Showing papers by "Orlando J. Rojas published in 2012"
01 Mar 2012
TL;DR: Cellulose nanocrystals from ramie fibers are studied as stabilizers of oil-in-water emulsions and the effect of temperature can be counterbalanced with the addition of salt which is explained by the reduction of electrostatic and steric interactions of poly(NIPAM)-g-CNCs at the oil-water interface.
Abstract: Cellulose nanocrystals (CNCs) from ramie fibers are studied as stabilizers of oil-in-water emulsions. The phase behavior of heptane and water systems is studied, and emulsions stabilized by CNCs are analyzed by using drop sizing (light scattering) and optical, scanning, and freeze-fracture electron microscopies. Water-continuous Pickering emulsions are produced with cellulose nanocrystals (0.05–0.5 wt%) grafted with thermo-responsive poly(NIPAM) brushes (poly(NIPAM)-g-CNCs). They are observed to be stable during the time of observation of 4 months. In contrast, unmodified CNCs are unable to stabilize heptane-in-water emulsions. After emulsification, poly(NIPAM)-g-CNCs are observed to form aligned, layered structures at the oil–water interface. The emulsions stabilized by poly(NIPAM)-g-CNCs break after heating at a temperature above the LCST of poly(NIPAM), which is taken as indication of the temperature responsiveness of the brushes installed on the particles and thus the responsiveness of the Pickering emulsions. This phenomenon is further elucidated via rheological measurements, in which viscosities of the Pickering emulsions increase on approach of the low critical solution temperature of poly(NIPAM). The effect of temperature can be counterbalanced with the addition of salt which is explained by the reduction of electrostatic and steric interactions of poly(NIPAM)-g-CNCs at the oil–water interface.
312 citations
TL;DR: In this paper, the tensile index, elongation and elastic modulus of nanofibrillated cellulose (NFC) and nanopaper were compared and the effect of residual cell wall components accessed.
Abstract: Unbleached (UN), oxygen-delignified and fully-bleached (FB) birch fibers with a residual lignin content of ca. 3, 2 and <1 %, respectively, were used to produce nanofibrillated cellulose (NFC) and nanopaper by using an overpressure device. The tensile index, elongation and elastic modulus of nanopaper were compared and the effect of residual cell wall components accessed. Under similar manufacturing conditions, UN NFC produced nanopaper with a density of 0.99 g/cm3, higher than that from FB NFC (0.7 g/cm3). This translated in much lower air permeability in the case of UN nanopaper (1 and 11 mL/min for UN and FB samples, respectively). Fundamentally, these observations are ascribed to the finer fibrils produced during microfluidization of UN fibers compared to those from lower yield counterparts (AFM roughness of 8 and 17 nm and surface areas of 124 and 98 m2/g for NFC from UN and FB fibers, respectively). As a result, values of stress at break and energy absorption of nanopaper from high yield fibers are distinctively higher than those from fully bleached NFC. Interactions of water with the surface and bulk material were affected by the chemical composition and structure of the nanofibrils. While UN nanopaper presented higher water contact angles their sorption capacity (and rate of water absorption) was much higher than those measured for nanopaper from FB NFC. These and other observations provided in this contribution are proposed to be related to the mechanoradical scavenging capacity of lignin in high shear microfluidization and the presence of residual heteropolysaccharides.
198 citations
TL;DR: A bacterial strain isolated from the fermentation of Colombian homemade vinegar was investigated as a new source of bacterial cellulose (BC) and the morphological, structural and chemical characteristics of the cellulose produced are similar to those expected for BC.
184 citations
TL;DR: Different cellulose pulps produced from sulfur-free chemical treatments of Empty Palm Fruit Bunch Fibers, a by-product from palm oil processing, generated distinct chemical and morphological characteristics and ensuing nanopaper properties that opens the possibility for valorization of such widely available bioresource.
174 citations
TL;DR: In this article, ultrathin films of aligned cellulose nanocrystals (CNCs) were assembled on mica supports by using electric field-assisted shear, and the relationship between polarization gradients and strain mechanics of the obtained films was examined by monitoring their deflection with an atomic force microscope operated in contact mode.
Abstract: Ultrathin films of aligned cellulose nanocrystals (CNCs) were assembled on mica supports by using electric field-assisted shear. The relationship between polarization gradients and strain mechanics of the obtained films was examined by monitoring their deflection with an atomic force microscope operated in contact mode. The piezoelectric response of the films was ascribed to the collective contribution of the asymmetric crystalline structure of the cellulose crystals. The magnitude of the effective shear piezoelectric constant (d25) of highly ordered CNC films was determined to be 2.1 A/V, which is comparable to that of a reference film of a piezoelectric metal oxide.
170 citations
TL;DR: The thermal stability of the system was observed to increase owing to a strong interaction of the lignin-PVA matrix with the dispersed CNCs, mainly via hydrogen bonding, as observed in Fourier transform infrared spectroscopy experiments.
170 citations
TL;DR: A new method to modify films of nanofibrillated cellulose (NFC) to produce non-porous, water-resistant substrates for diagnostics and demonstrates that antihuman IgG can be immobilized on the activated NFC surface using commercial piezoelectric inkjet printing.
Abstract: We introduce a new method to modify films of nanofibrillated cellulose (NFC) to produce non-porous, water-resistant substrates for diagnostics. First, water resistant NFC films were prepared from mechanically disintegrated NFC hydrogel, and then their surfaces were carboxylated via TEMPO-mediated oxidation. Next, the topologically functionalized film was activated via EDS/NHS chemistry, and its reactivity verified with bovine serum albumin and antihuman IgG. The surface carboxylation, EDC/NHS activation and the protein attachment were confirmed using quartz crystal microbalance with dissipation, contact angle measurements, conductometric titrations, X-ray photoelectron spectroscopy and fluorescence microscopy. The surface morphology of the prepared films was investigated using confocal laser scanning microscopy and atomic force microscopy. Finally, we demonstrate that antihuman IgG can be immobilized on the activated NFC surface using commercial piezoelectric inkjet printing.
129 citations
TL;DR: In this article, all-cellulose composite fibers were produced by electrospinning dispersions containing cellulose acetate (CA) and cellulose nanocrystals (CNCs), which were obtained after dispersion of CA with different degrees of substitution in a binary mixture of organic solvents.
Abstract: All-cellulose composite fibers were produced by electrospinning dispersions containing cellulose acetate (CA) and cellulose nanocrystals (CNCs). Precursor polymer matrices were obtained after dispersion of CA with different degrees of substitution in a binary mixture of organic solvents. The obtained fibers of CA loaded with CNCs had typical widths in the nano- and micro-scale and presented a glass transition temperature of 145 °C. The CA component was converted to cellulose by using alkaline hydrolysis to yield all-cellulose composite fibers that preserved the original morphology of the precursor system. Together with Fourier Transform Infrared Spectroscopy fingerprints the thermal behavior of the all-cellulose composite fibers indicated complete conversion of cellulose acetate to regenerated cellulose. Noticeable changes in the thermal, surface and chemical properties were observed upon deacetylation. Not only the thermal transitions of cellulose acetate disappeared but the initial water contact angle of the web was reduced drastically. Overall, we propose a simple method to produce all-cellulose composite fibers which are expected to display improved thermo-mechanical properties while keeping the unique features of the cellulose polymer.
105 citations
TL;DR: In this article, the adsorption and chemical conjugation of avidin and its deglycosylated form, neutravidin, on films of regenerated and nanofibrillar cellulose were investigated.
89 citations
TL;DR: The importance of molecular interactions and phase separation on the surface properties of fibers from lignin as an abundant raw material for the fabrication of new functional materials is highlighted.
Abstract: Sub-100 nm resolution local thermal analysis, X-ray photoelectron spectroscopy (XPS), and water contact angle (WCA) measurements were used to relate surface polymer distribution with the composition of electrospun fiber mats and spin coated films obtained from aqueous dispersions of lignin, polyvinyl alcohol (PVA), and cellulose nanocrystal (CNC). Defect-free lignin/PVA fibers were produced with radii which were observed to increase with lignin concentration and with the addition of CNCs. XPS and WCA results indicate a nonlinear relationship between the surface and the bulk compositions. A threshold around 50 wt % bulk composition was identified in which extensive partitioning of PVA and lignin components occurred on the surface below and above this value. In 75:25 wt % lignin/PVA solvent cast films, phase separated domains were observed. Using nanoscale thermal analyses, the continuous phase was determined to be lignin-rich and the discontinuous phase had a lignin/PVA dispersion. Importantly, the size of...
68 citations
TL;DR: It is concluded that sensors based on the proposed ultrathin films of lignocellulose can facilitate a better understanding of the complex events that occur during bioconversion of cellulosic biomass.
TL;DR: Wood-derived cellulosic fibers prepared in different ways were successfully employed to absorb simulated crude oil, demonstrating their possible use as absorbents in the case of oil spills.
Abstract: Wood-derived cellulosic fibers prepared in different ways were successfully employed to absorb simulated crude oil, demonstrating their possible use as absorbents in the case of oil spills. When dry fibers were used, the highest sorption capacity (six parts of oil per unit mass of fiber) was shown by bleached softwood kraft fibers, compared to hardwood bleached kraft and softwood chemithermomechanical pulp(CTMP) fibers. Increased refining of CTMP fibers decreased their oil uptake capacity. When the fibers were soaked in water before exposure to the oil, the ability of the unmodified kraft fibers to sorb oil was markedly reduced, whereas the wet CTMP fibers were generally more effective than the wet kraft fibers. Predeposition of lignin onto the surfaces of the bleached kraft fibers improved their ability to take up oil when wet. Superior ability to sorb oil in the wet state was achieved by pretreating the kraft fibers with a hydrophobic sizing agent, alkenylsuccinic anhydride (ASA). Contact angle tests on a model cellulose surface showed that some of the sorption results onto wetted fibers could be attributed to the more hydrophobic nature of the fibers after treatment with either lignin or ASA.
TL;DR: The results suggest that amphiphilic coatings suppress significantly adsorption of proteins as compared with PP fibers or PP surfaces coated with PHEMA brushes.
TL;DR: In situ lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to probe the lubrication behavior of an aqueous solution of poly(oxyethylene)-poly(oxypropylene)-poly (oxyethylenes) (PEO-PPO-PEO) symmetric triblock copolymer on thin films of polypropylene (PP), polyethylene (PE), and cellulose as discussed by the authors.
Abstract: In situ lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to probe the lubrication behavior of an aqueous solution of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) (PEO-PPO-PEO) symmetric triblock copolymer on thin films of polypropylene (PP), polyethylene (PE), and cellulose. LFM experiments were carried out while the substrates were immersed in water and in solutions of the copolymer. The friction coefficient on PP and PE was reduced after adsorption from the PEO-PPO-PEO aqueous solution while the opposite effect was observed for cellulose surfaces. A critical normal loading force, at which the friction coefficient of the lubricated and unlubricated surfaces is equal, was identified and related to the affinity of the polymer with the substrate. Further experiments were performed to mimic practical operations involving lubricant addition during manufacturing and postprocessing removal. XPS was used to verify the presence of the lubricant on the polymeric substra...
TL;DR: Hydrophilic coatings were produced on flat hydrophobic substrates featuring n-octadecyltrichlorosilane (ODTS) and synthetic polypropylene (PP) nonwoven surfaces through the adsorption of denatured proteins, yielding enhanced wettability.
TL;DR: The findings suggest that deconstruction of the cell wall to nanofibrils is an effective pretreatment to facilitate rapid and complete cellulose bioconversion.
Abstract: Rapid enzymatic saccharification of lignocellulosic nanofibrils (LCNF) was investigated by monitoring nanoscale changes in mass via quartz crystal microgravimetry and also by measuring reducing sugar yields. In only a few minutes LCNF thin films were completely hydrolyzed upon incubation in multi- component enzyme systems. Conversion to sugars and oligosac- charides of LCNF dispersed in water occurred in about 4 h (50 °C, pH 5). In contrast, a conversion of only 57% was observed for partially crystalline cellulose (Avicel) after 9 h, under same experimental conditions. Under conditions of high enzyme loading the presence of residual lignin and other macromolecules in the cell wall of LCNF did not appear to affect negatively the recorded high hydrolysis rates. Overall, our findings suggest that deconstruction of the cell wall to nanofibrils is an effective pretreatment to facilitate rapid and complete cellulose bioconversion.
TL;DR: A new method to produce molecular models for amorphous surface layers of polypropylene and cellulose was developed, which involved the use of a "soft" confining layer comprised of a xenon crystal that compacts the polymers into a density distribution and a degree of molecular surface roughness that corresponds well to experimental values.
Abstract: The goal of this work was to use molecular dynamics (MD) simulations to build amorphous surface layers of polypropylene (PP) and cellulose and to inspect their physical and interfacial properties. A new method to produce molecular models for these surfaces was developed, which involved the use of a “soft” confining layer comprised of a xenon crystal. This method compacts the polymers into a density distribution and a degree of molecular surface roughness that corresponds well to experimental values. In addition, calculated properties such as density, cohesive energy density, coefficient of thermal expansion, and the surface energy agree with experimental values and thus validate the use of soft confining layers. The method can be applied to polymers with a linear backbone such as PP as well as those whose backbones contain rings, such as cellulose. The developed PP and cellulose surfaces were characterized by their interactions with water. It was found that a water nanodroplet spreads on the amorphous cel...
TL;DR: In this article, a 3D non-woven microfibre structure was constructed by electrospinning hydrophobised cellulose derivatives, trimethylsilyl cellulose (TMSC) and cellulose triacetate (CTA), dissolved in a common solvent.
Abstract: Morphologies featured in bicomponent 2D ultrathin films were reproduced on 3D non-woven microfibre structures. Fibre networks were constructed by electrospinning hydrophobised cellulose derivatives, trimethylsilyl cellulose (TMSC) and cellulose triacetate (CTA), dissolved in a common solvent. Diverse morphologies were obtained depending on the polymer blend ratio: electrospinning of TMSC produced non-continuous micron fibres with shallow dints, TMSC/CTA 5 : 1 flat micron fibres with regular pore arrays, TMSC/CTA 1 : 1 wrinkled micron fibres decorated with shallow dints and occasional larger pores, TMSC/CTA 1 : 5 flat micron fibres with ellipsoidal porous structures and finally, CTA that led to smooth micron and submicron fibres. The fibre mats were ultra-hydrophobic with characteristic water contact angles of ca. 150 degrees. In addition, they were characterised by high contact angle hysteresis, and water droplets adhered to the substrate even after tilting the system upside down. Through conversion of the respective components to cellulose, chemical and adsorption properties of the fibre networks could be tuned without significantly altering the large-scale network morphology.
TL;DR: The concept proposed in this research is expected to open opportunities in fluid sorption in fiber systems for biomass pretreatment, and delivery of hydrophilic or lipophilic moieties in porous, lignocellulosics.
TL;DR: In this article, the authors report on the kinetics and extent of adsorption on silica and cellulose surfaces of glycin surfaces of soybeans and show that they can be used in different nonfood applications.
TL;DR: It is indicated that aqueous triblock copolymers of poly(ethylene oxide) and poly(propylene oxide) (PPO) (Pluronics, EO(m)PO(n)EO(m)) act as a boundary lubricant for hydrophobic surfaces but not for hydphilic ones.
Abstract: The MesoDyn method is used to investigate associative structures in aqueous solution of a nonionic triblock copolymer consisting of poly(propylene oxide) capped on both ends with poly(ethylene oxide) chains. The effect of adsorbing (hydrophobic) and nonadsorbing (hydrophilic) solid surfaces in contact with aqueous solutions of the polymer is elucidated. The macromolecules form self-assembled structures in solution. Confinement under shear forces is investigated in terms of interfacial behavior and association. The formation of micelles under confinement between hydrophilic surfaces occurs faster than in bulk aqueous solution while layered structures assemble when the polymers are confined between hydrophobic surfaces. Micelles are deformed under shear rates of 1 μs −1 and eventually break to form persistent, adsorbed layered structures. As a result, surface damage under frictional forces is prevented. Overall, this study indicates that aqueous triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) (Pluronics, EOmPOnEOm) act as a boundary lubricant for hydrophobic surfaces but not for hydrophilic ones.
TL;DR: Values of short span compression and tensile strength were the prime criteria for comparison based on industrial considerations and indicated that a 1 part soy protein to 3 parts cationic starch hybrid system resulted in the highest strength increase in comparison to solely either the soy protein or the cationIC starch as dry strength additives.
Abstract: A series of experiments were conducted on recycled pulp samples for the novel purpose of determining the efficacy of employing soy protein flour to increase the strength of dry paper. Values of short span compression and tensile strength were the prime criteria for comparison based on industrial considerations. Various conditions were considered to uncover effective schemes for applying the soy proteins under industrial-like papermaking conditions including alkaline versus acidic as well as high or low ionic content papermaking conditions. A hybrid system of starch, a dry strength additive currently used in paper furnishes, and soy protein was considered to study the possible existence of any synergistic chemical effects. Results indicated that a 1 part (by mass) soy protein to 3 parts cationic starch hybrid system resulted in the highest strength increase in comparison to solely either the soy protein or the cationic starch as dry strength additives.
TL;DR: Overall, the solution and adsorption properties of nonionic symmetric triblock copolymers in the presence of alcohols are rationalized by changes in solvency and the hydrophobic effect.
Abstract: This study investigates the effect of alcohols on the solution and adsorption properties of symmetric triblock nonionic copolymers comprising blocks of ethylene oxide (EO) and propylene oxide (PO) (EO(37)PO(56)EO(37)). The cloud point, surface tension, critical micelle concentration (CMC), and maximum packing at the air-water interface are determined, and the latter is compared to the amount of polymer that adsorbs from solution onto polypropylene (PP) and cellulose surfaces. The interaction energy and radius of micelles are calculated by using molecular dynamics (MD) simulations. Equivalent MD bead parameters were used in dynamic density functional theory (DDFT) simulations to study the influence of alcohols on the phase behavior of EO(37)PO(56)EO(37) and its adsorption on PP from aqueous solutions. The simulation results agree qualitatively with the experimental observations. Ethanol acts as a good cosolvent for EO(37)PO(56)EO(37) and reduces the amount of EO(37)PO(56)EO(37) that adsorbs on PP surfaces; however, little or no influence is observed on the adsorption on cellulose. Interestingly, longer chain alcohols, such as 1-pentanol, produce the opposite effect. Overall, the solution and adsorption properties of nonionic symmetric triblock copolymers in the presence of alcohols are rationalized by changes in solvency and the hydrophobic effect.