
and elongation. Therefore, at 3% talc content (sample no. 2 and no. 5) which had low
content of talc compared with sample no. 20 and 23 (5% talc), an increase of NRL content
seemed to give insignificant effect on flexural strength and elongation. An increase of NRL
proportion in the biofoam ingredients made the density of biofoam increase, which was in
accordance with a previous work (Shey et al. 2006). This could possibly be improved by
addition of talc, a foam nucleating agent.

Effect of nanocellulose on biofoam properties

Addition of nanocellulose into biofoam significantly enhanced flexural strength
and modulus because cellulose has a parallel chain orientation and crystalline structure;
however the percentage of elongation was decreased when nanocellulose was added, as
demonstrated in samples no. 29 and sample no. 6 (Table 2). An increase of nanocellulose
content from 10% to 20% substantially enhanced flexural strength and modulus of

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biobased foam from 1.4 and 74.4 MPa to 14.4 and 533.5 MPa, respectively. These results
corresponded to 956.6% and 616.9% increases of flexural strength and modulus,
respectively. This can be explained by strong interaction in the interface region between
nanocellulose, crosslinked starch, and NRL. It was reported that the increase of crosslink
density of rubber restricts the mobility of rubber chains in the presence of CNs (Cao et al.
2013). The results agreed with those of Floros and colleagues (2012), who studied the
addition of cellulose into a polyurethane (PU) matrix (Floros et al. 2012). An increase of
nanocellulose fiber added to PU caused increase of flexural strength and modulus while
the %elongation was reduced. However, in the present study when nanocellulose was
increased from 10% to 20%, percentage of elongation was insignificantly decreased from
2.8% to 2.6%, respectively. The results suggested that inappropriate nanocellulose
distribution throughout biofoam ingredients can cause the failure during the elongation test,
and therefore the orientation of nanocellulose is required to be arranged in parallel to
improve the biocomposite’s mechanical properties, as designed. It is important to note that
the mechanical disruption of bacterial cellulose (BC) and the development of an
reconstituted BC biofilm produce better fibre association and orientation of the fibrils,
which can promote higher thermal stability (de Souza et al. 2013). Nanocellulose provided
a higher stiffness and induces brittleness of the material. Therefore, the dispersion of the
filler is expected to be lower, and long entangled nanocellulose and its higher hydrophobic
character are required, resulting in a higher level of adhesion with the NRL and starch
matrix. Moreover, the biofoam density from the present study was slightly increased from
0.61 to 0.82 g cm-3 when nanocellulose content in batter was increased from 10% to 20%.
This was in good agreement with the work of Glenn and coworkers (2001), who found that
addition of softwood pulp fiber to the formulation of the baked starch foams improved
flexural properties and lowered the density (Glenn et al. 2001). The foam density could be
presumably reduced by adding nucleating or blowing agents. Nevertheless, from ANOVA
of flexural strength and modulus (Table 3), it was not the only effect of addition of
nanocellulose content that enhanced the flexural strength and modulus. In addition,
interaction between nanocellulose and NRL contents as well as nanocellulose and talc
contents gave considerable influence on flexural strength and modulus. Solely the
influence of an increase of NRL content significantly enhanced flexural strength and
modulus, however. The interaction effect of NRL and nanocellulose showed that an
increase of NRL content reduced flexural strength and modulus of biofoam. Thus, if
comparing the pair of sample no. 5 and 28, which contained high NRL content at 10%, the
flexural strength and modulus of biofoam were decreased, although the nanocellulose
content was increased.

Effect of talc on biofoam properties

To improve the cellular size distribution of biofoam, several studies have been
conducted of the effects of adding salts e.g. NaCl and CaCl2 (Zhou et al. 2006), nucleation
agent e.g. talc (Lee et al. 2009; Singh et al. 2010; Zhang and Sun 2007), as well as blowing
agent e.g. CaCO3 (Glenn et al. 2001) into the foam’s batter. Solid, insoluble particles (e.g.
talc particles) are often dispersed in the polymer matrix to provide heterogeneous
nucleation sites and control the number density and/or size distribution of bubbles in the
final foam (McClurg 2004). In the present work, talc was selected as an additive for the
biofoam formulation, as it is simple way to improve cellular size distribution of biofoam.
As demonstrated in Table 2, adding talc into biofoam gave increasing flexural strength but
decreasing percentage of elongation, as shown for sample no. 22 and sample no. 9. An

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increase of talc content from 1% to 5% considerably increased flexural strength from 2.1
MPa up to 5.5 MPa, which was a 158% increase of flexural strength. Similarly, the modulus
of biofoam was increased from 278.2 MPa to 323.3 MPa when talc content was increased
from 1% to 5%. In accordance, the results showed that increasing talc content from 1% to
5% caused an insignificant decrease of percentage of elongation from 2.0% to 1.7%. The
results agreed with those of Singh and coworkers (2010), who studied on improvement of
biocomposite properties containing cellulose fiber, talc, and polyhydroxybutyrate-co-
valerate (PHBV). This previous work reported that 20% talc and 20% cellulose fiber
resulted in a doubling of the elongation and increased flexural strength up to 22%. Thus,
the interaction effect of talc and nanocellulose significantly influenced elasticity and
strength of biofoam. With the presence of 5 wt% of untreated talc particles, the onset time
of cell nucleation was earlier (data not shown), and the foam density increased significantly
as shown in sample no. 33 compared to sample no. 9 in Table 2. Nonetheless, additional
theoretical studies on the effect of viscosity and elasticity of the polymer–nucleating agent
mixture on mechanical properties of biofoam are needed.
Surface appearance and light transmission images of biobased foam from sample
no. 25 are shown in Figs. 5(A) and 5(B), respectively. Light transmission imaging of
polystyrene (PS) foam is additionally illustrated in Fig. 5(C). It was observed that cell
distribution of PS foam was more uniform and homogeneous in the whole specimen
analyzed compared with those observed in biobased foam. However, the mechanical
properties of the biofoam sample having flexural strength of 0.4 MPa, percentage of
elongation of 3.1%, modulus of 43.5 MPa, and density of 0.44 g cm-3 were similar to those
of polystyrene foam having flexural strength of 0.5 MPa, elongation of 3.2%, modulus of
21.2 MPa, and density of 0.03 g cm-3 (Table 2). As illustrated in Fig. 5, denser foam made
of cassava starch/NRL/nanocellulose/talc was obtained (Fig. 5(A) and 5(B)) and looser
foam made of polystyrene (PS) was shown in Fig. 5(C). In this context, denser foams tend
to have thicker cell walls or higher solid fraction and hence are able to resist deformation
better than lower density foams with thinner cell walls or lower solid fraction. Addition of
nucleation agent (e.g. talc powder) in the present study increased foam densities; thus the
significant increases of the compressive strength, elastic modulus, and elastic deformation
energy were obtained. Hence, nucleation agents are suitable to refine the foam cell
structures to produce more rigid foams having high load-bearing capacity and yet able to
deform at higher stress levels to absorb impact energy and hence suitable for protecting
heavy goods (Zhou et al. 2006). Consequently, biofoam made of cassava
starch/NRL/nanocellulose/talc having thicker cellular wall (Fig. 5(B)) provided higher
resistance of impact energy and thus it was more suitable for packaging applications
relative to polystyrene (PS) foam having thinner cellular wall (Fig. 5(C)). Figures 5D to
5G additionally show SEM images of biofoam surface and cross-sectional area on biofoam
sample no. 20 (15% nanocellulose, 5% talc, 0.1% NRL, 38.5% distilled water) and sample
no. 7 (15% nanocellulose, 1% talc, 0.1 % NRL, and 38.5% distilled water). It was found
that higher content of talc (5% talc) in the biofoam formulation gave foam with lower
density (0.1 g cm-3) but smoother surface (Fig. 5(D)) and better cellular size distribution
(Fig. 5(E)). On the other hand, denser foam with 0.25 g cm-3 density was obtained from
sample no. 7 (1% talc), and a rougher surface and poor cellular size distribution were
obtained, as shown in Fig. 5(F) and 5(G), respectively.
Addition of water significantly decreased flexural strength, as demonstrated in
sample no. 3 and sample no. 4 (Table 2). An increase of water content from 33% to 44%
in the biobased foam caused decreased flexural strength from 4.6 MPa to 0.6 MPa.

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Likewise, the modulus of biofoam significantly decreased from 256.2 MPa to 38.0 MPa.
In contrast, the percentage of elongation increased from 2.7 to 3.7 % when water content
in biofoam was enhanced from 33% to 44%. The great importance lies in the starch
composition (amylose and amylopectin ratio) during thermal processing. Influence of
water on the Tg showed that the very branched amylopectin had a slightly lower glass
transition temperature than the amylose and starchy material containing water that is
generally in the glassy state, and therefore brittle under natural conditions (Mitrus and
Moscicki 2014). Nevertheless, an optimal water content in biofoam ingredients in the
present study substantially depended on the temperature of starch processing, as well as
quantity and type of added plasticizers, nanocellulose fiber and crosslinked starch. A
suitable water content in the ingredients of biofoam was required to improve the biofoam’s
mechanical and water resistance properties for production of packaging or other short-lived
materials derived from agro-polymers (Narkchamnan and Sakdaronnarong 2013).

ANOVA for Response Surface Quadratic Models

ANOVA results for Response Surface Reduced Quadratic models of each factor
namely flexural strength, elongation, modulus, and density are listed in Table 3. According
to the accuracy of the Box Behnken design and degrees of freedom of the quadratic models,
24 runs and 5 center points were performed. It was found that the term NRL in the model
gave significant effect on namely flexural strength, elongation, modulus, and density
(P<0.05). For flexural strength, the model F-value of 2.48 implies the model is significant.
There is only a 4.78% chance that an F-value this large could occur due to noise. Values
of "Prob > F" less than 0.0500 indicate model terms are significant. In this case C or NRL
content is a significant model term (P<0.05). Values greater than 0.1000 indicate the model
terms are not significant. In case of elongation model, the model F-value of 2.43 implies
the model is significant. There is only a 4.85% chance that an F-value this large could occur
due to noise. In this case B (Talc content) and C2 (NRL2) are significant model terms
(P<0.05). In terms of modulus, the model F-value of 3.07 implies the model is significant.
There is only a 1.92% chance that an F-value this large could occur due to noise. In this
case B (Talc), BC (Talc*NRL), and B2 (Talc2) are significant model terms (P<0.05). For
the biofoam density, C (NRL) is only significant model term. The model F-value of 2.71
implies the model is significant. There is only a 3.62% chance that an F-value this large
could occur due to noise. An increase of NRL content in biofoam ingredient enhanced the
foam density. Similarly, an increase of NRL content tended to slightly increase the flexural
strength. Meanwhile, elongation and density of material depended significantly on
interaction effect of NRL and talc contents as shown in the quadratic models. From the 3D
surface plot of talc and NRL contents (data not shown), an increase of NRL up to 10% and
Talc content up to 5% achieved the maximum elongation and density of material. From
statistical analysis, standard deviation of flexural strength, elongation and modulus and
density of foam from the quadratic models were 3.12 MPa, 0.95%, 181.11 MPa, and 0.2
g/cm3, respectively with corresponding R-square of 0.50, 0.57, 0.70, and 0.73, respectively.
Therefore the regression models to predict all responses were relatively robust.

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(A) (B) (C)

(D) (E)

(F) (G)

Fig. 5. Surface of biobased foam had mechanical properties similar to polystyrene foam (A) surface
of biobased foam sample no. 25 from digital camera, (B) surface of biobased foam sample no. 25
from digital microscope (×5 magnification), and (C) surface of polystyrene foam from digital
microscope (×5 magnification), and scanning electron microscopic images of (D) biofoam surface
(sample no. 20, 150 magnifications), (E) cross-sectional area (sample no. 20, 50 magnifications),
(F) biofoam surface (sample no. 7, 150 magnifications), and (G) cross-sectional area (sample no.
7, 50 magnifications)

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Table 2. Mechanical and Physical Properties of Biobased Foam from the Experimental Design
Sample no. Factorsa Responses
Flexural
NRL Distilled water Lignin Elongation Modulus Density
Nanocellulose (%) Talc (%) strength
(%) (%) (%) (%) (MPa) (g cm-3)
(MPa)
1 10 1 5.05 38.5 - 3.5±0.8 1.3±0.3 398.4±76.6 0.60
2 10 3 0.10 38.5 - 2.4±0.5 3.2±1.0 96.2±27.0 0.20
3 10 3 5.05 33.0 - 4.6±1.1 2.7±0.7 256.2±93.5 0.63
4 10 3 5.05 44.0 - 0.6±0.1 3.7±1.8 38.0±5.0 0.50
5 10 3 10.00 38.5 - 8.6±3.2 2.0±0.6 415.7±175.5 0.73
6 10 5 5.05 38.5 - 1.4±0.6 2.8±1.0 74.4±6.4 0.61
7 15 1 0.10 38.5 - 2.5±1.00 1.9±0.5 178.2±13.7 0.25
8 15 1 5.05 33.0 - 5.8±1.9 1.4±0.7 465.0±20.9 0.49
9 15 1 5.05 44.0 - 2.1±1.2 2.0±0.7 278.2±65.5 0.40
10 15 1 10.00 38.5 - 14.9±1.2 1.4±0.1 993.7±130.1 1.00
11 15 3 0.10 33.0 - 0.9±0.2 1.6±0.5 68.5±23.9 0.38
12 15 3 0.10 44.0 - 0.2±0.1 4.9±1.4 6.0±1.9 0.40
13b 15 3 5.05 38.5 - 5.7±3.8 3.0±1.4 146.2±24.6 0.70
14b 15 3 5.05 38.5 - 1.7±1.0 2.1±1.3 149.0±10.0 0.53
15b 15 3 5.05 38.5 - 2.8±0.4 1.3±0.2 259.5±92.3 0.80
16b 15 3 5.05 38.5 - 3.9±0.5 1.2±0.5 457.5±20.8 0.45
17b 15 3 5.05 38.5 - 2.2±2.6 1.3±0.4 70.5±70.3 0.38
18 15 3 10.00 33.0 - 4.6±0.3 2.0±0.1 268.2±81.6 0.87
19 15 3 10.00 44.0 - 2.8±4.1 4.9±0.7 17.6±1.4 1.34
20 15 5 0.10 38.5 - 1.0±0.8 3.1±1.0 54.9±6.8 0.10
21 15 5 5.05 33.0 - 2.4±1.1 2.2±0.5 148.5±69.5 0.54
22 15 5 5.05 44.0 - 5.5±1.4 1.7±0.1 323.3±74.1 0.66
23 15 5 10.00 38.5 - 1.0±0.0 5.9±1.5 38.2±19.0 1.10
24 20 1 5.05 38.5 - 8.9±1.1 1.5±0.8 921.8±71.7 0.63
25 20 3 0.10 38.5 - 0.4±0.3 3.1±1.8 43.5±6.3 0.44
26 20 3 5.05 33.0 - 1.5±0.7 1.7±0.6 117.1±48.8 0.78
27 20 3 5.05 44.0 - 2.2±1.4 1.4±0.5 291.6±30.2 0.30
28 20 3 10.00 38.5 - 3.1±2.5 2.6±1.2 37.3±3.2 0.72
29 20 5 5.05 38.5 - 14.4±4.4 2.6±0.7 533.5±178.4 0.82
L1 20 3 0.10 38.5 0.5 0.3±0.0 3.7±0.7 18.2±2.2 n.d.
L2 20 3 0.10 38.5 2.5 0.3±0.0 1.2±0.5 35.4±3.1 n.d.
Polystyrene foam 0.5±0.1 3.2±1.1 21.2±0.2 0.03
a
Calculated based on total solid dry weight and crosslinked cassava starch was added to 100% solid dry weight
b
Center points of the design
n.d. = not determined

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Water resistance of biofoam
The contact angle of the water drop test was used as indicator to demonstrate the
water resistance of the biofoam surface. An increase of contact angle corresponds to a more
highly hydrophobic character of the biofoam surface (Narkchamnan and Sakdaronnarong
2013). Extensive studies showed that starch could be used as ideal sustainable biobased
resource for biofoam production. The only drawback is its association with hydrophilicity
(Kumar and Siddaramaiah 2007). As illustrated in Fig. 6, the result showed that addition
of NRL (10 %) into biofoam ingredient significantly increased water resistance of biofoam,
as the contact angle was highest at 76.06 degrees (Fig. 6(C)). The result was in good
agreement with several previous work studying the influence of NRL introduced into starch
foam to anchor fillers (Shey et al. 2006; Afiq and Azura 2013; Konar et al. 2013). Rubber
latex is widely known to reduce the water sensitivity of starch-filled biocomposite
(Buchanan et al. 1975). In a combination of addition of cellulose, water resistance of
biocomposite was considerably improved due to the particular presence of residual lignin,
extractive substances and fatty acids at the surface of cellulose limits, comparatively, the
hydrophilic character of the filler (Bendahou et al. 2010). Reduction of talc content from
5% to 1% slightly increased the contact angle from 59.45 to 55.72 degrees (Fig. 6(B) and
6(D)). High water content in biofoam additionally reduced contact angle of water drop, in
other words high water content caused the biofoam to be more hydrophilic (Fig. 6(A)).
Addition of lignin into biofoam ingredient significantly enhanced surface hydrophobicity
of biofoam. As shown in Fig. 6(E), biofoam containing 20% nanocellulose, 3% talc, 0.1%
NRL, 38.5% distilled water without addition of lignin gave the water drop test contact
angle at 76.28 degrees. An increase of lignin content from 0% to 0.5% and 2.5% enhanced
the water drop contact angle to 76.53 and 80.07 degrees, respectively. Approximately 5%
enhancement of contact angle was achieved from biofoam containing 2.5% lignin.
However, addition of lignin at levels of more than 2.5% required additional reaction, e.g.
hydrolysis to produce polyols from lignin (Mahmood et al. 2013), in order to increase the
dissolution and compatibility of lignin molecules in biofoam ingredient. Thus, further
systematic study to increase lignin content in biofoam containing starch, talc, NRL, and
nanocellulose is necessary.
In addition to the cross-linking reaction of cassava starch, it has been revealed that
the use of the less polar milled wood lignin or phenolic lignin could increase the water
resistance of biocomposites in combination with laccase enzyme and a mediator, which is
an examples of a so-called laccase mediator system (Huttermann et al. 1980; Fackler et al.
2008; Narkchamnan and Sakdaronnarong 2013). Therefore, in the present work the
influence of phenolic lignin on mechanical properties of biofoam from cassava
starch/NRL/nanocellulose/talc was investigated.
As demonstrated in Table 2, proportion of biofoam sample no. 25 having similar
mechanical properties as PS foam was selected to test the effect of lignin on its properties.
Isolated lignin from sugarcane bagasse was added into the biofoam formulation at 0%
(sample no. 25), 0.5% (L1), and 2.5% (L2), while other ingredients were 20%
nanocellulose, 3% talc, 0.1% NRL, and 38.5% distilled water.
It was found that an optimal lignin content added into biofoam needed to be
determined. As shown in Table 2, addition of 0.5% lignin into biofoam containing 20%
nanocellulose, 3% talc, 0.1% NRL, and 38.5% distilled water gave the most favorable
effects on flexural strength, percentage of elongation, and modulus of biofoam, thus
mimicking PS foam.

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Table 3. ANOVA for Response Surface Reduced Quadratic Models of each
Response
Response 1 Flexural strength
Sum of Mean p-value
Source df F Value
Squares Square (Prob > F)
Model 192.50 8 24.06 2.48 0.0478 significant
A-Nanocellulose 7.36 1 7.36 0.76 0.3944
B-Talc 12.00 1 12.00 1.23 0.2796
C-NRL 63.48 1 63.48 6.53 0.0188
AB 14.44 1 14.44 1.49 0.2370
AC 3.06 1 3.06 0.32 0.5808
BC 38.44 1 38.44 3.96 0.0606
BD 11.56 1 11.56 1.19 0.2884
B^2 42.16 1 42.16 4.34 0.0503
Residual 194.35 20 9.72
Response 2 Elongation
Sum of Mean p-value
Source df F Value
Squares Square (Prob > F)
Model 23.03 10 2.30 2.43 0.0485 significant
A-Nanocellulose 0.65 1 0.65 0.69 0.4172
B-Talc 6.45 1 6.45 6.81 0.0177
C-NRL 0.083 1 0.083 0.088 0.7702
D-water 4.08 1 4.08 4.31 0.0525
AC 0.12 1 0.12 0.13 0.7233
AD 0.42 1 0.42 0.45 0.5127
BC 2.72 1 2.72 2.87 0.1073
CD 0.040 1 0.040 0.042 0.8395
C^2 8.30 1 8.30 8.76 0.0084
D^2 0.61 1 0.61 0.64 0.4338
Residual 17.05 18 0.95
Response 3 Modulus
Sum of p-value
Source df Mean Square F Value
Squares (Prob > F)
Model 1.210E+006 12 1.008E+005 3.07 0.0192 significant
A-Nanocellulose 36951.90 1 36951.90 1.13 0.3043
B-Talc 3.545E+005 1 3.545E+005 10.81 0.0046
C-NRL 1.459E+005 1 1.459E+005 4.45 0.0510
D-water 11334.45 1 11334.45 0.35 0.5648
AB 1033.62 1 1033.62 0.032 0.8613
AC 26520.12 1 26520.12 0.81 0.3819
AD 38553.32 1 38553.32 1.18 0.2944
BC 1.731E+005 1 1.731E+005 5.28 0.0354
BD 32688.64 1 32688.64 1.00 0.3330
B^2 2.231E+005 1 2.231E+005 6.80 0.0190
C^2 56491.81 1 56491.81 1.72 0.2079
D^2 47594.87 1 47594.87 1.45 0.2459

Residual 5.248E+005 16 32800.89

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Response 4 Density

Sum of Mean p-value

Source df F Value
Squares Square (Prob > F)
Model 1.52 14 0.11 2.71 0.0362 significant
A-Nanocellulose 0.015 1 0.015 0.37 0.5540
B-Talc 0.018 1 0.018 0.44 0.5174
C-NRL 1.33 1 1.33 33.18 < 0.0001
D-water 6.750E-004 1 6.750E-004 0.017 0.8985
AB 8.100E-003 1 8.100E-003 0.20 0.6595
AC 0.016 1 0.016 0.39 0.5419
AD 0.031 1 0.031 0.77 0.3962
BC 0.016 1 0.016 0.39 0.5419
BD 0.011 1 0.011 0.28 0.6077
CD 0.051 1 0.051 1.27 0.2794
A^2 2.530E-003 1 2.530E-003 0.063 0.8050
B^2 6.815E-004 1 6.815E-004 0.017 0.8980
C^2 0.017 1 0.017 0.43 0.5225
D^2 2.998E-003 1 2.998E-003 0.075 0.7882
Residual 0.56 14 0.040

Slightly decreased flexural strength and increased elongation was achieved when
0.5% lignin was added. Thus, lignin improved the elasticity of biofoam. The results agreed
with those of Sahoo and colleagues, who reported that addition lignin into polybutylene
succinate composite enhanced the tensile, flexural, and impact strength simultaneously
(Sahoo et al. 2011). Important functional groups, chemical units, and inter-unit linkages
present in lignin are phenolic AOH, aliphatic hydroxyl, carbonyl, alkyl aryl ether, biphenyl,
diaryl ether, phenylpropane, guaiacyl, and syringyl, etc. Therefore, there were reports on
considerable compatibility of lignin in starch matrix, natural fibers, and particularly
polystyrene. However, too much lignin added into biofoam (2.5% lignin) caused problems
related to reduction of elongation and led to stiffer foam that was unsatisfactory for
packaging applications.
The increase in the tensile strength at higher lignin content indicates a reinforcing
effect of lignin in crosslinked starch/NRL matrix that may be attributed to the similarity in
the solubility parameter of lignin and crosslinked starch/NRL matrix, crosslinking ability,
and the adhesive nature of lignin. The enhancement in the properties of biofoam indicates
an interaction, possibly polar–polar interaction between lignin and crosslinked starch
matrix via a hydrogen bond formation that could be possible between the hydroxyl group
of the crosslinked starch matrix and the hydroxyl group of lignin.

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(A) (B)

53.09 degrees 59.45 degrees

(C) (D)

76.06 degrees 55.72 degrees

(E) (F)

76.28 degrees 76.53 degrees

(G)

80.07 degrees

Fig. 6. Water drop test at 60 sec of biobased foam made of (A) 15% nanocellulose, 3% talc, 0.1%
NRL, 44% distilled water (sample no. 12), (B) 15% nanocellulose, 5% talc, 0.1% NRL, 38.5%
distilled water (sample no. 20), (C) 15% nanocellulose, 3% talc, 10 % NRL, 44% distilled water
(sample no. 19), (D) 15% nanocellulose, 1% talc, 0.1% NRL, 38.5% distilled water (sample no. 7),
(E) 20% nanocellulose, 3% talc, 0.1% NRL, 38.5% distilled water, (sample no. 25), (F) 20%
nanocellulose, 3% talc, 0.1% NRL, 38.5% distilled water, 0.5% lignin (sample no. L1), and (G) 20%
nanocellulose, 3% talc, 0.1% NRL, 38.5% distilled water, 2.5% lignin (sample no. L2).

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CONCLUSIONS

1. Lignin extraction from SCB in 40 %KOH solution at 120 oC for 1 h gave relatively high
lignin yield with the least hemicellulose contamination. The isolated lignin structure
was similar to that of lignin from black liquor from the pulp and paper industry.
2. Analysis of cellulose yield, XRD diffractometry, ATR-FTIR spectroscopy, and TEM
imaging indicated that 40 %KOH at 120 oC for 1 h was the most suitable condition for
cellulose extraction. To obtain nanocellulose, size reduction by the mechanical method
was selected according to superior fibril distribution and homogeneous shape.
3. Biocomposite foam produced from 20% nanocellulose fiber, 3% talc, 0.1% natural
rubber latex (NRL), 38.5% water, and 76.9% crosslinked cassava starch by weight had
equal mechanical properties as polystyrene foam. An increase of NRL resulted in
increased percent elongation of the biocomposite.
4. Addition of an optimal amount of lignin slightly decreased the flexural strength and
improved elasticity of biofoam, mimicking polystyrene foam’s mechanical properties,
which is beneficial for packaging application.

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Article submitted: August 5, 2014; Peer review completed: October 19, 2014; Revised
version received and accepted: November 11, 2014; Published: November 20, 2014.

Phaodee et al. (2015). “Biobased foam,” BioResources 10(1), 348-368. 368