Solvent-Dependent Dynamics of Cellulose Nanocrystals in Process-Relevant Flow Fields.

Flow-assisted alignment of anisotropic nanoparticles is a promising route for the bottom-up assembly of advanced materials with tunable properties. While aligning processes could be optimized by controlling factors such as solvent viscosity, flow deformation, and the structure of the particles themselves, it is necessary to understand the relationship between these factors and their effect on the final orientation. In this study, we investigated the flow of surface-charged cellulose nanocrystals (CNCs) with the shape of a rigid rod dispersed in water and propylene glycol (PG) in an isotropic tactoid state. In situ scanning small-angle X-ray scattering (SAXS) and rheo-optical flow-stop experiments were used to quantify the dynamics, orientation, and structure of the assigned system at the nanometer scale. The effects of both shear and extensional flow fields were revealed in a single experiment by using a flow-focusing channel geometry, which was used as a model flow for nanomaterial assembly. Due to the higher solvent viscosity, CNCs in PG showed much slower Brownian dynamics than CNCs in water and thus could be aligned at lower deformation rates. Moreover, CNCs in PG also formed a characteristic tactoid structure but with less ordering than CNCs in water owing to weaker electrostatic interactions. The results indicate that CNCs in water stay assembled in the mesoscale structure at moderate deformation rates but are broken up at higher flow rates, enhancing rotary diffusion and leading to lower overall alignment. Albeit being a study of cellulose nanoparticles, the fundamental interplay between imposed flow fields, Brownian motion, and electrostatic interactions likely apply to many other anisotropic colloidal systems.

Nanocellulose for Sustainable Water Purification.

Nanocelluloses (NC) are nature-based sustainable biomaterials, which not only possess cellulosic properties but also have the important hallmarks of nanomaterials, such as large surface area, versatile reactive sites or functionalities, and scaffolding stability to host inorganic nanoparticles. This class of nanomaterials offers new opportunities for a broad spectrum of applications for clean water production that were once thought impractical. This Review covers substantial discussions based on evaluative judgments of the recent literature and technical advancements in the fields of coagulation/flocculation, adsorption, photocatalysis, and membrane filtration for water decontamination through proper understanding of fundamental knowledge of NC, such as purity, crystallinity, surface chemistry and charge, suspension rheology, morphology, mechanical properties, and film stability. To supplement these, discussions on low-cost and scalable NC extraction, new characterizations including solution small-angle X-ray scattering evaluation, and structure-property relationships of NC are also reviewed. Identifying knowledge gaps and drawing perspectives could generate guidance to overcome uncertainties associated with the adaptation of NC-enabled water purification technologies. Furthermore, the topics of simultaneous removal of multipollutants disposal and proper handling of post/spent NC are discussed. We believe NC-enabled remediation nanomaterials can be integrated into a broad range of water treatments, greatly improving the cost-effectiveness and sustainability of water purification.

Sustainable Plant-Based Biopolymer Membranes for PEM Fuel Cells.

Carboxycellulose nanofibers (CNFs) promise to be a sustainable and inexpensive alternative material for polymer electrolyte membranes compared to the expensive commercial Nafion membrane. However, its practical applications have been limited by its relatively low performance and reduced mechanical properties under typical operating conditions. In this study, carboxycellulose nanofibers were derived from wood pulp by TEMPO oxidation of the hydroxyl group present on the C6 position of the cellulose chain. Then, citric acid cross-linked CNF membranes were prepared by a solvent casting method to enhance performance. Results from FT-IR spectroscopy, 13C NMR spectroscopy, and XRD reveal a chemical cross-link between the citric acid and CNF, and the optimal fuel cell performance was obtained by cross-linking 70 mL of 0.20 wt % CNF suspension with 300 µL of 1.0 M citric acid solution. The membrane electrode assemblies (MEAs), operated in an oxygen atmosphere, exhibited the maximum power density of 27.7 mW cm-2 and the maximum current density of 111.8 mA cm-2 at 80 °C and 100% relative humidity (RH) for the citric acid cross-linked CNF membrane with 0.1 mg cm-2 Pt loading on the anode and cathode, which is approximately 30 times and 22 times better, respectively, than the uncross-linked CNF film. A minimum activation energy of 0.27 eV is achieved with the best-performing citric acid cross-linked CNF membrane, and a proton conductivity of 9.4 mS cm-1 is obtained at 80 °C. The surface morphology of carboxycellulose nanofibers and corresponding membranes were characterized by FIB/SEM, SEM/EDX, TEM, and AFM techniques. The effect of citric acid on the mechanical properties of the membrane was assessed by tensile strength DMA.

Lamellar crystal-dominated surfaces of polymer films achieved via melt stretching-induced free surface crystallization.

Lamellar crystal-dominated (LCD) surfaces hold great superiority and broad prospects in polymer surface engineering. The key to this is avoiding the formation of an amorphous phase in the interlamellar region. Here we give a first report of achieving LCD surfaces of polyethylene films via melt stretching-induced free surface crystallization. We demonstrate that the resultant surface is constructed directly by orientated and edge-on lamellae within a surface depth of tens to hundreds of nanometers, while the normally existing amorphous phase is avoided. The crystallization-driven formation of the LCD surface has been ascribed to the heterogeneous chain dynamics of a melt free surface, that is, high chain mobility, low viscosity and loose chain entanglement, which facilitates the complete chain disentanglement during crystallization. In addition, we confirm that the surface morphology is controllable with respect to lamellar orientation, spacing and depth by changing the melt stretching strain or quenching the deformed melt. Meanwhile, owing to a possible kinetics competition between crystallization and chain disentanglement, the structural spacing of surface lamellae holds a positive correlation with the lamellar depth. Since free surface effects are immanent in polymer materials, the currently proposed melt processing strategy is demonstrated to be transferable to other semicrystalline polymers.

Sustainable carboxylated cellulose filters for efficient removal and recovery of lanthanum.

Carboxylated cellulose filters were fabricated by oxidation of a cellulose fibrous mat via TEMPO-mediated oxidation. These carboxylated cellulose filters were employed as sustainable filters for removal and recovery of lanthanum ions (La (III)) with high adsorption capability. The surface chemistry of the carboxylated cellulose fibers before and after adsorption of La (III) was investigated systematically. The distribution of La (III) on carboxylated cellulose fibers were explored by EDX mapping approach, which revealed that the adsorption occurred on both the surface and the internal structure of the cellulose fibers. The kinetics and isotherms of the adsorption were conducted to understand the adsorption mechanism of the carboxylated cellulose filter and to learn the maximum adsorption capacity for La (III) which was as high as 33.7 mg/g. The adsorption selectivity of the carboxylated cellulose filter for La (III) was determined when interfering ions including mono- and di-covalent ions were involved. The carboxylated cellulose filter exhibited high adsorption capability and high permeation flux evidenced by the breakthrough curves of the dynamic adsorption of La (III) under an extremely low pressure of 0.07 kPa. A variety of desorption reagents were selected to recover lanthanum from the carboxylated cellulose filter, where the optimized conditions for recovery were explored. Finally, a spiral wound cartridge of the carboxylated cellulose fibrous mat was fabricated and the removal and the recovery of La (III, 2.5 ppm) from massive lanthanum-containing water were demonstrated. It was very impressive that the high rejection ratio of 94.3% was achieved under the low pressure drop of 3.0 kPa remaining throughout the separation process, and the treated solution volume was high up to 21.4 L, which was about six-times higher than that of commercially available nanofibrous adsorption membranes, indicating that the carboxylated cellulose filter could be used as a highly efficient adsorption medium for industrial recovery of rare earth metals.

A Simple Approach to Prepare Carboxycellulose Nanofibers from Untreated Biomass.

A simple approach was developed to prepare carboxycellulose nanofibers directly from untreated biomass using nitric acid or nitric acid-sodium nitrite mixtures. Experiments indicated that this approach greatly reduced the need for multichemicals, and offered significant benefits in lowering the consumption of water and electric energy, when compared with conventional multiple-step processes at bench scale (e.g., TEMPO oxidation). Additionally, the effluent produced by this approach could be efficaciously neutralized using base to produce nitrogen-rich salts as fertilizers. TEM measurements of resulting nanofibers from different biomasses, possessed dimensions in the range of 190-370 and 4-5 nm, having PDI = 0.29-0.38. These nanofibers exhibited lower crystallinity than untreated jute fibers as determined by TEM diffraction, WAXD and 13C CPMAS NMR (e.g., WAXD crystallinity index was ∼35% for nanofibers vs 62% for jute). Nanofibers with low crystallinity were found to be effective for removal of heavy metal ions for drinking water purification.

A Criterion for Flow-Induced Oriented Crystals in Isotactic Polypropylene under Pressure.

Flow-induced oriented crystals have attracted considerable attention because they significantly increase stiffness and strength of polymer products. Naturally, understanding the necessary condition of forming oriented crystals is of importance for both industry and polymer physics. Following the concept of specific work of flow proposed by Mykhaylyk and co-workers, the expression of the specific work of flow, w (T,P) , was carefully summarized and verified that when w (T,P) is above a critical specific work of flow, w c(T,P) = (1.7 ± 0.7) × 107 J m-3 , oriented crystals in isotactic polypropylene can be induced by flow at pressures (50, 100, and 150 MPa) and at a undercooling of 65 K. The influences of pressure on w c(T,P) stem from two facets: one is the influence on the melt viscosity (the Barus law), and the other one is the influence on the equilibrium melting temperature (the Clapeyron equation). The current study can guide real processing to fabricate high-performance polymer products with oriented crystals.

Large Scale Production of Continuous Hydrogel Fibers with Anisotropic Swelling Behavior by Dynamic-Crosslinking-Spinning.

Hydrogel microfibers have been considered as a potential biomaterial to spatiotemporally biomimic 1D native tissues such as nerves and muscles which are always assembled hierarchically and have anisotropic response to external stimuli. To produce facile hydrogel microfibers in a mathematical manner, a novel dynamic-crosslinking-spinning (DCS) method is demonstrated for direct fabrication of size-controllable fibers from poly(ethylene glycol diacrylate) oligomer in large scale, without microfluidic template and in a biofriendly environment. The diameter of fibers can be precisely controlled by adjusting the spinning parameters. Anisotropic swelling property is also dependent on inhomogeneous structure generated in spinning process. Comparing with bulk hydrogels, the resulting fibers exhibit superior rapid water adsorption property, which can be attributed to the large surface area/volume ratio of fiber. This novel DCS method is one-step technology suitable for large-scale production of anisotropic hydrogel fibers which has a promising application in the area such as biomaterials.

Exploring the nature of cellulose microfibrils.

Ultrathin cellulose microfibril fractions were extracted from spruce wood powder using combined delignification, TEMPO-catalyzed oxidation, and sonication processes. Small-angle X-ray scattering of these microfibril fractions in a "dilute" aqueous suspension (concentration 0.077 wt %) revealed that their shape was in the form of nanostrip with 4 nm width and only about 0.5 nm thicknesses. These dimensions were further confirmed by TEM and AFM measurements. The 0.5 nm thickness implied that the nanostrip could contain only a single layer of cellulose chains. At a higher concentration (0.15 wt %), SAXS analysis indicated that these nanostrips aggregated into a layered structure. The X-ray diffraction of samples collected at different preparation stages suggested that microfibrils were delaminated along the (11̅0) planes from the Iß cellulose crystals. The degree of oxidation and solid-state (13)C NMR characterizations indicated that, in addition to the surface molecules, some inner molecules of microfibrils were also oxidized, facilitating the delamination into cellulose nanostrips.

Unprecedented access to strong and ductile poly(lactic acid) by introducing In Situ Nanofibrillar Poly(butylene succinate) for green packaging.

The notion of toughening poly(lactic acid) (PLA) by adding flexible biopolymers has generated enormous interest but has yielded few desirable advances, mainly blocked by the sacrifice of strength and stiffness due to uncontrollable phase morphology and poor interfacial interactions. Here the phase control methodology, that is, intense extrusion compounding followed by "slit die extrusion-hot stretching-quenching" technique, was proposed to construct well-aligned, stiff poly(butylene succinate) (PBS) nanofibrils in the PLA matrix for the first time. We show that generating nanosized discrete droplets of PBS phase during extrusion compounding is key to enable the development of in situ nanofibrillar PBS assisted by the shearing/stretching field. The size of PBS nanofibrils strongly dependent on the PBS content, showing an increased average diameter from 83 to 116 and 236 nm for the composites containing 10, 20, and 40 wt % nanofibrils, respectively. More importantly, hybrid shish-kebab superstructure anchoring ordered PLA kebabs were induced by the PBS nanofibrils serving as the central shish, conferring the creation of tenacious interfacial crystalline ligaments. The exceptional combination of strength, modulus, and ductility for the composites loaded 40 wt % PBS nanofibrils were demonstrated, outperforming pure PLA with the increments of 31, 51, and 72% in strength, modulus, and elongation at break (56.4 MPa, 1702 MPa, and 92.4%), respectively. The high strength, modulus, and ductility are unprecedented for PLA and are in great potential need for packaging applications.

Effects of molecular geometry on the self-assembly of giant polymer-dendron conjugates in condensed state.

A series of giant polymer-dendron conjugates with a dendron head and a linear polymer tail were synthesized via"click" chemistry between azide-functionalized polystyrene (PS(N), N: degree-of-polymerization) and t-butyl protected, alkyne-functionalized second generation dendron (tD), followed by a deprotection process to generate a dendron termini possessing nine carboxylic acid groups. The molecular structures were confirmed by nuclear magnetic resonance, size-exclusion chromatographic analyses, and matrix-assisted laser desorption ionization time-of-flight mass spectra. These well-defined conjugates can serve as a model system to study the effects of the molecular geometries on the self-assembly behaviour, as compared with their linear analogues. Four phase morphologies found in flexible linear diblock copolymer systems, including lamellae, bicontinuous double gyroids, hexagonal packed cylinders, and body-centred cubic packed spheres, were observed in this series of conjugates based on the results of small angle X-ray scattering and transmission electron microscopy. All of the domain sizes in these phase separated structures were around or less than 10 nm. A 'half' phase diagram was constructed based on the experimental results. The geometrical effect was found not only to enhance the immiscibility between the PS(N) tail and dendron head, but also systematically shift all of the phase boundaries towards higher volume fractions of the PS(N) tails, resulting in an asymmetrical phase diagram. This study may provide a pathway to the construction of ordered patterns of sub-10 nm feature size using polymer-dendron conjugates.

Recent Advances and Challenges in Anion Exchange Membranes Development/Application for Water Electrolysis: A Review.

In recent years, anion exchange membranes (AEMs) have aroused widespread interest in hydrogen production via water electrolysis using renewable energy sources. The two current commercial low-temperature water electrolysis technologies used are alkaline water electrolysis (AWE) and proton exchange membrane (PEM) water electrolysis. The AWE technology exhibited the advantages of high stability and increased cost-effectiveness with low hydrogen production efficiency. In contrast, PEM water electrolysis exhibited high hydrogen efficiency with low stability and cost-effectiveness, respectively. Unfortunately, the major challenges that AEMs, as well as the corresponding ion transportation membranes, including alkaline hydrogen separator and proton exchange membranes, still face are hydrogen production efficiency, long-term stability, and cost-effectiveness under working conditions, which exhibited critical issues that need to be addressed as a top priority. This review comprehensively presented research progress on AEMs in recent years, providing a thorough understanding of academic studies and industrial applications. It focused on analyzing the chemical structure of polymers and the performance of AEMs and established the relationship between the structure and efficiency of the membranes. This review aimed to identify approaches for improving AEM ion conductivity and alkaline stability. Additionally, future research directions for the commercialization of anion exchange membranes were discussed based on the analysis and assessment of the current applications of AEMs in patents.

Functionalization of cellulose acetate nanofibrous membranes for removal of particulate matters and dyes.

Particulates and organic toxins, such as microplastics and dye molecules, are contaminants in industrial wastewater that must be purified due to environmental and sustainability concerns. Carboxylated cellulose acetate (CTA-COOH) nanofibrous membranes were fabricated using electrospinning followed by an innovative one-step surface hydrolysis/oxidation replacing the conventional two-step reactions. This approach offers a new pathway for the modification strategy of cellulose-based membranes. The CTA-COOH membrane was utilized for the removal of particulates and cationic dyes through filtration and adsorption, respectively. The filtration performance of the CTA-COOH nanofibrous membrane was carried out; high separation efficiency and low pressure drop were achieved, in addition to the high filtration selectivity against 0.6-µm and 0.8-µm nanoparticles. A cationic Bismarck Brown Y, was employed to challenge the adsorption capability of the CTA-COOH nanofibrous membrane, where the maximum adsorption capacity of the membrane for BBY was 158.73 mg/g. The self-standing CTA-COOH membrane could be used to conduct adsorption-desorption for 17 cycles with the regeneration rate as high as 97.0 %. The CTA-COOH nanofibrous membrane has excellent mechanical properties and was employed to manufacture a spiral wound adsorption cartridge, which exhibited remarkable separation efficiency in terms of treated water volume, which was 5.96 L, and retention rate, which was 100 %.

Towards the Optimization of a Photovoltaic/Membrane Distillation System for the Production of Pure Water.

The production of pure water plays a pivotal role in enabling sustainable green hydrogen production through electrolysis. The current industrial approach for generating pure water relies on energy-intensive techniques such as reverse osmosis. This study unveils a straightforward method to produce pure water, employing real-world units derived from previously simulated and developed laboratory devices. This demonstrated system is cost-effective and boasts low energy consumption, utilizing membrane distillation (MD) driven by the waste heat harnessed from photovoltaic (PV) panels. In a previous study, modeling simulations were conducted to optimize the multi-layered MD system, serving as a blueprint for the construction of prototype devices with a suitable selection of materials, enabling the construction of field-testable units. The most efficient PV-MD device, featuring evaporation and condensation zones constructed from steel sheets and polytetrafluoroethylene (PTFE) membranes, is capable of yielding high-purity water with conductivity levels below 145 µS with high flux rates.

Aluminum-Crosslinked Nanocellulose Scaffolds for Fluoride Removal.

Anionic carboxylated cellulose nanofibers (CNF) are effective media to remove cationic contaminants from water. In this study, sustainable cationic CNF-based adsorbents capable of removing anionic contaminants were demonstrated using a simple approach. Specifically, the zero-waste nitro-oxidization process was used to produce carboxylated CNF (NOCNF), which was subsequently converted into a cationic scaffold by crosslinking with aluminum ions. The system, termed Al-CNF, is found to be effective for the removal of fluoride ions from water. Using the Langmuir isotherm model, the fluoride adsorption study indicates that Al-CNF has a maximum adsorption capacity of 43.3 mg/g, which is significantly higher than that of alumina-based adsorbents such as activated alumina (16.3 mg/g). The selectivity of fluoride adsorption in the presence of other anionic species (nitrate or sulfate) by Al-CNF at different pH values was also evaluated. The results indicate that Al-CNF can maintain a relatively high selectivity towards the adsorption of fluoride. Finally, the sequential applicability of using spent Al-CNF after the fluoride adsorption to further remove cationic contaminant such as Basic Red 2 dye was demonstrated. The low cost and relatively high adsorption capacity of Al-CNF make it suitable for practical applications in fluoride removal from water.

Cellulose Sulfate Nanofibers for Enhanced Ammonium Removal.

In this study, a sulfonation approach using chlorosulfonic acid (CSA) to prepare cellulose sulfate nanofibers (CSNFs) from raw jute fibers is demonstrated. Both elemental sulfur content and zeta potential in the CSNFs are found to increase with increasing CSA content used. However, the corresponding crystallinity in the CSNFs decreases with the increasing amount of CSA used due to degradation of cellulose chains under harsh acidic conditions. The ammonium adsorption results from the CSNFs with varying degrees of sulfonation were analyzed using the Langmuir isotherm model, and the analysis showed a very high maximum ammonium adsorption capacity (41.1 mg/g) under neutral pH, comparable to the best value from a synthetic hydrogel in the literature. The high ammonium adsorption capacity of the CSNFs was found to be maintained in a broad acidic range (pH = 2.5 to 6.5).

Highly Efficient Cationic/Anionic Cellulose Membranes for Removal of Cr(VI) and Pb(II) Ions.

To achieve high throughput, low-pressure drops, and high adsorption capacity of Cr(VI) and Pb(II) in industrial wastewater treatment, cellulose membranes containing cationic and anionic groups were fabricated, respectively. In this process, cost-effective cotton fabrics were oxidized using sodium periodate, followed by quaternary ammonium or sulfonation modifications. The chemical composition, surface morphology, and thermal and mechanical properties of the cellulose membranes were investigated by ATR-FTIR, solid-state NMR, SEM, TGA, and tensile experiments. Quaternary ammonium, aldehyde, and sulfonate groups were distributed on the cationic/anionic cellulose fibers as adsorption sites, which issue remarkable adsorption capability to the cellulose membranes. The highly toxic Cr(VI) and Pb(II) ions were used to challenge the adsorption capacity of the cationic and anionic cellulose membranes, respectively. The maximum adsorption capacities of Cr(VI) and Pb(II) ions were 61.7 and 63.7 mg/g, respectively, suggested by Langmuir isotherms, kinetics, and thermodynamics in the static experiments. The dynamic adsorption capability of cationic cellulose membranes against Cr(VI) ions was determined and compared with that of commercially available anionic-exchange membranes. Spiral wound filtration cartridges were fabricated by cationic and anionic cellulose membranes, respectively, and were used to adsorb Cr(VI) and Pb(II) from lab-made wastewater, respectively. The cationic cellulose cartridge can purify 4.4 L of wastewater containing 1.0 mg/L of Cr(VI) ions with a 100% removal ratio, while the pressure drop was retained at 246 Pa. Similarly, the anionic cellulose cartridge exhibited even more impressive adsorption capability; the removal ratio against Pb(II) was 99% when 8.6 L of 1.0 mg/L of Pb(II) ions containing wastewater was treated, and the pressure drop was retained at 234 Pa. A composite cartridge fabricated by the integration of cationic and anionic cellulose membranes was successfully employed to purify the wastewater containing Cr(VI) and Pb(II) simultaneously. The possible adsorption mechanism was proposed, and the recycling ability of the cellulose membranes was also discussed.

Bioactive polymer-enabled conformal neural interface and its application strategies.

Neural interface is a powerful tool to control the varying neuron activities in the brain, where the performance can directly affect the quality of recording neural signals and the reliability of in vivo connection between the brain and external equipment. Recent advances in bioelectronic innovation have provided promising pathways to fabricate flexible electrodes by integrating electrodes on bioactive polymer substrates. These bioactive polymer-based electrodes can enable the conformal contact with irregular tissue and result in low inflammation when compared to conventional rigid inorganic electrodes. In this review, we focus on the use of silk fibroin and cellulose biopolymers as well as certain synthetic polymers to offer the desired flexibility for constructing electrode substrates for a conformal neural interface. First, the development of a neural interface is reviewed, and the signal recording methods and tissue response features of the implanted electrodes are discussed in terms of biocompatibility and flexibility of corresponding neural interfaces. Following this, the material selection, structure design and integration of conformal neural interfaces accompanied by their effective applications are described. Finally, we offer our perspectives on the evolution of desired bioactive polymer-enabled neural interfaces, regarding the biocompatibility, electrical properties and mechanical softness.

A Comparative Study of Mechanism and Performance of Anionic and Cationic Dialdehyde Nanocelluloses for Dye Adsorption and Separation.

In this study, anionic dialdehyde cellulose (DAC) and cationic dialdehyde cellulose (c-DAC) nanofibrous adsorbents were prepared via a two-step reaction from bamboo pulp, using sodium periodate and Girard's reagent T as oxidizing and cationizing agents, respectively. The performance of DAC and c-DAC for selective dye adsorption and separation was evaluated by six different organic dyes (with varying charge properties) and certain binary mixtures. Both adsorbents could remove the dyes but with different capability, where DAC exhibited high adsorption efficiency against cationic dyes (e.g., the maximum adsorption capacity for Bismarck brown Y was 552.1 mg/g) and c-DAC exhibited high adsorption efficiency against anionic dyes (e.g., the maximum adsorption capacity for Congo red was 540.3 mg/g). To investigate the adsorption mechanism for these adsorbents, effects of contact time, initial pH value, initial dye concentration, and ionic strength on the adsorption activity against Congo red were investigated. The adsorption equilibrium data of DAC were found to fit best with the Langmuir isotherm model, whereas that of c-DAC were found to fit best with the Freundlich model. Both DAC and c-DAC adsorption kinetic data could be described by the pseudo-second-order kinetic model, and these adsorbents possessed stable adsorption efficiency in the pH range of 4-10. Furthermore, their dye adsorption capabilities were found to increase with increasing ionic strength (salt concentration). The distinctive complementary features of DAC and c-DAC will allow them to remove a wide range of organic dyes from industrial wastewater.