Structure Formation by 3D-Printing of Cellulose from Cellulose-NMMO-Water Solutions: Analysis of Extrusion, Regeneration, and Drying Stages.

Processing cellulose from 4-methyl morpholine n-oxide (NMMO)-water solutions is a completely circular route that produces biodegradable cellulose fibers or films while recovering reusable NMMO [Guo, Y.; Cai, J.; Sun, T.; Xing, L.; Cheng, C.; Chi, K.; Xu, J.; Li, T. The purification process and side reactions in the N-methylmorpholine-N-oxide (NMMO) recovery system. Cellulose 2021, 28(12), 7609-7617]. Despite proven success in two-dimensional applications, challenges in transitioning to three-dimensional objects arise from the critical changes that cellulose undergoes during deposition, regeneration, and postregeneration stages. While emphasizing the critical diffusion-driven precipitation during regeneration, this investigation explores the influence of extrusion temperature, printing alignment, regeneration, and drying processes on interfilament fusion, bonding, shape integrity, and mechanical properties. Three distinct drying processes: ambient, vacuum, and freeze-drying were investigated. Tensile and flexural bending tests provided insight into the delamination of dried specimens. Ambient and vacuum drying enhanced the properties of specimens, while freeze-drying resulted in a more stable shape. The findings contribute to advancing the understanding of 3D-printing cellulose from NMMO solutions, addressing crucial aspects of the extrusion, regeneration, and drying stages for enhanced applications in sustainable manufacturing.

Cellulose-Encapsulated Composite Electrolyte Design: Toward Chemically and Mechanically Enhanced Solid-Sodium Batteries.

Sulfide- and halide-based ceramic ionic conductors exhibit comparable ionic conductivity with liquid electrolytes and are candidates for high-energy- and high-power-density all-solid-state batteries. These materials, however, are inherently brittle, making them unfavorable for applications. Here, we report a mechanically enhanced composite Na+ conductor that contains 92.5 wt % of sodium thioantimonate (Na3SbS4, NSS) and 7.5 wt % of sodium carboxymethyl cellulose (CMC); the latter serves as the binder and an electrochemically inert encapsulation layer. The ceramic and binder constituents were integrated at the particle level, providing ceramic NSS-level Na+ conductivity in the NSS-CMC composite. The more than 5-fold decrease of electrolyte thickness obtained in NSS-CMC composite provided a 5-fold increase in Na+ conductance compared to NSS ceramic pellets. As a result of the CMC encapsulation, this NSS-CMC composite shows increased moisture resistivity and electrochemical stability, which significantly promotes the cycling performance of NSS-based solid-state batteries. This work demonstrates a well-controlled, orthogonal process of ceramic-rich, composite electrolyte processing: independent streams for ceramic particle formation along with binder encapsulation in a solvent-assisted environment. This work also provides insights into the interplay among the solvent, the polymeric binder, and the ceramic particles in composite electrolyte synthesis and implies the critical importance of identifying the appropriate solvent/binder system for precise control of this complicated process.

Recent advances in novel materials and techniques for developing transparent wound dressings.

Optically transparent wound dressings offer a range of potential applications in biomedical fields, as they allow for the monitoring of wound-healing progress without having to replace the dressing. These dressings must be impermeable to water and bacteria, yet permeable to moisture vapor and atmospheric gases in order to maintain a moist environment at the wound site. This review article provides a comprehensive overview of the types of wound dressings, novel wound-dressing materials, advanced fabrication techniques for transparent wound-dressing materials, and the key features and applications of transparent dressings for the healing process, as well as how they can improve healing outcomes. This review mainly focuses on presenting specifications of transparent polymeric wound-dressing materials, such as transparent electrospun nanofibers, transparent crosslinked hydrogels, and transparent composite films/membranes. Due to the advanced properties of electrospun nanofibers, such as large surface area, efficient incorporation of antibacterial molecules, a structure similar to the extracellular matrix, and high mechanical stability, they are often used in wound-dressing applications. We also highlight hydrogels or films for wound-healing applications, and their promotion of the healing process, provision of a moist environment and pain relief through cooling and high-water content, excellent biocompatibility, and bio-biodegradability. But as hydrogels or films fabricated with a single component have low mechanical strength and stability, recent trends have offered composite or hybrid materials to achieve typical wound-dressing requirements. Advanced wound dressings with transparency, high mechanical stability, and antimicrobial functionality are becoming a popular research avenue in the wound-dressing research field. Finally, the developmental prospects of new transparent wound-dressing materials for future research are presented.

High Mass Loading of Edge-Exposed Cu3P Nanocrystal in 3D Freestanding Matrix Regulating Lithiophilic Sites for High-Performance Lithium Metal Anode.

Lithium (Li) dendrites and volume expansion during repeated Li plating and stripping processes are the major obstacles to the development of advanced Li metal batteries. Li nucleation and dendrite growth can be controlled and inhibited spatially by using 3-dimensional (3D) hosts together with efficient lithiophilic materials. To realize next-generation Li-metal batteries, it is critical to effectively regulate the surface structure of the lithiophilic crystals. Herein, exposed-edged Cu3P faceted nanoparticles anchored along the interlaced carbon nanofibers (ECP@CNF) are developed as a highly efficient 3D Li host. Through the 3D interlaced rigid carbon skeleton, volume expansion can be accommodated. The (300)-dominant edged crystal facets of Cu3P with abundant exposed P3- sites not only exhibit strong micro-structural Li affinity but also have relatively high charge transference to nucleate uniformly and effectively, resulting in reduced polarization. Consequently, under a high current density of 10 mA cm-2 with a high discharge of depth (60%), ECP@CNF/Li symmetric cells demonstrate outstanding cycling stability for 500 h with a small voltage hysteresis of 32.8 mV. Notably, the ECP@CNF/Li∥LiFePO4 full cell exhibits a more stable cycling performance for 650 cycles under a high rate of 1 C, with capacity retention up to 92% (N/P = 10, 4.7 mg cm-2 LiFePO4). Even under a limit Li (3.4 mA h) with an N/P ratio of 2 (8.9 mg cm-2 LiFePO4), ECP@CNF/Li∥LiFePO4 full cell can also demonstrate excellent reversibility and stable cycling performance with higher utilization of Li. This work provides an insight view into constructing high-performance Li-metal batteries under more strict conditions.

Towards better understanding the stiffness of nanocomposites via parametric study of an analytical model modeling parameters and experiments.

The stiffness of polymeric materials can be improved dramatically with the addition of nanoparticles. In theory, as the nanoparticle loading in the polymer increases, the nanocomposite becomes stiffer; however, experiments suggest that little or no stiffness improvement is observed beyond an optimal nanoparticle loading. The mismatch between the theoretical and experimental findings, particularly at high particle loadings, needs to be understood for the effective use of nanoparticles. In this respect, we have recently developed an analytical model to close the gap in the literature and predict elastic modulus of nanocomposites. The model is based on a three-phase Mori-Tanaka model coupled with the Monte-Carlo method, and satisfactorily captures the experimental results, even at high nanoparticle loadings. The developed model can also be used to study the effects of agglomeration in nanocomposites. In this paper, we use this model to study the effects of agglomeration and related model parameters on the stiffness of nanocomposites. In particular, the effects of particle orientation, critical distance, dispersion state and agglomerate property, and particle aspect ratio are investigated to demonstrate capabilities of the model and to observe how optimal particle loading changes with respect these parameters. The study shows that the critical distance defining agglomerates and the properties of agglomerates are the key design parameters at high particle loadings. These two parameters rule the optimal elastic modulus with respect to particle loading. The findings will allow researchers to form design curves and successfully predict the elastic moduli of nanocomposites without the exhaustive experimental undertakings.

A predictive model towards understanding the effect of reinforcement agglomeration on the stiffness of nanocomposites.

Nanocomposite technologies can be significantly enhanced through a careful exploration of the effects of agglomerates on mechanical properties. Existing models are either overly simplified (e.g., neglect agglomeration effects) or often require a significant amount of computational resources. In this study, a novel continuum-based model with a statistical approach was developed. The model is based on a modified three-phase Mori-Tanaka model, which accounts for the filler, agglomerate, and matrix regions. Fillers are randomly dispersed in a defined space to predict agglomeration tendency. The proposed model demonstrates good agreement with the experimentally measured elastic moduli of spin-coated cellulose nanocrystal reinforced polyamide-6 films. The techniques and methodologies presented in the study are sufficiently general in that they can be extended to the analyses of various types of polymeric nanocomposite systems.

Bio-cleaning improves the mechanical properties of lignin-based carbon fibers.

Production of carbon fibers (CF) using renewable precursors has gained importance particularly in the last decade to reduce the dependency on conventional petroleum-based precursors. However, pre-treatment of these renewable precursors is still similar to that of conventional ones. Little work is put into greener pre-treatments and their effects on the end products. This work focuses on the use of bio-cleaned lignin as a green precursor to produce CF by electrospinning. Bio-cleaned kraft lignin A (Bio-KLA) and uncleaned kraft lignin A (KLA) were used to explore the effect of bio-cleaning on the diameter and mechanical properties of lignin fibers and CF. The effect of electric field, lignin-to-poly(ethylene oxide) (PEO) ratio and PEO molecular weight (MW) were evaluated by 33 factorial design using Design of Experiment (DOE). The electrospinning process parameters were optimized to obtain a balance between high elastic modulus and small fiber diameter. The model predicted optimized conditions were 50 kV m-1 electric field, 95/5 lignin-to-PEO ratio and 1000 kDa MW of PEO. When compared to KLA, Bio-KLA CFs showed a 2.7-fold increase in elastic modulus, 2-fold increase in tensile strength and 30% decrease in fiber diameter under the same optimum conditions. The results clearly show that bio-cleaning improved the mechanical properties of lignin derived CF.

Is suture comparable to wire for cerclage fixation? A biomechanical analysis.

BACKGROUND: Cerclage wire is the current standard for circumferential bone fixation. Advances in technology have improved modern sutures, allowing for expanded utility and broader application. The present study compared the strength and durability of cerclage fixation between modern suture materials and monofilament wire. METHODS: The Surgeon's Knot, the Nice Knot and the Modified Nice Knot, were each tied using three separate suture materials: no. 2 FiberWire (Arthrex, Naples, FL, USA), no. 2 Ultrabraid (Smith & Nephew, Andover, MA, USA) and no. 5 Ethibond (Johnson & Johnson, Somerville, NJ, USA). These sutures were compared with monofilament wire. Sutures were secured around a fixed diameter using three additional half hitches, whereas a 1.2-mm (18 gauge) stainless steel monofilament wire was used for comparison. One fellow and one orthopaedic surgery resident each tied five trials with every knot/material combination. Samples were subjected to cyclic loading and quasi-static load testing. Respectively, cyclic displacement over time and load to failure were analyzed. Clinical failure (3 mm of cyclic displacement) and absolute failure (opening of the knot or material failure) were the outcomes of interest. RESULTS: During cyclic loading, Ethibond displaced significantly less over time compared to monofilament wire (p < 0.003), whereas FiberWire showed no significant difference. Ultrabraid also behaved similar to wire, except displacing significantly more than wire only with the Surgeon's Knot (p = 0.02). During load to failure, Ethibond and FiberWire failed at significantly greater loads than monofilament wire (p < 0.001), whereas Ultrabraid performed similar to wire. Knot types did not appear to impact the results. CONCLUSIONS: High-performance sutures achieve superior results in biomechanical testing under cyclic and quasi-static load compared to monofilament wire, suggesting that they provide an alternative to wire for cerclage fixation with select clinical application. Biomechanical security of suture cerclage is dependent on suture material, although it is not altered significantly by choice of knot. An ex-vivo study with clinical application would further reinforce whether suture cerclage offers a valid alternative to wire cerclage.

Effect of Moisture on Shape Memory Polyurethane Polymers for Extrusion-Based Additive Manufacturing.

Extrusion-based additive manufacturing (EBAM) or 3D printing is used to produce customized prototyped parts. The majority of the polymers used with EBAM show moisture sensitivity. However, moisture effects become more pronounced in polymers used for critical applications, such as biomedical stents, sensors, and actuators. The effects of moisture on the manufacturing process and the long-term performance of Shape Memory Polyurethane (SMPU) have not been fully investigated in the literature. This study focuses primarily on block-copolymer SMPUs that have two different hard/soft (h/s) segment ratios. It investigates the effect of moisture on the various properties via studying: (i) the effect of moisture trapping within these polymers and the consequences when manufacturing; (ii) and the effect on end product performance of plasticization by moisture. Results indicate that higher h/s SMPU shows higher microphase separation, which leads to an increase of moisture trapping within the polymer. Understanding moisture trapping is critical for EBAM parts due to an increase in void content and a decrease in printing quality. The results also indicate a stronger plasticizing effect on polymers with lower h/s ratio but with a more forgiving printing behavior compared to the higher h/s ratio.

Current state of fabrication technologies and materials for bone tissue engineering.

A range of traditional and free-form fabrication technologies have been investigated and, in numerous occasions, commercialized for use in the field of regenerative tissue engineering (TE). The demand for technologies capable of treating bone defects inherently difficult to repair has been on the rise. This quest, accompanied by the advent of functionally tailored, biocompatible, and biodegradable materials, has garnered an enormous research interest in bone TE. As a result, different materials and fabrication methods have been investigated towards this end, leading to a deeper understanding of the geometrical, mechanical and biological requirements associated with bone scaffolds. As our understanding of the scaffold requirements expands, so do the capability requirements of the fabrication processes. The goal of this review is to provide a broad examination of existing scaffold fabrication processes and highlight future trends in their development. To appreciate the clinical requirements of bone scaffolds, a brief review of the biological process by which bone regenerates itself is presented first. This is followed by a summary and comparisons of commonly used implant techniques to highlight the advantages of TE-based approaches over traditional grafting methods. A detailed discussion on the clinical and mechanical requirements of bone scaffolds then follows. The remainder of the manuscript is dedicated to current scaffold fabrication methods, their unique capabilities and perceived shortcomings. The range of biomaterials employed in each fabrication method is summarized. Selected traditional and non-traditional fabrication methods are discussed with a highlight on their future potential from the authors' perspective. This study is motivated by the rapidly growing demand for effective scaffold fabrication processes capable of economically producing constructs with intricate and precisely controlled internal and external architectures. STATEMENT OF SIGNIFICANCE: The manuscript summarizes the current state of fabrication technologies and materials used for creating scaffolds in bone tissue engineering applications. A comprehensive analysis of different fabrication methods (traditional and free-form) were summarized in this review paper, with emphasis on recent developments in the field. The fabrication techniques suitable for creating scaffolds for tissue engineering was particularly targeted and their use in bone tissue engineering were articulated. Along with the fabrication techniques, we emphasized the choice of materials in these processes. Considering the limitations of each process, we highlighted the materials and the material properties critical in that particular process and provided a brief rational for the choice of the materials. The functional performance for bone tissue engineering are summarized for different fabrication processes and the choice of biomaterials. Finally, we provide a perspective on the future of the field, highlighting the knowledge gaps and promising avenues in pursuit of effective scaffolds for bone tissue engineering. This extensive review of the field will provide research community with a reference source for current approaches to scaffold preparation. We hope to encourage the researchers to generate next generation biomaterials to be used in these fabrication processes. By providing both advantages and disadvantage of each fabrication method in detail, new fabrication techniques might be devised that will overcome the limitations of the current approaches. These studies should facilitate the efforts of researchers interested in generating ideal scaffolds, and should have applications beyond the repair of bone tissue.

Effects of interfacial interactions and interpenetrating brushes on the electrospinning of cellulose nanocrystals-polystyrene fibers.

This study investigated the electrospinning of polystyrene solutions using added unmodified and modified (with grafted nitrobenzene and trifluoromethyl benzene functionalities and polystyrene brushes) cellulose nanocrystals (CNCs). A strong correlation existed between the formation of beads on the fibers and the degree of dispersion of CNC particles in the electrospinning mixtures. Agglomerates of CNC particles always concentrated in the form of beads. The best dispersion in N,N dimethylformamide (DMF) mixtures was obtained using CNC-2 surfaces that were modified using trifluoromethyl benzene functional groups. Using CNC-2 also resulted in both uniform and bead-free electrospun fibers. Despite good dispersion in DMF, the use of grafted polystyrene (PS) chains with CNC-g resulted in beads above a 1.0% concentration level. This result is attributed to more favorable interactions between the CNC-g brushes during the DMF solvent evaporation stage of electrospinning. The electrospinning of CNC/PS nanocomposites at very low CNC concentrations (<1.0%) showed strong adhesion bonds at the polymer-CNC interfaces. Excellent mechanical properties were also produced by using interpenetrating networks of surface brushes.