Bio-high density polyethylene films embedded with organoclay and zinc pyrithione

Abstract

Bio-high density polyethylene (BHDPE) films with organoclay and antimicrobial additives (zinc pyrithione) were evaluated. The composites were prepared in a single-screw extruder using the melt intercalation technique, and the films were obtained by flat extrusion. The diffractograms indicated the formation of an intercalated nanocomposite (BHDPE/6 wt% of clay). Infrared spectra suggested that the polymer predominates over the antimicrobial agent bands. Thermal stability was slightly reduced by up to 3°C. The clay and antimicrobial agent reduced the melting point and crystallinity of BHDPE by up to 12 °C and 13.3%, respectively. In addition, the presence of clay and antimicrobial agent significantly (p < 0.05) affected all mechanical properties. Proliferation of Staphylococcus aureus demonstrated that both evaluated additives did not significantly (p > 0.05) inhibit microbial growth. The results emphasize a promising application of the films for packaging that does not require antimicrobial control, with films highlighted by 6 wt% of clay.

Keywords:
cloisite 20a^®; flat films; microbial activity

1. Introduction

The change in habits and the increase in consumerism in recent decades led to technological innovations and, consequently, to the greater production of consumer goods, which led to an increase in the production of packaging[¹]. Current packages have specific functions and information to improve quality and food safety. They must increase shelf life and monitor the safety and quality of packaging products. Nanotechnology can extend the essential functions of packaging: containment, protection and preservation, and marketing[²].

Among the innovations in the plastic packaging, those produced from green polyethylene or biopolyethylene (BPE)[²,³]. This material has less environmental impact during its synthesis, processing, or degradation than conventional polymers[³]. It has the same functions, characteristics, and applications as polyethylene (PE) derived from fossil resources. However, BPE uses 70% less fossil fuels and emits approximately 170% less greenhouse gases than PE derived from petroleum. In this way, it becomes a viable alternative to conventional polymers for packaging high-consumption products, such as food packaging[⁴].

In this scenario, plastic packaging transformed to become more attractive. It now has known features like active packaging. These active packages have a system that predicts or estimates food quality and safety[⁵]. It also releases substances that prolong the shelf life of the product. Among these innovations, antimicrobial packaging stands out for offering additional protection against microorganisms[⁶].

Generally, antimicrobial additives are divided into organic and inorganic systems. Organic materials include phenols, halogenated compounds[⁷], and quaternary ammonium salts[⁸]. Inorganic materials include metals[⁹], phosphates [¹⁰], oxides[¹¹], and organoclays[¹²,¹³].

Metal complexes, including palladium[¹⁴], copper, nickel[¹⁵], silver, cadmium[¹⁵], present an alternative for incorporation antimicrobial agents. Zinc pyrithione (ZPT), a zinc complex, appears as an option because it is often used in personal care products, such as shampoos and soaps, due to its antifungal and antibacterial properties[¹⁶]. The ZPT has a melting point of 240 °C, which allows for easy processing with most thermoplastics and elastomers, demonstrating compatibility with PE when dispersed in an ethylene vinyl acetate (EVA) matrix[⁶].

It is pertinent to highlight that the European Cosmetics Regulation[¹⁷] classifies zinc pyrithione as having reproductive toxicity, making it banned in EU cosmetics since March 2022. On the other hand, the US Food and Drug Administration (FDA)[¹⁸] indicates ZPT as an antimicrobial agent to inhibit bacterial growth on the surface of films made of polyolefin and polyester.

Many studies have evaluated the antimicrobial action of low-density polyethylene (LDPE) films with ZnO[⁹,¹⁹]. Galli et al.[⁶] studied the effect of ZnO in the LDPE/EVA blend, and Rokbani et al.[²⁰] analyzed the effect of ZnO on LDPE compatibilized with maleic anhydride. Conversely, there are also studies examining the utilization of organoclay, such as Cloisite 15A, 20A, or 30B, as an antimicrobial agent incorporated into PE[²¹], LDPE[²²], and linear low-density polyethylene (LLDPE)[²³]. These inquiries indicate that Cloisite 20A clay emerges as a promising alternative for imparting antimicrobial attributes to polymeric films.

Therefore, this study aimed to evaluate and compare the microbial activity of bio-high density polyethylene (BHDPE) films incorporated with organoclay (Cloisite 20A®)[²¹-²³] and zinc pyrithione dispersed in EVA[⁶]. The films were produced by flat extrusion using the melt intercalation technique and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TGA), differential scanning calorimetry (DSC), and tensile test. The antimicrobial activity was assessed against Staphylococcus aureus.

2. Materials and Methods

2.1 Materials

Bio-high-density polyethylene (BHDPE), grade SGM9450F, contains at least 96% bio-based (ASTM D6866), melt flow rate of 0.33 g/10min (190 ºC/5.0kg -ASTM D1238), was used as received and supplied by BRASKEM (Camaçari, Brazil). The filler incorporated into the BHDPE matrix was Cloisite 20A^®, provided by Southern Clay Products (Gonzales, Texas, USA). A commercial antimicrobial agent, marterbach zinc pyrithione dispersed in EVA, Sanitized^® MB E 22-70 (Burgdorf, Switzerland), was used as received[²⁴].

Strains of Staphylococcus aureus (ATCC 25923 - Gram-positive) were cultured as target microorganism to evaluate antimicrobial activity. Brain Heart Infusion Broth (BHI) broth agar was used as a culture medium.

2.2 Preparation of nanocomposite films

Samples of BHDPE/Cloisite 20A® and BHDPE/Sanitized® MB E 22-70 (Table 1) were extruded in a single screw extruder AX Plásticos AX-16 (Diadema, Brazil), operating with temperature zones (200, 205, and 210 °C) and screw speed at 50 rpm, as previously reported[²⁵]. The films were prepared in the same single-screw extruder with the same temperature profile and screw speed of 60 rpm using a flat die of 220 mm width and cylindrical cooling rollers. The formulation of the samples are in Table 1.

Table 1
Formulation of the samples.

Sample	BHDPE	Cloisite 20A®	Sanitized® MB E 22-70
BHDPE	100.0	-	-
PC3	97.0	3.0	-
PC6	94.0	6.0	-
PB1	99.5	-	0.5
PB2	99.0	-	1.0

• Formulations expressed in wt% in relation to the polymeric matrix.

2.3 Characterization of films

2.3.1 X-ray diffraction

The crystalline parameters of the films and organoclay were determined using a Shimadzu XRD 6000 (Kyoto, Japan) diffractometer operating in the angular range (2θ) from 5 to 50° using CuKα radiation (λ = 1.5418 Å).

2.3.2 Fourier transform infrared spectroscopy

Changes in the FTIR characteristic band evaluated the interaction between BHDPE, organoclay, and antimicrobial agent. Fourier transform infrared spectroscopy (FTIR) analyses were performed on a Perkin Elmer SPECTRUM 400 (FT-IR/FT-NIR) (Waltham, Massachusetts, USA) spectrometer scanning from 650 to 4000 cm^-1 with resolution of 4 cm^-1.

2.3.3Thermal analysis

The thermal stability of the samples was analyzed by thermogravimetry (TGA/DTG) and the thermal behavior and crystallinity of the films were analyzed by differential scanning calorimetry (DSC) using a TA Instrument SDT Q600 V20.9 Build 20 (New Castle, Delaware, USA) equipment, operating at a heating rate of 10 °C.min^-1, from room temperature to 550 °C, under argon gas flow (100 mL.min^-1). The degree of crystallinity (Xc) of the samples was calculated by Equation 1[²⁶]:

${\text{X}}_{\text{c}}=\left\{\Delta {\text{H}}_{\text{m}}/\left[\left(1-\text{w}\right)\Delta {\text{H}}_{\text{m}}^{\text{o}}\right]\right\}\times 100\%$ (1)

where ΔH_m is the measured heat of fusion, $\Delta {\text{H}}_{\text{m}}^{\text{o}}$ is the heat of fusion of 100% crystalline HDPE (293 J.g^-1)[²⁷], and w is the weight fraction of organoclay or antimicrobial agent in the polymer matrix. These thermal analyses provide crucial insights into the behaviors of materials in films, which are fundamental for evaluating their suitability in specific applications[²⁸].

2.3.4 Tensile test

The mechanical behavior of the properties (elastic modulus, strength, and elongation at break) were evaluated according to ASTM D882-18[²⁹] in a Shimadzu AGS-X universal testing machine with a speed of 20 mm.min^-1 and a load cell of 5 kN. Five test specimens were analyzed for each composition in dimensions 120 x 25 mm². Properties were reported in terms of mean ± standard deviation. Tukey’s test for post hoc comparisons evaluated the effect of compositions on each property, considering a significance level of 5% (p < 0.05).

2.3.5 Antimicrobial activity

Staphylococcus aureus (ATCC 25923 - Gram-positive) was used as the target microorganism to evaluate antimicrobial activity[¹²,¹³]. The strain was first cultured in brain heart infusion (BHI) agar and placed in an incubator BOD Lucadema Luca 161/01 (São José do Rio Preto, Brazil) at 37 ºC for 24 h. Subsequently, films incorporated with the antimicrobial agent were submerged in a suspension containing approximately 10⁶ CFU.mL^-1 of bacteria were used to contaminate the samples and 10 ml of BHI broth[³⁰]. As a positive control, test tubes containing only BHI broth and bacterial suspension, and as a negative control, test tubes with BHI broth and BHDPE were used. All test tubes were incubated at 37°C for 4 h. Then, serial dilutions were performed, seeded in Petri dishes containing standard agar for counting and incubated at 37°C for 48 h. The test was performed in triplicate, and the results were expressed in colony-forming units per milliliter (CFU.mL^-1). Antimicrobial activity was evaluated based on antimicrobial performance and sensitivity standards[³⁰,³¹]. The effect of different compositions on antimicrobial activity was statistically evaluated by Tukey's test for post hoc comparisons, considering a significant difference of 5%.

3. Results and Discussions

3.1 Structural characterization

XRD diffraction patterns of organoclay (Cloisite 20A®), pure BHDPE, and their films containing clay (PC3 and PC6) and antimicrobial additive (PB1 and PB2) are in Figure 1.

Figure 1
(a) X-ray diffraction patterns of BHDPE, clay, PC3, PC6, PB1 and PB2 systems, and (b) detail of the displacement of the characteristic clay peaks in the PC3 and PC6 systems.

Three crystalline peaks on BHDPE can be verified (Figure 1-a), the most intense in the angular range at 2θ = 21.5º corresponding to the (110) plane, the other two less intense at 2θ = 23.9º and 2θ = 36.4º corresponding to the (200) and (020) plans, respectively. These data corroborate the semicrystalline of BHDPE[²⁵], and the peaks match the specific crystallographic planes. Cloisite 20A® has characteristic peak at 2θ = 3.40º corresponding to (001) plane associated with the galleries that are expanded by the presence of organic salt, as well as the peaks at 2θ equal to 7.06º corresponding to the (002) plane, corroborating the data reported in the literature[³²].

The diffraction planes (position 2θ) were slightly shifted to smaller angles with basal distance d001 = 2.64 nm in organophilic clay to 2.63 nm and 2.97 nm in systems PC3 and PC6, respectively (Figure 1-b). This displacement suggests that there was even a partial interlacing of the polymeric chains between the clay layers. The formation of a possible intercalated/exfoliated nanocomposite in PC6 film, as previously reported[³³]. Dias et al.[³³] systematically examined the structural attributes of polyurethane nanocomposites containing inorganic particles, specifically synthetic talc and organophilic clay. At the same time, the plans incorporating the antimicrobial additive did not change the structure of the polymeric matrix. Similar results were found in different nanocomposites HDPE/chlorhexidine diacetate[³⁴].

3.2 Infrared spectroscopy (FTIR)

Infrared spectra in the region of 500 to 4000 cm-1 of pure BHDPE, Cloisite 20A® clay, antimicrobial agent, and their films containing clay (PC3 and PC6) and antimicrobial additive (PB1 and PB2) are in Figure 2.

Figure 2
Infrared spectra of the BHDPE, Cloisite 20A® clay, antimicrobial agent, PB1, PB2, PC3, and PC6 systems.

BHDPE infrared spectrum presents transmission bands close to 2900 and 1450 cm^-1, which correspond to the axial and angular deformation movements of the C–H bonds, respectively, and close to 1380 cm^-1, which corresponds to the symmetric angular deformation of the methyl group[³⁵]. The band at 720 cm^-1 refers to the C–H vibration of the –CH₂– groups of the amorphous part[³⁶].

Cloisite 20A^® clay spectrum has a considerable absorption at 1023cm^-1 attributed to the extension of the Si-O band[³⁷]. Characteristic bands of BHDPE were maintained in the PB1 and PB2 systems and possibly overlapped those of the antimicrobial additive due to the low content. It detected a small band close to 1000 cm^-1 in PC3 and PC6 films, referring to the Si-O bond[³⁸].

The bands at 3636 and 3395 cm^-1 are attributed to O–H stretching from silicate and water, respectively. At 1639 cm^-1 is related to O–H bending, and 1040 cm^-1 is due to Si–O–Si stretching vibration from silicate[³⁹]. According to Cervantes-Uc et al.[³⁹], some bands in organoclay samples spectra which cannot exhibited in the sodium clays. These bands were attributed to C–H vibrations of asymmetric stretching, symmetric stretching and bending of the methylene groups located at 2924, 2842 and 1475 cm^-1, respectively, in the chemical structure of the surfactant.

According to Zhang et al.[⁴⁰], the powerful absorption at 1050 cm^-1 may be assigned to the Si–O stretch. The 3000 and 1500 cm^-1 regions which are attributed to C–H stretching and bending, respectively, from the organic portion of the organoclays. The characteristic peaks of alkylammonium can occur at 2926 and 2852 cm^-1 and are assigned to asymmetric stretch vibration of –CH₃ and –CH₂, respectively. The band at 1470 cm^-1 is attributed to the symmetrical stretching vibration of –CH₂. Similar results for Closite 20A clay were reported by Naderi-Samani et al.[⁴¹]. According to Pittol et al.[⁴²], the pirithione structure is shown in the band at 763 cm^-1, attributed to aromatic =C–H out-of-plane deformation vibrations.

3.3 Thermal stability

TGA/DTG thermograms of BHDPE and their films containing clay (PC3 and PC6) and antimicrobial additives (PB1 and PB2) are in Figure 3. Nanocomposite films exhibited thermal stability similar to the control film (pure BHDPE) (Figure 3a). The degradation initiation temperature (T₁₀), referring to a 10% mass loss, the 50% mass loss (T₅₀), the peak temperature decomposition (T_p) (DTG peak in Figure 3b) and the percentage of residue at 550ºC (R%) are reported in Table 2.

Figure 3
(a) TGA and (b) DTG of BHDPE, PB1, PB2, PC3, and PC6 systems.

Table 2
Thermal decomposition of the BHDPE, PB1, PB2, PC3, and PC6 systems and its residue.

Samples	T10 (ºC)	T50 (°C)	Tp (°C)	R% (at 550ºC)
BHDPE	456.6	483.2	489.4	0.08
PC3	451.1	479.8	482.3	2.70
PC6	455.5	479.9	483.4	3.34
PB1	455.8	484.1	489.5	1.25
PB2	454.3	479.6	486.7	1.89

The T₁₀ of BHDPE starts around 400ºC[²⁵,⁴³], and there was no variation for PB1, PB2, PC3, and PC6 systems, as shown in Figure 3 and Table 2. The clay and antimicrobial additive did not affect the film degradation temperatures (T₁₀ and T₅₀). Similar results were found in nanocomposites of LDPE/EVA/graphene oxide[⁴³].

From T_p values, it was verified that PC3 and PC6 presented a reduction of approximately 7ºC, PB2 of 3ºC, and PB1 maintained this temperature compared with BHDPE film. Thus, the clay decreased the degradation temperature, while the antimicrobial additive did not compromise the thermal stability, according to the percentage of residue at 550ºC (Table 2). The residue values at 550ºC were consistent with previously reported works using LDPE/EVA[²⁵,⁴²] and HDPE/clay[²¹,²³].

3.4 Thermal behavior

Changes in the thermal transitions is verified through the results obtained by the DSC analyses. The thermal properties obtained: a melting temperature (Tm), heat of fusion (∆H_m), and degree of crystallinity (Xc) are in Table 3.

Table 3
Thermal properties of BHDPE, PC3, PC6, PB1, and PB2 systems.

Samples	Tm (°C)	ÄHm (J.g-1)	Xc (%)
BHDPE	139.2	134.7	46.0
PC3	134.1	115.6	39.5
PC6	121.3	119.4	40.8
PB1	127.4	96.4	32.9
PB2	127.2	95.8	32.7

The essential parameters for studying thermal properties were Tm and Xc. BHDPE had a Tm around 130°C[²⁵,⁴⁴,⁴⁵]. Compositions with clay reduced of approximately 5°C for PC3 and 18°C for PC6 relative to BHDPE. Previous studies with HDPE and incorporation of 5 and 10 wt% of montmorillonite clay[⁴⁴] indicated a reduction in thermal stability for samples with 5 wt% of clay and an improvement in strength for those with 10 wt% of clay. Films with antimicrobial additives (PB1 and PB2) also reduced 12°C, possibly due to the EVA matrix responsible for carrying the antimicrobial agent.

As shown in Table 3, the evaluated Xc was lower about BHDPE, to a lesser extent for films with clay and films with antimicrobial additives. This behavior suggests that the EVA that supports the antimicrobial agent acted in the plasticization of polyethylene. Previous studies with LDPE/EVA/graphene oxide nanocomposites[⁴⁴] noted a decrease in Tm and Xc in systems containing only PE and EVA due to the partial miscibility of these two polymers.

3.5 Mechanical behavior

BHDPE films and their systems with additions of clay (PC3 and PC6) and antimicrobial additive (PB1 and PB2) were analyzed in uniaxial tensile tests, whose stress-strain curves are represented in Figure 4, and the mechanical properties (yield stress, tensile strength, strain at break, elastic modulus) are present in Table 4.

Figure 4
Representative stress-strain curves of BHDPE, PC3, PC6, PB1, and PB2 films.

Table 4
Mechanical properties of BHDPE, PB1, PB2, PC3, and PC6 systems.

Material	Yield Stress (MPa)	Tensile Strength (MPa)	Strain at Break (%)	Elastic Modulus (MPa)
BHDPE	58.2 ± 7.1b	58.8 ± 7.6b	291.4 ± 11.1b	1384.8 ± 38.6c
PC3	33.1 ± 0.8c	38.6 ± 4.7c	231.7 ± 10.7c	2692.2 ± 25.9b
PC6	91.5 ± 12.9a	83.2 ± 12.9a	335.1 ± 12.9a	5794.0 ± 82.1a
PB1	25.7 ± 1.4c	29.3 ± 1.1cd	253.0 ± 4.8c	1366.2 ± 56.3c
PB2	15.3 ± 2.0c	18.2 ± 2.0d	50.7 ± 6.4d	517.7 ± 38.0d

• Different letters (a-d) indicate a significant difference between the treatments by Tukey’s test (p < 0.05).

Generally, the predominance of ductile behavior can be observed where the material presents elastic behavior at low deformations. After a specific stress, the film plastically deforms up to the rupture stress[⁴⁵]. The BHDPE films obtained a tensile strength of 58.8 ± 7.6 MPa, while the PC3 and PC6 films showed a reduction of 34.3% and an increase of 41.5%, respectively. The decrease in resistance for PC3 indicated the formation of agglomerates in the polymeric matrix, suggesting a microcomposite structure. The clay particle agglomerates acted as defects, altering the mechanical behavior[⁸]. This behavior has been reported in several previous studies with bamboo fiber and particulate coconut shell hybrid PVC composite[⁴⁶] and polysulfone/ZnO composites[⁴⁷]. Also, comparing the behavior of the PC3 film with the BHDPE, there is a minor deformation with an increase in the modulus of elasticity[⁴⁸].

However, for PC6 films, an increase in tensile strength, deformation, and modulus of elasticity was observed, indicating that the clay in this composition was better dispersed[⁴⁹], corroborating the formation of a nanocomposite (Figure 1-b). The mechanical properties are influenced by the aspect ratio of charge, degree of charge dispersion in the polymeric matrix, and charge adhesion at the matrix interface. Antagonistic results due to the increase in clay content have already been reported[²⁶] as in aluminum oxide (Al₂O₃) nanoparticles[⁴⁹].

The antimicrobial additive affected the tensile strength. This property was reduced by almost 50% and 70% for PB1 and PB3 films, respectively. However, the lowest content of the microbial agent (PB1) did not significantly affect (p < 0.05) the modulus of concerning the pure BHDPE film. Nevertheless, the PB2 films showed a drastically reduced elastic modulus value, a recorded reduction of 62.9%. This behavior is related to the presence of EVA, the masterbach matrix that contains the antimicrobial additive. The increase in EVA content implies a reduction in crystallinity[⁵⁰], as already reported by the DSC analyses (Table 3), and, consequently, may have promoted an increase in the mobility of the amorphous phases which causes a decrease in rigidity. Similar results were reported in previous studies due to the presence of EVA in PE/EVA/ZnO nanocomposites[⁶] and in the HDPE/EVA blend[⁵⁰].

3.6 Antimicrobial activity

The antimicrobial activity behavior of BHDPE and its systems containing Cloisite 20A® and antimicrobial additives using the method of diffusion in liquid medium by Staphylococcus aureus bacteria is showen in Figure 5. Values for colony forming units ranged from 0.72 to 0.78 CFU.mL^-1 and did not show significant difference (p > 0.05). Indicating that the presence of clay and commercial antimicrobial agent behaved similarly to pure polymer. Skoura et al.[¹³] found no significant difference in antimicrobial activity against S. aureus when comparing the poly(caprolactone) matrix with intercalated nanocomposites filled with saponite clay organophilically modified using dimethyldioctadecylammonium bromide.

Figure 5
Counting of seed colony forming units of Staphylococcus aureus. The means are not significantly different (p > 0.05).

Organically modified clays can present antimicrobial activity due to the quaternary ammonium compounds that act in the adsorption of the microbial cell surface, diffusion, and disruption of the cytoplasmic membrane, causing cell death[¹²,²¹,²²]. The antimicrobial action of quaternary ammonium compounds depends on their chemical structure, and the more hydrophobic ones, such as those present in Cloiste 20A^®, may not impact microbial communities due to their low availability in the aqueous phase[⁸]. On the other hand, the selected commercial antimicrobial agent, Sanitized® MB E 22-70, disrupts the cellular metabolic process of unwanted microorganisms like bacteria and fungi[²⁴].

The results corroborate that the amount of colony-forming units for PC3, PC6, PB1, and PB2 were close to that of BHDPE, which was the negative control. Studies with 2-vinyl pyridine-styrene-divinylbenzene copolymers in contact with the bacteria Escherichia coli did not show bactericidal activity for any of the evaluated concentrations[⁵⁰]. Similar behavior was reported in the study with reduced graphene oxide composites prepared by poly(3-(3'-thienyloxy)-propyltrimethyl-ammonium bromide) grafting[⁵¹].

The antibacterial capacity of polymers depends not only on the efficiency of the introduced bactericidal group but also on the content of these groups and their accessibility by the contaminated solution[²¹,²²]. For packaging applications that require this antimicrobial control, it is necessary to develop polymeric supports with a physical-chemical structure that favors migration to the film surface and consequent diffusion in the medium.

The intercalated/exfoliated structure is characterized by the interaction between the barrier effect of clay particles and the catalytic effect of residual surfactant salts, which possibly impacted the predicted antimicrobial efficacy of organophilic clays[⁵²].

4. Conclusions

In this work, BHDPE flat films and their films containing Cloisite 20A® organoclays (PC3 and PC6) and antimicrobial additive (zinc pyrithione dispersed in EVA) (PB1 and PB2) were developed evaluated. The addition of the antimicrobial additive did not promote changes in the crystalline structure of BHDPE. However, the addition of clay promoted displacement of the refraction peaks with increased in the basal interplanar distance, suggesting the formation of an intercalated/exfoliated nanocomposite. By FTIR spectra, it was noted the presence of clay into nanocomposites. Howerver, it was impossible to differenciate the characteristic bands of EVA since there may have been overlapping of the bands or because of the low content in the composition. The degradation temperature did not change for PB1, but there was a 3°C reduction for the other films compared to pure BHDPE. A melting temperature and crystallinity were reduced in all systems. Both additives significantly affect (p < 0,05) all mechanical properties, with better results for films with 6 wt% of clay (PC6), and the different content of additives did not significantly reduce (p > 0.05) the proliferation of Staphylococcus aureus bacteria. Finally, it believes that flat films with promising properties were developed for application in packages that do not require biological control.

6. Acknowledgements

The authors extend their appreciation to Universidade Federal do Piauí, Fundação de Amparo à Pesquisa do Estado do Piauí, and Conselho Nacional de Desenvolvimento Cientifico e Tecnológico (CNPq) for their valuable support. This research has been financially supported by CNPq [process number: 308446/2018-6] and [process number: 308309/2022-7].

• How to cite: Mesquita, P. J. P., Braz, C. J. F., Alves, T. S., & Barbosa, R. (2024). Bio-high density polyethylene films embedded with organoclay and zinc pyrithione. Polímeros: Ciência e Tecnologia, 34(1), e20240010. https://doi.org/10.1590/0104-1428.20230100

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Publication Dates

• Publication in this collection
  22 Mar 2024
• Date of issue
  2024

History

• Received
  13 Nov 2023
• Reviewed
  11 Feb 2024
• Accepted
  23 Feb 2024