José Manoel Marconcini

Cellulose micro/nanofibres from Eucalyptus kraft pulp: Preparation and properties

There is growing interest in cellulose nanofibres from renewable sources for several industrial applications. However, there is a lack of information about one of the most abundant cellulose pulps: bleached Eucalyptus kraft pulp. The objective of the present work was to obtain Eucalyptus cellulose micro/nanofibres by three different processes, namely: refining, sonication and acid hydrolysis of the cellulose pulp. The refining was limited by the low efficiency of isolated nanofibrils, while sonication was more effective for this purpose. However, the latter process occurred at the expense of considerable damage to the cellulose structure. The whiskers obtained by acid hydrolysis resulted in nanostructures with lower diameter and length, and high crystallinity. Increasing hydrolysis reaction time led to narrower and shorter whiskers, but increased the crystallinity index. The present work contributes to the different widespread methods used for the production of micro/nanofibres for different applications.

Biodegradable polymer blends based on corn starch and thermoplastic chitosan processed by extrusion.

Blends of thermoplastic cornstarch (TPS) and chitosan (TPC) were obtained by melt extrusion. The effect of TPC incorporation in TPS matrix and polymer interaction on morphology and thermal and mechanical properties were investigated. Possible interactions between the starch molecules and thermoplastic chitosan were assessed by XRD and FTIR techniques. Scanning Electron Microscopy (SEM) analyses showed a homogeneous fracture surface without the presence of starch granules or chitosan aggregates. Although the incorporation of thermoplastic chitosan caused a decrease in both tensile strength and stiffness, films with better extensibility and thermal stability were produced.

Ecotoxicological effects of carbon nanotubes and cellulose nanofibers in Chlorella vulgaris.

BackgroundMWCNT and CNF are interesting NPs that possess great potential for applications in various fields such as water treatment, reinforcement materials and medical devices. However, the rapid dissemination of NPs can impact the environment and in the human health. Thus, the aim of this study was to evaluate the MWCNT and cotton CNF toxicological effects on freshwater green microalgae Chlorella vulgaris.ResultsExposure to MWCNT and cotton CNF led to reductions on algal growth and cell viability. NP exposure induced reactive oxygen species (ROS) production and a decreased of intracellular ATP levels. Addition of NPs further induced ultrastructural cell damage. MWCNTs penetrate the cell membrane and individual MWCNTs are seen in the cytoplasm while no evidence of cotton CNFs was found inside the cells. Cellular uptake of MWCNT was observed in algae cells cultured in BB medium, but cells cultured in Seine river water did not internalize MWCNTs.ConclusionsUnder the conditions tested, such results confirmed that exposure to MWCNTs and to cotton CNFs affects cell viability and algal growth.

Brucite nanoplates reinforced starch bionanocomposites

In this paper the mechanical reinforcement of nano-sized brucite, Mg(OH)(2) in a series of bionanocomposite films based on starch was investigated. Brucite nanoplates with an aspect ratio of 9.25 were synthesized by wet precipitation and incorporated into starch matrices at different concentrations (0-7.5 wt.%). Scanning electron microscopy revealed a high degree of nanoplate dispersion within the starch bionanocomposites and good interfacial adhesion between the filler and matrix. The brucite nanoplates formed agglomerates at high concentrations. The reinforcement factor values of the bionanocomposites were higher than the values predicted from the Halphin-Tsai model, which was attributed mainly to the high surface area of the nanoplates. Brucite (1 wt.%) nearly doubled the elastic modulus of starch films. Thermogravimetric analyses indicated some interaction between starch and the brucite that modified their decomposition profiles. Mechanical tests of glycerol plasticized bionanocomposites showed that the reinforcing efficiency of brucite remained high even at 10 wt.% and 20 wt.% of plasticizer.

Evaluation of reaction factors for deposition of silica (SiO2) nanoparticles on cellulose fibers

This study aimed to evaluate reaction conditions for deposition of SiO2 nanoparticles on the surface of cellulose fibers and their influence on moisture adsorption of the hybrid organic-inorganic material formed. SiO2 nanoparticle deposition was carried out with the sol-gel process testing four reaction times (2, 12, 18, and 24h) and three contents of the tetraethyl-orthosilicate (TEOS) precursor (1.9, 4.2 and 8.4g g(-1) of cellulose fiber). Modification time and TEOS content directly influence the amount of Si deposited on the fiber surface, nanoparticle diameter distribution, thermal stability, and resistance to moisture adsorption. There is a tendency of slight increase of nanoparticle size and the amount of Si deposited with increasing reaction time. SiO2 nanoparticles were bonded on the surface of the cellulose fibers and are able to improve thermal stability of the material, increasing onset degradation temperature. The moisture adsorption capacity of the modified cellulose fiber was reduced up to 50%.

Nutraceutically Inspired Pectin–Mg(OH)2 Nanocomposites for Bioactive Packaging Applications

This paper reports on the development of bioactive edible films based on pectin as a dietary matrix and magnesium hydroxide (Mg(OH)2) nanoplates as a reinforcing filler. Nanocomposites of high-methoxyl (HM) and low-methoxyl (LM) pectins were prepared using the casting method at concentrations of Mg(OH)2 ranging from 0.5 to 5 wt %. Atomic force microscopy and FTIR spectroscopy were employed to characterize the nanocomposite structure. The tensile properties and thermal stability of the nanocomposites were also examined to ascertain the effect of Mg(OH)2 inclusion and degree of methoxylation. The results provided evidence that the Mg(OH)2 nanoplates were uniformly dispersed and interacted strongly with the film matrix. The mechanical and thermal properties were significantly improved in the nanocomposite films compared to the control. Mg(OH)2 nanoplates were more effective in improving properties of LM pectin. Preliminary migration studies using arugula leaves confirmed that pectin-Mg(OH)2 nanocomposites can release magnesium hydroxide by contact, demonstrating their potential for magnesium supplementation in bioactive packaging.

Starch/fiber/poly(lactic acid) foam and compressed foam composites

Composites of starch, fiber, and poly(lactic acid) (PLA) were made using a foam substrate formed by dehydrating starch or starch/fiber gels. PLA was infiltrated into the dry foam to provide better moisture resistance. Foam composites were also compressed into plastics using force ranging from 4–76 MPa. Tensile strength increased with increasing compression force applied to the foam sample. The samples became increasingly transparent with compression forces approaching 76 MPa. PLA infusion into starch and starch/fiber foam composites resulted in PLA content of 20% and 33%, respectively and provided moisture resistance to the outer regions of the foam samples. The PLA-infused foam samples increased in tensile strength when compressed up to 29 MPa. The PLA-infused compressed samples had greater moisture resistance and had intermediate rates of mineralization compared to the control samples.

How the chemical nature of Brazilian hardwoods affects nanofibrillation of cellulose fibers and film optical quality

A wide range of alternative cellulose fibers for the development of new green nanomaterials can be obtained from Brazil’s natural resources. The objective of the work is to evaluate the influence of the chemical composition of hardwoods on the nanofibrillation process and optical quality of nanofiber films. Wood wastes were selected from three native Amazonian species and from exotic planted Eucalyptus grandis species. Wood sawdust was submitted to chemical alkali and bleaching pretreatments. Nanofibers were produced from the bleached fibers after 10, 20, 30 and 40 passes through a Super Mass Colloider grinder, and films were produced by the casting method. Raw sawdust, alkali-treated fibers and bleached fibers were evaluated by the major chemical components, syringyl/guaiacyl ratio, Fourier transformed infrared spectroscopy, oxygen/carbon ratio and scanning electron microscopy. Morphological characteristics of nanofibers and films were analyzed by transmission and scanning electron microscopies. Optical parameters studied for the films were the opacity, total color difference and b value. The main challenge to delignification was attributed to the low syringyl/guaiacyl ratio. The different chemical natures of Amazonian and eucalyptus hardwoods greatly affected pretreatments and, consequently, the nanofibrillation and optical quality of the films. Consequences observed for highly purified cellulose starting fibers are: (1) lower diameters for individual nanofiber elements; (2) fewer opaque and colored films produced from nanofibers; (3) a tendency to stabilization of the nanofibrillation process after 20 passes through the grinder. For species whose chemical nature hindered cellulose purification, the increased number of passes through the grinder continuously decreased the opacity.

Biocomposite of cassava starch reinforced with cellulose pulp fibers modified with deposition of silica (SiO 2 ) nanoparticles

Eucalyptus pulp cellulose fibers were modified by the sol-gel process for SiO2 superficial deposition and used as reinforcement of thermoplastic starch (TPS). Cassava starch, glycerol, and water were added at the proportion of 60/26/14, respectively. For composites, 5% and 10% (by weight) of modified and unmodified pulp fibers were added before extrusion. The matrix and composites were submitted to thermal stability, tensile strength, moisture adsorption, and SEM analysis. Micrographs of the modified fibers revealed the presence of SiO2 nanoparticles on fiber surface. The addition of modified fibers improved tensile strength in 183% in relation to matrix, while moisture adsorption decreased 8.3%. Such improvements were even more effective with unmodified fibers addition. This result was mainly attributed to poor interaction between modified fibers and TPS matrix detected by SEM analysis.

Solid state ball milling as a green strategy to improve the dispersion of cellulose nanowhiskers in starch-based thermoplastic matrices

This study reports the use of solid state ball milling (SSBM) for dispersing cellulose nanowhiskers (CNWs) in starch-based thermoplastics. Prior to conventional drying, interwhiskers agglomeration was minimized by coating the CNWs with pectin, a vegetable hydrocolloid polysaccharide. SSBM and melt-processing were employed to prepare the nanocomposites. A strong correlation between mechanical reinforcement and nanowhisker dispersion was proven by results of tensile tests, scanning electron microscopy and dynamical mechanical thermal analysis. The starch–pectin–CNW nanocomposites showed high dispersion of the nano-sized filler in the matrix, thus SSBM shows great potential when compared to sol–gel, casting/evaporation and other methods to disperse these promising nanoparticles.