This study investigates the barrier properties of hybrid coatings obtained with the sol-gel method applied to a 30 µm Biaxially Oriented Polypropylene (BOPP) film, with the aim of developing sustainable, cost-effective, and recyclable alternatives to conventional multilayer structures. Different formulations were obtained and tested, including silanes alone, PVA-silane mixture, bilayer systems (silanes as base, PVA as the top layer), and standalone PVA coatings. The characterization of the obtained sols included density, viscosity, and solid content measurements. Scanning Electron Microscopy (SEM) of coated samples revealed that PVA minimized cracking, particularly when used in bilayer systems or alone. Energy Dispersive Spectroscopy (EDS) analysis and mapping confirmed uniform coating distribution and identified the presence of only the desired elements. Cross-sectional SEM analysis validated the uniformity of coating thickness in most cases. Oxygen and carbon dioxide transmission rates (OTR and CO2TR) measurements were conducted at 23 °C and 37°C (RH=0%). All coatings improved gas barrier properties (Barrier Improvement Factor from 2 to 60 times), with the best results when PVA was used alone or in bilayer systems. Coating thickness had minimal impact on gas barrier properties, as confirmed by statistical analysis. Water Vapor Transmission Rate (WVTR) tests at 37°C (RH=100%) showed an average permeation reduction of 1.5 times, with better results when PVA was mixed with silanes. Light transmittance measurements at 350-850 nm showed a negligible improvement of transparency after coating deposition. Contact angle measurements confirmed the effectiveness of corona treatment in enhancing deposition and showed that coatings reduced surface wettability, particularly when PVA was used as a top or standalone layer. Adhesion test demonstrated strong bonding of all the coatings with the substrate. Durability test after 72 hours of exposure to 100% relative humidity revealed that PVA-containing coatings exhibited fewer defects, with the best results achieved when used alone. Food safety assessment indicated PVA-only coatings as safe for food contact, as the presence of GLYMO requires further analysis. Despite PVA significantly improved most of the tested properties, its presence represented a liming factor for different recyclability guidelines, making silane-only coatings the more viable solution for applications where recyclability is prioritized.
Questo studio analizza le proprietà barriera di rivestimenti ibridi ottenuti con il metodo sol-gel applicati a film di polipropilene biorientato (BOPP) con spessore 30 µm, con l’obiettivo di sviluppare alternative sostenibili, economiche e riciclabili alle tradizionali strutture multistrato. Sono state formulate e testate diverse composizioni, tra cui silani puri, miscela di PVA e silani, sistemi bilayer (silani come strato base, PVA come strato superiore) e solo PVA. La caratterizzazione dei sol ha incluso misure di densità, viscosità e contenuto solido. L'analisi al microscopio elettronico a scansione (SEM) ha evidenziato che il PVA minimizza la formazione di cricche, soprattutto nei sistemi bilayer o da solo. L’analisi e la mappatura mediante spettroscopia a dispersione di energia (EDS) hanno confermato una distribuzione uniforme del rivestimento e la presenza degli elementi desiderati. L’analisi SEM della sezione ha validato la correttezza dello spessore dei rivestimenti nella maggior parte dei casi. Le misurazioni dei tassi di trasmissione a ossigeno (OTR) e anidride carbonica (CO₂TR) sono state condotte a 23°C e 37°C (RH=0%). Tutti i rivestimenti hanno migliorato le proprietà barriera tra 2 e 60 volte, con i migliori risultati ottenuti in presenza del PVA, soprattutto quando utilizzato da solo oppure nei bilayer. L’analisi statistica ha confermato che lo spessore del rivestimento ha avuto un impatto minimo sulle proprietà barriera ai gas. I test sul tasso di trasmissione del vapore acqueo (WVTR) a 37°C (RH=100%) hanno mostrato una riduzione media di 1.5 volte, con prestazioni migliori nella miscela di PVA e silani. La misurazione della trasmittanza nel range 350-850 nm ha evidenziato un miglioramento della trasparenza. La misura dell'angolo di contatto ha confermato sia l'efficacia del trattamento corona nel migliorare la deposizione sia una riduzione della bagnabilità superficiale, in particolare con il PVA come strato unico. Il test di adesione ha dimostrato un forte legame tra i rivestimenti e il substrato. Le prove di durabilità, dopo 72 ore di esposizione a (RH=100%), hanno rivelato che i rivestimenti contenenti PVA presentavano meno difetti, con i migliori risultati ottenuti quando utilizzato da solo. La valutazione della sicurezza alimentare ha indicato che i rivestimenti di solo PVA sono sicuri, mentre la presenza del GLYMO richiede ulteriori analisi. Nonostante il PVA abbia migliorato significativamente la maggior parte delle proprietà testate, la sua presenza rappresenta un fattore limitante per diverse linee guida sulla riciclabilità, rendendo i rivestimenti di soli silani la soluzione più idonea per applicazioni in cui la riciclabilità è prioritaria.
Hybrid sol-gel barrier coatings for food packaging BOPP
Facchinetti, Federico
2023/2024
Abstract
This study investigates the barrier properties of hybrid coatings obtained with the sol-gel method applied to a 30 µm Biaxially Oriented Polypropylene (BOPP) film, with the aim of developing sustainable, cost-effective, and recyclable alternatives to conventional multilayer structures. Different formulations were obtained and tested, including silanes alone, PVA-silane mixture, bilayer systems (silanes as base, PVA as the top layer), and standalone PVA coatings. The characterization of the obtained sols included density, viscosity, and solid content measurements. Scanning Electron Microscopy (SEM) of coated samples revealed that PVA minimized cracking, particularly when used in bilayer systems or alone. Energy Dispersive Spectroscopy (EDS) analysis and mapping confirmed uniform coating distribution and identified the presence of only the desired elements. Cross-sectional SEM analysis validated the uniformity of coating thickness in most cases. Oxygen and carbon dioxide transmission rates (OTR and CO2TR) measurements were conducted at 23 °C and 37°C (RH=0%). All coatings improved gas barrier properties (Barrier Improvement Factor from 2 to 60 times), with the best results when PVA was used alone or in bilayer systems. Coating thickness had minimal impact on gas barrier properties, as confirmed by statistical analysis. Water Vapor Transmission Rate (WVTR) tests at 37°C (RH=100%) showed an average permeation reduction of 1.5 times, with better results when PVA was mixed with silanes. Light transmittance measurements at 350-850 nm showed a negligible improvement of transparency after coating deposition. Contact angle measurements confirmed the effectiveness of corona treatment in enhancing deposition and showed that coatings reduced surface wettability, particularly when PVA was used as a top or standalone layer. Adhesion test demonstrated strong bonding of all the coatings with the substrate. Durability test after 72 hours of exposure to 100% relative humidity revealed that PVA-containing coatings exhibited fewer defects, with the best results achieved when used alone. Food safety assessment indicated PVA-only coatings as safe for food contact, as the presence of GLYMO requires further analysis. Despite PVA significantly improved most of the tested properties, its presence represented a liming factor for different recyclability guidelines, making silane-only coatings the more viable solution for applications where recyclability is prioritized.File | Dimensione | Formato | |
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2025_04_Facchinetti_Tesi_01.pdf
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Descrizione: Testo della Tesi
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2025_04_Facchinetti_Executive Summary_02.pdf
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Descrizione: Executive Summary
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https://hdl.handle.net/10589/236247