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Communication

Application of a Filler in the Form of Micronized Chalcedonite to Biodegradable Materials Based on Thermoplastic Starch as an Element of the Sustainable Development of Polymeric Materials

by
Jacek Garbarski
and
Mariusz Fabijański
*
Polymer Processing Department, Faculty of Mechanical and Industrial Engineering, Warsaw University of Technology, 85 Narbutta Street, 02-524 Warsaw, Poland
*
Author to whom correspondence should be addressed.
Sustainability 2025, 17(6), 2731; https://doi.org/10.3390/su17062731
Submission received: 12 February 2025 / Revised: 17 March 2025 / Accepted: 18 March 2025 / Published: 19 March 2025
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Abstract

:
Thermoplastic starch (TPS) is one of the most-used biodegradable materials, alongside polylactide (PLA), and is a promising alternative to traditional plastics. However, unmodified TPS has processing limitations due to its mechanical properties and susceptibility to moisture. Modern TPS modifications often lead to the loss of its full biodegradability, which limits its contribution to reducing polymer waste and the circular economy. This article presents a novel TPS-based material enriched with micronized chalcedonite, which improves the mechanical properties of the composite while maintaining biodegradability. An assessment of processing in injection molding technology and tests of strength, hardness, impact strength, and water absorption depending on the filler content were carried out. The results obtained indicate that the use of chalcedonite not only strengthens the material structure but also contributes to reducing the demand for synthetic additives, which can reduce the amount of difficult-to-dispose polymer waste. The development of more durable and fully biodegradable materials based on TPS is a step towards sustainable development, enabling the reduction in plastic in the environment and supporting the idea of a circular economy. The research results open new perspectives for ecological composites that can be used in various industrial sectors, reducing the negative impact of plastics on the environment.

1. Introduction

Nowadays, biodegradable materials are gaining importance in the polymer industry, which is mainly due to the growing requirements for environmental protection. In their case, traditional recycling is not widely used, because they naturally decompose under appropriate conditions. Biodegradable materials decompose into products that are neutral to the environment in composting conditions or, as in the case of thermoplastic starch, in natural conditions [1,2,3,4,5]. Most often, these materials are used in the production of packaging. The packaging industry is their key area of use due to the growing demand for ecological alternatives to traditional plastics. Packaging is not required to maintain strict dimensional tolerances or detailed mechanical properties such as fatigue strength, surface work under friction conditions, etc. However, basic mechanical properties, a low price, and the so-called product lifetime are important [6,7,8,9,10,11]. These are the purposes for which biodegradable materials are modified with various fillers, including the mineral filler used in this work, micronized chalcedonite [12,13,14,15,16].
Natural starch, the so-called native starch, is a polysaccharide with the formula shown in Figure 1. It is interesting that both starch and cellulose are polysaccharides that do not differ from each other chemically [17,18,19,20]. From a chemical point of view, they could be products of the polycondensation of glucose (monosaccharide) (Figure 1). The essential difference between starch and cellulose is the different molecular weight and structure of the macromolecule. Cellulose has a much higher molecular weight than starch and has numerous branches and “tangles” of the chain [21,22,23]. Therefore, humans can digest starch, while cellulose can only be digested by some herbivorous animals (from Latin: cavia porcellus, bos taurus taurus, equus caballus, and others) [24,25,26,27,28,29,30].
Starch is commonly found in potatoes, corn, and flour products. Thermoplastic starch is obtained from native starch by modifying its crystal structure in mechanical processing at an elevated temperature. Since the melting point of pure starch exceeds its degradation temperature, plasticizers such as glycerin are used in the processing. Under the influence of heat and shear stress, the crystalline structure of starch grains is broken down, leading to the formation of a linear phase, giving it properties typical of thermoplastics [31,32,33,34,35].
Micronized chalcedonite as a filler can offer several significant advantages over traditionally used mineral fillers such as calcium carbonate (CaCO3), especially in applications involving biopolymers such as thermoplastic starch (TPS). Chalcedonite, a form of microcrystalline silica (SiO2), is characterized by its better ability to form stronger interactions with the polymer matrix. Unlike calcium carbonate, which can limit adhesion to polymers, chalcedonite can provide better dispersion and adhesion in mixtures with thermoplastic starch [36,37].
Chalcedonite exhibits higher chemical resistance than, for example, calcium carbonate, which can react with acids, which under certain conditions can lead to material degradation. Additionally, chalcedonite can exhibit greater thermal stability compared to CaCO3, which can decompose at higher temperatures, releasing carbon dioxide (CO2) [38,39,40].
Compared to calcium carbonate, chalcedonite offers better compatibility with polymers, higher chemical resistance, a potential improvement in mechanical properties, and a lower tendency to absorb moisture. Thanks to these properties, it can be a more advanced and functional filler for biodegradable materials such as TPS, especially in the context of modern, ecological polymer processing technologies [41,42].
The aim of this work was to conduct a detailed analysis of the basic mechanical properties and water absorption capacity of a composite material based on modified thermoplastic starch (TPS). Particular attention was paid to assessing the effects of different contents of micronized chalcedonite as a filler on key mechanical properties, such as tensile strength, the modulus of elasticity, and strain at break. The material’s ability to absorb moisture was also analyzed, which is important in the context of its potential applications in environments with increased humidity.
Modified thermoplastic starch and micronized chalcedonite are modern, pro-ecological solutions in the field of polymer materials, consistent with the concept of sustainable development. Their use in the materials industry can contribute to reducing the negative impact on the environment through increased biodegradability, the reduced use of fossil raw materials, and reduced greenhouse gas emissions, including CO2. Additionally, the use of a mineral filler can improve some functional properties of the material, while reducing the amount of waste generated. Thanks to this, composites based on TPS and chalcedonite can be an attractive alternative to traditional synthetic polymers, especially in the context of implementing more sustainable technologies in the plastics industry.
The use of these materials in new-generation composites can support the circular economy, enabling the reuse of raw materials and reducing the production of waste that is difficult to dispose of. By modifying TPS with natural fillers, such as micronized chalcedonite, it is possible to obtain more durable and at the same time biodegradable materials that can replace traditional plastics in many industrial applications.
Additionally, reducing the share of synthetic components in composites leads to a reduction in the carbon footprint associated with the production and disposal of polymer materials. The introduction of innovative biocomposites into the industrial cycle can significantly contribute to reducing greenhouse gas emissions, both at the production stage and at the end of the product life cycle. Further research into the optimization of these materials, including improving their mechanical properties and adapting them to technological requirements, can further increase their potential in the green polymer sector. In the long term, the development of such new-type composites can support global efforts towards climate neutrality and the implementation of innovative solutions in the field of ecological engineering materials [7,8,9,10].

2. Materials and Methods

In this work, a material based on thermoplastic starch was used, which is a mixture of polymers obtained from renewable natural resources. It is characterized by the ability to biodegrade, which means that it decomposes under the influence of environmental factors. Thanks to this, it can be composed in natural conditions with the participation of microorganisms. It is produced by Grupa Azoty (Tarnów, Poland) under the trade name Envifill MB 173 [43]. Table 1 presents the characteristics of the material.
In this study, micronized chalcedonite Crusil M10, produced by CRUSIL Sp. z o.o. (Inowłódz, Poland) [44] was used as a filler. This substance is a variety of silica (SiO2), containing up to 97% of this compound, with a highly developed pore system. Due to its structure, it is characterized by high reactivity and a large specific surface area, which allows for its wide application in various fields. An analysis of the chemical composition showed a dominant content of silica and only trace amounts of calcium, magnesium, aluminum, iron, and manganese oxides. Due to the limited availability of chalcedonite deposits, it is considered a unique rock. In Poland, its deposits occur in the areas of Dobrzynka, Gapinin, Lubocza, and Teofilów on the Rawska Upland near Tomaszów Mazowiecki. Table 2 presents the composition of micronized chalcedonite M10 [41,44]. Table 3 presents the physical parameters. This material consists of over 97% silicon dioxide, which allows it to be classified as silica. Among the other ingredients, the largest share is aluminum oxide (also known as corundum), while the content of other oxides does not exceed 1% [44].
The test samples were produced using a Ponar Żywiec UT90 (Żywiec, Poland) horizontal screw injection molding machine from the UT series, designed for processing thermoplastics. This machine has a five-point, two-lever mold closing system and a screw plasticizing system driven directly by a high-torque hydraulic motor. The process also uses a set of peripheral devices, including an injection mold with replaceable inserts, a thermostat, a DARwag electronic scale, a KC 100/200 dryer, and a plastic recycling mill.
The Envifill MB 173 raw material with the filler added was dried in a drawer dryer at 80 °C for 48 h. After drying, the material was homogenized in a rotary mixer to obtain a uniform mixture. The percentage share of the individual components in the mixture with the filler is presented in Table 4.
After determining the appropriate operating parameters of the injection molding machine, the test samples were formed. Dumbbell and paddles and bars elements were made for further testing. The injection process was carried out in accordance with the established technological conditions, ensuring the optimal quality and repeatability of samples. During production, key parameters were controlled, such as cylinder temperature, injection pressure, and cooling time, in order to obtain materials with a uniform structure and appropriate mechanical properties. The color of the samples changed with the change in the filler content. Detailed data of the process settings are presented in Table 5, while the view of the samples is presented in the photo (Figure 2).
Before starting the tests for determining the mechanical properties, all samples were conditioned at a constant temperature of 23 °C and a humidity of 50% for 120 h.
The mechanical properties in static tensile testing were evaluated according to ISO 527-2 [45] using a Heckert (Germany) Fu1000e testing machine equipped with a 10 kN measuring head. The test involved the static tensile testing of standardized samples at a constant speed of 2 mm/min, in accordance with relevant industry standards [45,46]. During the procedure, the force and elongation at break were continuously monitored and recorded. The hardness test was carried out according to the Shore “D” scale in accordance with ISO 868 [47], using an electronic hardness tester from XINGWEIQIANG (China).
The impact strength was determined by the Charpy method using a pendulum impact hammer from Wolfgang Ohst (Germany) in accordance with ISO 179-1 [48]. Water absorption after seven days was also measured in accordance with ISO 62 [49].

3. Results and Discussion

The injection process was systematically monitored by regular measurements of the mass of individual samples, which allowed for the assessment of the stability of the entire process and the homogeneity of the obtained materials. Regular mass control also allowed for the detection of any deviations in the quality of the samples and enabled a quick response to adjust the process parameters. Table 6 presents the average values of the mass of the samples, which depended on the filler content in the material. The analysis of the results showed a clear trend of increasing the mass of the samples with the increase in the amount of filler. This may result from the change in the density of the material mixture, where the presence of filler affects the increase in the unit mass of the sample. Additionally, the change in the flow properties of the material during the injection process, because of the use of filler, may lead to more effective filling of the mold, which also affects the final mass of the samples.
The results of the static test are presented in Table 7. The stress–strain curves for the samples with filler were rectilinear and similar to each other. The samples were subject to sudden rupture. Only in the case of the pure material was a slight neck formation observed, followed by rupture. This is presented in Figure 3. The sample stress–strain curves are presented in Figure 4.
During the process, the maximum stress, elongation at maximum stress, and Young’s modulus were determined. Figure 5, Figure 6 and Figure 7 show the changes in these parameters depending on the filler content.
Almost all mechanical values, except for Young’s modulus (Figure 7), are reduced. The characteristics of the stress–strain curves remain unchanged, except for the pure material (Figure 3), for which neck formation is observed (Figure 4). In the remaining cases, the curves show a linear character, and the material undergoes a brittle fracture. Despite the reduced mechanical values, their level is not low enough to exclude the material from potential applications. The small scatter of results indicates a homogeneous distribution of the filler in the polymer matrix, which indicates a good quality of the manufacturing process and well-selected parameters.
Impact strength measurements were performed on a pendulum impact hammer according to the Charpy method on standardized unnotched samples using a hammer with an impact energy of 4 J. The results are presented in Table 8 and Figure 8.
The impact strength value with filler decreased; however, with increasing filler content, no rapid deterioration was observed; on the contrary, with 10% wt. and 15% wt. filler, it remained at a constant level. For this measurement, a slight scatter of results was observed, as evidenced by the standard deviation value.
The hardness measurement results are presented in Table 9 and Figure 9. It was observed that the values for each of the samples oscillate around the value of 60 degrees on the Shore D scale. For the pure sample without filler, the average value is the lowest, compared to the samples with filler. With the increase in the content of micronized chalcedonite, the average hardness value of all samples increases. A quite interesting phenomenon is also observed in the case of samples with 5% wt. and 10% wt. content. The difference between the average measurement values in these two series is only 0.1. It can therefore be stated that the difference is minimally noticeable with a relatively large difference in the content of micronized chalcedonite.
The last stage of the laboratory tests was a detailed analysis of water absorption, aimed at assessing the material’s ability to absorb moisture, which is an important aspect in assessing its performance properties, especially in the context of biodegradability. For this purpose, the prepared samples were placed in a vessel filled with water at room temperature, which provided natural operating conditions for the test. The test procedure consisted of measuring the initial mass of the samples before immersion in water, and then regularly monitoring the mass after a period of seven days, during which the samples were soaked in water. After the soaking period, each sample was thoroughly dried and weighed again, and then the difference in mass between the samples before and after soaking was calculated, which was an indicator of water absorption. The obtained values were compared and presented in Table 10, which allowed for an assessment of the effect of filler content and other factors on the material’s properties in the context of its ability to absorb water.
During the measurements, a slight increase in the mass of the samples was observed after their exposure to water. The largest mass increase was noted for samples containing 15% wt. of the filler, which may be related to the porous structure of micronized chalcedonite (Table 10). The possibility of absorbing a larger amount of water and its deposition in the filler structure indicates a potential effect on the properties of the material, including its biodegradation. The observed phenomenon suggests that the hygroscopicity of the filler may be of significant importance for its further functional properties, in particular, for the biodegradation process. The potential role of retained water in degradation processes should be verified by long-term environmental studies. This is a good justification for further research in order to understand the mechanism of water absorption by the filler and its effect on the overall properties of the obtained material.

4. Conclusions

The conducted experimental studies clearly indicate that the addition of micronized chalcedonite has a significant effect on all the analyzed properties of the material. A clear decrease in mechanical strength is noticeable, which at the same time goes hand in hand with a significant decrease in the deformation at fracture. These changes lead to a significant increase in Young’s modulus, which indicates an increase in the stiffness of the material. However, it is worth noting that this increase in stiffness is accompanied by a decrease in the material’s ability to deform before fracture, which may limit its ability to absorb energy. Such changes make it difficult to clearly determine whether the addition of micronized chalcedonite has a clearly positive or negative effect on the material’s properties. This effect may depend on specific application requirements, in which both the strength and flexibility of the material are simultaneously important.
On the other hand, the hardness of the material increases, which should be considered a positive phenomenon, because Envifill itself is a rather soft material. And the decrease in impact strength, which changes only slightly with the content of micronized chalcedonite but is always significantly smaller than that of the pure material, is rather unexpected. This may be related to the formation of micronized chalcedonite agglomerates. In such a case, the tests should be repeated, paying more attention to preventing filler agglomeration.
The increase in water absorption should be considered a positive phenomenon, as it facilitates biodegradability, while the deterioration in dimensional tolerances is not, as mentioned in the introduction, a significant factor. Regardless of the quantitative results obtained in experimental studies, it should be stated that the addition of micronized chalcedonite has a beneficial effect, as firstly, it reduces the price of the material, and secondly, it indirectly reduces its negative impact on the environment. It should be remembered that the base material is a mixture of biodegradable polymers based on thermoplastic starch, while micronized chalcedonite is not a biodegradable material, but is completely neutral to the environment.
It is also necessary to take into account an important aspect related to the use of this filler, due to its high hardness and increased content in the material, which contributes to the intensification in the wear of the working elements of the processing equipment, in particular screws, cylinders, and nozzles. The obtained results provide a good basis for more advanced research aimed at explaining the phenomena occurring between the material and the filler.
In summary, composites based on modified thermoplastic starch (TPS) with the addition of micronized chalcedonite can have a wide range of applications in various industries, especially where biodegradability and sustainability are key. They can be used in the production of ecological disposable packaging, especially in the food and cosmetics sectors, where materials with controlled stiffness and mechanical resistance are required. Chalcedonite can additionally improve the barrier properties of these materials, reducing moisture and gas permeability. Thanks to their mechanical properties, TPS composites with chalcedonite can be used in the production of biodegradable technical elements, such as flower pots, biodegradable cutlery, industrial packaging elements, or agricultural components (e.g., seed covers and biodegradable mulching films). In the construction sector, they can be used as ecological insulating materials or lightweight structural composites with limited environmental impact. Additionally, the possibility of modifying their properties by regulating the amount of filler makes them attractive for manufacturers of materials with a sustainable life cycle.

Author Contributions

M.F.: data collection, formal analysis, sample preparation, and investigation; J.G.: literature review, validation, manuscript preparation, and critical analysis of results. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data are in the article.

Conflicts of Interest

The authors declare no conflicts of interest.

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  47. ISO 868; Plastics—Determination of Water Absorption. ISO: Geneva, Switzerland, 2008.
  48. ISO 179-1; Plastics—Determination of Charpy Impact Properties—Part 1: Non-Instrumented Impact Test. ISO: Geneva, Switzerland, 2010.
  49. PN-EN ISO 62; Plastics—Determination of Water Absorption. ISO: Geneva, Switzerland, 2008.
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Figure 1. Chemical formula of saccharides: (a) glucose; (b) starch and cellulose [24].
Figure 1. Chemical formula of saccharides: (a) glucose; (b) starch and cellulose [24].
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Figure 2. View of samples with various filler content; 0—pure material; 5%—5% wt. filler content; 10%—10% wt. filler content; 15%—15% wt. filler content.
Figure 2. View of samples with various filler content; 0—pure material; 5%—5% wt. filler content; 10%—10% wt. filler content; 15%—15% wt. filler content.
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Figure 3. Tensile stress curves: (a) for pure material; (b) for 10% wt. filler content.
Figure 3. Tensile stress curves: (a) for pure material; (b) for 10% wt. filler content.
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Figure 4. The moment of neck appearance for material without filler.
Figure 4. The moment of neck appearance for material without filler.
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Figure 5. Change in elongation at maximum stress depending on the filler content.
Figure 5. Change in elongation at maximum stress depending on the filler content.
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Figure 6. Change in maximum stress depending on filler content.
Figure 6. Change in maximum stress depending on filler content.
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Figure 7. Change in Young’s modulus depending on the filler content.
Figure 7. Change in Young’s modulus depending on the filler content.
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Figure 8. Impact strength depending on filler content.
Figure 8. Impact strength depending on filler content.
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Figure 9. Change in hardness depending on the amount of filler.
Figure 9. Change in hardness depending on the amount of filler.
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Table 1. Basic properties of Envifill MB 173 material [43].
Table 1. Basic properties of Envifill MB 173 material [43].
PropertiesStandardi.u.Value
DensityISO 1183g/cm31.25
MFR (190 °C/2.16 kg)ISO 1133g/10 min30
Tensile strengthISO 527-1,-2MPa50
Elongation at breakISO 527-1-2%10
Young’s modulusISO 527-1,-2MPa2600
Bending stressISO 178MPa70
Ball indentation hardnessISO 2039-1MPa115
Vicat softening pointISO 306°C60
Table 2. Chemical composition of micronized chalcedonite Crusil M10 [44].
Table 2. Chemical composition of micronized chalcedonite Crusil M10 [44].
Chemical Composition % wt.
SiO2>97
Al2O3<2.2
Fe2O2<0.2
CaO<0.1
MgO<0.1
K2O<0.3
Na2O<0.1
TiO2<0.1
Table 3. Physical parameters of micronized chalcedonite Crusil M10 [44].
Table 3. Physical parameters of micronized chalcedonite Crusil M10 [44].
Specific density2.60 g/cm3
Bulk density0.45–0.55 g/cm3
Shaken density0.60–0.65 g/cm3
Loss on ignition LOI (1 h 950 °C) 1.37%
Normal fire resistance
PN-EN 993-12sP 		173 (1730 °C)
Granulation D-90≤10 μm
Granulation D-50 ≤3 μm
Optical propertiesL/a/b84.16/0.95/4.57
Table 4. Composition of individual Envifill + Crusil M10 mixtures.
Table 4. Composition of individual Envifill + Crusil M10 mixtures.
Envifill MB173, % wt.Crusil M10, % wt.
1000
955
9010
8515
Table 5. Sample injection process parameters.
Table 5. Sample injection process parameters.
Injection ParametersValues
Injection:
Speed30%
Pressure120 bar
Processing temperaturezone 1190 °C
zone 2190 °C
zone 3 170 °C
zone 4170 °C
zone 580 °C
Pressure:
Time10 s
Holding pressure30 bar
Closing force:
Average880 N
Closing the mold:
Pressure170 bar
Speed40%
Mold protection time10 s
Cycle time120 s
Against pressure5 bar
Mold opening:
Against pressure10 bar
Cooling time15 s
Temperature30 °C
Table 6. Changes in sample weight depending on the Crusil M10 filler content.
Table 6. Changes in sample weight depending on the Crusil M10 filler content.
Filler Content, % wt.051015
Average value24.3424.9925.7126.19
Standard deviation0.0060.0370.0660.268
Measurement uncertainty, 95%, k = 2±0.002±0.012±0.021±0.085
Table 7. Results from the tensile test depending on the filler content.
Table 7. Results from the tensile test depending on the filler content.
Filler Content, % wt.Elongation at Maximum Stress
ε, %		Maximum Stress
σ, MPa		Young’s Modulus
E, MPa
08.87 ± 0.4456.80 ± 2.842353.87 ± 117.70
56.11 ± 0.3052.07 ± 2.602995.13 ± 149.75
105.44 ± 0.2749.20 ± 2.463169.49 ± 158.47
154.14 ± 0.2141.30 ± 2.063492.77 ± 174.63
Table 8. Impact strength depending on filler content.
Table 8. Impact strength depending on filler content.
Filler Content, % wt.051015
Average value, kJ/m224.5016.5014.3814.38
Standard deviation4.3782.6223.1873.449
Measurement uncertainty, 95%, k = 2±1.384±0.829±1.008±1.091
Table 9. Hardness strength depending on filler content (Shore “D” degree).
Table 9. Hardness strength depending on filler content (Shore “D” degree).
Filler Content, % wt.051015
Average value, Shore “D” degree58.5059.4059.5060.65
Standard deviation1.1301.3501.2020.474
Measurement uncertainty, 95%, k = 2±0.357±0.427±0.380±0.150
Table 10. Change in weight of samples after seven days of soaking in water.
Table 10. Change in weight of samples after seven days of soaking in water.
Filler Content,
% wt.		Weight of Samples Before Immersion in Water, gSample Weight After 7 Days of Immersion in Water, gDifference
in Mass, g
010.5610.600.04
510.8210.870.05
1011.1711.220.05
1511.3611.430.07
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MDPI and ACS Style

Garbarski, J.; Fabijański, M. Application of a Filler in the Form of Micronized Chalcedonite to Biodegradable Materials Based on Thermoplastic Starch as an Element of the Sustainable Development of Polymeric Materials. Sustainability 2025, 17, 2731. https://doi.org/10.3390/su17062731

AMA Style

Garbarski J, Fabijański M. Application of a Filler in the Form of Micronized Chalcedonite to Biodegradable Materials Based on Thermoplastic Starch as an Element of the Sustainable Development of Polymeric Materials. Sustainability. 2025; 17(6):2731. https://doi.org/10.3390/su17062731

Chicago/Turabian Style

Garbarski, Jacek, and Mariusz Fabijański. 2025. "Application of a Filler in the Form of Micronized Chalcedonite to Biodegradable Materials Based on Thermoplastic Starch as an Element of the Sustainable Development of Polymeric Materials" Sustainability 17, no. 6: 2731. https://doi.org/10.3390/su17062731

APA Style

Garbarski, J., & Fabijański, M. (2025). Application of a Filler in the Form of Micronized Chalcedonite to Biodegradable Materials Based on Thermoplastic Starch as an Element of the Sustainable Development of Polymeric Materials. Sustainability, 17(6), 2731. https://doi.org/10.3390/su17062731

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