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The current level of packaging consumption imposes a need to fabricate single-use food packaging with renewable and compostable materials, such as bio-polyesters (e.g., polylactic acid, PLA and polybutylene succinate, PBS) or cellulose, but their use is still problematic. Fabrication of bio-compostable composites can specifically address impeding challenges, and adhesive lamination, achieved with compostable glue, is becoming more and more popular with respect to the less versatile hot lamination. In this context, plasma activation, a chemical-free oxidation technique of a material’s surface, is used to increase the affinity of three different biomaterials (cellulose, PLA and PBS) toward a compostable polyurethane adhesive to decrease its amount by gluing bio-polyesters to cellulose. Optical Microscopy reveals activation conditions that do not affect the integrity of the materials, while Water Contact Analyses confirm the activation of the surfaces, with contact angles decreased to roughly 50 deg in all cases. Unexpectedly, ζ-potential analyses and subtractive infrared spectroscopy highlight how the activation performed superficially etches cellulose, while for both PLA and PBS, a general decrease in surface potential and an increase in superficial hydroxyl group populations confirm the achievement of the desired oxidation. Thus, we rationalize continuous activation conditions to treat PLA and PBS and to glue them to neat cellulose. While no beneficial effect is observed with activated PLA, bi-laminate composites fabricated with activated PBS fulfill the benchmark for adhesion strength using less than before, while oxygen permeation analyses exclude plasma-induced etching even at a nanoscale.

Nanocellulose materials have been widely used in biomedicine, food packaging, aerospace, composite material, and other fields. In this work, cellulose obtained from Camellia shells through alkali boiling and subbleaching was micro-dissolved and regenerated using the DMAc (N,N-Dimethylacetamide)/LiCl system, and TOCNs (TEMPO-oxidized cellulose nanofibers) with different degrees of oxidation. The membrane was prepared by filtration of polytetrafluoroethylene (pore size 0.1 μm), and the oxidized nanocellulose film was obtained after drying, Then, the crystallinity, mechanical properties and oxygen barrier properties of the TOCN film were investigated. Furthermore, based on TS (tea saponin) from Camellia oleifera seed cake and TOCNs, TS-TOCN film was prepared by the heterogeneous reaction. The TS-TOCN film not only shows excellent oxygen barrier properties (the oxygen permeability is 2.88 cc·m−2·d−1) but also has good antibacterial effects on both Gram-negative and Gram-positive bacteria. The antibacterial property is comparable to ZnO-TOCN with the same antibacterial content prepared by the in-situ deposition method. Antioxidant activity tests in vitro showed that TS-TOCN had a significant scavenging effect on DPPH (2,2-Diphenyl-1-picrylhydrazyl) radicals. This design strategy makes it possible for inexpensive and abundant Camellia oleifera remainders to be widely used in the field of biobased materials.

The current level of packaging consumption imposes a need to fabricate single-use food packaging with renewable and compostable materials, such as bio-polyesters (e.g., polylactic acid, PLA and polybutylene succinate, PBS) or cellulose, but their use is still problematic. Fabrication of bio-compostable composites can specifically address impeding challenges, and adhesive lamination, achieved with compostable glue, is becoming more and more popular with respect to the less versatile hot lamination. In this context, plasma activation, a chemical-free oxidation technique of a material's surface, is used to increase the affinity of three different biomaterials (cellulose, PLA and PBS) toward a compostable polyurethane adhesive to decrease its amount by gluing bio-polyesters to cellulose. Optical Microscopy reveals activation conditions that do not affect the integrity of the materials, while Water Contact Analyses confirm the activation of the surfaces, with contact angles decreased to roughly 50 deg in all cases. Unexpectedly, ζ-potential analyses and subtractive infrared spectroscopy highlight how the activation performed superficially etches cellulose, while for both PLA and PBS, a general decrease in surface potential and an increase in superficial hydroxyl group populations confirm the achievement of the desired oxidation. Thus, we rationalize continuous activation conditions to treat PLA and PBS and to glue them to neat cellulose. While no beneficial effect is observed with activated PLA, bi-laminate composites fabricated with activated PBS fulfill the benchmark for adhesion strength using less than before, while oxygen permeation analyses exclude plasma-induced etching even at a nanoscale.

Biodegradable polymers suffer from inherent performance limitations that severely limit their practical application. Their functionalization by coating technology is a promising strategy to significantly improve their physical properties for food packaging. In this study, we investigated the double coating technique to produce multifunctional, high barrier and heat-sealable biodegradable films. The systems consisted of a web layer, made of poly(lactide) (PLA) and poly(butylene-adipate-co-terephthalate) (PBAT), which was first coated with a poly(vinyl) alcohol based layer, providing high barrier, and then with a second layer of PLA + ethylene-bis-stereamide (EBS) wax (from 0 to 20%), to provide sealability and improve moisture resistance. The films were fully characterized in terms of chemical, thermal, morphological, surface and functional properties. The deposition of the PVOH coating alone, with a thickness of 5 μm, led to a decrease in the oxygen transmission rate from 2200 cm3/m2 d bar, for the neat substrate (thickness of 22 μm), to 8.14 cm3/m2 d bar (thickness of 27 μm). The deposition of the second PLA layer did not affect the barrier properties but provided heat sealability, with a maximum bonding strength equal to 6.53 N/25 mm. The EBS wax incorporation into the PLA slightly increased the surface hydrophobicity, since the water contact angle passed from 65.4°, for the neat polylactide layer, to 71° for the 20% wax concentration. With respect to the substrate, the double-coated films exhibited increased stiffness, with an elastic modulus ca. three times higher, and a reduced elongation at break, which, however still remained above 75%. Overall, the developed double-coated films exhibited performances comparable to those of the most common synthetic polymer films used in the packaging industry, underlining their suitability for the packaging of sensitive foods with high O2-barrier requirements.

Nanocellulose materials have been widely used in biomedicine, food packaging, aerospace, composite material, and other fields. In this work, cellulose obtained from Camellia shells through alkali boiling and subbleaching was micro-dissolved and regenerated using the DMAc ( N , N -Dimethylacetamide)/LiCl system, and TOCNs (TEMPO-oxidized cellulose nanofibers) with different degrees of oxidation. The membrane was prepared by filtration of polytetrafluoroethylene (pore size 0.1 μm), and the oxidized nanocellulose film was obtained after drying, Then, the crystallinity, mechanical properties and oxygen barrier properties of the TOCN film were investigated. Furthermore, based on TS (tea saponin) from Camellia oleifera seed cake and TOCNs, TS-TOCN film was prepared by the heterogeneous reaction. The TS-TOCN film not only shows excellent oxygen barrier properties (the oxygen permeability is 2.88 cc·m -2 ·d -1 ) but also has good antibacterial effects on both Gram-negative and Gram-positive bacteria. The antibacterial property is comparable to ZnO-TOCN with the same antibacterial content prepared by the in-situ deposition method. Antioxidant activity tests in vitro showed that TS-TOCN had a significant scavenging effect on DPPH (2,2-Diphenyl-1-picrylhydrazyl) radicals. This design strategy makes it possible for inexpensive and abundant Camellia oleifera remainders to be widely used in the field of biobased materials.

In this study, ethylene vinyl alcohol (EVOH) nanocomposites elaborated by melt blending with four different fillers were investigated. Two graphene and two graphite fillers displaying various shapes were selected. The morphology, microstructure, thermal, mechanical, and barrier properties of the nanocomposite films prepared for 2 wt% fillers were analyzed with the aim to establish structure–function properties relationships. The nanocomposites properties significantly depended on the nature of the incorporated filler. The nanocomposite film prepared with the expanded graphite filler exhibited the highest Young modulus value (E = 1430 MPa) and the best barrier properties. Indeed, barrier properties, rarely studied at high water activities, evidenced a significant improvement with a decrease of the water vapor permeability by a factor 1.8 and of the oxygen permeabilities by a factor close to 2, for a critical water activity higher than 0.95. An increase of the thermal stability was also evidenced for this nanocomposite. It was shown that for all studied nanocomposites, the properties could be related to the dispersion state of the fillers and the simultaneous increase of the crystallinity of the matrix. A specific equation was proposed to take into account these both parameters to accurately predict the nanocomposite barrier properties.

Nanobrick wall hybrid coating with super oxygen barrier properties were fabricated on polyethylene terephthalate (PET) film using a quadlayer (QL) assembly of polyelectrolytes and nanoplateles. A quadlayer assembly consists of three repeat units of polyacrylic acid (PAA), poly (dimethyl diallyl ammonium chloride) (PDDA) and layered α-zirconium phosphate (α-ZrP). PDDA with positive charges can assemble alternatively with both α-ZrP and PAA with negative charges to form nanobrick wall architectures on the surface of PET film via the electrostatic interaction. The lamellar structure of α-ZrP platelets and the dense QL assembly coating can greatly reduce the oxygen transmission rate (OTR) of PET film. Compared to pristine PET film, the OTR of PET (QL)19 is reduced from 57 to 0.87 cc/m2/day. Moreover, even with 19 QLs coating, PET (QL)19 composite film is still with an optical transparency higher than 90% and a haze lower than 10%. Therefore, the transparent PET (QL)n composite films with super oxygen barrier properties show great potential application in food packaging and flexible electronic packaging.

Cellulose nanocrystals (CNCs) exhibit outstanding gas barrier properties, which supports their use as a biobased and biodegradable barrier coating on flexible food packaging materials. As highly hydrophilic biopolymers, however, CNCs have a strong sensitivity to water that can be detrimental to applications with fresh foods and in moist conditions due to the loss of barrier properties. In this work, the oxygen and water vapor permeability of polyethylene terephthalate (PET) films coated with CNCs obtained from cotton linters were measured at varying levels of relative humidity, both in adsorption and desorption, and from these data, the diffusion and solubility coefficients were estimated. Therefore, the characterization of CNCs was aimed at understanding the fundamentals of the water-CNCs interaction and proposing counteractions. The CNCs’ moisture absorption and desorption isotherms at 25 °C were collected in the range of relative humidity 0–97% using different techniques and analyzed through GAB (Guggenheim-Anderson-de Boer) and Oswin models. The effects of moisture on the water status, following the freezable water index, and on the crystal structure of CNCs were investigated by Differential Scanning Calorimetry and by X-ray Powder Diffraction, respectively. These findings point to the opportunity of coupling CNCs with hydrophobic layers in order to boost their capabilities as barrier packaging materials.

Biodegradable polymers suffer from inherent performance limitations that severely limit their practical application. Their functionalization by coating technology is a promising strategy to significantly improve their physical properties for food packaging. In this study, we investigated the double coating technique to produce multifunctional, high barrier and heat-sealable biodegradable films. The systems consisted of a web layer, made of poly(lactide) (PLA) and poly(butylene-adipate-co-terephthalate) (PBAT), which was first coated with a poly(vinyl) alcohol based layer, providing high barrier, and then with a second layer of PLA + ethylene-bis-stereamide (EBS) wax (from 0 to 20%), to provide sealability and improve moisture resistance. The films were fully characterized in terms of chemical, thermal, morphological, surface and functional properties. The deposition of the PVOH coating alone, with a thickness of 5 μm, led to a decrease in the oxygen transmission rate from 2200 cm 3 /m 2 d bar, for the neat substrate (thickness of 22 μm), to 8.14 cm 3 /m 2 d bar (thickness of 27 μm). The deposition of the second PLA layer did not affect the barrier properties but provided heat sealability, with a maximum bonding strength equal to 6.53 N/25 mm. The EBS wax incorporation into the PLA slightly increased the surface hydrophobicity, since the water contact angle passed from 65.4°, for the neat polylactide layer, to 71° for the 20% wax concentration. With respect to the substrate, the double-coated films exhibited increased stiffness, with an elastic modulus ca. three times higher, and a reduced elongation at break, which, however still remained above 75%. Overall, the developed double-coated films exhibited performances comparable to those of the most common synthetic polymer films used in the packaging industry, underlining their suitability for the packaging of sensitive foods with high O 2 -barrier requirements.

In this study, ethylene vinyl alcohol (EVOH) nanocomposites elaborated by melt blending with four different fillers were investigated. Two graphene and two graphite fillers displaying various shapes were selected. The morphology, microstructure, thermal, mechanical, and barrier properties of the nanocomposite films prepared for 2 wt% fillers were analyzed with the aim to establish structure-function properties relationships. The nanocomposites properties significantly depended on the nature of the incorporated filler. The nanocomposite film prepared with the expanded graphite filler exhibited the highest Young modulus value (E = 1430 MPa) and the best barrier properties. Indeed, barrier properties, rarely studied at high water activities, evidenced a significant improvement with a decrease of the water vapor permeability by a factor 1.8 and of the oxygen permeabilities by a factor close to 2, for a critical water activity higher than 0.95. An increase of the thermal stability was also evidenced for this nanocomposite. It was shown that for all studied nanocomposites, the properties could be related to the dispersion state of the fillers and the simultaneous increase of the crystallinity of the matrix. A specific equation was proposed to take into account these both parameters to accurately predict the nanocomposite barrier properties.

Nanobrick wall hybrid coating with super oxygen barrier properties were fabricated on polyethylene terephthalate (PET) film using a quadlayer (QL) assembly of polyelectrolytes and nanoplateles. A quadlayer assembly consists of three repeat units of polyacrylic acid (PAA), poly (dimethyl diallyl ammonium chloride) (PDDA) and layered α-zirconium phosphate (α-ZrP). PDDA with positive charges can assemble alternatively with both α-ZrP and PAA with negative charges to form nanobrick wall architectures on the surface of PET film via the electrostatic interaction. The lamellar structure of α-ZrP platelets and the dense QL assembly coating can greatly reduce the oxygen transmission rate (OTR) of PET film. Compared to pristine PET film, the OTR of PET (QL) 19 is reduced from 57 to 0.87 cc/m²/day. Moreover, even with 19 QLs coating, PET (QL) 19 composite film is still with an optical transparency higher than 90% and a haze lower than 10%. Therefore, the transparent PET (QL) n composite films with super oxygen barrier properties show great potential application in food packaging and flexible electronic packaging.

This paper introduces a boron nitride nanosheet (BNNS)-reinforced cellulose nanofiber (CNF) film as a sustainable oxygen barrier film that can potentially be applied in food packaging. Most commodity plastics are oxygen-permeable. CNF exhibits an ideal oxygen transmission rate (OTR) of <1 cc/m²/day in highly controlled conditions. A CNF film typically fabricated by the air drying of a CNF aqueous solution reveals an OTR of 19.08 cc/m²/day. The addition of 0⁻5 wt % BNNS to the CNF dispersion before drying results in a composite film with highly improved OTR of 4.7 cc/m²/day, which is sufficient for meat and cheese packaging. BNNS as a 2D nanomaterial increases the pathway of oxygen gas and reduces the chances of pinhole formation during film fabrication involving water drying. In addition, BNNS improves the mechanical properties of the CNF films (Young's modulus and tensile strength) without significant elongation reductions, probably due to the good miscibility of CNF and BNNS in the aqueous solution. Addition of BNNS also produces negligible color change, which is important for film aesthetics. An in vitro cell experiment was performed to reveal the low cytotoxicity of the CNF/BNNS composite. This composite film has great potential as a sustainable high-performance food-packaging material.

Cellulose nanocrystals (CNCs) exhibit outstanding gas barrier properties, which supports their use as a biobased and biodegradable barrier coating on flexible food packaging materials. As highly hydrophilic biopolymers, however, CNCs have a strong sensitivity to water that can be detrimental to applications with fresh foods and in moist conditions due to the loss of barrier properties. In this work, the oxygen and water vapor permeability of polyethylene terephthalate (PET) films coated with CNCs obtained from cotton linters were measured at varying levels of relative humidity, both in adsorption and desorption, and from these data, the diffusion and solubility coefficients were estimated. Therefore, the characterization of CNCs was aimed at understanding the fundamentals of the water-CNCs interaction and proposing counteractions. The CNCs' moisture absorption and desorption isotherms at 25 °C were collected in the range of relative humidity 0⁻97% using different techniques and analyzed through GAB (Guggenheim-Anderson-de Boer) and Oswin models. The effects of moisture on the water status, following the freezable water index, and on the crystal structure of CNCs were investigated by Differential Scanning Calorimetry and by X-ray Powder Diffraction, respectively. These findings point to the opportunity of coupling CNCs with hydrophobic layers in order to boost their capabilities as barrier packaging materials., Competing Interests: The authors declare no conflict of interest.