Hexavalent Chromium Removal from Industrial Wastewater by Adsorption and Reduction onto Cationic Cellulose Nanocrystals.

Cationic cellulose nanocrystals (CCNC) are lignocellulosic bio-nanomaterials that present large, specific areas rich with active surface cationic groups. This study shows the adsorption removal of hexavalent chromium (Cr(VI)) from industrial wastewaters by the CCNC. The CCNC were synthetized through periodate oxidation and Girard's reagent-T cationization. The high value of CCNCs cationic groups and anionic demand reveal probable nanocrystal-Cr(VI) attraction. Adsorption was performed with synthetic Cr(VI) water at different pH, dosage, Cr(VI) concentration and temperature. Fast removal of Cr(VI) was found while operating at pH 3 and 100 mg·L-1 of dosage. Nevertheless, a first slower complete removal of chromium was achieved by a lower CCNC dosage (40 mg·L-1). Cr(VI) was fully converted by CCNC into less-toxic trivalent species, kept mainly attached to the material surface. The maximum adsorption capacity was 44 mg·g-1. Two mechanisms were found for low chromium concentrations (Pseudo-first and pseudo-second kinetic models and continuous growth multi-step intraparticle) and for high concentrations (Elovich model and sequential fast growth-plateau-slow growth intraparticle steps). The Sips model was the best-fitting isotherm. Isotherm thermodynamic analysis indicated a dominant physical sorption. The Arrhenius equation revealed an activation energy between physical and chemical adsorption. CCNC application at selected conditions in industrial wastewater achieved a legal discharge limit of 40 min.

Gaining control of bacterial cellulose colonization by polyhydroxyalkanoate-producing microorganisms to develop bioplasticized ultrathin films.

Synergistic methodological strategies based on the fields of microbial biotechnology and materials science open up an enormous range of possibilities for the sustainable production of advanced materials with predictable properties. This study shows how naturally produced polyhydroxyalkanoate (PHA) particles are introduced into bacterial cellulose (BC) driven by their bacterial producers. Thanks to an extensive knowledge of the internal structure of BC, it was possible to control the colonization process, i.e. loading and localization of PHA. A subsequent acid treatment favored the PHA-BC bonding at the position reached by the bacteria. These biodegradable films showed improved mechanical and barrier properties even with respect to reference plastic films 8 times thicker, reaching a Young's modulus 4.25 times higher and an oxygen permeability 3 times lower than those of polyethylene terephthalate (PET) films. Owing to the versatility of the method, a wide variety of materials can be developed for very diverse fields of application.

Critical comparison of the properties of cellulose nanofibers produced from softwood and hardwood through enzymatic, chemical and mechanical processes.

Current knowledge on the properties of different types of cellulose nanofibers (CNFs) is fragmented. Properties variation is very extensive, depending on raw materials, effectiveness of the treatments to extract the cellulose fraction from the lignocellulosic biomass, pretreatments to facilitate cellulose fibrillation and final mechanical process to separate the microfibrils. Literature offers multiple parameters to characterize the CNFs prepared by different routes. However, there is a lack of an extensive guide to compare the CNFs. In this study, we perform a critical comparison of rheological, compositional, and morphological features of CNFs, produced from the most representative types of woody plants, hardwood and softwood, using different types and intensities of pretreatments, including enzymatic, chemical and mechanical ones, and varying the severity of mechanical treatment focusing on the relationship between macroscopic and microscopic parameters. This structured information will be exceedingly useful to select the most appropriate CNF for a certain application based on the most relevant parameters in each case.

When microbial biotechnology meets material engineering.

Bacterial biopolymers such as bacterial cellulose (BC), alginate or polyhydroxyalkanotes (PHAs) have aroused the interest of researchers in many fields, for instance biomedicine and packaging, due to their being biodegradable, biocompatible and renewable. Their properties can easily be tuned by means of microbial biotechnology strategies combined with materials science. This provides them with highly diverse properties, conferring them non-native features. Herein we highlight the enormous structural diversity of these macromolecules, how are they produced, as well as their wide range of potential applications in our daily lives. The emergence of new technologies, such as synthetic biology, enables the creation of next-generation-advanced materials presenting smart functional properties, for example the ability to sense and respond to stimuli as well as the capacity for self-repair. All this has given rise to the recent emergence of biohybrid materials, in which a synthetic component is brought to life with living organisms. Two different subfields have recently garnered particular attention: hybrid living materials (HLMs), such as encapsulation or bioprinting, and engineered living materials (ELMs), in which the material is created bottom-up with the use of microbial biotechnology tools. Early studies showed the strong potential of alginate and PHAs as HLMs, whilst BC constituted the most currently promising material for the creation of ELMs.

Correlation between rheological measurements and morphological features of lignocellulosic micro/nanofibers from different softwood sources.

The transition of nanocellulose production from laboratory to industrial scale requires robust monitoring systems that keeps a quality control along the production chain. The present work aims at providing a deeper insight on the main factors affecting the rheological behavior of (ligno)cellulose micro/nanofibers (LCMNFs) and cellulose micro/nanofibers (CMNFs) and how they could correlate with their characteristics. To this end, 20 types of LCMNFs and CMNFs were produced combining mechanical refining and high-pressure homogenization from different raw materials. Aspect ratio and bending capacity of the fibrils played a key role on increasing the viscosity of the suspensions by instigating the formation of entangled structures. Surface charge, reflected by the cationic demand, played opposing effects on the viscosity by reducing the fibrils' contact due to repulsive forces. The suspensions also showed increasing shear-thinning behavior with fibrillation degree, which was attributed to increased surface charge and higher water retention capacity, enabling the fibrils to slide past each other more easily when subjected to flow conditions. The present work elucidates the existing relationships between LCMNF/CMNF properties and their rheological behavior, considering fibrillation intensity and the initial raw material characteristics, in view of the potential of rheological measurements as an industrial scalable characterization technology.

Enhanced Morphological Characterization of Cellulose Nano/Microfibers through Image Skeleton Analysis.

The present paper proposes a novel approach for the morphological characterization of cellulose nano and microfibers suspensions (CMF/CNFs) based on the analysis of eroded CMF/CNF microscopy images. This approach offers a detailed morphological characterization and quantification of the micro and nanofibers networks present in the product, which allows the mode of fibrillation associated to the different CMF/CNF extraction conditions to be discerned. This information is needed to control CMF/CNF quality during industrial production. Five cellulose raw materials, from wood and non-wood sources, were subjected to mechanical, enzymatic, and (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)-mediated oxidative pre-treatments followed by different homogenization sequences to obtain products of different morphologies. Skeleton analysis of microscopy images provided in-depth morphological information of CMF/CNFs that, complemented with aspect ratio information, estimated from gel point data, allowed the quantification of: (i) fibers peeling after mechanical pretreatment; (ii) fibers shortening induced by enzymes, and (iii) CMF/CNF entanglement from TEMPO-mediated oxidation. Being mostly based on optical microscopy and image analysis, the present method is easy to implement at industrial scale as a tool to monitor and control CMF/CNF quality and homogeneity.

In-depth characterization of the aggregation state of cellulose nanocrystals through analysis of transmission electron microscopy images.

Dispersion of cellulose nanocrystals (CNCs) is of utmost importance to guarantee their reliable application. Nevertheless, there is still no consensual method to characterize CNC aggregation. The hypothesis of this paper is that dispersion could be quantified through the classification of aggregates detected in transmission electron microscopy images. k-Means was used to classify image particulate elements of five CNC samples into groups according to their geometric features. Particles were classified into five groups according to their maximum Feret diameter, elongation, circularity and area. Two groups encompassed the most application-critical aggregates: one integrated aggregates of high complexity and low compactness while the other included elongated aggregates. In addition, the characterization of CNC dispersion after different levels of sonication was achieved by assessing the change in the number of elements belonging to each cluster after sonication. This approach could be used as a standard for the characterization of the aggregation state of CNCs.

Industrial Application of Nanocelluloses in Papermaking: A Review of Challenges, Technical Solutions, and Market Perspectives.

Nanocelluloses (NC) increase mechanical and barrier paper properties allowing the use of paper in applications actually covered by other materials. Despite the exponential increase of information, NC have not been fully implemented in papermaking yet, due to the challenges of using NC. This paper provides a review of the main new findings and emerging possibilities in this field by focusing mainly on: (i) Decoupling the effects of NC on wet-end and paper properties by using synergies with retention aids, chemical modification, or filler preflocculation; (ii) challenges and solutions related to the incorporation of NC in the pulp suspension and its effects on barrier properties; and (iii) characterization needs of NC at an industrial scale. The paper also includes the market perspectives. It is concluded that to solve these challenges specific solutions are required for each paper product and process, being the wet-end optimization the key to decouple NC effects on drainage and paper properties. Furthermore, the effect of NC on recyclability must also be taken into account to reach a compromise solution. This review helps readers find upscale options for using NC in papermaking and identify further research needs within this field.

Hairy cationic nanocrystalline cellulose as a novel flocculant of clay.

HYPOTHESIS: The present paper investigates, for the first time, the potential of cationic hairy cellulose nanocrystals (CNCC) to induce the flocculation of a model suspension of kaolinite. CNCC belong to a brand new family of nanocelluloses characterized for presenting a crystalline rod-like body and functionalized amorphous chains at both ends. Given that these chains can be easily tuned, these nanocelluloses present a high potential as fit-to-purpose flocculants. EXPERIMENTS: CNCC were produced through periodate oxidation, cationization and thermal treatment of cellulose. Flocculation was monitored by both photometric dispersion analysis and laser reflectance. Flocs were characterized by the determination of zeta potential, supernatant turbidity removal and optical microscopy. A recently developed machine learning random forest regression model was used to estimate fractal dimension (Df) from chord length distribution data. FINDINGS: Although a high efficiency was achieved for CNCC dosages between 7.5 and 75 mg/g, the maximum floc size and the fastest flocculation were found near the isoelectric point (10-30 mg/g). Thus, CNCC acted through charge neutralization mechanism. The model used to estimate flocs Df was found very successful to describe the flocculation process. The clay/CNCC flocs Df values suggest a relation between floc conformation and CNCC dosage, presenting an opener structure when closer to the isoelectric point.

Microalgae harvesting with the novel flocculant hairy cationic nanocrystalline cellulose.

This paper investigates the flocculation of Chlorella sorokiniana suspensions with a novel cellulose derivative, namely hairy cationic nanocrystalline cellulose (CNCC). CNCC are a brand new family of nanocellulose characterized by having two positively charged amorphous ends joint through a common crystalline shaft. Flocculation was monitored through laser reflectance and its mechanism was studied by means of zeta potential, fractal dimension and turbidity removal. CNCC dosage and shear rate were varied and their effect on floc morphology and filterability were assessed. CNCC effectively flocculated the cultures at dosages well below and over the isoelectric point, being the flocculation mechanisms and floc strength highly dependent on the doses applied. The filtration propensity of flocculated suspensions proved highly sensitive to small differences in flocs' geometry. The aggregation process entailed two phases, a first one in which the CNCC adsorbed on the surface of microalgal cells according to a flat random deposition up to reaching a maximal cell coverage, and a second one in which the free spots left were progressively covered with orthogonally deposited CNCC, being this later configuration the main responsible for intercellular attachment. The present work demonstrates that CNCC is an effective flocculant of microalgal cell suspensions and constitutes an alternative worth exploring for the aggregation of other cells' suspensions.

In situ production of bacterial cellulose to economically improve recycled paper properties.

This study focusses on the in-situ production of bacterial cellulose in recycled pulps to increase the quality of fibers in the suspension. The effect of different dosages of the upgraded pulp on the mechanical, physical and optical properties of handsheets was assessed. Papers produced with pulps cultivated in agitation exhibited increments in both tensile and tear indexes of 12.2% and 14.2%, respectively. Thus, flexibility of the paper was also improved. On the other hand, pulps enhanced with static culture fail to improve tensile index of paper, while tear index was increased by 12.4%. The production mechanism for both types of culture was proposed. In agitated culture, bacteria were found to coat the primary fibers, improving their quality. In the case of static culture, heterogeneous systems were observed since recycled fibers tended to sediment while bacteria moved to the surface of the culture broth in search of oxygen. Hence, the in situ production of BC with recycled fibers can, therefore, be an alternative to replace conventional paper strengthening agents. The results attained indicate that the in-situ production of upgraded pulps can be implemented in paper mills cultivating pulp streams sterilized through low cost, non-exhaustive operations, such as ozone or ultraviolet radiation.

Low-fibrillated bacterial cellulose nanofibers as a sustainable additive to enhance recycled paper quality.

Bacterial cellulose is a biological macromolecule synthesized by bacteria of high purity and crystallinity. Bacterial cellulose nanofibers (BCNF) have been produced by soft homogenization and added to a recycled pulp to improve its quality. The benefits of BCNF on mechanical, physical and optical paper properties have been quantified and the retention mechanism of the BCNF in the paper network has been proposed. The use of BC to improve paper strength is usually limited by the decrease of tear index. The novelty of this work is that these two effects are decoupled by the addition of BCNF of low fibrillation (35.2%). In this way, some BCNF clusters are produced together with the individual nanofibers. Thus, with the addition of 3% BCNF, tensile and tear indexes as well as strain at break were improved by 11.1, 7.6, and 66.8%, respectively. Furthermore, the clusters were retained in the fiber network not only by hydrogen bonding, but also by physical retention within the gaps. Therefore, the addition of BCNF not only increases the mechanical properties of paper but also makes the handsheets more flexible and facilitates filler retention.

Direct production of cellulose nanocrystals from old newspapers and recycled newsprint.

Cellulose nanocrystals (CNC) are high added value products which can be used in many applications. In this research, CNC were directly produced from two recycled papers: old newspapers (ONP) and 100% recycled newsprint (NP). CNC were also obtained from NP by previously isolating the cellulose particles by alkali and bleaching treatments. CNC yield and quality was assessed through lignin and ash determination, X-ray diffraction analysis, atomic force microscopy and thermogravimetric analysis. Not only crystallinities resulted similar (92-95%), but also aspect ratios (L/d) (each in the range of 50-120). However, different CNC purities and hydrolysis and process yields were obtained. Thus, CNC purity decreased from 93 to 77%, hydrolysis yield was reduced from 64 to 58% but process yield strongly improved from 35 to 60% when no pretreatment was used. Therefore, this study proves the viability of the direct production of CNC from recycled papers.