RESUMO
In this paper, we have optimized a low-temperature atomic layer deposition (ALD) of SiO2 using AP-LTO® 330 and ozone (O3) as precursors, and demonstrated its suitability to surface-modify temperature-sensitive bio-based films of cellulose nanofibrils (CNFs). The lowest temperature for the thermal ALD process was 80°C when the silicon precursor residence time was increased by the stop-flow mode. The SiO2 film deposition rate was dependent on the temperature varying within 1.5-2.2 Å cycle-1 in the temperature range of 80-350°C, respectively. The low-temperature SiO2 process that resulted was combined with the conventional trimethyl aluminium + H2O process in order to prepare thin multilayer nanolaminates on self-standing CNF films. One to six stacks of SiO2/Al2O3 were deposited on the CNF films, with individual layer thicknesses of 3.7 nm and 2.6 nm, respectively, combined with a 5 nm protective SiO2 layer as the top layer. The performance of the multilayer hybrid nanolaminate structures was evaluated with respect to the oxygen and water vapour transmission rates. Six stacks of SiO2/Al2O with a total thickness of approximately 35 nm efficiently prevented oxygen and water molecules from interacting with the CNF film. The oxygen transmission rates analysed at 80% RH decreased from the value for plain CNF film of 130 ml m-2 d-1 to 0.15 ml m-2 d-1, whereas the water transmission rates lowered from 630 ± 50 g m-2 d-1 down to 90 ± 40 g m-2 d-1This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'.
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The Cellulose nanofibrils (CNF), also referred to as nanocellulose, is one of the most studied bio-based material in recent year, which has good potential in the future for packaging applications due to its excellent mechanical strength and oxygen barrier properties. In the future, CNF films may also find new applications for example in printed electronics, if the surface smoothness of CNF films can be improved. One way to improve surface smoothness is to use thin coating solutions with zero porosity, such as molar mass controlled cellulose ester coatings. In this study, we have coated CNF films using molar mass controlled cellulose esters with different side chain lengths forming 3-layer film (ester-CNF-ester). These coatings improved significantly the smoothness of CNF films. The 3-layer films have also good water vapor barrier and mechanical properties and the films are heat-sealable, which enable various new applications in the future.
Assuntos
Celulose/química , Ésteres/química , Nanofibras/química , Interações Hidrofóbicas e Hidrofílicas , Peso Molecular , PorosidadeRESUMO
Herein we present a simple method to render cellulosic materials highly hydrophobic while retaining their breathability and moisture buffering properties, thus allowing for their use as functional textiles. The surfaces are coated via layer-by-layer deposition of two natural components, cationic poly-l-lysine and anionic carnauba wax particles. The combination of multiscale roughness, open film structure, and low surface energy of wax colloids, resulted in long-lasting superhydrophobicity on cotton surface already after two bilayers. Atomic force microscopy, interference microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy were used to decouple structural effects from changes in surface energy. Furthermore, the effect of thermal annealing on the coating was evaluated. The potential of this simple and green approach to enhance the use of natural cellulosic materials is discussed.
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A concept for direct surface modification on self-standing films of cellulose nanofibrils (CNF) is demonstrated using an aminosilane group in cellulose compatible solvent (dimethyl acetamide, DMA). The chemically modified structure efficiently prevents the oxygen molecules from interacting with the nanocellulose film in the presence of water molecules. Oxygen permeability values lower than 1mLmmm-2day-1atm-1 were achieved at extremely high levels of relative humidity (RH95%). The aminosilane reaction is compared to conventional hydrophobization reaction using hexamethyldisilazane. The differences with respect to interactions between cellulosic nanofibrils, water and oxygen molecules taking place with aminated and silylated CNF films correlated with the degree of surface substitution, surface hydrophilicity and permeability of the formed layer. The self-condensation reactions taking place on the film surface during aminosilane-mediated bonding were decisive for low oxygen permeability. Experimental evidence on the importance of interfacial processes that hinder the water-cellulose interactions while keeping film's low affinity towards oxygen is demonstrated.
RESUMO
Nanofibrillated cellulose (NFC) and hemicelluloses have shown to be highly promising renewable components both as barrier materials and in novel biocomposites. However, the hydrophilic nature of these materials restricts their use in some applications. In this work, the usability of modified O-acetyl galactoglucomannan (GGM) for modification of NFC surface properties was studied. Four GGM-block-structured, amphiphilic derivatives were synthesized using either fatty acids or polydimethylsiloxane as hydrophobic tails. The adsorption of these GGM derivatives was consecutively examined in aqueous solution using a quartz crystal microbalance with dissipation monitoring (QCM-D). It was found that the hydrophobic tails did not hinder adsorption of the GGM derivatives to cellulose, which was concluded to be due to the presence of the native GGM-block with high affinity to cellulose. The layer properties of the adsorbed block-co-polymers were discussed and evaluated. Self-standing NFC films were further prepared and coated with the GGM derivatives and the effect of the surface modification on wetting properties and oxygen permeability (OP) of the modified films was assessed.
Assuntos
Celulose/química , Mananas/química , Nanofibras/química , Celulose/metabolismo , Interações Hidrofóbicas e Hidrofílicas , Mananas/metabolismoRESUMO
In this study, we present a rapid method to prepare robust, solvent-resistant, nanofibrillated cellulose (NFC) films that can be further surface-modified for functionality. The oxygen, water vapor, and grease barrier properties of the films were measured, and in addition, mechanical properties in the dry and wet state and solvent resistance were evaluated. The pure unmodified NFC films were good barriers for oxygen gas and grease. At a relative humidity below 65%, oxygen permeability of the pure and unmodified NFC films was below 0.6 cm(3) µm m(-2) d(-1) kPa(-1), and no grease penetrated the film. However, the largest advantage of these films was their resistance to various solvents, such as water, methanol, toluene, and dimethylacetamide. Although they absorbed a substantial amount of solvent, the films could still be handled after 24 h of solvent soaking. Hot-pressing was introduced as a convenient method to not only increase the drying speed of the films but also enhance the robustness of the films. The wet strength of the films increased due to the pressing. Thus, they can be chemically or physically modified through adsorption or direct chemical reaction in both aqueous and organic solvents. Through these modifications, the properties of the film can be enhanced, introducing, for example, functionality, hydrophobicity, or bioactivity. Herein, a simple method using surface coating with wax to improve hydrophobicity and oxygen barrier properties at very high humidity is described. Through this modification, the oxygen permeability decreased further and was below 17 cm(3) µm m(-2) d(-1) kPa(-1) even at 97.4% RH, and the water vapor transmission rate decreased from 600 to 40 g/m(2) day. The wax treatment did not deteriorate the dry strength of the film. Possible reasons for the unique properties are discussed. The developed robust NFC films can be used as a generic, environmentally sustainable platform for functional materials.