3.1. Infrared Spectroscopy
The FTIR analyses of the cast films formed by both GAmb alone and GAmb added glycerol, Fig. 1, allowed the identification of the functional groups present in the biopolymer, as well as to evaluate the effect of increasing the concentration of glycerol in the film.
In Fig. 1, the characteristic vibrational band of hydroxyl groups -O-H was observed at approximately 3400 cm− 1, while the band corresponding to the vibrational stretch of -C-H, characteristic of methyl and methylene groups, was observed at 2927 cm− 1. Furthermore, the vibrational bands at 1616 cm− 1 and 1421 cm− 1 can be attributed to the vibrational stretching of symmetric and asymmetric -C = O groups, respectively. Therefore, the 1038 cm− 1 band can be attributed to the vibrational stretch of -C-O-C- of uronic acid [21]. Moreover, the FTIR results of GAmb films indicate that the biopolymer is mainly constituted by α-L-Arabinofuranose and β-Galactopyranose units, Fig. S1 (supplementary material), suggesting that its basic structure is mainly composed of arabinogalactan heteropolysaccharides.
Still in Fig. 1, it is possible to verify that the increase in the concentration of glycerol in the GAmb films promotes an increase in the intensity of the FTIR bands, which indicates that this behavior may have resulted from hydrogen bonds between the -OH groups of the plasticizer and the biopolymer.
3.2. Study of moisture content and water solubility
Figure 2 shows the moisture content and water solubility studies of the GAmb films prepared with glycerol; this study was not performed for the GAmb film without the presence of glycerol due to the fragility of the films. The moisture contents of the films ranged from 8.4%, for the GAmb/Gly(10) film, to 12.7%, for the GAmb/Gly(30) film. Therefore, these values indicated the existence of few water molecules adhered to the molecular chains of the GAmb biopolymer with glycerol, which could guarantee greater durability of the packaged product due to the lower amount of water present in the GAmb films.
The moisture content found for GAmb films makes them promising materials for applications in minimally processed food packaging, such as fruits, fish fillets, and others, as they have lower moisture contents than those reported in the literature for different films based on polysaccharides, as in chitosan, pectin and lemongrass essential oil films, which had a moisture content ranging from 28.78–31.35% [11]. Therefore, films with lower moisture content tend to have lower interactions between the water molecules in the films and the packaged product, resulting in greater efficiency in food preservation.
Different explanations can justify the lower moisture content of GAmb films, one of which can be attributed to the chemical structure of the polysaccharide, where the dense crosslinking between the chains decreased the accessibility of -OH groups by the water molecules [25].
The water solubility values of GAmb/Gly films ranged from 33–49% (Fig. 2); in addition, considering the hydrophilic nature of GAmb, the films were not fully dissolved in water, but partially lost their integrity with time. Water solubility results indicated that GAmb/Gly films have moderate water resistance.
3.3. Film diffractograms
Figure 3 shows the XRD patterns of GAmb and GAmb/Gly films, with the broad peak close to 20°, indicating that the gum has an amorphous characteristic. This amorphous characteristic is also noticed in other gums, such as chitosan and Arabic gum [28]. The films containing glycerol at concentrations of 10–30% showed results similar to those obtained for the GAmb film without glycerol (GAmb); however, an increase in intensity was observed at the 20° peak for the films with plasticizer, confirming the presence of glycerol in the biopolymer. Accordingly, the plasticizer facilitated the development of GAmb-based films without changing the amorphous character of the heteropolysaccharide, even after the addition of higher percentages of glycerol.
3.4. Biodegradability
The biodegradation of GAmb films with glycerol is shown in Fig. 4; thus, GAmb films showed increasing biodegradation over the fourteen days test and higher percentages of glycerol did not influence the biodegradation of GAmb, justified by the similar behavior of the biodegradation curves as a function of mass loss.
Initially, on the first three days, the decomposition process of the films occurred in an accelerated manner for all GAmb films with glycerol; for example, a mass loss of ≈24% was observed for the GAmb/Gly(20) film on the first day, while on the second day this value was ≈48%, and subsequently, on the third day, it was ≈59%.
After the third day, biodegradation continued to increase, but slowly, as the results showed that the mass loss intervals decreased. On the sixth day, the film had already been ≈81% biodegraded; on the tenth day, it was ≈92%, and by the end of the fourteenth day the film was practically all biodegraded, showing a mass loss of ≈98%. After 14 days, it was not possible to measure the mass of GAmb/Gly films.
The CO2 (mg) values produced in the mineralization process of GAmb films with 10–30% glycerol are also shown in Fig. 4. Initially, it is observed that the curves of GAmb/Gly films have similar behavior, even in higher amounts of plasticizer, demonstrating that glycerol did not influence the mineralization process of GAmb films, as was observed in biodegradation by loss (a) of mass.
The release of carbon dioxide occurred gradually and increasingly during the 14 days of testing, for example, the film with 20% Gly had, on the first day, a release of 0.0440 mg of CO2; on the fifth day; 0.286 mg of CO2; on the ninth day, 0.999 mg of CO2; and, finally, on the fourteenth day, 1.51 mg of CO2. In addition, all films had similar behavior to the film with 20% glycerol. These results indicate that the biodegradation process of GAmb films by the release of carbon dioxide (b) was effective and corroborated the biodegradation test by loss of mass. Therefore, the low degree of crystallinity of GAmb may have positively influenced the rapid biodegradation process of the films, as well as its ability to retain water molecules. Tables (S1 and S2), with the values of the mass loss and CO2 release tests, are found in the supplementary material.
Figure 5 also shows the images of GAmb films with biodegraded glycerol every two days, totaling 14 days. It is observed that the loss of mass occurred gradually, as with the film with 20% Gly: on the second day, a mass loss of ≈47% was recorded; on the sixth day, ≈81%; on the tenth day, ≈92%; and, on the fourteenth, ≈98%. Therefore, the visual biodegradation analysis of the films, shown in Fig. 5, corroborates those observed in Fig. 4. These results showed that the development of GAmb-based films for biodegradable packaging is promising, mainly due to the rapid biodegradability of GAmb films. These results are interesting, according to the literature, in comparison with polylactic acid films, a biopolymer widely used in biodegradable packaging, as its complete biodegradation can occur in months [7].
3.5. Mechanical properties
Films based on biopolymers must resist the stress encountered during their application to protect and maintain the integrity of the food, and they must also be flexible, adapting themselves to possible deformations without breaking [19]. Thus, Fig. 6 shows the stress-strain curves of GAmb plus glycerol films in different percentages, and Table 1 shows the values of the modulus of elasticity, tensile strength, and elongation to rupture obtained in the mechanical test of the films.
Figure 6 shows a change in the mechanical behavior of GAmb films, from brittle to ductile, as the percentage of glycerol is increased. From a mechanical point of view, there was a decrease in tensile strength with the increasing percentage of Gly among GAmb films with 10% Gly (6.41 MPa), 15% Gly (5.43 MPa), 20% Gly (4.70 MPa), 25% Gly (4.16 MPa) and 30% Gly (2.30 MPa). This is due to the glycerol plasticizer, which, when added to the biopolymer, promotes an increase in the free volume between the biopolymer chains, leading to greater chain mobility and film flexibility. Therefore, this behavior, caused by the addition of plasticizer, is important to make the GAmb film applicable in packaging, as it increases its deformation capacity.
The film with 10% glycerol is very rigid, that is, not very flexible, with an elastic modulus of 8.51 Mpa and elongation to break of 1.26%, which is not interesting for packaging applications due to its rigidity. However, the other films had acceptable deformations for packaging. In that case, the film with 15% Gly had a modulus of 3.44 Mpa and elongation of 2.73%; the one with 20% Gly had a modulus of 1.72 Mpa and elongation 12.20%; the one with 25% Gly had a 0.89 Mpa modulus of elasticity and 16.76% elongation, and the one with 30% Gly had a 0.33 Mpa modulus of elasticity and 21.79% elongation. All values are presented in Table 1 and, in graphic form, in Fig. 6. Therefore, among the films, those that presented the best mechanical values for packaging purposes are among the films with 15% and 30% Gly.
According to the data shown in Table 1, the samples containing the plasticizer glycerol showed an increase in the elongation to rupture, indicating that the presence of Gly acted by increasing the deformation capacity of the films with 15%, 20%, 25% and 30% Gly.
Table 1
Values obtained in the mechanical test of GAmb films with 10%, 15%, 20%, 25%, and 30% glycerol.
Samples | Modulus of Elasticity (MPa) | Tensile Strength (MPa) | Elongation to break (%) |
GAmb/Gly(10) | 8.51 ± 0.0150 | 6.41 ± 0.0277 | 1.26 ± 0.0057 |
GAmb/Gly(15) | 3.44 ± 0.0329 | 5.43 ± 0.0190 | 2.73 ± 0.0133 |
GAmb/Gly(20) | 1.72 ± 0.3883 | 4.70 ± 0.0164 | 12.20 ± 0.0866 |
GAmb/Gly(25) | 0.89 ± 0.0128 | 4.16 ± 0.0132 | 16.76 ± 0.0132 |
GAmb/Gly(30) | 0.33 ± 0.0046 | 2.30 ± 0.0161 | 21.79 ± 0.0733 |
5.6. Transmittance determination and visual aspect
The light transmittance spectra of GAmb films without glycerol (GAmb) and containing Gly at different concentrations are shown in Fig. 7. The values found were displayed in Table 2, at wavelengths ranging from 300nm to 800nm.
The light transmittances of GAmb films were below 50% (Fig. 7) and, as the percentage of glycerol was increased from 10–30% of Gly, the transmittance values gradually decreased: at 400 nm, it decreased by 22.17–12.50%; at 600 nm, it decreased from 33.25–19.75%; and, at 800 nm, it decreased from 35.72–22.02%, as shown in Table 2. The results showed that GAmb films became less transparent with the increasing amount of Gly. The reduction in the transmittance values of the films was possibly due to the presence of the plasticizer, which may have acted as an obstacle to the passage or the scattering of light in the film matrix [3].
Also, as stated above, the results of GAmb films with glycerol were better than for other biopolymer films, such as cassia gum [5], gum arabic [13] and chitosan/shellac [30] which had transmittance greater than 80%. Meanwhile, GAmb films’ transmittance was below 50%, acting as a more efficient barrier against the passage of UV (ultraviolet) and visible light. Although light transmission decreases with increasing Gly concentration, GAmb films remained transparent. Thus, the results indicated that GAmb films are interesting for applications in transparent packaging and that glycerol can reduce the effect of UV and visible light on packaged products.
Table 2
Transmittance values of GAmb films.
| Transmittance (%) |
| 300nm | 400nm | 500nm | 600nm | 700nm | 800nm |
GAmb | 7.33 | 28.26 | 37.35 | 41.46 | 43.88 | 45.46 |
GAmb/Gly(10) | 4.89 | 22.17 | 30.01 | 33.25 | 34.78 | 35.72 |
GAmb/Gly(15) | 4.36 | 20.09 | 27.69 | 30.82 | 32.63 | 33.78 |
GAmb/Gly(20) | 3.30 | 17.97 | 25.40 | 28.50 | 30.34 | 31.32 |
GAmb/Gly(25) | 2.36 | 13.91 | 20.26 | 23.36 | 25.03 | 26.11 |
GAmb/Gly(30) | 2.83 | 12.50 | 17.51 | 19.75 | 21.09 | 22.02 |
Figure 8 shows the images of the Amburana cearensis gum films and, first, ripples and cracks are observed in the GAmb film, indicating its fragility. Furthermore, this fragility can be attributed to the strong intermolecular bonds of the compounds that make up the polysaccharide, providing less mobility to the molecular chains and resulting in a rigid and brittle film [17].
As explained above, the use of glycerol for the development of GAmb-based films was important, since this plasticizer, when it remains in the intermolecular spaces of the polymer chains, can promote a reduction in intermolecular forces, increasing the mobility of molecules and providing films flexibility [10]. Thus, the insertion of glycerol provided the formation of flexible and still transparent films, and the best proportions of glycerol for the formation of GAmb-based films are between 10% and 30%.