Physical and chemical modifications of cellulose fibers for food packaging applications

Cellulose - Cellulose fibers have gained considerable interest for use as gas barriers and reinforcing fillers in food packaging materials because of their interesting properties, including...     

Multi-functional coating of cellulose nanocrystals for flexible packaging applications

In this paper, we systematically address the performance of cellulose nanocrystals (CNs) coated flexible food packaging films. Firstly, the morphology of CNs from cotton linters and homogeneity of its coating on different substrates were characterized by transmission electronic microscopy and atomic force microscopy. Then, the 1.5 μm thick CNs coating on polyethylene terephthalate (PET), oriented polypropylene, oriented polyamide (OPA), and cellophane films were characterized for their mechanical, optical, anti-fog, and barrier properties. CNs coating reduces the coefficient of friction while maintaining high transparency (~90 %) and low haze (3–4 %) values, and shows excellent anti-fog properties and remarkable oxygen barrier (oxygen permeability coefficient of CNs coating, P’O₂, 0.003 cm³ μm m^?2 24 h^?1 kPa^?1). In addition, the Gelbo flex test combined with oxygen permeance (PO₂) measurements and optical microscopy are firstly reported for evaluating the durability of coatings, revealing that the CNs coated PET and OPA provide the best performance among the investigated coated films. CNs are therefore considered to be a promising multi-functional coating for flexible food packaging.     

Construction of hydroxyethyl cellulose/silica/graphitic carbon nitride solid foam for adsorption and photocatalytic degradation of dyes

In the present study, novel hydroxyethyl cellulose/silica/graphitic carbon nitride (HEC/SiO₂/C₃N₄) solid foams with hierarchical porous structure have been successfully fabricated with gas bubbles template combination with freeze-drying method. Compared with HEC/SiO₂/C₃N₄-50 without gas foaming, the HEC/SiO₂/C₃N₄-80 with air bubbles template had larger pore volume and higher porosity and specific surface area, which not only exhibited faster adsorption rate, but also presented higher saturated adsorption capacity towards methylene blue (MB) and methyl violet (MV). From the experimental results, it was found that HEC/SiO₂/C₃N₄-80 had high adsorption capacities of 132.45 mg/g and 206.62 mg/g for MB and MV, respectively, and the adsorption process fitted the Langmuir adsorption isotherm and pseudo-second-order rate equation. Additionally, benefiting from its higher adsorption capacity and light-harvesting capability, HEC/SiO₂/C₃N₄-80 exhibited relatively higher photocatalytic degradation efficiencies against MB and MV under visible light irradiation than HEC/SiO₂/C₃N₄-50. More importantly, compared with the bare g-C₃N₄ powder, the HEC/SiO₂/C₃N₄ solid foams could be more easily separated from the treated water, which facilitated their recycle and reuse. Therefore, the good adsorption capacity, high photocatalytic degradation activity and recyclability of the HEC/SiO₂/C₃N₄ solid foam made it a promising candidate for the removal of organic dyes from wastewater.     

Rheological properties of hexadecyl dimethyl amine modified carboxymethyl hydroxyethyl cellulose solutions and its gelling process

To obtain a new fracturing fluid viscosifier, hexadecyl dimethyl amine was used to modify carboxymethyl hydroxyethyl cellulose (CMHEC) to obtain a product called HD-CMHEC with high viscosity. The rheological properties of HD-CMHEC solutions and CMHEC solutions were studied. For the concentration of 0.3%, the viscosity of CMHEC and HD-CMHEC solutions is, respectively, 19.0?mPa?·?s and 73.6?mPa?·?s, respectively. The viscosity of HD-CMHEC solution increases 2.8 times than before. The thixotropy and viscoelasticity of HD-CMHEC solutions become stronger. As a typical viscoelastic fluid, HD-CMHEC solutions show better rheological performance than that of CMHEC solutions. The gelling process of HD-CMHEC solutions under steady shear was studied in detail. The concentrations of HD-CMHEC solutions, shear rates, and crosslinking agent were investigated. Viscosity versus time curves during the crosslinking process were obtained. The four-parameter crosslinking rheokinetics equation can describe the gelling process of HD-CMHEC solutions under different conditions well. Study on the gelling process of HD-CMHEC solutions under steady shear contributes to the understanding of gel formation, and provides theoretical guidance for exploration and exploitation of the system.     

Rheological properties of cellulose nanocrystal-embedded polymer composites: a review

Nanotechnology provides useful insights into the behavioural properties of materials from the nanoscale point of view, enabling researchers to develop new materials that were previously inconceivable. Cellulose is an ideal candidate for nanomaterial for nanotechnology because of its nanofibrillar structure, abundance, renewability, biodegradability and eco-friendly nature. Nanocrystalline cellulose materials have become the focus many studies related to these materials and their applications. This review summarises the current knowledge on the field of nanomaterials, focussing mainly on the rheological behaviour of polymer nanocomposites embedded with nanocrystalline cellulose. This review will enable better understanding of the use of nanocrystalline cellulose for the development and applications of cellulose nanocrystal-based nanocomposites.     

Preparation and properties of cellulose/silver nanoparticle composites with in situ-generated silver nanoparticles using Ocimum sanctum leaf extract

In the present work, silver nanoparticles were in situ-generated in cellulose matrix using Ocimum sanctum leaf extract as a reducing agent. Regenerated wet cellulose films were first immersed in O. sanctum leaf extract and then it was allowed to diffuse into the films. The leaf extract–diffused wet films were dipped in different concentrated aq.AgNO₃ solutions. The leaf extract inside the wet films reduced AgNO₃ into nanosilver. The dry composite films were black in color. Some of the nanoparticles were also formed outside the film in the solution. The nanoparticles were viewed by transmission electron microscopy and scanning electronic microscopy techniques. The composite films showed good antibacterial activity. The cellulose, matrix, and the composite films were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis techniques. The tensile properties of the composite films were higher than those of the matrix. These biodegradable films can be used for packaging and medical purposes.     

Positron annihilation lifetime study of PTFE/silica composites

Positron annihilation lifetime spectroscopy (PALS) was used to study the microstructure of PTFE/silica composites. The positron lifetimes (τ_n) and intensities (I_n) of PTFE and the composites (30-62% silica) were measured at room temperature as a function of specimen thickness. Four lifetime components were found in PTFE and the composites. The longer lifetime components, τ₃ = 1.4 ns and τ₄ = 4.4 - 4.1 ns, were interpreted to be due to the presence of two different sized free volume cavity distributions within the PTFE/silica composites. A strong silica concentration dependence was found in the bulk intensities (I_3b and I_4b). The I_3b value increased from 13.0% in PTFE to 28.2% in the 62% composite, while the I_4b value decreased from 17.5% in PTFE to 4.5% in the 62% composite. The smaller-void size, free volume fraction (τ₃I_3b) values increased linearly between 0 and 100% silica concentration, while the larger void size, free volume fraction (τ₄I_4b) values decreased nonlinearly with silica concentration. Since silica has a long lifetime component (τ₃ = 1.6 ns), this behavior is ascribed to silica particles occupying the large free volume cavities (370 ų) in the PTFE/silica composites. © 1996 John Wiley & Sons, Inc.     

Industrially produced PET nanocomposites with enhaced properties for food packaging applications

Gas permeation of polymers is one of the important factors to be considered in the selection of materials for many packaging applications, such as modified atmosphere packaging (MAP) for foods. Poly (ethylene therephthalate) (PET) is known to exhibit very low gas permeation compared with most polymers such as polystyrene, polyethylene and polypropylene. However, MAP applications require better barrier performance than that of PET. In the present work PET trays reinforced with organically modified sepiolite, fibrillar nanoclay, have been produced at industrial processes. Permeability to water vapour, oxygen and carbon dioxide has been studied in PET nanocomposites as well as their microstructure through transmission electron and scanning electronic microscopy (TEM and SEM), and their mechanical properties. Results show a better performance in barrier properties as well as an increase in tensile strength, and impact resistance when the sepiolite content is lower than 2.5%.     

Surface chemical modification of microfibrillated cellulose: improvement of barrier properties for packaging applications

Heterogeneous acetylation of microfibrillated cellulose (MFC) was carried out to modify its physical properties and at the same time to preserve the morphology of cellulose fibrils. The overall reaction success was assessed by FTIR together with the degree of substitution (DS) defined by titration and the degree of surface substitution (DSS) evaluated by means of XPS. Dynamic contact angle measurements confirmed the hydrophobicity improvement relative to non-modified samples. The increase of contact angle upon reaching a certain reaction time and some decrease following the further acetylation was confirmed. Mechanical properties of MFC films made from chemically modified material were evaluated using tensile strength tests which showed no significant reduction of tensile strength. According to SEM images, dimension analysis and tensile strength data, the acetylation seemed not to affect the morphology of cellulose fibrils.     

In-situ synthesis and immobilization of silver nanoparticles on microfibrillated cellulose for long-term antibacterial applications

Cellulose - Synthesis of nanocomposites containing silver nanoparticles (AgNPs) has drawn growing interest owing to their antimicrobial activity and tuneable physicochemical properties. In this...     

热致液晶性羟乙基纤维素醋酸酯/聚乙烯共混物的热行为

本文用DSC方法研究了热致液晶性羟乙基纤维素醋酸酯（HECA）与聚乙烯（PE）共混物的相转变过程．结果表明，HECA与PE不相容，但当HECA含量＞50％时，则明显影响PE的结晶过程，使其在冷却过程中出现多重结晶。将共况物在393K退火，可改善PE结晶缺陷；在425K退火，可提高HECA液晶相的取向度。     

Recyclable grease-proof cellulose nanocomposites with enhanced water resistance for food serving applications

Cellulose - Recyclable cellulose nanofibril (CNF) and lignin-containing cellulose nanofibril (LCNF) coated wood flour composites were fabricated using a vacuum-filtration process for food serving...     

Study of migration of active components of phosphorescent oxygen sensors for food packaging applications

A study of migration of the active components of oxygen sensors into food is presented. Six types of sensors, based on different oxygen sensitive dyes (two metalloporphyrins and one ruthenium dye), polymers (polystyrene and polysulfone) and support materials, were exposed to a number of standard ‘food simulants’ recommended by FDA/EU guidelines and then assayed for migration or sensor components and changes in oxygen calibration. Both metalloporphyrin sensor dyes leached only in olive oil and in 95% ethanol (used as a positive control), at maximum levels of 19.22 μg/dm² for PtOEPK and 113.96 μg/dm² for PtTFPP. The RuDPP dye showed maximum leaching in 95% ethanol (25.19 μg/dm²) while also migrating in an acidic aqueous simulant. Planar supports such as polyester tended to enhance the stability of the sensor. Migration of the styrene monomer from the polystyrene encapsulation medium was concluded to be low enough to be insignificant. Migration of sensor components was shown to correlate with the changes in sensor response to oxygen. Based on these results, sensor combinations were ranked on the basis of their resistance to leaching and their general stability, safety and suitability for use on a large scale in packaged foods and related food applications was proven.     

Arrowroot starch-based films incorporated with a carnauba wax nanoemulsion,cellulose nanocrystals,and essential oils: a new functional material for food packaging applications

Arrowroot starch (AA)-based films incorporated with a carnauba wax nanoemulsion (CWN), cellulose nanocrystals (CNCs), and essential oils (EOs) from Mentha spicata (MEO) and Cymbopogon martinii (CEO) were produced using the casting technique and then characterized in terms of their water barrier, tensile, thermal, optical, and microstructural properties and in vitro antifungal activity against Rhizopus stolonifer and Botrytis cinerea. Whereas the incorporation of CNCs decreased the moisture content and water vapor permeability of the AA/CWN/CNC film, the additional incorporation of either EO decreased the transparency and affected the microstructure of the AA/CWN/CNC/EO nanocomposites. MEO and CEO incorporation improved the thermal stability of the films and provided excellent protection against fruit-spoiling fungi. Because of their excellent barrier properties against fungal growth, water vapor permeability, and ultraviolet and visible light, these AA/CWN/CNC/EO films have promising potential for application as active food packaging or coating materials.

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Graphene/polymer composites for energy applications

Graphene has wide potential applications in energy-related systems, mainly because of its unique atom-thick two-dimensional structure, high electrical or thermal conductivity, optical transparency, great mechanical strength, inherent flexibility, and huge specific surface area. For this purpose, graphene materials are frequently blended with polymers to form composites, especially when fabricating flexible devices. Graphene/polymer composites have been explored as electrodes of supercapacitors or lithium ion batteries, counter electrodes of dye-sensitized solar cells, transparent conducting electrodes and active layers of organic solar cells, catalytic electrodes, and polymer electrolyte membranes of fuel cells. In this review, we summarize the recent advances on the synthesis and applications of graphene/polymer composites for energy applications. The challenges and prospects in this field have also been discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Fluorescent labels to study thermal transitions in epoxy/silica composites

The analysis of the fluorescent response from the dansyl moiety as a function of temperature has been used to estimate the thermal transitions in silica particle/epoxy-based composite materials. Silica particles were surface-coated with 3-aminopropyltriethoxysilane (APTES) and 3-aminopropylmethyldiethoxysilane (APDES). 5-Dimethylamino-1-naphtalenesulfonyl chloride (DNS) and 5-dimethylaminonaphthalene-1-(2-aminoehyl)) sulfonamide (DNS-EDA) were selectively attached to the silanized silica particles and to the epoxy matrix respectively. The fluorescence results, interpreted in terms of the model of interpenetrating polymer networks, suggest that (i) independent of the silane coating, the interfacial region is slightly more rigid and heterogeneous than the epoxy bulk and (ii) the interface generated with APTES seems to be more flexible than that obtained with APDES.     

Preparation and properties of epichlorohydrin-cross-linked chitosan/hydroxyethyl cellulose based CuO nanocomposite films

This study introduces an effective route to fabricate chitosan (CS)-based film. The films were prepared through cross-linking reaction between CS and hydroxyethyl cellulose (HEC) using epichlorohydrin (ECH) as the cross-linker and simultaneously in-situ loading with CuO nanoparticles. FT-IR and loading efficiency results indicated the occurrence of inter- and intra-molecular cross-linking reaction between CS and HEC. XRD and EDS analyses showed that the CuO nanoparticles were evenly deposited onto CS film matrixes. SEM characterization showed that the films were of compact, dense and uniform cross morphologies, as well as obvious voids. The films also exhibited desired swelling ratio and water vapor permeability. The enhanced tensile strength was obtained with a maximum value of 77.02?±?3.26 MPa, while the stretch-ability slightly decreased. The thermal stability of the films decreased after cross-linking with HEC. The antibacterial ability of the films was generally improved with the increase of HEC and ECH contents.

Graphical abstract

Preparation and properties of epichlorohydrin-cross-linked chitosan/hydroxyethyl cellulose based CuO nanocomposite films

     

Photochemical incorporation of silver quantum dots in monodisperse silica colloids for photonic crystal applications.

We developed a novel method to fabricate nanocomposite monodisperse SiO2 spheres (approximately 100 nm) containing homogeneously dispersed Ag quantum dots (approximately 2 to 5 nm). The inclusion morphology is controlled through the timing of the photochemical reduction of silver ions during hydrolysis of tetraethoxysilane in a microemulsion. Depending on the timing, Ag quantum dots can be directed to different annuli within the SiO2 spheres, as well as onto the SiO2 sphere surfaces. The embedded Ag quantum dots show a plasmon resonance absorption band at 438 nm. These Ag@SiO2 particles have significant surface charge and readily self-assemble into crystalline colloidal array (CCA) photonic crystals which Bragg-diffract light in the visible region. The magnitude of the plasmon resonance absorption depends on the CCA Bragg diffraction condition. The negative dielectric constant of the silver nanoparticles may be decreasing the silica-silver nanodot composite refractive index below that of the water medium. We may be observing an analogue of the Borrmann effect previously observed in X-ray scattering, where the incident and diffracted electric field standing wave becomes localized in regions of small CCA crystal absorption.     

Preparation and characterization of cellulose acetate/polysiloxane composites

Composites of cellulose acetate and polysiloxane were prepared using 3-isocyanatepropyltriethoxysilane, as a coupling agent. The structure, the thermal and dynamic-mechanical behaviors, and the morphology of the obtained composites were investigated. The composites showed phase separation which was confirmed by the presence of siloxane micro- and nano-domains dispersed in the cellulose acetate matrix, with good interfacial adhesion between the phases. The results demonstrated that the incorporation of a polysiloxane phase on a cellulose acetate matrix caused a decrease in the glass transition temperature, storage modulus and hardness. The proposed methodology was seen to be convenient for the preparation of cellulose acetate/polysiloxane composites with useful properties.