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European Journal of Applied Sciences – Vol. 12, No. 6
Publication Date: December 25, 2024
DOI:10.14738/aivp.126.17981.
Araújo, A. M. C. F., Freitas, D. F. S., Souza, Y. C. A., Albitres, G. A. V., Garcia, E. E., Cestari, S. P., Miguel, M. A. L., & Mendes, L. C.
(2024). Building and Evaluating A Green and Multifunctional Composite Based on Poly (butylene adipate-coterephthalate) with
Zirconium Phosphate and Clove Essential Oil. European Journal of Applied Sciences, Vol - 12(6). 353-375.
Services for Science and Education – United Kingdom
Building and Evaluating A Green and Multifunctional Composite
Based on Poly (butylene adipate-coterephthalate) with
Zirconium Phosphate and Clove Essential Oil
A.M.C.F. Araújo
Universidade Federal do Rio de Janeiro, Instituto de Microbiologia Paulo de Góes,
Centro de Ciências da Saúde, Bloco I, Ilha do Fundão, Rio de Janeiro, Brazil
D.F.S. Freitas
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora
Eloisa Mano, Centro de Tecnologia, Bloco J, Ilha do Fundão, Rio de Janeiro, RJ,
Brazil
Y.C.A. Souza
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora
Eloisa Mano, Centro de Tecnologia, Bloco J, Ilha do Fundão, Rio de Janeiro, RJ,
Brazil
G.A.V. Albitres
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora
Eloisa Mano, Centro de Tecnologia, Bloco J, Ilha do Fundão, Rio de Janeiro, RJ,
Brazil
E.E. Garcia
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora
Eloisa Mano, Centro de Tecnologia, Bloco J, Ilha do Fundão, Rio de Janeiro, RJ,
Brazil
S.P Cestari
Centre for Innovation in Polymer Engineering (PIEP), Universidade do Minho,
Campus de Azurém, Edifício 15, 4800-058 Guimarães - Portugal
M.A.L. Miguel
Universidade Federal do Rio de Janeiro, Instituto de Microbiologia Paulo de Góes,
Centro de Ciências da Saúde, Bloco I, Ilha do Fundão, Rio de Janeiro, Brazil
L.C. Mendes
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora
Eloisa Mano, Centro de Tecnologia, Bloco J, Ilha do Fundão, Rio de Janeiro, RJ,
Brazil
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Services for Science and Education – United Kingdom 354
European Journal of Applied Sciences (EJAS) Vol. 12, Issue 6, December-2024
ABSTRACT
Although poly(butylene-adipate-terephthalate) (PBAT) is derived from fossil
sources, it is classified as a biodegradable polymer because of its predominantly
aliphatic ester structure. Synthetic Zirconium phosphate (ZrP) has been widely
studied for its notable properties in various fields of human activity. Clove oil (CO)
is an eco-friendly material with notable antioxidant and antimicrobial properties.
In this context, the present study aimed to develop a green and multifunctional
composite based on PBAT incorporated with ZrP, modified ZrP, and CO. The wide- angle X-ray diffraction revealed that the presence of CO promoted the
delamination of the phosphates. The thermogravimetric analysis indicated that
ZrP and modified ZrP slightly improved the thermal stability of PBAT. The
calorimetric evaluations revealed that both ZrP and modified ZrP acted as
heterogeneous nucleating agents, increasing the degree of crystallization of PBAT
by approximately 70–85%. The incorporation of phosphates and clove oil
enhanced the hydrophobicity of the composite films by 20–50%. The
thermomechanical analysis indicated a reduction in the glass transition
temperature of PBAT and an increase in its linear coefficient of thermal expansion.
The type of phosphate and the amount of clove oil influenced the polymer’s
molecular relaxation behavior. Antimicrobial testing confirmed that the
composite effectively inhibited the growth of Gram-positive bacteria
(Staphylococcus aureus and Bacillus cereus) ands the yeast Candida albicans.
Keywords: PBAT, zirconium phosphate, clove oil, thermal and surface properties,
microbial barrier.
INTRODUCTION
In contemporary society, the reliance on petroleum-derived polymers has grown
substantially. However, the use of these polymers presents significant challenges due to the
finite nature of oil and gas resources, environmental concerns regarding their degradation,
and the risk of cross-contamination during recycling processes. To reduce dependence on
petroleum-based polymers, there has been a gradual shift toward replacing non- biodegradable polymers, commonly used in engineering applications, with environmentally
friendly, biodegradable alternatives. [1-2] In the context of biodegradable products, one
promising application is the replacement of petroleum-based polymers with antimicrobial
packaging. However, developing such materials poses a significant challenge in the food
safety and shelf-life extension market. This difficulty arises from the broad range of microbial
pathogens that can contaminate food and cause illness upon consumption.
Antimicrobial packaging systems play a crucial role in mitigating this risk. Various methods
are available for incorporating antimicrobial activity into polymeric materials. These
methods include directly integrating antimicrobial agents into the polymers, applying
antimicrobial coatings to polymer surfaces, immobilizing antimicrobials through chemical
grafting, or using polymers with intrinsic antimicrobial properties. [3] The synthetic
aliphatic-aromatic copolyester poly (butylene adipate-co-terephthalate) (PBAT) is derived
from fossil fuel-based resources and exhibits biodegradability due to the specific functional
groups in its structure. The aliphatic component contributes to its biodegradability, while the
aromatic segment imparts superior mechanical properties compared to other biodegradable
polymers. [4] These functional groups allow PBAT to be broken down by bacteria under
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355
Araújo, A. M. C. F, Freitas, D. F. S., Souza, Y. C. A., Albitres, G. A. V., Garcia, E. E., Cestari, S. P., Miguel, M. A. L., & Mendes, L. C. (2024). Building and
Evaluating A Green and Multifunctional Composite Based on Poly (butylene adipate-coterephthalate) with Zirconium Phosphate and Clove
Essential Oil. European Journal of Applied Sciences, Vol - 12(6). 353-375.
URL: http://dx.doi.org/10.14738/aivp.126.17981
specific conditions. PBAT exhibits remarkable properties, including high elongation at break
and exceptional flexibility, surpassing those of many other biodegradable polyesters. Notably,
these characteristics are comparable to those of low-density polyethylene (LDPE).
Consequently, PBAT shows significant promise as a biodegradable material. Its versatility
allows for applications in various fields, including packaging materials, hygiene products, and
biomedical applications. However, it is essential to acknowledge that PBAT’s mechanical
properties are inferior to those of conventional plastics, which somewhat limits its broader
utilization. [1,2,5] Clove oil, extracted through the distillation of the flowers, stems, and leaves
of the clove tree, serves as a widely recognized flavoring agent. It contains a multitude of
components, many of which display varying levels of antioxidant activity. Notably, eugenol
(4-allyl-2methoxyphenol) constitutes 90–95% of clove oil’s composition. [6] Numerous
scientific reports indicate that clove oil and its primary active compound, eugenol, exhibit
beneficial effects on Gram-negative bacteria such as Escherichia coli, Salmonella, and
Pseudomonas aeruginosa, as well as Gram-positive bacteria including Staphylococcus,
Streptococcus, and Listeria. These effects are attributed to the inhibition of bacterial
migration, adhesion, virulence factor expression, and biofilm formation. [7] Over time, the
antimicrobial activity of essential oils diminishes due to their volatile nature. They are
likewise prone to instability, reacting sensitively to oxygen, light, and heat during processing.
To preserve and maintain their antimicrobial effects, encapsulating these oils within a
delivery system is essential. Researchers have been exploring inorganic carriers as a means
to load essential oils. [8-9] Active packaging is an emerging application of biodegradable
polymers, offering the potential to enhance antimicrobial activity in films and showing
promise over time in industries ranging from biomedical to food packaging. In a study by
Morelli and collaborators, natural oil extracted from Copaifera multijuga was incorporated
into poly (lactic acid) (PLA). The resulting films demonstrated antibacterial properties
against Bacillus subtilis. The authors concluded that these films show promise as
biodegradable active packaging. [10] The investigation of polymer nanocomposites has
gained widespread prominence in both academic and industrial domains. In this context,
nanoparticles play a pivotal role in meeting both short-term and long-term requirements.
Their well-defined structure, size, stability, and uniform dispersion within the polymeric
matrix significantly enhance material properties and overall performance. Consequently, the
synergistic interaction between the polymer and the filler results in novel hybrid materials
with advanced capabilities. Numerous studies have focused on the preparation of
PBAT/organoclay nanocomposites. While most aim to optimize the properties of these
systems by adding small load content, significant enhancements in nanocomposite properties
are achieved only when strong interactions occur between the polymer chains and the
silicate lamellae. These improvements depend on both the dispersion state of the organoclays
within the polymer matrix and the specific nature and composition of the organoclay used
[11]. Many authors have evaluated bioactive nanocomposites using silver nanofillers, which
act by inactivating the deoxyribonucleic acid (DNA) of microorganisms [12]. Films with
layered nanofillers for food packaging have also been studied for their barrier properties,
which hinder the pathway of intercalant molecules, promoting prolonged protection and
extending shelf life. Venkatesan et al. prepared a composite based on PBAT blends, improving
mechanical strength, thermal properties, and antimicrobial activity against Escherichia coli
using zinc oxide [3]. The same authors studied the intercalation of montmorillonite with
octadecylamine and incorporated it into the PBAT matrix. The antimicrobial evaluation