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This work outlines a systematic and detailed study of the modification of anatase TiO2 with tungsten (W). The impact this coupling has on the temperature of the anatase to rutile phase transition and the photocatalytic degradation of 1,4-dioxane, a highly toxic compound that is increasingly present in water bodies is also studied. TiO2 composite photocatalysts with 2, 4, 8 and 16 mol. % W, respectively, were produced using a sol-gel process and then calcined between 500−1000 °C. The crystallinity and phase composition of pure and W-TiO2 photocatalysts were examined using X-ray Diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All W-TiO2 composite photocatalysts demonstrated 100 % anatase crystalline phase at calcination temperatures as high as 800 °C. Due to the retention of 26 % anatase after calcination at 950 °C, 8 mol. % W was established as the optimum W loading for the development of high temperature stable anatase W-TiO2 composite photocatalysts. The % anatase content also significantly impacts the photocatalytic activity of the W-TiO2 composite photocatalysts. In the presence of solar light, 100 % of 1,4-dioxane was successfully degraded by 2-W-TiO2, 4-W-TiO2 and 8-W-TiO2 composite photocatalysts, respectively, calcined at 800 °C. However, as the calcination temperature increases and the % anatase content decreases, only 70 % of 1,4-dioxane was degraded when using 4-W-TiO2 and 8-W-TiO2 calcined at 900 °C. The highest % removal of 1,4-dioxane was also achieved using 8-W-TiO2 calcined at both 800 and 900 °C. 8-W-TiO2 is therefore considered the optimum sample for both photocatalysis and phase transition temperature.

The production of high filler-loaded recycled papers is often affected by high values of linting and low values of strength. In the first case, the accumulation of lint particles from paper’s surface on the printing blanket affects the quality of the printed paper and the pressroom’s productivity. In the second case, increasing the use of fillers and recycling cycles lead to poor paper strength. Cellulose nanofibers (CNFs) are receiving a great deal of attention due to their potential as a reinforcement aid for high filler-loaded papers through filler–fiber interaction and interfiber bonding. It is already proven that high quality CNFs can reduce linting, although their industrial application is limited by their high production cost. The objective of this research is, therefore, to quantify the effect of applying lower grade, more sustainable CNFs on linting phenomena and on the mechanical properties of recycled papers. Eucalyptus, pine and triticale residues were used as cellulose sources, and the CNFs were produced minimizing the chemical pretreatment before homogenization. Addition of 3 wt% of CNFs from pine residues into the recycled paper with 15.7 wt% of total filler reduced linting by 40% and increased tensile strength by 15.1%; further improvements on linting and mechanical properties were achieved at 5 wt%. Moreover, the increase in drainage time can be overcome by the addition of a retention aid, in this case a coagulant-cationic polyacrylamide-bentonite system, commonly used in paper mills.

In the present work, lignocellulosic micro/nanofibers (LCMNF) were produced from pine sawdust. For that, pine sawdust was submitted to alkali treatment and subsequent bleaching stages, tailoring its chemical composition with the purpose of obtaining effective LCMNF. The obtained LCMNF were characterized and incorporated to recycled cardboard boxes with the purpose of producing recycled paper. The obtained results showed that it was possible to obtain LCMNF with the same reinforcing potential than those cellulose nanofibers (CNF) prepared by oxidative or other chemical methods In fact, the obtained papers increased the breaking length of recycled cardboard from 3338 m to 5347 m, being a value significantly higher than the requirements to produce paper bags. Overall, the studied strategies could allow a significant reduction of paper basis weight, with the consequent material saving and, thus, contribution to the environment.

The use of nanocelluloses as strength-enhancing additives in papermaking is widely known since both cellulose nanofibers (CNF) and nanocrystals (CNC) present similar composition than paper but their exceptional properties in the nanometer scale confers a paper quality enhancement. However, some agglomeration problems in CNF and CNC through hydrogen bonding cause a lower improvement of mechanical properties of paper. Therefore, a better dispersion of both nanocelluloses can maximize their effect on paper properties, thus reducing the needed dose to get the same increment in tensile strength and then reducing material costs. To ease the implementation of these nanocelluloses in the production process of recycled paper, typically used operations of these industries have been used. Among them, those devoted to improve the homogeneous mixture of nanocellulose in the pulp suspension have been assessed. Firstly, pulping conditions were studied, including pulping time, temperature and need for soaking as variables. Secondly, some dispersing agents used in papermaking were considered, studying the effect of different types and doses. The highest tensile strength of paper was achieved by applying long pulping times (60 min), getting increments up to 30% with the use of soaking and polyacrylamide as retention system. However, with the use of a low dose of a dispersing agent (0.003%), tensile index can be still increased up to 20.6% avoiding these long times. This study can be of great interest of those researchers trying to implement the use of nanocelluloses as strength additive in papermaking.

Cellulose nanofibers (CNF) have increasing relevance in different applications, for instance, in the paper industry as a sustainable strength additive. This application is especially beneficial for recycled paper, which reaches higher product quality despite its limitations. CNF change paper properties and also can affect the production process, especially the drainage stage, in which retention additives (RA) are commonly used to promote interaction of cellulose fibers. CNF probably interact with fibers and RA, affecting the drainage stage. However, these interactions vary depending on the type and flocculation mechanism of RA. This research is aimed at establishing possible synergies between CNF and RA to improve paper strength, avoiding negative effects on the drainage process. No further RA were used to retain CNF, taking advantage of the RA already used in the process. Polyvinylamine, chitosan, cationic starch, C-PAM, and C-PAM-B were selected as RA. CNF from eucalyptus kraft pulp and corn stalk organosolv pulp were tested. Strength properties of laboratory sheets were studied, and interactions were assessed by measuring Z-potential. Synergies between PVA, chitosan, C-PAM, and C-PAM-B with CNF were found. Drainage time decreased ranging between 30 and more than 40% using CNF. Strength depended on RA and formation quality. Among the studied options, CNF with C-PAM-B or chitosan resulted in the best formation and higher strengths with a significant drainage time reduction.

Agro-wastes valorization focusses on production of high value-added products, such as cellulose nanofibers (CNF), and contributes to reduce the environmental impact of these residues. CNF have been used successfully as papermaking additives and some previsions maintain that this sector will become the most important, demanding CNF at a reasonable cost. Furthermore, the optimization of the production process of CNF from agricultural residues would contribute to the goals of a circular economy, the development of rural areas and the costs reduction by producing CNF of the minimum quality fit-for-use in recycled paper. In this study, CNF was produced from two agricultural residues; corn (C-CNF) and rape (R-CNF) stalk pulps, pretreated with bleaching, refining and TEMPO-mediated oxidation. Coagulant and cationic polyacrylamide (dual system) and chitosan were the retention systems. Results show the difficulty of predicting the effect of CNF based on their properties, as fibrillation degree or anionic charge, on the improvement of mechanical properties of recycled paper. That is proved by the low differences in tensile index (TI) improvement (∼15% by adding 0.5% C-CNF combined with dual system), obtained with CNF with very different properties. The expensive TEMPO pretreatment could be avoid by applying bleaching pretreatment to the corn pulp, increasing the TI up to 15% without affecting drainage and decoupling the simultaneous deterioration of drainage with TI improvement (drainage time decreased nearly 50% and 20% adding bleached R-CNF and C-CNF, respectively, combined with chitosan). Similar improvements on TI can be achieved by replacing the dual retention system by chitosan without addition of CNF, but the combination of CNF and chitosan allows achieving the highest TI values.

Although the positive effect that cellulose nanofibers (CNF) can have on paper strength is known, their effect on flocculation during papermaking is not well understood, and most relevant studies have been carried out in presence of only cationic starch. Flocculation is the key to ensuring retention of fibers, fines, and fillers, and furthermore floc properties have a great influence on paper quality. The aim of this research is to study the interactions between CNF and flocculants by assessing the effect of two types of CNF, from eucalyptus and corn, on the flocculation process induced by three different retention systems [a dual system, polyvinylamine (PVA), and cationic starch as reference]. The results showed that CNF interacted with the flocculants in different ways, affecting flocculation efficiency and floc properties. In general, addition of CNF increased floc stability and minimized overdosing effects. Moreover, presence of CNF increased floc size for given PVA dose; therefore, CNF addition could contribute to improve the wet end in the paper machine if combined with the optimal flocculant and dose.

This paper shows that incorporation of Cu inhibits the anatase to rutile phase transition at temperatures above 500 °C. The control sample, with 0% Cu contained 34.3% anatase at 600 °C and transitioned to 100% rutile by 650 °C. All copper doped samples maintained 100% anatase up to 600 °C. With 2% Cu doping, anatase fully transformed to rutile at 650 °C, at higher Cu contents of 4% & 8% mixed phased samples, with 27.3% anatase and 74.3% anatase respectively, are present at 650 °C. All samples had fully transformed to rutile by 700 °C. 0%, 4% and 8% Cu were evaluated for photocatalytic degradation of 1, 4 dioxane. Without any catalyst, 15.8% of the 1,4 dioxane degraded upon irradiation with light for 4 h. Cu doped TiO2 shows poor photocatalytic degradation ability compared to the control samples. Density functional theory (DFT) studies of Cu-doped rutile and anatase show formation of charge compensating oxygen vacancies and a Cu2+ oxidation state. Reduction of Cu2+ to Cu+ and Ti4+ to Ti3+ was detected by XPS after being calcined to 650–700 °C. This reduction was also shown in DFT studies. Cu 3d states are present in the valence to conduction band energy gap upon doping. We suggest that the poor photocatalytic activity of Cu-doped TiO2, despite the high anatase content, arises from the charge recombination at defect sites that result from incorporation of copper into TiO2.

Corn stalk, an agricultural waste, was valorized by the production of cellulose nanofibers (CNF), which were tested for improving recycled paper properties. CNF from eucalyptus kraft pulp (E-CNF) was used as a reference. Addition of 0.5% wt. CNF produced from corn organosolv pulp (C-CNF) to recycled paper increased the tensile index by 20%, whereas the same improvement with E-CNF was achieved at 1.5% wt. Tensile index was further enhanced by increasing the E-CNF, whereas C-CNF achieved its maximum effect at this dose. Different recycled furnish compositions were studied to evaluate C-CNF as a product additive. C-CNF improved tensile strength in all the different recycled furnishes studied. The tensile index improvement caused by C-CNF did not depend on the proportions of old newspaper and old magazine paper used. Addition of C-CNF to recycled corrugated board fluting increased the tensile strength, but to a slightly lower extent than in the case of recycled newsprint paper.

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.

Nanocellulose materials have emerged as a new family of nanomaterials of great interest. That is due to their environmental advantages, including their production from renewable resources, their biodegradability, biocompatibility and their high potential availability. The production processes and the properties of CNF, CNC and BC (aspect ratio, mechanical strength, elastic modulus and thermal stability, high surface area, low density and oxygen permeability, etc) will be described in detailed. Their potential applications in relation to their properties will be mentioned in general terms as an introduction to the specific applications described in the other sections (e.g. papermaking, composites, packaging, electronic devices, coatings, biomedicine, automotive, etc). The description could be focussed on the traditional and emerging trends for their production, their characterization and the quality demanded for the final applications.

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.

This paper examines the modification of anatase TiO2 with hexagonal boron nitride (hBN) and the impact this coupling has on the temperature of the anatase to rutile phase transition and photocatalytic activity. All samples were 100% anatase when calcined up to 500 °C. At 600 °C, all BN-modified samples contain mixed rutile and anatase phases, with 8% and 16% BN–TiO2 showing the highest anatase contents of 64.4% and 65.5% respectively. The control sample converted fully to rutile at 600 °C while the BN modified sample converted to rutile only at 650 °C. In addition to TiO2 phase composition, XRD also showed the presence of bulk boron nitride peaks, with the peak at 26° indicating the graphite-like hBN structure. Density functional theory calculations of hBN-rings adsorbed at the anatase (101) surface show strong binding at the interface; new interfacial bonds are formed with key interfacial features being formation of B–O–Ti and N–Ti bonds. Models of extended hBN sheets at the anatase (101) surface show that formation of B–O and N–Ti bonds along the edge of the hBN sheet anchor it to the anatase surface. 16% BN–TiO2 at 500 °C showed a significant increase in the photocatalytic degradation of 1,4-dioxane when compared with pure anatase TiO2 at 500 °C. This arises from the effect of hBN on anatase. The computed density of states (DOS) plots show that interfacing anatase with BN results in a red shift in the TiO2 energy gap; N-p states extend the valence band maximum (VBM) to higher energies. This facilitates transitions from high lying N-p states to the Ti-d conduction band. A simple photoexcited state model shows separation of electrons and holes onto TiO2 and BN, respectively, which promotes the photocatalytic activity.

The recycled paper and board industry needs to improve the quality of their products to meet customer demands. The refining process and strength additives are commonly used to increase mechanical properties. Interfiber bonding can also be improved using cellulose nanofibers (CNF). A circular economy approach in the industrial implementation of CNF can be addressed through the in situ production of CNF using side cellulose streams of the process as raw material, avoiding transportation costs and reducing industrial wastes. Furthermore, CNF fit for use can be produced for specific industrial applications.This study evaluates the feasibility of using two types of recycled fibers, simulating the broke streams of two paper machines producing newsprint and liner for cartonboard, to produce in situ CNF for direct application on the original pulps, old newsprint (ONP), and old corrugated container (OCC), and to reinforce the final products. The CNF were obtained by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated oxidation and homogenization at 600 bar. Handsheets were prepared with disintegrated recycled pulp and different amounts of CNF using a conventional three-component retention system. Results show that 3 wt.% of CNF produced with 10 mmol of NaClO per gram of dry pulp improve tensile index of ONP ~30%. For OCC, the same treatment and CNF dose increase tensile index above 60%. In both cases, CNF cause a deterioration of drainage, but this effect is effectively counteracted by optimising the retention system.

Extending the limits of paper recycling by increasing the number of recycling cycles results in decreased mechanical properties due to the irreversible hornification of cellulose fibers. This process alters the fiber structure and properties because of the repeated chemical and mechanical treatments that occur during wetting and drying. As a result, poor tensile strength is the main source of customer complaints to paper manufacturers. Cellulose nanofibers (CNF) from bleached eucalyptus and pine pulps were investigated as potential strength additives because of their proven contribution to interfiber bonding. These results were compared to the results obtained using different families of strength additives. The effects on the mechanical properties of recycled old corrugated containers were studied by measuring bursting, tensile, and short span compressive strength. Cellulose nanofibers and cationic polyacrylamide (cPAM) improved the mechanical strength properties when they were added at doses around 4 wt.%. A combination of CNF and cPAM was also tested. The effects of the combined additives were not as high as expected compared to the results achieved individually. The CNF from pine pulp resulted in the highest increase in bursting index when combined with cPAM, achieving an increase of over 93%. The combination of CNF from eucalyptus pulp and cPAM increased the bursting index over 60%.