Effect of compatibilization on thermal degradation kinetics of HDPE-based composites containing cellulose reinforcements

Dynamic thermogravimetric analysis under nitrogen flow was used to investigate the thermal decomposition process of high-density poly(ethylene) (HDPE)-based composites reinforced with cellulose fibers obtained from the recycling of multilayer carton scraps, as a function of the cellulose content and the compatibilization. The Friedman, Flynn–Wall–Ozawa, and Coats–Redfern methods were used to determine the apparent activation energy (E _a) of the thermal degradation of the cellulose component into the composites. E _a has been found dependent on the cellulose amount and on the cellulose/polymer matrix interfacial adhesion. In particular, it has been evidenced an increase of the cellulose thermal stability as a consequence of the improved interfacial adhesion between the components in NFR composites.     

Nanocellulose: A Fundamental Material for Science and Technology Applications

Recently, considerable interest has been focused on developing greener and biodegradable materials due to growing environmental concerns. Owing to their low cost, biodegradability, and good mechanical properties, plant fibers have substituted synthetic fibers in the preparation of composites. However, the poor interfacial adhesion due to the hydrophilic nature and high-water absorption limits the use of plant fibers as a reinforcing agent in polymer matrices. The hydrophilic nature of the plant fibers can be overcome by chemical treatments. Cellulose the most abundant natural polymer obtained from sources such as plants, wood, and bacteria has gained wider attention these days. Different methods, such as mechanical, chemical, and chemical treatments in combination with mechanical treatments, have been adopted by researchers for the extraction of cellulose from plants, bacteria, algae, etc. Cellulose nanocrystals (CNC), cellulose nanofibrils (CNF), and microcrystalline cellulose (MCC) have been extracted and used for different applications such as food packaging, water purification, drug delivery, and in composites. In this review, updated information on the methods of isolation of nanocellulose, classification, characterization, and application of nanocellulose has been highlighted. The characteristics and the current status of cellulose-based fiber-reinforced polymer composites in the industry have also been discussed in detail.     

Biological control of cellulose

The enhancement of bacterial cellulose (BC) productivity using sucrose as a carbon source has been obtained by the co-cultivation of two different types of acetic acid bacteria. BC yields for the given mix ratio of bacteria were larger than that of control. The contents of water-soluble polymer (WSP) in the BC composites (BCCs) are a range of 5–30 wt-%. This will be due to the formation of glucose and fructose through the hydrolysis of sucrose by sucrase secreted from Acetobacter sp. In addition, this preparation method would be applied to synthesize a new type of BC having both high biodegradability and other functions.     

Use of Biopolymers for the Removal of Metal Ion Contaminants from Water

Summary: Naturally abundant biosorbants such as chitin and chitosan are recognized as excellent metal ligands, forming stable complexes with many metal ions, and serving as effective protein coagulating agents. Chitosan is a heteropolymer made of D-glucosamine and a small fraction of N-acetyl-D-glucosamine residues. Therefore, the adsorption ability of chitosan is found to be much higher than that of chitin, which has relatively fewer amino groups. Zeolites are crystalline microporous aluminosilicates with ion exchange properties suitable for a wide range of applications in catalysis and separation of liquid and gaseous mixtures. Incorporation in chitosan membranes is an effective method to control the diffusion outside the zeolite crystals and appropriately designed composite systems can find numerous opportunities for applications in wastewater treatment. In this paper we present the synthesis of zeolite-chitosan and zeolite-ethyl cellulose composites by encapsulation of clinoptilolite using a gelling solution of chitosan or an ethyl cellulose solution in ethyl acetate. The adsorption process of Cu²⁺ and Cd²⁺ on some adsorbents was investigated: clinoptillolite tuff (0.05 mm), chitosan flakes, ethyl cellulose, zeolite-chitosan and zeolite- ethyl cellulose composites. Zeolite-chitosan composites have been prepared by encapsulation of zeolites by a gelling solution of chitosan. Micrometric crystals of clinoptillolite were dispersed in a 3% chitosan solution in 1% aqueous acetic acid. The chitosan gel was formed and the zeolite crystals were encapsulated during the gelling process. The same procedure was used to obtain zeolite – ethyl cellulose composites. Study of the metal ion retention properties of different adsorbent materials was carried out using a steady state regime. The concentration of heavy metal ions in supernatant was determined by the atomic absorption spectrophotometric method. Adsorption isotherms of metal ions on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models.     

Grafting amount and structural characteristics of microcrystalline cellulose functionalized with different aminosilane contents

Cellulose - Microcrystalline cellulose (MCC) has unique properties and its use as reinforcement for polymer composites has been increasing. However, the intrinsic incompatibility with most polymers...     

Durability of Cellulosic-Fiber-Reinforced Geopolymers: A Review

Geopolymers have high early strength, fast hardening speed and wide sources of raw materials, and have good durability properties such as high temperature resistance and corrosion resistance. On the other hand, there are abundant sources of plant or cellulose fibers, and it has the advantages of having a low cost, a light weight, strong adhesion and biodegradability. In this context, the geopolymer sector is considering cellulose fibers as a sustainable reinforcement for developing composites. Cellulosic-fiber-reinforced geopolymer composites have broad development prospects. This paper presents a review of the literature research on the durability of cellulosic-fiber-reinforced geopolymer composites in recent years. In this paper, the typical properties of cellulose fibers are summarized, and the polymerization mechanism of geopolymers is briefly discussed. The factors influencing the durability of cellulosic-fiber-reinforced geopolymer composites were summarized and analyzed, including the degradation of fibers in a geopolymer matrix, the toughness of fiber against matrix cracking, the acid resistance, and resistance to chloride ion penetration, high temperature resistance, etc. Finally, the influence of nanomaterials on the properties of geopolymer composites and the chemical modification of fibers are analyzed, and the research on cellulosic-fiber-reinforced geopolymer composites is summarized.     

The Impact of Filler Geometry on Polylactic Acid-Based Sustainable Polymer Composites

Recently, biocomposites have emerged as materials of great interest to the scientists and industry around the globe. Among various polymers, polylactic acid (PLA) is a popular matrix material with high potential for advanced applications. Various particulate materials and nanoparticles have been used as the filler in PLA based matrix. One of the extensively studied filler is cellulose. However, cellulose fibres, due to their hydrophilic nature, are difficult to blend with a hydrophobic polymer matrix. This leads to agglomeration and creates voids, reducing the mechanical strength of the resulting composite. Moreover, the role of the various forms of pure cellulose and its particle shape factors has not been analyzed in most of the current literature. Therefore, in this work, materials of various shapes and shape factors were selected as fillers for the production of polymer composites using Polylactic acid as a matrix to fill this knowledge gap. In particular, pure cellulose fibres (three types with different elongation coefficient) and two mineral nanocomponents: precipitated calcium carbonate and montmorillonite were used. The composites were prepared by a melt blending process using two different levels of fillers: 5% and 30%. Then, the analysis of their thermomechanical and physico-chemical properties was carried out. The obtained results were presented graphically and discussed in terms of their shape and degree of filling.     

Synthese et etude de celluloses echangeuses d'ions. Leur emploi dans l'epuration des eaux residuaires de l'industrie textile—1: Synthese d'une cellulose greffee par des chaines poly (acide acrylique) et d'une cellulose renfermant des fonctions ammonium quaternaire

For use as ion exchangers and particularly as purification agents for textile industrial effluents, cellulose grafted with polyacrylic acid and cellulose substituted by quaternary ammonium functions have been prepared. For both syntheses, the influences of experimental parameters have been studied in detail and the optimum conditions for large-scale preparation have been determined. Large amounts of modified cellulose have been obtained and tested in industry (cf. part III). The grafting by acrylic acid has been carried out by the ceric-ion method; the quaternary ammonium cellulose has been obtained by condensation of cellulose with epoxy propyl triethyl ammonium chloride. Synthesis of this salt in the presence of cellulose has been achieved so that the quaternary ammonium cellulose can be obtained from cellulose and epichlorhydrin in one step.     

Functionalization of nanofibrillated cellulose with silver nanoclusters: fluorescence and antibacterial activity

Native cellulose nanofibers are functionalized using luminescent metal nanoclusters to form a novel type of functional nanocellulose/nanocluster composite. Previously, various types of cellulose fibers have been functionalized with large, non-luminescent metal nanoparticles. Here, mechanically strong native cellulose nanofibers, also called nanofibrillatedcellulose (NFC), microfibrillatedcellulose (MFC) ornanocellulose, disintegrated from macroscopic cellulose pulp fibers are used as support for small and fluorescent silver nanoclusters. The functionalization occurs in a supramolecular manner, mediated by poly(methacrylic acid) that protects nanoclusters while it allows hydrogen bonding with cellulose, leading to composites with fluorescence and antibacterial activity.     

高分子基质作用下碳酸钙的仿生合成

依据生物矿化的基本原理,在动态条件下,通过仿生合成的方法,以三种高聚物：聚乙三醇、聚乙烯醇、羟乙基纤维作为有机基质,分别合成了高聚物含量不同的三种CaCO~3/高聚物复合材料,这些无机/有机复合材料与生物体内经过生物矿化作用所形成的生物矿物颇为相似,具有独特的微观结构形态和一定的取向,这些结果对于具有生物相容性和优异性能的碳酸钙功能的合成具有一守的指导意义。     

以离子液体为介质的纤维素加工与功能化

纤维素作为自然界中储量最大的天然高分子,被认为是未来世界能源与化工的主要原料.但由于分子链间存在丰富氢键网络以及高度结晶的聚集态结构特点,天然纤维素不熔化、难溶解,造成纤维素的加工极其困难,纤维素材料的传统生产工艺复杂且污染严重,极大限制了纤维素材料的广泛应用.近年来,人们发现一些特定结构的离子液体能够高效溶解纤维素,为纤维素的加工和功能化提供了新的多用途平台.本文从"溶解纤维素的离子液体、纤维素溶解机理与溶液性质、以离子液体制备再生纤维素材料和以离子液体为介质合成纤维素衍生物"4个方面详细介绍了本课题组在此领域的研究进展.     

Microfibrillated cellulose and new nanocomposite materials: a review

Due to their abundance, high strength and stiffness, low weight and biodegradability, nano-scale cellulose fiber materials (e.g., microfibrillated cellulose and bacterial cellulose) serve as promising candidates for bio-nanocomposite production. Such new high-value materials are the subject of continuing research and are commercially interesting in terms of new products from the pulp and paper industry and the agricultural sector. Cellulose nanofibers can be extracted from various plant sources and, although the mechanical separation of plant fibers into smaller elementary constituents has typically required high energy input, chemical and/or enzymatic fiber pre-treatments have been developed to overcome this problem. A challenge associated with using nanocellulose in composites is the lack of compatibility with hydrophobic polymers and various chemical modification methods have been explored in order to address this hurdle. This review summarizes progress in nanocellulose preparation with a particular focus on microfibrillated cellulose and also discusses recent developments in bio-nanocomposite fabrication based on nanocellulose.     

Chemical Modification of Reducing End‐Groups in Cellulose Nanocrystals

Native plant cellulose has an intrinsic supramolecular structure. Consequently, it can be isolated as nanocellulose species, which can be utilized as building blocks for renewable nanomaterials. The structure of cellulose also permits its end‐wise modification, i.e., chemical reactions exclusively on one end of a cellulose chain or a nanocellulose particle. The premises for end‐wise modification have been known for decades. Nevertheless, different approaches for the reactions have emerged only recently, because of formidable synthetic and analytical challenges associated with the issue, including the adverse reactivity of the cellulose reducing end and the low abundance of newly introduced functionalities. This Review gives a full account of the scientific underpinnings and challenges related to end‐wise modification of cellulose nanocrystals. Furthermore, we present how the chemical modification of cellulose nanocrystal ends may be applied to directed assembly, resulting in numerous possibilities for the construction of new materials, such as responsive liquid crystal templates and composites with tailored interactions.     

Preparation and Characterization of Modified Cellulose Fiber-Reinforced Polyvinyl Alcohol/Polypyrrolidone Hybrid Film Composites

In this work, cellulose was modified by using 2-(trifluromethyl)benzoylchloride by base catalyzed reaction. Modification of cellulose was confirmed by IR studies. The biodegradable composite films were developed by a film casting method using modified cellulose with poly(vinyl alcohol) and polypyrrolidone in different compositions. Film composites showed good biodegradability. Better barrier and mechanical properties showed by film composites as the percentage of modified cellulose increased. This indicates the importance of modified cellulose as a reinforcing agent. After analyzing these properties of film composites we came to the conclusion that, these biocomposites can be used for membrane and packaging applications.     

Cellulose nanomaterials review: structure, properties and nanocomposites

This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them. It summarizes cellulose nanoparticles in terms of particle morphology, crystal structure, and properties. Also described are the self-assembly and rheological properties of cellulose nanoparticle suspensions. The methodology of composite processing and resulting properties are fully covered, with an emphasis on neat and high fraction cellulose composites. Additionally, advances in predictive modeling from molecular dynamic simulations of crystalline cellulose to the continuum modeling of composites made with such particles are reviewed (392 references).     

Roles of xyloglucan and pectin on the mechanical properties of bacterial cellulose composite films

Xyloglucan and pectin are major non-cellulosic components of most primary plant cell walls. It is believed that xyloglucan and perhaps pectin are functioning as tethers between cellulose microfibrils in the cell walls. In order to understand the role of xyloglucan and pectin in cell wall mechanical properties, model cell wall composites created using Gluconacetobacter xylinus cellulose or cellulose nanowhiskers (CNWs) derived there from with different amounts of xyloglucan and/or pectin have been prepared and measured under extension conditions. Compared with pure CNW films, CNW composites with lower amounts of xyloglucan or pectin did not show significant differences in mechanical behavior. Only when the additives were as high as 60 %, the films exhibited a slightly lower Young’s modulus. However, when cultured with xyloglucan or pectin, the bacterial cellulose (BC) composites produced by G. xylinus showed much lower modulus compared with that of the pure BC films. Xyloglucan was able to further reduce the modulus and extensibility of the film compared to that of pectin. It is proposed that surface coating or tethering of xyloglucan or pectin of cellulose microfibrils does not alone affect the mechanical properties of cell wall materials. The implication from this work is that xyloglucan or pectin alters the mechanical properties of cellulose networks during rather than after the cellulose biosynthesis process, which impacts the nature of the connection between these compounds.     

Analysis of moisture sorption in lyocell-polypropylene composites

The preparation of composites by thermoforming of intermingled fibre slivers is an efficient method to receive high performance and lightweight materials. Cellulosic fibres have benefits like low density and sustainability but the sorption of water due to the high hydrophilicity of the cellulose requires attention. The swelling of the wet fibres changes the fibre-matrix adhesion and as a consequence, the mechanical strength of the composite is influenced negatively. In this study, the thermoplastic polypropylene was combined with lyocell fibres as reinforcement. Moisture sorption isotherms of cellulose/polypropylene composites were recorded as function of relative humidity. Additionally, the specific surface area was analysed by the Brunauer–Emmett–Teller model. It has been found, that the moisture sorption is influenced by the polypropylene (PP) ratio in the composites. At 60% relative humidity the moisture uptake of the lyocell fibres was reduced from 10.8 to 5.8% for lyocell embedded in a composite with 50% polypropylene. Besides the hysteresis between moisture sorption/desorption cycles was found to be proportional to the increased content of PP. The “Parallel Exponential Kinetics” (PEK) model was used to analyse the kinetics of moisture sorption of these composites in more detail. With the help of the PEK model the sorption/desorption kinetics were described by a fast and slow moisture sorption/desorption process. The capacity for rapid moisture sorption is reduced by the formation of PP layers on the lyocell surface. The share of slow moisture sorption increased with increasing PP content in the composite. The results support understanding of the interaction of water with cellulose containing composites.     

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.     

Melting Processing of Biodegradable Cellulose Diacetate/Starch Composites

Natural polymers and their derivatives are attracting increasing interest as promising biodegradable materials that can meet the environmental and recycling demands from society. This study prepared biodegradable composites of cellulose diacetate and starch, and examined their physical and thermal properties. In addition, the morphology of the composites was examined by scanning electron microscopy. For melt processing, epoxidized soybean oil, as a lubricant, and triacetine, as a plasticizer, were added to the composites. The optimal conditions for the preparation of the biodegradable composites were determined. Increasing the amount of starch in the composites resulted in further enhancement of the processability of cellulose diacetate. The tensile strength and Young's modulus decreased, and the amount of elongation and T_g value increased with increasing amount of starch.     

Sustainable optically transparent composites based on epoxidized soy-bean oil (ESO) matrix and high contents of bacterial cellulose (BC)

Production of transparent composites from totally renewable resources with extraordinary potential for different applications can be made possible using cellulose. Composites of epoxidized soybean oil (ESO)/bacterial cellulose (BC) nanofibers have been prepared with high fiber content. Due to the nano-order scale network-like structure of BC nanofibers, composite films present high transparency even at high BC content. Transparency of films has been analyzed by UV–visible spectroscopy observing that only 15% of matrix transmittance is lost in the nanocomposites. ESO/BC composites show better mechanical properties with increasing BC content. Composites combine high stiffness and good ductility due to the incorporation of BC network structure in ESO matrix.