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Melt compounding of spray-dried cellulose nanofibrils/polypropylene and their application in 3D printing
Abstract Micro- and nano-scale cellulosic fillers exhibit excellent dispersion and distribution within a thermoplastic matrix during the process of melt compounding or injection molding. In this study, spray-dried cellulose nanofiber (SDCNF) powders were manufactured using a pilot-scale rotating disk atomizer spray dryer. Bleached Kraft pulp (BKP), unbleached Kraft pulp (UKP), and old corrugated cardboard pulp (OCC) fibrillated at a fines level of 90% were used as feedstock materials for spray-drying. BKP-, UKP-, and OCC- SDCNFs were compounded with polypropylene using a twin screw co-rotating extruder. Maleic anhydride grafted polypropylene (MAPP) was used as a coupling agent in the composite formulations. The tensile, flexural, and impact properties of SDCNF-filled PP composites increased at 10 wt% SDCNF loading. The presence of SDCNFs in the PP matrix resulted in faster crystallization and a 12% reduction in the degree of crystallinity of the neat PP. The coefficient of thermal expansion (CTE) of neat PP was reduced by up to 31% attributable to the presence of the SDCNFs. Application of the SDCNF-reinforced PP composites in 3D printing reduced the shrinkage rate of the printed neat PP by 39%, and the printability of the PP was significantly improved with the addition of the SDCNFs.
Designing Antifouling and Antimicrobial Interfaces: Structural Characterization using CryoEM, Automated Microscopy, and AI Image Segmentation
The design of functionalized surfaces for interactions with biological systems is critical across sectors such as healthcare, energy, and agriculture. Tailoring materials for specific applications, such as antifouling and antimicrobial surfaces, demands a comprehensive understanding of topology and chemistry across multiple length and time scales on both biological and materials systems. This work presents the development and characterization of nanostructured surfaces with controlled topographies and chemistries that enhance bacterial membrane disruption, reduce biofilm formation, and improve antimicrobial and antifouling capabilities. Two specific use cases will be presented - the use of cellulose nanocrystals (CNCs) for bacterial growth inhibition and the development of antifouling surfaces to prevent protein and bacterial adsorption [1-4]. By leveraging large language models (LLMs) for image segmentation and training [5], we enable automated analysis of terabyte-scale cryogenic electron microscopy (cryoEM) datasets. This analysis provides statistical insights into the biotic/abiotic interface and facilitates automated electron microscopy experiments to mitigate time and dose. The integration of cryogenic electron tomography (cryoET) and cryogenic focused ion beam (cryoFIB) milling enables high-resolution, near-native-state imaging and 3D reconstructions of bio/material interfaces [6]. Orthogonal characterization techniques and computational modeling further enhances our understanding, offering a robust platform for the design and optimization of next-generation functional surfaces [7].
High Purity and Reduced Defects Hard Carbon Synthesis for Sodium-Ion Batteries
Hard carbon (HC) is the state-of-the-art anode material for sodium-ion batteries; however, the high-temperature carbonization of precursors (>1100 °C) often introduces inorganic impurities, an issue that remains largely underexplored. Here, we report a simple synthesis strategy for producing high purity HC by carbonizing a cellulose-derived precursor at 1400 °C under a slightly reducing Ar–H2 atmosphere on a graphite substrate, thereby eliminating the aluminum contamination observed during conventional carbonization on an alumina substrate under Ar. In addition, the modified synthetic condition reduces surface defects and the concentration of oxygen-containing functional groups, thereby altering the interphase formation on the HC surface. At a current density of 20 mA g−1, the impurity-rich HC exhibited an initial coulombic efficiency (ICE) of 74.1% and a reversible capacity of 248.8 mAh g−1. In sharp contrast, the high purity HC delivered a significantly improved ICE of 90.1% and a reversible capacity of 345.1 mAh g−1. These results underscore the critical importance of impurity and defect control during HC synthesis and highlight the clear electrochemical advantages of high purity HC with reduced defects for sodium-ion battery anodes.
Towards the scale-up production of cellulose nanocomposites using melt processing: A critical review on structure-processing-property relationships
Cellulose nanomaterials (CNMs) naturally exist in plant biomass. The success of extraction of CNMs opened up a new era of using plant biomass for innovative industrial applications. Because CNMs are abundant, renewable, biodegradable, transparent, light weight and low in cost, they are ideal materials for large volume applications such as packaging, automotive, building and infrastructure. In many potential application areas, CNM-enable products appear in a composite form, mostly polymer composites. Additionally, the industrial-scale manufacturing of CNM/thermoplastic composites remains as a set of unsolved problems for academia and industry. A prime challenge in applications is the nanoscale dispersion of CNMs in thermoplastic matrices during melt processing. Both bench-scale and pilot-scale studies have been conducted to solve the dispersion issue of CNMs. In this article, research related to the dispersion of CNMs in thermoplastic matrices during melt processing were critically reviewed. All research papers were classified into three groups: chemically-aided dispersion, physically-aided dispersion and mechanically-aided dispersion. Numerous factors affect the CNM dispersion and the mechanical performance of its nanocomposites. There are material-related factors, including CNM types and forms, polymer matrices, surface modification, coupling agents, etc. Furthermore, extrusion processing parameters also play a significant role, covering screw rotation speed, extrusion barrel temperature settings and screw design. In addition, the material-related factors interact with the processing-related factors. Understanding all factors and their interactions are important for moving CNM nanocomposites research a step further towards industrial-relevant production, which is the final ambitious goal of this manuscript.
Graphene oxide precursor effects on 3D-printed carbon scaffolds
Manganese oxide (MnO 2 ), an earth-abundant material, is a promising component for energy storage devices, with uses in both pseudocapacitors and batteries. However, high MnO 2 loading often leads to reduced performance due to poor ion diffusion. 3D printing, particularly using the direct ink writing (DIW) technique, offers a solution by enabling the fabrication of electrodes with hierarchical porous structures and open channels that enhance mass transport and ion diffusion. Previous work demonstrated that 3D-printed graphene aerogels with MnO 2 coatings exhibited excellent electrochemical performance, even with thick electrodes, due to their optimized structure. Building on this work, the current study investigates the performance differences between aerogels developed using graphene oxide (GO) and reduced graphene oxide (rGO) as carbon precursors. Both materials were incorporated into thixotropic inks, 3D-printed into lattice structures, and carbonized. Despite expected similarities between the final graphene aerogel, rGO-based aerogels exhibited superior areal capacitance, compared to GO-based aerogels. These differences are attributed to the lower oxygen content and defect density of rGO, which influence its interaction with cellulose viscosifiers in the ink formulation. Brunauer–Emmett–Teller (BET) surface area analysis revealed that rGO aerogels exhibit a larger surface area and mesoporous structure, further enhancing their performance. When coated with MnO 2 , rGO-based aerogels maintained their superior capacitive behavior over GO-based aerogels. This study highlights the effect of carbon precursor on the end performance of graphene aerogels.
Boosting the electrochemical performance with functionalized dry electrodes for practical all-solid-state batteries
A functionalized dry electrode (FDE) incorporating solvate-ionic-liquid-infiltrated ethyl cellulose demonstrates the criticality of the role of the conductive binder for achieving improved electrochemical performance in all-solid-state batteries.
Use of Ionic Liquids for Hemp Fiber Degumming
Degumming or retting to remove pectin, lignin, and hemicellulose is a critical step in the production of high-quality hemp fibers. Current technologies, including traditional water or dew retting, as well as chemical, enzymatic, and physical degumming processes, have inherent environmental risks and produce fibers of varying qualities. Herein we explore the use of an ionic liquid (IL) capable of dissolving pectin, lignin, and hemicellulose, but not cellulose, in combination with different oxidating agents to degum hemp. In this study, we observed that treating raw hemp fibers with the IL choline acetate ([Cho][OAc]), alone or in combination with aqueous H 2 O 2 , led to a reduction in the gummy materials and lignin content of the resulting samples of up to 63 and 78%, respectively. More importantly, the high crystallinity and low reduction in tensile strength of the resulting fibers make these novel and relatively simple IL-based processes promising alternatives toward the sustainable preparation of hemp-based materials suitable for use in the textile industry.
Organic Solvent Free Process to Fabricate High Performance Silicon/Graphite Composite Anode
Cycling stability is a key challenge for application of silicon (Si)-based composite anodes as the severe volume fluctuation of Si readily leads to fast capacity fading. The binder is a crucial component of the composite electrodes. Although only occupying a small amount of the total composite mass, the binder has major impact on the long-term electrochemical performance of Si-based anodes. In recent years, water-based binders including styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) have attracted wide research interest as eco-friendly and low-cost alternatives for the conventional poly(vinylidene difluoride) (PVDF) binder in Si anodes. In this study, Si-based composite anodes are fabricated by simple solid mixing of the active materials with subsequent addition of SBR and CMC binders. This approach bypasses the use of toxic and expansive organic solvents. The factors of binder, silicon, and graphite materials have been systematically investigated. It is found that the retained capacities of the anodes are more than 440 mAh/g after 400 cycles. These results indicate that organic solvent free process is a facile strategy for producing high performance silicon/graphite composite anodes.
Ammonia Fiber Expansion (AFEX) Pretreatment of Lignocellulosic Biomass
Lignocellulosic materials are plant-derived feedstocks, such as crop residues (e.g., corn stover, rice straw, and sugar cane bagasse) and purpose-grown energy crops (e.g., miscanthus, and switchgrass) that are available in large quantities to produce biofuels, biochemicals, and animal feed. Plant polysaccharides (i.e., cellulose, hemicellulose, and pectin) embedded within cell walls are highly recalcitrant towards conversion into useful products. Ammonia fiber expansion (AFEX) is a thermochemical pretreatment that increases accessibility of polysaccharides to enzymes for hydrolysis into fermentable sugars. These released sugars can be converted into fuels and chemicals in a biorefinery. Here, we describe a laboratory-scale batch AFEX process to produce pretreated biomass on the gram-scale without any ammonia recycling. The laboratory-scale process can be used to identify optimal pretreatment conditions (e.g., ammonia loading, water loading, biomass loading, temperature, pressure, residence time, etc.) and generates sufficient quantities of pretreated samples for detailed physicochemical characterization and enzymatic/microbial analysis. The yield of fermentable sugars from enzymatic hydrolysis of corn stover pretreated using the laboratory-scale AFEX process is comparable to pilot-scale AFEX process under similar pretreatment conditions. This paper is intended to provide a detailed standard operating procedure for the safe and consistent operation of laboratory-scale reactors for performing AFEX pretreatment of lignocellulosic biomass.
Solid, hydrophobic aggregators and methods of making and using the same
Disclosed herein are aggregators that can be cellulosic particles having high oil sorption capacity, high hydrophobicity, high buoyancy in water, and an aggregation quality that can support environmental remediation of hydrocarbon spills (e.g., crude oil spills) by various cleanup strategies including burning, skimming, or bioremediation. Also disclosed are methods of making the materials and methods of using the materials for environmental remediation.
Beneficiation of Stillwater Complex Rock for the Production of Lunar Simulants
The availability of pure, high calcium plagioclase would be a significant asset in any attempt to manufacture high-quality lunar simulants. A suitable plagioclase product can be obtained from materials obtained from the Stillwater Complex of Montana. The access, geology, petrology, and mineralogy of the relevant rocks and the mill tailings are described here. This study demonstrates successful plagioclase recovery from mill tailings produced by the Stillwater Mine Company. Hydrogen peroxide was used to remove carboxymethyl cellulose from the tailing. The characteristics of the plagioclase products are shown and locked grains are identified as a limit to achievable purity. Based on the experimental results, flowsheets were developed showing how these resources could be processed and made into 'separates' of (1) high calcium plagioclase and (2) orthopyroxene/clinopyroxene with the thought that they would be combined later to make simulant.
Emperor's new clothes: Novel textile-based supercapacitors using sheep wool fiber as electrode substrate
Textile-based supercapacitors (TSCs) are being used to meet the ever-increasing demand for mobile, safe, and convenient energy sources to power personal electronic devices. To that end, the smart textiles used in wearable technology need to be made from highly conductive yarns that are easily manufacturable. To date, synthetic- and cellulosic-based yarns have been exclusively used for the fabrication of TSCs, while other yarns have not been explored. Here, we used conductive protein-based yarns for TSCs and report on the use of wool coated with Ti 3 C 2 T x MXene as a potential electrode material. To knit TSCs, wool and cotton yarns were coated with MXene flakes and their surfaces were characterized using Scanning Electron Microscopy (SEM) and X-Ray Photoelectron Spectroscopy (XPS). The electrochemical characterization was conducted to examine the performance of wool- and cotton-based MXene electrodes as substrates and determine charge storage and resistive behavior. These tests showed that wool TSCs exhibited more pseudocapacitive behavior, while cotton TSCs exhibited a wider current range. At a scan rate of 5 mV/s, cotton TSCs presented an areal capacitance of 823.9 mF/cm 2 while this value for the wool TSCs was 284 mF/cm 2 . The performance of yarns was also tested under various mechanical deformation conditions and after washing in order to assess the stability of TSCs. This study indicates the potential of protein-based yarns as electrode substrates for integration of MXene to fabricate smart textile-based devices.
Cellulose-based composites and methods of making the same
Disclosed herein are a cellulose particle and a binder, where the cellulose particle has a cellulose core and a surface group, and the binder interacts with the surface group to form a composite.
Highly transparent silanized cellulose aerogels for boosting energy efficiency of glazing in buildings
Abstract To maintain comfortable indoor conditions, buildings consume ~40% of the energy generated globally. In terms of passively isolating building interiors from cold or hot outdoors, windows and skylights are the least-efficient parts of the building envelope because achieving simultaneously high transparency and thermal insulation of glazing remains a challenge. Here we describe highly transparent aerogels fabricated from cellulose, an Earth-abundant biopolymer, by utilizing approaches such as colloidal self assembly and procedures compatible with roll-to-roll processing. The aerogels have visible-range light transmission of 97–99% (better than glass), haze of ~1% and thermal conductivity lower than that of still air. These lightweight materials can be used as panes inside multi-pane insulating glass units and to retrofit existing windows. We demonstrate how aerogels boost energy efficiency and may enable advanced technical solutions for insulating glass units, skylights, daylighting and facade glazing, potentially increasing the role of glazing in building envelopes.
Intumescent Coatings as Fire Retardants
The development of fire-retardant coatings to protect surfaces which may be exposed to fire or extreme heat is a subject of intense interest to many industries. A fire-retardant paint has been developed which represents a new chemical approach for preparing intumescent coatings, and potentially, is very important to fire-prevention authorities. The requirements for a superior coating include ease of application, suitability to a wide variety of surfaces and finishes, and stability over an extended period of time within a broad range of ambient temperature and humidity conditions. These innovative coatings, when activated by the heat of a fire, react to form a thick, low-density, polymeric coating or char layer. Water vapor and sulphur dioxide are released during the intumescent reaction. Two fire-protection mechanisms thus become available: (1) the char layer retards the flow of heat, due to the extremely low thermal conductivity; and (2) water vapor and sulfur dioxide are released, providing fire quenching properties. Still another mechanism functions in cases where the char, by virtue of its high oxidation resistance and low thermal conductivity, reaches a sufficiently high temperature to re-radiate much of the incident heat load. The coatings consist of dispersions of selective salts of a nitro-amino-arornatic compound. Specifically, para-nitroaniline bisulfate and the ammonium salt of para-nitroaniline-ortho sulphuric acid (2-amino-5-nitrobenzenesulphuric acid) are used. Suitable vehicles are cellulose nitrate of lacquer grade, a nitrite-phenolic modified rubber, or epoxy-polysulfide copolymer. Three separate formulations have been developed. A solvent is usually employed, such as methylethyl ketone, butyl acetate, or toluene, which renders the coatings suitably thin and which evaporates after the coatings are applied. Generally, the intumescent material is treated as insoluble in the vehicle, and is ground and dispersed in the vehicle and solvent like an ordinary coating pigment. The char found on intumescence is better in terms of yield and physical properties than chars obtained from many previously known intumescent materials. Prior to intumescence, the coating has a density of 85 pounds per cubic foot. After intumescence, the density is approximately 0.3 pounds per cubic loot. The linear expansion of the coatings ranges from 70 to 200 times the applied coating thickness.
Effects of antibacterial peptide-producing Bacillus subtilis, gallic acid, and cellulase on fermentation quality and bacterial community of whole-plant corn silage
In the current study, we assessed the effects of antibacterial peptide-producing Bacillus subtilis (BS), gallic acid (GA) and cellulase (CL) on the fermentation quality and bacterial community of various varieties of whole-plant corn silage. Three different varieties of whole-plant corn (Yuqing386, Enxiai298, and Nonghe35) were treated with 0.02% BS (fresh material basis), 0.2% GA (fresh material basis) and 0.02% CL (fresh material basis), after which 45 days of anaerobic fermentation were conducted. With the exception of its low dry matter content, the results showed that Yuqing386’s crude protein, water-soluble carbohydrate, and lactic acid contents were significantly higher than those of the other two corn varieties. However, its acid detergent fiber and cellulose contents were significantly lower than those of the other two corn varieties. Among the three corn variety silages, Yuqing386 had the highest relative abundance of Lactobacillus at the genus level and the biggest relative abundance of Firmicutes at the phylum level. In addition, the three additives markedly enhanced the quantity of dry matter and crude protein as compared to the control group. The application of GA considerably decreased the level of neutral detergent fiber while significantly increasing the content of lactic acid and water-soluble carbohydrates. Even though all additives enhanced the structure of the bacterial community following silage, the GA group experienced the greatest enhancement. On a phylum and genus level, the GA group contains the highest relative abundance of Firmicutes and Lactobacillus , respectively. Overall, of the three corn varieties, Yuqing386 provides the best silage qualities. GA has the biggest impact among the additions employed in this experiment to enhance the nutritional preservation and fermentation quality of whole-plant corn silage.
Cellulose acetate membranes exhibit exceptional monovalent to divalent cation selectivities
Salt transport properties of cellulose acetate membranes are reported for a series of chloride salts with mono- valent and divalent cations (LiCl, NaCl, MgCl 2 , CaCl 2 ). Measurements include salt permeability and sorption, with diffusivity values calculated from the permeability and sorption results. We report an exceptionally high LiCl/MgCl 2 selectivity of 750:1. Salts with similar valence (LiCl and NaCl; MgCl 2 and CaCl 2 ) have similar transport properties. The high monovalent/divalent selectivity arises from differences in both sorption and diffusion, with a LiCl/MgCl 2 solubility selectivity of about 11 and a diffusivity selectivity of about 70. Atomistic molecular dynamics simulations show that ions tend to reside in isolated clusters of water. Increasing ion charge strengthens ion–water interactions relative to ion–polymer interactions, explaining the reduced sorption of divalent ions. Diffusion of ions through the membrane occurs via hop-like motion between water clusters. Lithium diffuses faster than magnesium due to weaker ion–water coordination for lithium, which allows for greater mobility within water clusters and more frequent hopping. Altogether, our atomistic simulations suggest that the high LiCl/MgCl 2 selectivity is linked to cellulose acetate’s high water/salt selectivity and is a consequence of low water content and relatively uniform water distribution.