3.1. Textural Parameters
The texture parameters of plastic spoons are shown in
Table 2. Four types of plastic spoons were used for the measurement of hardness. According to the European directive 904/2019 [
4], from July 2021, plastic spoons will be restricted and will not be sold in the European countries.
The comparison of experimentally produced biodegradable spoons with different xantan concentrations is shown in
Table 3. Thanks to its polymer structure and hydrophilic properties, xantan serves as a perfect binder. The resulting solutions are resistant to high temperatures, and therefore xanthan gum is suitable for the preparation of baked products [
9,
10]. Though, from the
Table 3 it can be perceived that hardness increased statistically significantly (
p < 0.05) with a higher amount of xantan only for the sample 2PX1
S (the dried sample with lower content of millet flour).
The analysis showed that a sample with the same composition, but not dried, achieved a higher hardness with the addition of 2.5 g of xanthan (1522.01 ± 320.51 g) compared to a formulation with 5 g (1220.30 ± 505.66 g). A statistically significant (
p < 0.05) difference was found between 2PX1
S and 3PX1
S samples (
Table 3). In 2018, Encina-Zelada et al. [
11] studied the effect of xanthan gum on the physico-chemical, rheological, and textural properties of gluten-free bread. The study showed that a greater addition of xanthan a mixture of rice, corn and quin flour resulted in lower stickiness and cohesiveness of the dough, but the dough was still firmer, with good consistency and viscosity. The best results were achieved by loaves with an amount of xanthan of 1.5–2.5% and with 110% addition of water [
11]. Certainly, the texture parameters of experimentally produced biodegradable spoons were affected by the presence of so-called “gluten” proteins—prolamins and glutelins, able to create a harder texture [
12].
Drying at high temperature (60 °C) had a great influence on the hardness of the spoons. During drying, water is removed, and the product becomes more durable and stronger [
13]. Samples (2PX1
x and 3PX1
x) containing xanthan were baked at two different temperatures, at 180 and 240 °C for 10 min.
The sample with a lower addition of xanthan (2.5 g) showed a lower hardness (1522.01 ± 320.51 g) than a sample containing 5 g of xanthan (1971.62 ± 908.61 g). The highest hardness was reached in the 3PX1 sample (2763.61 ± 345.08 g), baked at 240 °C. The results suggest that the hardness increased with a higher temperature. Likewise, a significant effect of xanthan on textural properties was demonstrated too. A statistically significant difference was found between a sample with 2.5 g of xanthan, baked at 180 °C, and a sample with 5 g of xanthan, baked at 240 °C. The dough changes its structure irreversibly during baking. The first changes occur at a temperature of 15–40 °C, when the fat melts. At 70 °C, the starch begins to gelatinize, and as the temperature rises to 90 °C, the baked products become firmer. Water evaporates when it exceeds 100 °C and the product loses its original semi-solid consistency [
14].
The hardness of biodegradable spoons prepared from gluten free millet flour with different water contents is shown in
Table 4.
From the results it can be read that the highest hardness is achieved in samples with 40 mL of water. The highest hardness was shown by the dried sample with the addition of 40 mL of water (1553.75 ± 641.37 g), the lowest hardness was measured in the non-dried sample with 50 mL of water (542.75 ± 68.63 g). Spoons prepared with 20 mL of water were not measured as they disintegrated after baking. There was a statistically significant (
p < 0.05) difference between dried and non-dried sample (with the addition of 50 mL and 30 mL of water), containing 50 mL of water. Similar results were obtained for samples of spoons with 30 mL of water (
Table 4). During baking, the water begins to evaporate at temperatures over 100 °C. In this phenomenon, water gets from the dough to the surface and causes a color change. The color changing affects sensory properties of the product and consequently consumers’ acceptance [
14]. According to the study conducted in 2013 by De la Hera et al. [
15], the amount of hydration and the grain size of the used flour play an important role in the quality of gluten-free bread (the study used rice flour for analysis). As a result, the product achieved high hardness and low volume at lower hydration.
The texture was also evaluated for samples prepared with and without addition of palm oil. The results are shown in
Table 5.
The highest hardness was obtained with the dried sample 1PS (6204.51 ± 2711.98 g), which did not include palm oil in its recipe. In contrast, the lowest hardness was measured for a 3P sample with 10 g of oil. The results showed that the addition of palm oil negatively affected the hardness of experimentally produced spoons (
Table 6). Statistically significant (
p < 0.05) differences between samples with and without oil addition were found between the following samples: 2P, 1PS and 2PS.
Samples containing xanthan were analyzed for the effect of palm oil addition on spoon hardness. The results are shown in
Table 7. A statistically significant difference (
p < 0.05) was observed for the 2PX1
yS sample, the other results were not statistically significant (
p > 0.05).
Higher values were obtained for dried samples, not including palm oil in their recipe. The addition of 5 g of oil resulted in a relative reduction in hardness. Conversely, this was the case for non-dried samples. The highest hardness of the 2PX1
yS sample was mainly due to drying at 60 °C, but the addition of 5 g of xanthan was also significant, helping to create stable products with optimal structure. The results showed that the presence of more xanthan increases the hardness of the spoons only after drying. Fat is added to the dough to improve the texture and taste of the product. After baking, the spoons had a more attractive appearance [
14].
In their study examining the effect of dough mixing time on the properties of biscuits, Manohar and Rao [
16] state that as the fat level increases, the strength of the biscuits decreases and, conversely, their brittleness increases. This statement is in the accordance of studies finding that triacylglycerols significantly affect the crystallization processes, and consequently increases hardness [
17].
The hardness of biodegradable spoons with different ratios of smooth wheat and grape flour is shown in
Table 7.
The same ratio (1:1) of smooth wheat flour and grape flour showed the highest hardness. From the results it can be read that higher addition of grape seed flour resulted in a lower hardness of the spoons.
Samples of biodegradable spoons with the highest hardness were selected and subsequently their recipe was improved by the addition of grape flour in various concentrations (0%, 5%, 10% and 20%), the obtained results are shown in
Table 8 (the samples were baked at 240 °C for 10 min). The highest hardness was reached in spoons with 5% addition of grape flour, that were dried. An exception is the 9
S sample, that reached the highest hardness with 10% addition of different amounts of grape flour were found within samples 9, 11S and 12 (
Table 8). Grape flour was added to the recipe due to the significant amount of bioactive compounds, especially fiber and polyphenols, substances with antioxidant and anti-inflammatory effects [
18]. Ross et al. [
19] carried out an analysis examining the acceptability of bread that was enriched with different concentrations of grape flour (10%, 7.5% and 5%). The lowest grape seed flour concentration 5%, proved to be the most suitable amount. A higher proportion of grape flour. The reason is the lower proportion of millet flour in the recipe compared to other examined samples. Statistically significant differences (
p < 0.05) between the samples has a negative effect on sweetness and causes a feeling of bitterness.
3.2. Antioxidant Profile of Biodegradable Spoons
The amounts of total polyphenols and antioxidant activity in selected samples of spoons that reached the highest hardness are shown in
Table 9.
Statistically significant differences (
p < 0.05) were found in almost all detected values of polyphenols, only the samples 2PX1
y and 9
y did not differ significantly. The highest proportion of polyphenolic substances was achieved in the sample 11
z (0.038 ± 0.00 mg/g), prepared from a higher amount of millet flour, with 20% addition of grape seed flour and 5 g of xanthan. The baking temperature was 240 °C. Conversely, the lowest amount of polyphenols was found in the sample 1P (0.007 ± 0.00 mg/g), prepared only from plain and millet flour in the same ratio, baked at 180 °C. The results show that the enrichment of the products with grape seed flour significantly (
p < 0.05) affected the amount of polyphenols in the final product. This finding is in accordance with the study examining the effect of adding grape seed flour to waffles [
20]. The increased amount of polyphenols in sample 11
z is also due to the addition of millet flour, made by grinding millet. The study showed that millet crop is rich in phenolic compounds, including antioxidants and beta-glucans [
21].
The highest DPPH value was found in sample 11 z (25.91 ± 0.10%), on the contrary, samples 1P and 2PX1 y showed zero values. The FRAP method showed the highest antioxidant activity in the sample 11 z (21.57 ± 0.14 µmol/g), the lowest value was shown in the sample 2PX1 y (0.73 ± 0.04 µmol/g). Statistically significant (p < 0.05) differences were found between all tested samples.
From the obtained data it can be concluded that grape flour had a significant effect on the antioxidant activity and the amount of polyphenols. This fact is in accordance with an experiment from 2021, examining the effect of the addition of grape flour in concentrations of 1%, 3%, 5% and 10% on the antioxidant activity and total polyphenols [
20]. The most acceptable samples were with 10% addition of flour. This concentration did not fundamentally affect the sensory properties of the product [
20]. The study conducted by Levent et al. [
22] found that the grape seeds had higher antioxidant properties compared to rice flour, chickpea flour, carrot flour, flaxseeds, pomegranate seeds and poppy seeds. Nakov et al. [
23] found that the addition of 4%, 6%, 8% and 10% of grape pomace powder statistically (
p < 0.05) increased the antioxidant activity of cakes.
The previous study showed that when heated to temperatures higher than 180 °C, the product loses a significant amount of total polyphenols and also reduces its antioxidant properties [
19]. The amount of catechin and epicatechin decreased with increasing temperature. On the contrary, there was an increase in gallocatechin and gallic acid. It was also evidenced by the study that antioxidant activity is related to contents of catechin and epicatechin [
19].