Potential of NIR spectroscopy for predicting cellulose nanofibril quality in commercial bleached Kraft pulp of Eucalyptus.

Multivariate models were developed to classify cellulose nanofibril (CNF) fibrillation by a quality index from near infrared (NIR) spectra. Commercial pulps of Eucalyptus spp. were used to produce cellulose nanofibrils by means of a fibrillator mill. After each of the five passes through the mill, samples were collected and analyzed for energy consumption and fiber classification. As a standard, pulps were oxidized with TEMPO reagent followed by a single pass through the mill to compare the resulting quality of CNFs produced by each method. NIR spectra of CNFs were associated with quality indices determined by conventional laboratory analyses that included morphology, turbidity, mechanical properties, X-ray diffraction and quality index measurements. Principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were applied to the spectral and experimental data. Fibrillator milling to obtain CNFs was efficient and resulted in gel formation following the third pass through the mill. NIR spectroscopy combined with PLS-DA was used successfully to create a model to classify quality of CNFs with 96 % certainty in 3 wt% solutions. These findings suggest that NIR spectroscopy holds promise for estimating CNF quality in suspension, particularly in real-time industrial applications where reliable estimates are crucial.

The potential of nanofibrillated cellulose from Hevea brasiliensis to produce films for bio-based packaging.

Cellulose micro/nanofibril (MNFC) films are an interesting alternative to plastic-based films for application in biodegradable packaging. In this study, we aimed to produce and characterize MNFC films obtained from alkaline-pretreated rubberwood (Hevea brasiliensis) waste and Eucalyptus sp. commercial pulp. MNFC and films were evaluated regarding microstructure; crystallinity; stability; and physical, optical, mechanical, and barrier properties. A combined quality index (QI) was also calculated. Eucalyptus MNFC suspensions were more stable than H. brasiliensis. Both films had a hydrophobic surface (>90°) and high grease resistance (oil kit 12). H. brasiliensis films had lower transparency (26.4 %) and high crystallinity (∼89 %), while Eucalyptus films had lower permeability and higher mechanical strength. The QI of MNFC was 51 ± 5 for H. brasiliensis and 55 ± 4 for Eucalyptus, showing that both types of raw material have potential for application in the packaging industry and in the reinforcement of composites, as well as for high value-added applications in products made from special materials.

Impact of accelerated aging cycles on the performance of extruded cement-based composites reinforced with non-bleached eucalyptus fibers.

Thermo-mechanical pulping produces well-individualized fibers compared to wood particles and less fragile fibers compared to Kraft pulping, besides presenting higher volume, higher yield, and lower production cost, which can be an exciting alternative for the fiber-cement industries. This study evaluated the impact of soak and dry-aging cycles on the performance of extruded composites reinforced with non-bleached eucalyptus fibers. The cement matrix comprised cement (70%) and limestone (30%). Composites were reinforced with 1 to 5% of eucalyptus fiber by cement mass and tested on the 28th day of cure at 99% relative humidity and after 400 accelerated aging cycles. The water absorption and apparent porosity gradually increased with the reinforcement level. Composites with 4 and 5% fibers showed the highest toughness (0.21 and 0.23 kJ/m2, respectively). The aging by 400 soak-dry cycles reduced the composites' water absorption and apparent porosity. The modulus of elasticity (MOE), rupture (MOR), and toughness increased, except for toughness for composites reinforced with 1 and 5% fibers, explained by the cementitious matrix's continuous hydration, fiber mineralization, and natural carbonation. In general, eucalyptus thermo-mechanical fibers were suitable for producing cementitious composites. Cementitious composites with 3% fibers presented a higher MOR, MOE, low water absorption, and apparent porosity after 400 accelerated aging cycles. In addition, the composites with 4% fibers also presented remarkable improvements in these properties. The aging cycles did not result in composites with less resistance, a positive fact for their application as tiles and materials for external use in civil construction.

Effect of different pre-treatments on the redispersion capacity of spray-dried microfibrillated cellulose: Elaboration and characterization of biofilms.

This study aimed to evaluate the influence of the addition of the cationic surfactant cetyltrimethylammonium bromide (CTAB) in microfibrillated cellulose (MFC/CNFs) suspensions submitted to different pretreatments to produce redispersible spray-dried (SD) MFC/CNFs. Suspensions pretreated with 5 % and 10 % sodium silicate and oxidized with 2,2,6,6,-tetramethylpiperidinyl-1-oxyl (TEMPO) were modified with CTAB surfactant and subsequently dried by SD. The SD-MFC/CNFs aggregates were redispersed by ultrasound to produce cellulosic films by the casting method. In summary, the results demonstrated that the addition of CTAB surfactant to the TEMPO-oxidized suspension was critical to achieving the most effective redispersion. The experimental results obtained using micrographs, optical (UV-Vis), mechanical, water vapor barrier properties, and the quality index confirmed that the addition of CTAB to the TEMPO-oxidized suspension favored the redispersion of spray-dried aggregates, development of cellulosic films with attractive properties, offering possibilities for the elaboration of new products, for example, in the production of bionanocomposites with higher mechanical performance. This research brings interesting insights into the redispersion and application of SD-MFC/CNFs aggregates, strengthening the commercialization of MFC/CNFs for industrial use.

Mandacaru cactus as a source of nanofibrillated cellulose for nanopaper production.

In this work, nanofibrillated cellulose (NFC) was extracted from cactus Cereus jamacaru DC. (mandacaru) for nanopaper production. The technique adopted includes alkaline treatment, bleaching, and grinding treatment. The NFC was characterized according to its properties and scored based on a quality index. Particle homogeneity, turbidity, and microstructure of the suspensions were evaluated. Correspondingly, the optical and physical-mechanical properties of the nanopapers were investigated. The chemical constituents of the material were analyzed. The sedimentation test and the zeta potential analyzed the stability of the NFC suspension. The morphological investigation was performed using environmental scanning electron microscopy (ESEM) and transmission electron microscopy (TEM). X-ray diffraction (XRD) analysis revealed that Mandacaru NFC has high crystallinity. Thermogravimetric analysis (TGA) and mechanical analysis were also used and revealed good thermal stability and good mechanical properties of the material. Therefore, the application of mandacaru is interesting in sectors such as packaging and electronic device development, as well as in composite materials. Given its score of 72 points on a quality index, this material was presented as an attractive, facile, and innovative source for obtaining NFC.

Substitution of petrochemical compounds for polyphenols of natural origin reinforced with cellulose nanofibrils to formulate adhesives for wood bonding.

Vegetable tannins are excellent options to produce adhesives for the panel industry since they have the capacity to reduce formaldehyde emissions and are derived from renewable sources. They also allow for the possibility of increasing the resistance of the glue line through the use of natural reinforcements such as cellulose nanofibrils. Condensed tannins, polyphenols isolated from tree bark, are widely studied for the production of natural adhesives as an alternative to commercial synthetic adhesives. So, the purpose of our research is to show a natural adhesive alternative for wood bonding. Therefore, the objective of the study was to evaluate the quality of tannin adhesives of different species reinforced with different nanofibrils and thus predict which adhesive is the most promising at different concentrations of reinforcement and with different types of polyphenols. To meet this objective, polyphenols were extracted from the bark, nanofibrils were obtained, and both processes followed the current standards. Then, the adhesives were produced, their properties were characterized, and they were chemically analyzed via Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). A mechanical shear analysis of the glue line was also performed. According to the results, the addition of cellulose nanofibrils affected the physical properties of the adhesives, mostly the content of solids and the gel time. In the FTIR spectra, the OH band of the 5% Pinus and 5% Eucalyptus (EUC) TEMPO in the barbatimao adhesive and the 5% EUC of the cumate red adhesive were reduced, possibly due to their higher moisture resistance. Mechanical tests of the glue line showed that barbatimao with 5% Pinus and cumate red with 5% EUC performed best in the dry and wet shear tests. The control was the best-performing sample in the test of the commercial adhesives. The cellulose nanofibrils used as reinforcement did not change the thermal resistance of the adhesives. Therefore, the addition of cellulose nanofibrils to these tannins is an interesting means of increasing the mechanical strength, as occurred in commercial adhesive with 5% EUC. Thus, the physical and mechanical properties of tannin adhesives were better with reinforcement, making it possible to expand the use of these adhesives in the panel industry. At the industrial level, it is important to replace synthetic products with natural ones. Besides environmental and health issues, there is the question of the value of petroleum-based products, which have been widely studied so that they can be replaced.

Comparison of pre-treatments mediated by endoglucanase and TEMPO oxidation for eco-friendly low-cost energy production of cellulose nanofibrils.

Specific kinds of enzymes have been used as an eco-friendly pre-treatment for mechanical extraction of cellulose nanofibrils (CNFs) from vegetal pulps. Another well-established pre-treatment is the 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-mediated oxidation, which has gained considerable attention. Pre-treatments assist in fiber swelling, facilitating mechanical fibrillation, and reducing energy consumption; however, some of these methods are extremely expensive. This work aimed to evaluate the influence of enzymatic pre-treatment with endoglucanase on the energy consumption during mechanical fibrillation of cellulose pulps. Bleached pulps from Eucalyptus sp. and Pinus sp. were pre-treated with endoglucanase enzyme compared to TEMPO-meditated oxidation. Average diameters of CNFs pre-treated with enzymes were close to that found for TEMPO-oxidized nanofibrils (TOCNFs). Results showed that enzymatic pre-treatment did not significantly modify the pulp chemical and morphological characteristics with efficient stabilization of the CNFs suspension at higher supernatant turbidity. Energy consumption of pulps treated with endoglucanase enzymes was lower than that shown by pulps treated with TEMPO, reaching up to 58% of energy savings. The enzyme studied in the pulp treatment showed high efficiency in reducing energy consumption during mechanical fibrillation and production of films with high mechanical quality, being an eco-friendly option for pulp treatment.

Developing a Biodegradable Film for Packaging with Lignocellulosic Materials from the Amazonian Biodiversity.

The development of packaging films made from renewable raw materials, which cause low environmental impact, has gained attention due to their attractive properties, which have become an exciting option for synthetic films. In this study, cellulose micro/nanofibrils (MFC/NFC) films were produced with forest residues from the Amazon region and evaluated for their potential to generate alternative packaging to traditional plastic packaging. The MFC/NFC were obtained by mechanical fibrillation from fibers of açaí seeds (Euterpe oleracea), titica vine (Heteropsis flexuosa), and commercial pulps of Eucalyptus sp. for comparison. The fibrillation of the titica vine culminated in higher energy expenditure on raw materials. The açaí films showed a higher tensile strength (97.2 MPa) compared to the titica films (46.2 MPa), which also showed a higher permeability rate (637.3 g day-1 m-2). Films of all raw materials scored the highest in the grease resistance test (n° 12). The films produced in the study showed potential for use in packaging for light and low moisture products due to their adequate physical, mechanical, and barrier characteristics. New types of pre-treatments or fibrillation methods ecologically correct and viable for reducing energy consumption must be developed, mainly for a greater success of titica vine fibrillation at the nanoscale.

Bio-based films/nanopapers from lignocellulosic wastes for production of added-value micro-/nanomaterials.

The growing demand for products with lower environmental impact and the extensive applicability of cellulose nanofibrils (CNFs) have received attention due to their attractive properties. In this study, bio-based films/nanopapers were produced with CNFs from banana tree pseudostem (BTPT) wastes and Eucalyptus kraft cellulose (EKC) and were evaluated by their properties, such as mechanical strength, biodegradability, and light transmittance. The CNFs were produced by mechanical fibrillation (after 20 and 40 passages) from suspensions of BTPT (alkaline pre-treated) and EKC. Films/nanopapers were produced by casting from both suspensions with concentrations of 2% (based in dry mass of CNF). The BTPT films/nanopapers showed greater mechanical properties, with Young's modulus and tensile strength around 2.42 GPa and 51 MPa (after 40 passages), respectively. On the other hand, the EKC samples showed lower disintegration in water after 24 h and biodegradability. The increase in the number of fibrillation cycles produced more transparent films/nanopapers and caused a significant reduction of water absorption for both raw materials. The permeability was similar for the films/nanopapers from BTPT and EKC. This study indicated that attractive mechanical properties and biodegradability, besides low cost, could be achieved by bio-based nanomaterials, with potential for being applied as emulsifying agents and special membranes, enabling more efficient utilization of agricultural wastes.

Eco-friendly laccase and cellulase enzymes pretreatment for optimized production of high content lignin-cellulose nanofibrils.

Lignin-cellulose nanofibrils (LCNF) are of attracting an increasing interest due to the benefits of maintaining the lignin in the nanomaterial composition. The production of LCNF requires considerable energy consumption, which has been suppressed employing pretreatment of biomass, in which it highlights those that employ enzymes that have the advantage of being more environmentally friendly. Some negative aspects of the presence of lignin in the fiber to obtain cellulose nanofibrils is that it can hinder the delamination of the cell wall and act as a physical barrier to the action of cellulase enzymes. This study aimed to evaluate the impact of a combined enzymatic pretreatment of laccase and endoglucanase for high content lignin LCNF production. The morphological and chemical properties, visual aspect and stability, crystallinity, mechanical properties, rheology, barrier properties and quality index were used to characterize the LCNF. The laccase loading used was efficient in modifying the lignin to facilitate the action of the endoglucanase on cellulose without causing the removal of this macromolecule. This pretreatment improved the quality of LCNF (61 ± 3 to 71 ± 2 points) with an energy saving of 42% and, therefore, this pretreatment could be suitable for industrial production for a variety of applications.

Copaiba oil and vegetal tannin as functionalizing agents for açai nanofibril films: valorization of forest wastes from Amazonia.

The applicability of cellulose nanofibrils (CNFs) has received attention due to their attractive properties. This study proposes the functionalization of açai CNFs with copaiba oil and vegetal tannins to produce films with potential for packaging. Bio-based films were evaluated by vapor permeability, colorimetry, and mechanical strength. CNFs were produced by mechanical fibrillation, from suspensions of bleached açai fibers and commercial eucalipytus pulp. Moreover, copaiba oil and vegetal tannin were added to the CNFs to produce films/nanopapers by casting from both suspensions with concentrations of 1% (based on CNF dry mass). The bulk densities of the eucalyptus CNF films were higher (1.126-1.171 g cm-3) compared to the açai CNF ones. Films from eucalyptus and açai pulps containing copaiba oil and tannins presented higher Tonset and Tmax, respectively (312 and 370 °C). Films with açaí CNFs functionalized with copaiba oil and tannin showed the lowest permeability value (370 g day-1 m-2). Films produced with eucalyptus pulp, and eucalyptus pulp functionalized with copaiba oil highlighted by superior mechanical strength, achieving 133.8 and 121.4 MPa, respectively. The evaluation of colorimetry showed a greater tendency to yellowing for açai films, especially those functionalized with vegetal tannins. Besides the low cost, functionalized vegetal-based nanomaterials could have attractive properties, with potential for application as some kind of packaging, for transporting basic products, such as breads, flours, or products with low moisture content, enabling efficient utilization of forest wastes.

Influence of hemicellulose content and cellulose crystal change on cellulose nanofibers properties.

This study aimed to evaluate the properties of cellulose nanofibers (CNFs) with different hemicellulose contents and cellulose II polymorphs. A link was found between these polysaccharides and the properties of CNFs. A decrease in crystallinity (from 69 to 63%) and changes in the crystalline structure of cellulose subjected to an alkaline environment were observed, promoting the partial conversion of cellulose I to cellulose II (from 2 to 42%) and preventing CNFs production at NaOH concentrations higher than 5%. Most treatments showed pseudoplastic fluid behavior, except for the 10% NaOH treatment over 2 h, which showed Newtonian fluid behavior. The quality index of the reference CNFs (TEMPO-oxidized) was the highest (80 ± 3), followed by that of the 5% NaOH-treated (68 ± 3 and 22% energy savings compared to the untreated sample), and the untreated (63 ± 3) samples; and the 10% NaOH treatments had quality indices of 51 ± 3 and 32 ± 1, respectively.

Redispersion and structural change evaluation of dried microfibrillated cellulose.

Commercializing dried microfibrillated cellulose (MFC) has always been a challenge mainly due to the tendency of MFC to aggregate. In this study MFC samples were submitted to drying/redispersion cycles at different temperatures. Morphology, crystallinity and mechanical performance of films were analyzed throughout the cycles. Microscopy images, particle size and stability in water showed that aggregation happens more severely with 5 drying/redispersion cycles and at drying temperatures of 75 and 100 °C. Particles once-dried at 20 °C formed the same size and web-like structure as the MFC-control. Crystallinity and crystallite sizes increased with drying/redispersion cycles especially when dried at 75 and 100 °C, however drying/redispersion cycles also led to a reduction in mechanical performance due to aggregation. While oven-drying is not the most suitable method, milder action at room temperature once-drying led to suspension stability in water, morphology and mechanical properties close to never-dried MFC, which makes this treatment a feasible option to maintain cellulose quality.

Artificial neural network and partial least square regressions for rapid estimation of cellulose pulp dryness based on near infrared spectroscopic data.

The content of water in fiber suspension and affects pulp refining, bleaching and draining operations. Cellulose pulp dryness estimate through near infrared (NIR) spectroscopy coupled with multivariate regressions or artificial neural network (ANN) techniques are not well explored yet. In this study models were developed to estimate cellulose pulp dryness in pads based on the NIR spectra. Thus, the cellulose pulp pads (4 mm thick) were weighed and their NIR spectra were obtained in several stages during desorption from 13.1 to 98.3% of content of solids. Partial least square regression (PLS-R) was developed from whole NIR spectra (1300 Absorbance values) and six spectral variables (from 1300) were selected for developing the PLS-R (6) and the ANN model. Both trained neural network and regression can predict pulp dryness of unknown cellulose pulp pads from their NIR data with an error of 2.5%. PLS-R models based on whole NIR spectra showed accurate predictions (the R² of lab-determined and estimated values plot was 0.99) while the ANN showed the same predictive performance from only six NIR variables. Predictive models developed from full NIR spectra and those based on only 6 variables were compared. Our findings indicate that NIR spectroscopy coupled with multivariate analysis and Artificial neural networks are a promising tool for monitoring the weight variation due to dewatering of the cellulose pulps in real time.

Bio-based thin films of cellulose nanofibrils and magnetite for potential application in green electronics.

The objective of this work was to prepare bio-based thin films and evaluate the additions of magnetite and glycerol on the physico-chemical (flexibility, wettability and barrier properties) and dielectric properties of cellulose/chitosan-based films. The films were prepared by solution casting and presented a suitable dispersion of the constituents observed by SEM and FTIR. The films were thermally stable up to 150 °C and had a higher flexibility, wettability and lower barrier properties upon addition of glycerol. The calculated dielectric constant (εr) for the composite films was based on measurements of capacitance, at 100 and 1000 Hz, with the additions of magnetite and glycerol more than doubling the εr increasing the charge storage capacity. The bio-based thin films have potential to be used as insulators in capacitors on the production of green electronics thus, reducing toxic and nonrenewable e-waste generation.

Study of morphological properties and rheological parameters of cellulose nanofibrils of cocoa shell (Theobroma cacao L.).

Cocoa shell was evaluated as a precursor for cellulose nanofibrils (NFCs) using mechanical defibrillation. Its morphology was analysed using optical microscopy and scanning electron microscopy with field emission. Rheological and mechanical behaviour were evaluated through flow curves with a strain rate ranging from 0 to 300 s-1 at 25 °C and by means of oscillatory frequency sweeps (0.01 Hz-10 Hz) and shear stress (3 Pa). The thermal-mechanical behaviour was determined by a temperature sweep with a heating rate of 3 °C min-1 and a temperature range of 25 °C-100 °C. Micrographs identified the presence of protoxilem with a mean diameter of 23.34 nm. The flow curve showed the characteristic behaviour of a pseudoplastic fluid. The storage module (G') and the loss modulus (G″) were dependent on the frequency applied, indicating that the material exhibits a weak gel characteristic. The viscoelastic characteristics were influenced by temperature. Therefore, cocoa shell is a new alternative in the production of nanocellulose.

Renewable hybrid nanocatalyst from magnetite and cellulose for treatment of textile effluents.

A hybrid catalyst was prepared using cellulose nanofibrils and magnetite to degrade organic compounds. Cellulose nanofibrils were isolated by mechanical defibrillation producing a suspension used as a matrix for magnetite particles. The solution of nanofibrils and magnetite was dried and milled resulting in a catalyst with a 1:1 ratio of cellulose and magnetite that was chemically and physically characterized using light, scanning electron and transmission electron microscopies, specific surface area analysis, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffraction, catalytic potential and degradation kinetics. Results showed good dispersion of the active phase, magnetite, in the mat of cellulosic nanofibrils. Leaching and re-use tests showed that catalytic activity was not lost over several cycles. The hybrid material produced was tested for degradation of methylene blue dye in Fenton-like reactions resulting in a potential catalyst for use in degradation of organic compounds.

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%.