Study of plasticizing effect of Agave syrup of thermoplastic starch

(TPS) biofilms by method of extrusion and casting

Casas-González M.R.,1*Rodríguez-González F.J.1
1
Polymers Processing Department, Centro de Investigación en Química Aplicada,
CP 25294, Saltillo, Coahuila, Mexico.
email: mayela700@hotmail.com

INTRODUCTION
TPS has been considered a potential candidate for the development of edible
biofilms due to their thermoplastic behavior (Mali et al., 2005). TPS biofilms can be
obtained by different processing techniques such as casting (Maran, J.P et al.,
2013) and extrusion method (Li, M. et al., 2011) where the starch is gelatinized
and plasticized under high shear stress. TPS has been obtained from the
disruption of starch granule in the presence of high-boiling point plasticizers
(Bastioli 2001). The most commonly used plasticizer is glycerol (Fang et al., 2004).
On the other hand, agave syrup is a source of sugars obtained after scraping
stalks Agave salmiana. It is rich in sugars (such as maltose and fructose), dextrans
and polysaccharides such as inulin, in addition to fructooligosacharides (FOS) also
contains concentrations of maltooligosaccharides (Casas-Gonzalez, 2012) which
can be used as plasticizers. The objective of this work was to compare the
plasticizing action of agave syrup and glycerin in TPS biofilms prepared by
extrusion and casting methods.

MATERIALS AND METHODS

Potato starch was acquired from Penford Food (France). Glycerol was purchased
from Proquisa-Mexico, and agave syrup Agroindustries Faroc (Mexico).
Films of potato starch were prepared by: 1) Casting. In a jacketed reactor, a
suspension at 10% solids (starch + plasticizer) was gelatinized at 90°C for 30 min.
The filmogenic solution was deposited on polystyrene plates and evaporated at
60°C for 16 h. Biofilms were formulated with agave syrup (TPSM) or glycerol
(TPSG) in concentrations of 30, 35, 40% with respect to starch. 2) Extrusion. A
suspension of starch-plasticizer-water was fed to the feeding zone of a twin-screw
extruder ZSK30 (Werner & Pfleiderer) equipped with 9 heating zones at a rate of
3.5 k/h, 150 rpm and 90ºC (Tena-Salcido et al., 2008). TPS extruded films
plasticized with glycerol (TPSGE) and agave syrup (TPSME) were stored in a
desiccator before characterization. Water absorption and water solubility indexes
(WAI and WSI, respectively) were determined by the method described by
Anderson et al. (1969) and the relative loss of plasticizer (RLP) was calculated
according to Casas-Gonzalez et al. (2014). The DMA measurements were
performed using a TA-Instruments DMAQ800 equipment under multifrequency
mode operation, from -150° to 150°C, at 5 °C/min, a frequency of 1Hz and
amplitude of 20 µm used Dual Cantilever clamp.
RESULTS AND DISCUSSION

Biofilms prepared by extrusion showed lower WAI values than those obtained by
casting (Table 1). The decrease in WAI could be attributed to the alignment of
starch molecules during both the pass through the die and the process of
calendering. Rodriguez-Castellano (2013) mentions that increasing screw speed
thermally damaged starch WAI reducing due to starch degradation. Moreover,
TPSGE biofilms have WAI values higher than those of TPSME biofilms. WAI
values of TPSGE tended to be higher because glycerol has better plasticizing
action than sugars, as might be the case agave syrup (Van der Burgt, et al., 1996
and Mathew, A. P., et al., 2002).
Relative loss of
Method Sample WAI (g/g) WSI (%)
plasticizer (%)
TPS-0 15.788 8.20 0
TPS-G30 16.085 17.10 38
TPS-G35 12.394 19.80 41
Casting TPS-G40 11.985 33.30 70
TPS-M30 12.194 19.10 44
TPS-M35 12.675 22.60 49
TPS-M40 14.679 26.40 54
Extrusion TPS-G30E 7.444 23.00 58
TPS-G35E 5.056 25.30 57
TPS-G40E 6.451 29.60 62
TPS-M30E 3.381 23.90 61
TPS-M35E 2.846 29.30 68
TPS-M40E 3.331 30.90 65

Table 1. Effect of type and concentration of plasticiser in TPS biofilms.

In the case of WSI, it was observed that biofilms obtained by casting have lower
than those prepared by extrusion. It is probable that the depolymerization
underwent by starch during the high-shear processing increased the soluble
fraction of TPSE (Fakhouri, F. M. et al, 2013). On the other hand, WSI values were
also dependent of the plasticizer content, thus the higher the concentration of
plasticizer the greater the WSI values. Nemeth et al., (2010) reported that
increasing the glycerol content in TPS films increased the dry matter content
soluble in water.
The LRP refers to the amount of plasticizer that reaches out of the biofilm in an
aqueous medium, to find the equilibrium, resulting in 70% of PRL in biofilms TPSG-
40 (Table 1). However the TPS-M biofilms, have less PRL, having greater capacity
plasticizer permanence in the polymer matrix. This is attributed to that agave syrup
containing compounds of higher molecular weight (polymer-oligomers and
monosaccharides) compared with glycerin (lower molecular weight) that interact
with the starch, generate less free space that allow exists less migration plasticizer
to the surface of the polymer matrix (Casas-Gonzalez, 2012), releasing only the
low molecular weight compounds containing agave nectar and maintaining
prebiotic FOS, inulin and dextrans in the polymer matrix.
Dynamic mechanical analysis (DMA)

The rheological properties of TPSG, TPSGE, and TPS-M TPS-ME biofilms are
shown in Figure 1. G' values of TPSG and TPSGE biofilms showed two transitions:
the first one at about -75°C corresponding to plasticizer-rich domains and the
second at around 45ºC assigned to starch-rich domains (Rodriguez-Gonzalez, F.
J., et al., 2004, Da Roz, Carvalho, Gandini, and Curvelo, 2006;. Khanh et al.,
2015). Conversely, most of TPSM and TPSME biofilms showed just one transition
at around 50°C which could be associated to starch-rich domains as observed in
Figure 1b (Rodriguez-Gonzalez, F. J., et al., 2004).

Figure 1. Effect of glycerin content (a) and agave syrup (b) on the storage module
TPS biofilms.

Some authors have related the maximum of loss modulus (log G”) to the glass
transition temperature (Tg) of biofilms. The analysis of G” confirmed that TPSG
and TPSGE biofilms have two thermal transitions and that both are dependent of
glycerol content. As reported in the literature, the thermal transitions dropped as
glycerol content increased. However, the first transition seemed to be less
dependent on both the glycerol content and the process for preparing TPS biofilms
than the second one (Fig. 2).
Unexpectedly, G” values of TPSM and TPSME biofilms evidenced the presence of
two thermal transitions. In the case of TPS-M biofilms, the first thermal transition
increased from -40° to -28°C as the concentration of agave syrup decreased from
40 to 30%.

Figure 2. Effect of glycerin content (a) and agave syrup (b) on the loss module TPS
biofilms.
CONCLUSION

The extrusion method is a good alternative for obtaining TPS-M biofilms as it

provides a better mixing effect and distribution of plasticizer in biofilm formation.
The biofilms TPS-GE starch-rich domains have more defined compared to TPS-G
biofilms. Agave syrup has a greater effect of permanence within the polymer matrix
to obtain lower loss of plasticizer that migrates to the surface while maintaining the
high molecular weight compounds bonded to the biofilm (prebiotics) and releasing
only low molecular weight sugars. The Tg of plasticized biofilms agave syrup
increases with increasing concentration of plasticizer and decreases to be obtained
by the extrusion method.

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