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openaire: EC/H2020/788489/EU//BioELCell A major challenge exists in the preparation of scaffolds for bone regeneration, namely, achieving simultaneously bioactivity, biocompatibility, mechanical performance and simple manufacturing. Here, cellulose nanofibrils (CNF) are introduced for the preparation of scaffolds taking advantage of their biocompatibility and ability to form strong 3D porous networks from aqueous suspensions. CNF are made bioactive for bone formation through a simple and scalable strategy that achieves highly interconnected 3D networks. The resultant materials optimally combine morphological and mechanical features and facilitate hydroxyapatite formation while releasing essential ions for in vivo bone repair. The porosity and roughness of the scaffolds favor several cell functions while the ions act in the expression of genes associated with cell differentiation. Ion release is found critical to enhance the production of the bone morphogenetic protein 2 (BMP-2) from cells within the fractured area, thus accelerating the in vivo bone repair. Systemic biocompatibility indicates no negative effects on vital organs such as the liver and kidneys. The results pave the way towards a facile preparation of advanced, high performance CNF-based scaffolds for bone tissue engineering.

International audience; Nanocellulose has generated a great deal of interest as a source of nanometer-sized reinforcement, because of its good mechanical properties. In the last few years, nanocellulose has also attracted much attention due to environmental concerns. This review presents an overview of recent developments in this area, including the production, characterization, properties, and range of applications of nanocellulose-based biodegradable polymers, thermoplastic polymers, and porous nanocomposites. After explaining the unique properties of nanocellulose and its various preparation techniques, an orderly introduction of various nanocellulose-reinforced biodegradable polymers such as starch, proteins, alginate, chitosan, and gelatin is provided. Subsequently, the effects of nanocellulose on the properties of thermoplastic polymers such as polyamides, polysulfone, polypropyrol, and polyacronitril are reported. The paper concludes with a presentation of new finding and cutting-edge studies on nanocellulose foam and aerogel composites. Three different types of aerogels, i.e., pristine nanocellulose-based aerogels, modified nanocellulose-based aerogels, and nanocellulose-based templates for aerogels, are discussed, as well as their preparation techniques and properties. In the case of foam composites, the research focus has been on two major preparation techniques, i.e., solvent-mixing/foaming and melt-mixing foaming, their respective challenges, and the properties of the final composites. In some cases, a comparison study between cellulose nanocrystals and cellulose nanofiber-reinforced biodegradable polymers, thermoplastics, and porous nanocomposites was carried out. Considering the vast amount of research on nanocellulose-based composites, special emphasis on such composites isprovided at the end of the review.

In this work, we explore the architecture of highly porous foams based on cellulose nanofibers (CNFs) prepared by using cationic surfactants (e.g., C12TAB, C14TAB, and C16TAB) as modifying agents. The addition of surfactants to CNF suspensions led the nanoparticles surface to be covered by these molecules, reducing the ζ-potential from −35 to −8 mV, which, together with hydrophobic interactions of adsorbed surfactants, causes CNF flocculation. After freeze-casting and lyophilization, mechanical properties and pores structure of the low-density foams obtained (15.6–30.9 mg cm−3) proved to be strongly dependent on nanofibers agglomeration degree. The primary causes of such dependence could not be observable by scanning electron microscopy but were found to be very significant on X-ray microtomography analysis. Total porosity, pore-size, and wall thickness of the foams were calculated and related to the surfactant chain size. Surface areas from 4.7 to 48.6 m2 g−1, obtained by n-decane adsorption, are reported.

The influence of ice-crystals growing direction over the organization of cellulose nanofibers as freeze-casted foams is reported. This tuning was achieved by changing the metallic (copper) area of the sample molds which altered the freezing-front behavior, causing an oriented foam structure in certain directions. This orientation imparted different microarchitectures to the foams, leading to different pores sizes and wall thicknesses which could be characterized by advanced image techniques based on microtomography. As consequence, mechanical properties, such as compression modulus, have changed. In this study, a statistical approach is used to validate all the results obtained.

International audience; Research on nanocellulose has significantly increased over the past few decades, owing to the various attractive characteristics of this material, such as renewability, widespread availability, low density, excellent mechanical properties, economic value, biocompatibility, and biodegradability. Nanocellulose categorized into two main types, namely cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). In this review, we present the recent advances made in the production of CNFs and CNCs. In addition to the conventional mechanical and chemical treatments used to prepare CNFs and CNCs, respectively, other promising techniques as well as pretreatment processes have been also proposed in recent times, in an effort to design an economically efficient and eco-friendly production route for nanocellulose. Further, while the hydrophilic nature of nanocellulose limits its use in polymeric matrices and in some industrial applications, the large number of hydroxyl groups on the surface of nanocellulose provides a suitable platform for various kinds of modification treatments. The various chemical and physical surface treatment procedures reported for nanocellulose have been reviewed in this paper. Finally, in this review, we summarize the life cycle assessment studies conducted so far on nanocellulose, which quantify the environmental impact of nanocellulose products. The current paper is a comprehensive review of the recent literature on nanostructured cellulose.

International audience; Cellulose nanocrystal (CNC)-reinforced poly(lactic acid) (PLA) nanocomposites were prepared by twin-screw extrusion followed by injection-molding using a masterbatch approach. Noncovalent modification of CNCs was performed with two different poly(l-lactide) (PLLA)-based surfactants to improve the filler/matrix compatibility. They both have a PLLA block that is expected to improve the compatibility with the PLA matrix and differ by the polar head. It consists of either a poly(ethylene glycol) (PEG) block (PEG-b-PLLA) or an imidazolium group (Im-PLLA), that is able to interact with the surface of the CNCs. The morphological, structural, thermal, rheological, and mechanical properties of the nanocomposites were investigated. The different modes of interaction of the polar head of the surfactant lead to different properties. However, the global decrease in the molecular weight of PLA, induced by the short PLLA blocks from the surfactants and the possible degradation during melt processing, results in a plasticization effect and impacts the crystallization of the matrix.

Made available in DSpace on 2019-10-06T17:00:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-05-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) In the present study, we report the preparation of antifungal and non-cytotoxic polymer nanocomposites with potential application in biomedical materials. Dodecanethiol-protected silver nanoparticles (AgNPs-DDT) were synthesized by a reduction/precipitation method and dispersed in chloroform to obtain stable colloidal dispersions. PBAT-based nanocomposites containing 0.25, 0.5 and 2 wt% AgNPs-DDT were prepared by casting method. The incorporation of AgNPs-DDT in PBAT matrix resulted in nanocomposites which combine improved mechanical performance and antifungal properties with a non-cytotoxic characteristic. School of Chemical Engineering University of Campinas (UNICAMP) Brazilian Nanotechnology National Laboratory (LNNano) Brazilian Center for Research in Energy and Materials (CNPEM) Department of Oral Biosciences and Diagnosis Institute of Science and Technology Universidade Estadual Paulista (UNESP) Physiological Science Department Piracicaba Dental School University of Campinas (UNICAMP) Instituto de Macromoléculas Professora Eloísa Mano (IMA) Universidade Federal do Rio de Janeiro (UFRJ) Department of Oral Biosciences and Diagnosis Institute of Science and Technology Universidade Estadual Paulista (UNESP) FAPESP: 2016/08595-1 FAPESP: 2016/09588-9

Supramolecular assembly of biobased components in water is a promising strategy to construct advanced materials. Herein, electrostatic complexation was used to prepare wet-resilient foams with improved mechanical property. Small-angle X-ray scattering and cryo-transmission electron microscopy experiments showed that suspensions with oppositely charged cellulose nanofibers are a mixture of clusters and networks of entangled fibers. The balance between these structures governs the colloidal stability and the rheological behavior of CNFs in water. Foams prepared from suspensions exhibited maximum compressive modulus at the mass composition of 1:1 (ca 0.12 MPa), suggesting that meaningful attractive interactions happen at this point and act as stiffening structure in the material. Besides the electrostatic attraction, hydrogen bonds and hydrophobic contacts may also occur within the clustering, improving the water stability of cationic foams. These results may provide a basis for the development of robust all- cellulose materials prepared in water, with nontoxic chemicals.

Besides interesting properties and potential applications, cellulose nanocrystals (CNCs) present some limitations which remain a challenge in many application fields. These nanomaterials are sensitive to thermal degradation due to their natural source and surface characteristics, limiting their processing at high temperature. In this study, pristine sisal fibers were bleached using different acid (ABF) and basic (BBF) techniques prior to sulfuric acid hydrolysis under the same conditions. This procedure provided two CNCs with different characteristics (ACNC and BCNC). The compositions of the bleached cellulosic pulps were characterized and was found that ABF and BBF presented different cellulose contents of 61.5 and 72.4% respectively. It clearly impacts the thermal behavior of the obtained nanomaterials, leading BCNC to present a maximum degradation temperature of approximately 100 °C higher than ACNC. Other CNC characteristics, such as surface charge, crystallinity and aspect ratio also seem to play an important role in relation to the thermal behavior. A decrease in the stability and the modification of the volatile content and composition were observed during the thermal degradation.

Cellulose nanofibers (CNF) can present a high viscosity and thixotropic behavior when dispersed in water. In this work, CNF isolated from sugarcane bagasse and modified by N-oxyl-2,2,6,6-tetramethylpiperidine (TEMPO) oxidation was added to a solution of carboxymethyl cellulose (CMC). This process produced an unexpected viscosity due to a synergistic effect that was observed macroscopically through rheology analysis. The phenomenon known as depletion flocculation was observed, which was caused by the reduction of the excluded volume. The interactions of the system were studied by ultraviolet-visible spectroscopy (UV-Vis), optical microscopy, and cryogenic transmission electron microscopy (cryo-TEM), which demonstrated the presence of the particle/polymer repulsion and subsequent formation of domains composed of aligned micro and nanocellulose particles clusters and nanofibers distributed throughout the sample, forming a percolated 3D structure responsible for a strong gelling and colloidal stability.

International audience; Cellulose nanocrystals (CNC) and nanofibrils (CNF) were obtained by acid hydrolyzis and mechanical treatment, respectively, of cellulosic fibers from paper. Additionally, surface modification was performed for CNC by neutralization (NaOH) and oxidation (TEMPO). The thermal stability, surface properties and rheological behavior of these nanomaterials were compared. A clear difference in CNC surface was found upon neutralization and oxidation treatments, leading to distinct thermal behaviors. Optical and rheological properties were found to be predominantly by the particles size, being strongly affected by inertial effects.

Cellulose nanofibers (CNF) were isolated from Curaua fibers (Ananas erectifolius L. B. Smith) through a mechanical grinder preceded by mild chemical treatment. Morphology and surface characteristics of the fibers were followed until it reaches the nanoscale as long and flexible nanofibers. In aqueous suspensions, SAXS techniques revealed that such nanofibers present a twisted ribbon structure while rheological measurements demonstrate its high viscosity and a thixotropic behavior. These characteristics suggests the potential application of CNF in biomedical field, which, in turn, stimulates the toxicological studies of such materials. The obtained materials do not show any sign of cytotoxicity by direct or indirect assays for cell viability and cell morphology using Vero cells. Moreover, during the adhesion test, the cells demonstrated higher affinity to the CNF surface. It can be related to its surface properties and its obtaining conditions, which did not use any hazardous chemicals.

Cellulose nanocrystals (CNCs) are appealing nanomaterials for the reinforcement of polymeric materials. It is now well established that high mechanical properties are obtained when preparing the nanocomposite by casting/evaporation methods and using CNC contents above the percolation threshold. This phenomenon results from the formation of a stiff CNC network within the matrix meaning that the properties of the matrix play only a limited role on the mechanical properties of the material when the matrix is in the rubbery state. In subpercolation concentration or when using a different processing technique, the level of understanding is less clear, mainly when the CNC-induced crystallization of the matrix interferes with the reinforcing mechanism. In this study, we used CNCs with different aspect ratios to prepare nanocomposites by extrusion with polybutyrate adipate terephthalate as matrix. The impact of CNC on the crystallinity of the matrix and mechanical properties of the nanocomposite has been investigated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2284–2297

Cellulose nanocrystals (CNCs) were isolated from soy hulls by acid sulfuric hydrolysis. The resulting CNCs were characterized using TEM, AFM, WAXS, elemental analysis and TGA. The CNCs have a high crystallinity, specific surface area and aspect ratio. The aspect ratio (around 100) is the largest ever reported in the literature for a plant cellulose source. These CNCs were used as a reinforcing phase to prepare nanocomposite films by casting/evaporation using natural rubber as matrix. The mechanical properties were studied in both the linear and non-linear ranges. The reinforcing effect was higher than the one observed for CNCs extracted from other sources. It may be assigned not only to the high aspect ratio of these CNCs but also to the stiffness of the percolating nanoparticle network formed within the polymer matrix. Moreover, the sedimentation of CNCs during the evaporation step was found to play a crucial role on the mechanical properties.

Composite materials were prepared by extrusion and injection molding from polybutyrate adipate terephthalate (PBAT) and high aspect ratio cellulose nanocrystals (CNCs) extracted from capim dourado fibers. Three CNC contents were used, corresponding to 0.5, 1, and 2 times the theoretical percolation threshold. Small-amplitude oscillary shear (SAOS) experiments show that as the CNC content increases, a more elastic behavior is observed but no percolating network can form within the polymeric matrix as a result of the high shear rates involved during the injection-molding process. Annealing of the samples at 170 °C was performed, and the possible reorganization of the nanofiller was investigated. This reorganization was further elucidated using 2D-SAOS and creep experiments.

Natural rubber (NR) latex particles were oxidized using KMnO4 as oxidant to promote the insertion of hydroxyl groups in the surface polyisoprene chains. Different degrees of oxidation were investigated. Both unoxidized and oxidized NR (ONR) latex were used to prepare nanocomposite films reinforced with cellulose nanocrystals (CNCs) by casting/evaporation. The oxidation of NR was carried out to promote chemical interactions between the hydroxyl groups of ONR with those of CNCs through hydrogen bonding. The effect of the degree of oxidation of the NR latex on the rheological behavior of CNC/NR and CNC/ONR suspensions, as well as on the mechanical, swelling and thermal properties of ensuing nanocomposites was investigated. Improved properties were observed for intermediate degrees of oxidation but they were found to degrade for higher oxidation levels.

Cellulose nanocrystals (CNCs) were produced from eucalyptus wood pulp using three different methods: (i) classical sulphuric acid hydrolysis (CN-I), (ii) acid hydrolysis of cellulose previously mercerized by alkaline treatment (MCN-II), and (iii) solubilization of cellulose in sulphuric acid and subsequent recrystallization in water (RCN-II). The three types of CNCs exhibited different morphologies and crystalline structures that were characterized using complementary imaging, diffraction and spectroscopic techniques. CN-I corresponded to the type I allomorph of cellulose while MCN-II and RCN-II corresponded to cellulose II. CN-I and MCN-II CNCs were acicular particles composed of a few laterally-bound elementary crystallites. In both cases, the cellulose chains were oriented parallel to the long axis of the particle, although they were parallel in CN-I and antiparallel in MCN-II. RCN-II particles exhibited a slightly tortuous ribbon-like shape and it was shown that the chains lay perpendicular to the particle long axis and parallel to their basal plane. The unique molecular and crystal structure of the RCN-II particles implies that a higher number of reducing chain ends are located at the surface of the particles, which may be important for subsequent chemical modification. While other authors have described nanoparticles prepared by regeneration of short-chain cellulose solutions, no detailed description was proposed in terms of particle morphology, crystal structure and chain orientation. We provide such a description in the present paper.