Fibrous Polymers Research Articles

Quaternarized chitosan nanofiber and ZIF aerogel composites for synergetic CO2 cycloaddition catalysis

Chemical upcycling of CO2, a major greenhouse gas, is attracting significant attention as a crucial strategy to combat global warming. The production of cyclic carbonate using metal-organic frameworks and their composites using nanofibrous carbohydrate polymer are promising ways to convert CO2 into valuable products. However, the current role of fibrous polymers is restricted to serving as physical substrates. This study seeks to expand the functionality of quaternarized chitosan nanofibers into synergistic catalysts in addition to their physical support role. A novel aerogel composite using Co/Zn-ZIF catalyst and quaternarized chitosan nanofiber (Q-CsNF+) was fabricated, and its hierarchical pore structure was extensively discussed. The obtained ZIF/Q-CsNF+ composite can synergistically convert epoxide to cyclic carbonate by acting as a co-catalyst. Moreover, we determined the predominant factors influencing catalytic activity in CO2 cycloaddition, especially by examining the interplay between CO2 affinity and co-catalyst effects. This research provides fundamental insight into developing CO2 cycloaddition catalysts using nature-derived fibrous polymers, opening new avenues for sustainable and efficient CO2 utilization.

(Invited) Advanced Electrode Processing for Next Generation Batteries

The development of environmentally friendly processing techniques is a key requisite for future sustainable battery development. The so-called DRYtraec® process is a solvent-free process developed as a viable approach to replace slurry-based binders by fibrous polymers and produce laminated electrodes with a low carbon footprint. It has been demonstrated to work for both, liquid and solid electrolyte batteries. NMC cathodes can be produced in a wide range of loading. For lithium sulfur batteries carbon/sulfur composites can be processed without sulfur loss. In particular in the field of solid state batteries it shows significant advantages. All-solid-state lithium-ion batteries are promising candidates to overcome safety and energy limitations of established lithium-ion batteries (LIBs). Excellent results have been reported for sulfide based electrolytes on a small scale. More and more companies announce their first pilot production lines. Therefore, scalable concepts for material and component development are of crucial need. We evaluate this process for the fabrication of thin argyrodite separator films and compare it with slurry-based separators in ASSBs. To test new cell concepts and components under relevant conditions, it is important to manufacture prototype cells with thin separator layers and flexible housing. Therefore, we prepared slurry-free pouch cells based on Ni-rich NMC cathodes and PVD-synthesized Si anodes.The presentation highlights recent developments of the DRYtraec® process and its application to ASSBs, LiS and LIBs.

Accumulation characteristics and ecological risk evaluation of microplastics in sediment cores from the artificial reef area and surrounding seas of Haizhou Bay, north China

One significant “sink” for microplastic (MP) pollution is the sediments. There's a considerable lack of reliable data regarding the historical status of MPs contamination in sediments within marine ranching. In this research, the study area encompassed Haizhou bay marine ranching and adjacent seas. The primary objective was to explore the potential relationships between the accumulation of MPs and both the sample depth and sediment characteristics within the cores. The results unveiled significant contamination of MPs within the sediment cores. The average MPs concentration of sediment was 1.01 ± 1.28 n/g. Fibrous polymers and particles smaller than 1000 μm were frequently found in the sediment. The abundance of MPs exhibited a tendency to decrease with an increase in sediment depth. Artificial reefs and currents affected on MPs distribution in sediment cores. The accumulation of MPs showed a significant correlation (P < 0.05) with the sediment content of different particle sizes, suggesting that the composition of sediment can serve as an indicator of the abundance of MPs. The risk of MP pollution in the sediments of the study area was assessed by establishing a risk assessment model using concentration data of MPs and polymer types. Due to the higher hazard score of polymers (PA and PET) in MPs, the Polymer hazard index (PHI) was elevated to grade II. However, it had a Pollution load index (PLIzone) value of 1.95 (level I). This suggested that contamination was minimal, yet the ecological risk remained relatively high. The ecological risk assessment of MPs served as the foundation for gaining a detailed understanding of the distribution characteristics of MPs. It also furnished essential data support for conducting a comprehensive assessment, developing feasible management strategies, and establishing water quality standards related to plastic waste.

Microplastics in coral reef sediments underestimated? They may hide in biominerals

Microplastics (MPs) may be underestimated in coral reef sediments. Current pretreatments for determining MPs in the sediments are mainly density separation and organic matter removal, ignoring MPs that may be embedded or encrusted in biominerals. This could lead to discrepancies in assessing the potential risk of MPs contamination. To confirm whether MPs in coral reef sediments are underestimated, a two-step sequential digestion, including organic matter removal (H2O2 digestion) and biomineral removal (HCl digestion), was performed on sediments from the coral reef area of the South Penghu Marine National Park (SPMNP, Taiwan). The MPs abundance and characteristics of the two steps were analyzed separately. The results showed that the average MPs abundance after HCl digestion (78 ± 42 MPs/kg) was significantly higher than that of H2O2 digestion (38 ± 25 MPs/kg). The MPs diversity integrated index (MPDII) in coral reef sediments was low (MPDII = 0.35), and MPs were mainly small (<2.0 mm, 91.3 %), fibrous (93.5 %), colored (60.9 %), and rayon polymers (73.9 %). Correlation analysis showed that MPs in biominerals mainly dominated MPs in the sediments. These results confirm that current assessments of MPs contamination levels in biomineral-rich sediments may be underestimated and uncertain. In addition, the mineralization of organisms in SPMNP reef regions was affected by MPs from moderate to high levels, depending on the proportion of MPs in biominerals.

Fabrication of Hydrophobic Poly(vinylidene fluoride) Membranes with Manipulated Micromorphology and Enhanced Strength

In this work, an ethanol/water/glycerol ternary coagulation bath system was used to fabricate a hydrophobic PVDF membrane, which will have a considerable impact on the micromorphology. This change will further affect the performance of the membrane. After introducing glycerol into the coagulation bath, the precipitation process was finely regulated. The obtained results implied that glycerol could inhibit solid-liquid separation and promoted liquid-liquid separation. A pleasant discovery was that the mechanical properties of the membrane were improved because of the more fibrous polymers formed by liquid-liquid separation. Besides, a more uniform pore size can be achieved. A fascinating symmetrical interconnected fibrous and spherulitic structure was depicted by membranes fabricated with a coagulation bath consisting of 6% water, 34% ethanol, and 60% glycerol. This membrane had a high water contact angle of 146.6° and a small mean pore size of 0.46 μm. Enhanced tensile strength and elongation at break evidenced that the membrane enjoyed good robustness and flexibility. This facile approach provided the possibility to prepare membranes with tailored pore size and the required strength.

Biomass-derived hierarchically porous carbon-supported MnOx enable fast ion/electron transport at high operating voltages

Metal oxide/carbon composite systems have been investigated extensively for fabrication of supercapacitors. To obtain high capacitance, a thick pseudocapacitive layer loaded on a conventional carbon support inevitably leads to high dead volume and poor rate/power characteristics. Herein, we propose a strategy with biomass-derived hierarchical porous carbon as supports to bridge two critical but mutually exclusive properties of supercapacitors: high capacitance and rapid ion/charge transport. Highly dispersed deposition of nanosized MnO2 and MnO on hierarchically porous carbon were achieved through slow redox reaction controlled by gradual hydrolysis of fibrous polymers remaining in the hydrothermal carbon. High surface area, ultrathin pseudocapacitance layer, and wide voltage window (1.6–2 V) improve the synergy between the high energy density of MnOx and the high power density of porous carbon. The maximum energy density of 40.95 Wh kg−1 (at 180 W kg−1) and power density of 9000 W kg−1 (at 23.85 Wh kg−1) was realized for the assembled asymmetric/symmetric supercapacitors in aqueous electrolytes. More importantly, a cycle life comparable to that of carbon-based double-layer capacitors (95.6% capacitance retention after 10,000 charge/discharge cycles) could be achieved. Furthermore, density functional theory (DFT) was also conducted to elaborate the differences between manganese valence states for in-depth understanding. The characteristics of low cost, environmental friendliness, and excellent performance highlight the great promise of biomass waste in designing carbon supports for electrochemical applications.

Dense, porous, and fibrous scaffolds composed of PHBV, PCL, and their 75:25 blend: an in vitro morphological and cytochemical characterization

In tissue engineering bioresorbable polymers are commonly used to mimetize a damaged tissue characteristics. In spite of that, we did not find a comparative study of the response of the same cell to dense, porous, and fibrous biomaterials. The present work aimed to study the in vitro of pure polymers [poly (ε-caprolactone) (PCL) and poly (hydroxybutyrate-co-hydroxyvalerate) (PHBV)] and their 75:25 blend in dense, porous, and fibrous forms in Vero cells, a fibroblast cell line. The biomaterials were characterized morphologically by scanning electron microscopy (SEM). The MTT assay was used for analysis of possible cytotoxicity. Vero cells were cultured on biomaterials for 120 h and submitted to SEM, morphological and cytochemical analyses. The dyes used were crystal violet (morphology), toluidine blue at pH 4.0 (for nucleic acids and glycosaminoglycans) and 2.5 (for glycosaminoglycans only), periodic acid-Schiff reactive (for neutral sugars), xylidine ponceau at pH 2.5 (for total proteins), and picrosirius/hematoxylin (for selective collagen analysis). The biomaterials studied were not considered citocytotoxic. The cells were able to adhere to and proliferate on the substrates. The cytochemical data indicate that the cells have high functional activity, with high protein synthesis on the scaffolds but do not accumulate acid or neutral sugars. The cells on the fibrous polymers appear to be more elongated, following the shape of the fibers. Regarding the scaffold form (porous or fibrous), the in vitro data do not show great superiority of one type to the other. Then, all the polymers tested are suitable for tissue engineering.

Enhancing Stem Cell-Based Therapeutic Potential by Combining Various Bioengineering Technologies.

Stem cell-based therapeutics have gained tremendous attention in recent years due to their wide range of applications in various degenerative diseases, injuries, and other health-related conditions. Therapeutically effective bone marrow stem cells, cord blood- or adipose tissue-derived mesenchymal stem cells (MSCs), embryonic stem cells (ESCs), and more recently, induced pluripotent stem cells (iPSCs) have been widely reported in many preclinical and clinical studies with some promising results. However, these stem cell-only transplantation strategies are hindered by the harsh microenvironment, limited cell viability, and poor retention of transplanted cells at the sites of injury. In fact, a number of studies have reported that less than 5% of the transplanted cells are retained at the site of injury on the first day after transplantation, suggesting extremely low (<1%) viability of transplanted cells. In this context, 3D porous or fibrous national polymers (collagen, fibrin, hyaluronic acid, and chitosan)-based scaffold with appropriate mechanical features and biocompatibility can be used to overcome various limitations of stem cell-only transplantation by supporting their adhesion, survival, proliferation, and differentiation as well as providing elegant 3-dimensional (3D) tissue microenvironment. Therefore, stem cell-based tissue engineering using natural or synthetic biomimetics provides novel clinical and therapeutic opportunities for a number of degenerative diseases or tissue injury. Here, we summarized recent studies involving various types of stem cell-based tissue-engineering strategies for different degenerative diseases. We also reviewed recent studies for preclinical and clinical use of stem cell-based scaffolds and various optimization strategies.

Porphyrin Tripod as a Monomeric Building Block for Guest-Induced Reversible Supramolecular Polymerization

A porphyrin tripod (DPZnT) connected through a triazole bridge was prepared as a monomeric building block for guest-induced supramolecular polymerization. Although the lone pair electrons in triazolic nitrogen potentially bind to the zinc porphyrin units through axial ligation, the intrinsic steric hindrance suppressed the coordination of the triazole bridge to the porphyrin unit in DPZnT. Therefore, DPZnT formed spherical nanoparticles through π–π interactions. The addition of 1,3,5-tri(pyridin-4-yl)benzene (Py3B) caused the guest-induced fibrous supramolecular polymerization of DPZnT by forming a 1:1 host–guest complex, which was further assembled into a fibrous polymer. Furthermore, addition of Cl– to DPZnT induced the transformation of spherical nanoparticles to networked supramolecular polymers. The fibrous and networked supramolecular polymers of DPZnT obtained by adding Py3B or Cl– were depolymerized to their original spherical particles after adding Cu(ClO4)2 or AgNO3, respectively.

Qualifying the contribution of fiber diameter on the acrylate-based electrospun shape memory polymer nano/microfiber properties.

Fibrous shape memory polymers (SMPs) have received growing interest in various applications, especially in biomedical applications, which offer new structures at the microscopic level and the potential of enhanced shape deformation of SMPs. In this paper, we report on the development and investigation of the properties of acrylate-based shape memory polymer fibers, fabricated by electrospinning technology with the addition of polystyrene (PS). Fibers with different diameters are manufactured using four different PS solution concentrations (25, 30, 35, and 40 wt%) and three flow rates (1.0, 2.5, and 5.0 μL min-1) with a 25 kV applied voltage and 17 cm electrospinning distance. Scanning electron microscope (SEM) images reveal that the average fiber diameter varies with polymer concentration and flow rates, ranging from 0.655 ± 0.376 to 4.975 ± 1.634 μm. Dynamic mechanical analysis (DMA) and stress-strain testing present that the glass transition temperature and tensile values are affected by fiber diameter distribution. The cyclic bending test directly proves that the electrospun SMP fiber webs are able to fully recover; additionally, the recovery speed is also affected by fiber diameter. With the combination of the SMP material and electrospinning technology, this work paves the way in designing and optimizing future SMP fibers properties by adjusting the fiber diameter.

Short-time acoustic and hydrodynamic cavitation improves dispersibility and functionality of pectin-rich biopolymers from citrus waste.

Pectin is a valuable biopolymer used as a natural, clean label additive for thickening and gelling. However, industry faces issues with dispersibility and stability of pectin formulations. To address these issues, the effect of short processing time (30–180 s) with hydrodynamic (HC) and acoustic cavitation (AC) on the dispersibility and gelling functionality of mandarin pectin-rich polysaccharide (M-PRP) was investigated. Short-time processing with HC and AC did not affect polymer composition. HC, but not AC, decreased polydispersity index (PDI) from 0.78 to 0.68 compared to the control. Electron and atomic force microscopy showed that HC and AC decreased aggregation of fibrous and matrix polymers. Both treatments increased apparent viscosity significantly from 0.059 Pa s to 0.30 Pa s at 10 −s. The pectin dispersions showed good gelling capacity upon addition of calcium (final conc. 35 mM). HC and AC treatments for 150 s led to gels that were 7 and 4 times stronger (as measured by peak force) than the control with more homogeneous, less porous structures. In conclusion, short-time HC and AC can improve the dispersibility and functionality of citrus pectin without affecting composition, and are promising technologies to facilitate the use of pectin in industry applications.

Tacking with curvilinear knives for grinding fibrous plant polymers

The method for calculating the main technological parameters of a set with a curved shape of knives is presented. The aim of the work is to design a disk set with circumferential knives and to determine dependencies that allow predicting the technical and technological parameters of this set, the quality of the resulting semi-finished product during grinding, increasing the productivity of the grinding plant and reducing energy consumption during grinding. For the first time, a numerical method has been developed for calculating the second cutting length (Ls) of a knife set with a curved shape of knives, taking into account the main geometric parameters of the set. The geometric construction of the knife set of grinding machines allows to purposefully predict its use for various modes of the grinding process in the production of certain types of finished products. The research results can be used in the design of new types of headsets, their manufacture and operation.

Constitutive Modeling of multi-stimuli-responsive shape memory polymers with multi-functional capabilities

Nowadays, shape memory polymers (SMPs)-based devices are required to be much smarter to produce large shape memory recovery and recovery force with lower working temperatures in order to enable multi-functionality in them. They could play a vital role in the advancement of multi-functional soft robot manipulators, biomedical tools and wearable devices where the working temperatures is a key challenge and must be around the body temperature, or in sustainable smart systems with low energy consumption. The aim of this paper is to introduce thermo-electro-magneto-responsive fibrous SMPs (TEMFSMPs) as a new class of SMPs with highly enhanced shape recovery and recovery force and reduced working temperature. A three-dimensional constitutive model is developed to simulate thermo-electro-magneto-visco-hyperelastic behaviors of SMPs under large deformation for the first time. Constitutive relations are derived by adopting an electro-magneto-visco-hyperelasticity theory and implementing it in a thermo-mechanical cycle of SMPs. To improve the strength of thermo-electro-magneto-responsive SMPs, a bunch of fibers is also embedded into the SMP matrix. Then, the proposed model for thermo-electro-magneto-responsive fibrous shape memory polymers (TEMFSMPs) under uniaxial tension and complex loading regimes such as simultaneous torsion and extension are solved semi-analytically. In addition, the thermo-mechanical response through the proposed model is validated via available SMP experimental tests. Numerical results reveal that electro-magnetic features can significantly enhance shape memory recovery and recovery force of TEMFSMPs and lower their working temperatures. It is found that the electro-magnetic field, the orientation, and stiffness of fibers can effectively be set to tune the shape memory effect and bio-applicability of TEMFSMPs with highly enhanced stress/strain recovery and reduced working temperature.

Process parametric optimization in drilling of CFRP composites using GRA method

In the modern world, lightweight fibrous composites materials with high mechanical properties are the first choice for structural design purpose. Excellent mechanical properties and easy to make and shape quality make it the prime substance for aeronautics as well as automobile manufacturing units. However, drilling of these non-homogenous fibrous polymers is quite tricky in compare to the other traditional metal. In this paper, eighteen different sets of the parametric combination were derived, using Taguchi’s L 18 orthogonal array. Grey relational analysis (GRA) has been used to find the optimal drilling parameter setting by optimizing the three performance characteristics, like thrust force, torque, and delamination factor. The axial thrust force was found to be the most influential feature in predicting delamination factor. However, the thrust force was maximum at high feed and low spindle speed and higher tool point angle. Analysis of variance is also used for predicting the most contributing parameter and it was found out that, feed rate has the maximum impact in drilling carbon fiber reinforced plastics (CFRP).

Wide Angle X-Ray Scattering to Study the Atomic Structure of Polymeric Fibers

Natural fibrillar-like macromolecules find applications in several fields, thanks to their peculiar features, and are considered perfect building blocks for natural and artificial functional materials. Indeed, fibrous proteins (such as collagen or fibroin) are commonly used in scaffold fabrication for biomedical applications, due to the high biophysical similarity with the extracellular matrix (ECM) which stimulates tissue regeneration. In the textile industry, cellulose-based fabrics are widely used in place of cotton and viscose, which both have sustainability issues related to their fabrication. With this in mind, the structural characterization of the materials at molecular scale plays a fundamental role in gaining insight into the fiber assembly process. In this work, we report on three fibers of research interest (i.e., type I collagen, silk fibroin extracted from Bombyx mori, and cellulose) to show the power of wide-angle X-ray scattering to characterize both intra- and intermolecular parameters of fibrous polymers. The latest possibilities offered in the X-ray scattering field allow one to study fibers at solid state or dispersed in solutions as well as to perform quantitative scanning X-ray microscopy of tissues entirely or partially made by fibers.

Natural Fibrous Polymers for Tissue Engineering

Natural Fibrous Polymers for Tissue Engineering

Cereal Bioactive Compounds: A Review

Cereal grains and wholegrain cereal products (rich in fibrous polymers) are the excellent sources of numerous unique substances rating among biologically active compounds such as dietary fiber (arabinoxylans, beta-glucans, cellulose, lignin and lignans), sterols, tocopherols, tocotrienols, alkylresorcinols, phenolic acids, vitamins and microelements. Cereals have been staple foods both directly for human consumption and ready available to the human diet. The major cereals consumed worldwide are wheat, rice, maize, barley, oats, rye, millet, sorghum. Bioactive compounds of whole-grains are present in the bran/germ fraction of cereal-grains and least in endosperm. The bioactive components in cereals help in reducing the risk of chronic diseases act as a functional ingredient. Bioactive compounds in whole-grain cereals have not received as much attention as in fruits and vegetables due to difficult in extractions and some have antinutritional role. These health benefits are achieved through multifactorial physiological mechanisms including antioxidant activity, mediation of hormones, enhancement of immune system and facilitation of substance transit through the digestive tract, butyric acid production in the colon, and absorption.

Strain-Stiffening in Dynamic Supramolecular Fiber Networks.

The cytoskeleton is a highly adaptive network of filamentous proteins capable of stiffening under stress even as it dynamically assembles and disassembles with time constants of minutes. Synthetic materials that combine reversibility and strain-stiffening properties remain elusive. Here, strain-stiffening hydrogels that have dynamic fibrous polymers as their main structural components are reported. The fibers form via self-assembly of bolaamphiphiles (BA) in water and have a well-defined cross-section of 9 to 10 molecules. Fiber length recovery after sonication, H/D exchange experiments, and rheology confirm the dynamic nature of the fibers. Cross-linking of the fibers yields strain-stiffening, self-healing hydrogels that closely mimic the mechanics of biological networks, with mechanical properties that can be modulated by chemical modification of the components. Comparison of the supramolecular networks with covalently fixated networks shows that the noncovalent nature of the fibers limits the maximum stress that fibers can bear and, hence, limits the range of stiffening.

Leaf-Inspired Self-Healing Polymers

Summary Hierarchical multiphase fibrous morphologies provide strength and elasticity for biological species, facilitating responses to environmental changes. Wound closure of leaves is one example. If polymers can be formed in a similar manner by introducing multiphase-separated morphologies, self-healing in a variety of commodity materials can be achieved. In these studies, we demonstrate the role of phase morphologies, interphases, and viscoelasticity-driven shape memory effects on self-healing. We synthesized phase-separated polycaprolactone-polyurethane fibrous thermoplastic polymers in which microphase separation facilitates the formation of stable interfacial regions between hard and soft segments. Self-healing can be repeated many times. This behavior is attributed to the shape memory effect, given that micron-scale interphase reduces chain slippage, enabling entropic energy storage during damage. Chemically identical but nanophase-separated copolymers do not exhibit this behavior. These studies show that self-healing can be achieved by morphology control and facilitated by thermal or other volume-induced transitions.

Silkworm silk-based materials and devices generated using bio-nanotechnology.

Silks are natural fibrous protein polymers that are spun by silkworms and spiders. Among silk variants, there has been increasing interest devoted to the silkworm silk of B. mori, due to its availability in large quantities along with its unique material properties. Silk fibroin can be extracted from the cocoons of the B. mori silkworm and combined synergistically with other biomaterials to form biopolymer composites. With the development of recombinant DNA technology, silks can also be rationally designed and synthesized via genetic control. Silk proteins can be processed in aqueous environments into various material formats including films, sponges, electrospun mats and hydrogels. The versatility and sustainability of silk-based materials provides an impressive toolbox for tailoring materials to meet specific applications via eco-friendly approaches. Historically, silkworm silk has been used by the textile industry for thousands of years due to its excellent physical properties, such as lightweight, high mechanical strength, flexibility, and luster. Recently, due to these properties, along with its biocompatibility, biodegradability and non-immunogenicity, silkworm silk has become a candidate for biomedical utility. Further, the FDA has approved silk medical devices for sutures and as a support structure during reconstructive surgery. With increasing needs for implantable and degradable devices, silkworm silk has attracted interest for electronics, photonics for implantable yet degradable medical devices, along with a broader range of utility in different device applications. This Tutorial review summarizes and highlights recent advances in the use of silk-based materials in bio-nanotechnology, with a focus on the fabrication and functionalization methods for in vitro and in vivo applications in the field of tissue engineering, degradable devices and controlled release systems.