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At least 19 records

Processes for treating cellulosic material

Disclosed are processes for pretreating cellulosic materials in liquid water by heating the materials in liquid water at a temperature at or above their glass transition temperature but not substantially exceeding 220.degree. C., while maintaining the pH of the reaction medium in a range that avoids substantial autohydrolysis of the cellulosic materials. Such pretreatments minimize chemical changes to the cellulose while leading to physical changes which substantially increase susceptibility to hydrolysis in the presence of cellulase.

Ladisch, Michael R.↗

Structure Development of the Interphase between Drying Cellulose Materials Revealed by In Situ Grazing-Incidence Small-Angle X-ray Scattering

The nano- to microscale structures at the interface between materials can define the macroscopic material properties. These structures are extremely difficult to investigate for complex material systems, such as cellulose-rich materials. The development of new model cellulose materials and measuring techniques has opened new possibilities to resolve this problem. We present a straightforward approach combining micro-focusing grazing-incidence small-angle X-ray scattering and atomic force microscopy (AFM) to investigate the structural rearrangements of cellulose/cellulose interfaces in situ during drying. Based on the results, we propose that molecular interdiffusion and structural rearrangement play a major role in the development of the properties of the cellulose/cellulose interphase; this model is representative of the development of the properties of joint/contact points between macroscopic cellulose fibers.

36 MATERIALS SCIENCE↗

Ignition and subsequent flame spread over a thin cellulosic material

Both ignition and flame spread on solid fuels are processes that not only are of considerable scientific interest but that also have important fire safety applications. Both types of processes, ignition and flame spread, are complicated by strong coupling between chemical reactions and transport processes, not only in the gas phase but also in the condensed phase. In most previous studies, ignition and flame spread were studied separately with the result that there has been little understanding of the transition from ignition to flame spread. In fire safety applications this transition is crucial to determine whether a fire will be limited to a localized, temporary burn or will transition into a growth mode with a potential to become a large fire. In order to understand this transition, the transient mechanisms of ignition and subsequent flame spread must be studied. However, there have been no definitive experimental or modeling studies, because of the complexity of the flow motion generated by buoyancy near the heated sample surface. One must solve the full Navier-Stokes equations over an extended region to represent accurately the highly unstable buoyant plume and entrainment of surrounding gas from far away. In order to avoid the complicated nature of the starting plume problem under normal gravity, previous detailed radiative ignition models were assumed to be one-dimensional or were applied at a stagnation point. Thus, these models cannot be extended to include the transition to flame spread. The mismatch between experimental and calculated geometries means that theories cannot be compared directly with experimental results in normal gravity. To overcome the above difficulty, theoretical results obtained without buoyancy can be directly compared with experimental data measured in a microgravity environment. Thus, the objective of this study is to develop a theoretical model for ignition and the transition to flame spread and to make predictions using the thermal and chemical characteristics of a cellulosic material which are measured in normal gravity.

Nakabe, Kazuyoshi↗

The effect of fire retardants on the fire response characteristics of cellulosic materials

The resistance to ignition of fire retardant-treated wood, cotton, and cellulose insulation was studied. The proprietary composition used to treat wood was found to increase resistance to ignition and to reduce smoke toxicity. Cotton treated with boric acid (added by padding on or by vapor phase process) was found to have increased resistance to ignition and decreased smoke toxicity. Boric acid increased the resistance of cellulose insulation to ignition but also slightly increased the smoke toxicity.

Hilado, C. J.↗

Heat and Mass Transport from Thermally Degrading Thin Cellulosic Materials in a Microgravity Environment

Attention is given to a theoretical model describing the behavior of a thermally thin cellulosic sheet heated by external thermal radiation in a quiescent microgravity environment. This model describes thermal and oxidative degradation of the sheet and the heat and mass transfer of evolved degradation products from the heated cellulosic surface into the gas phase. Two calculations are carried out: heating without thermal degradation, and heating with thermal degradation of the sheet with endothermic pyrolysis, exothermic thermal oxidative degradation, and highly exothermic char oxidation. It is shown that pyrolysis is the main degradation reaction. Self-sustained smoldering is controlled and severely limited by the reduced oxygen supply.

Kushida, G.↗

An experimental study of the influence of elevated buoyancy levels on flame spread rate over thermally thin cellulosic materials

The role of buoyancy on the flame spread rate over paper and its effect on extinction was studied by changing the gravity level and pressure. It was found that the flame spread rate decreases as the buoyancy induced flow increases. A method for correlating flame spread data using dimensionless parameters is presented. The Damkohler number is shown to be the dependent variable.

Shang, P. C.↗

Additive Manufacturing with Cellulose-Based Composites: Materials, Modeling, and Applications

Recent advances in large-scale additive manufacturing (AM) with polymer-based composites have enabled efficient production of high-performance materials. Cellulose nanomaterials (CNMs) have emerged as bio-based feedstocks due to their exceptional strength and sustainability. However, challenges such as hornification and poor dispersion in polymer matrices still limit large-scale CNM–polymer composite manufacturing, requiring novel strategies. Here, this review outlines an approach starting with atomic-level simulations to link molecular composition to key parameters like bulk density, viscosity, and modulus. These simulations provide data for finite element analysis (FEA), which informs large-scale experiments and reduces the need for extensive trials. The strategy explores how atomic interactions impact the morphology, adhesion, and mechanical properties of CNM-based composites in AM processes. The review also discusses current developments in AM, along with predictions of mechanical and thermal properties for structural applications, packaging, flexible electronics, and hydrogel scaffolds. By integrating experimental findings with molecular dynamics (MD) simulations and finite element modeling (FEM), valuable insights for material design, process optimization, and performance enhancement in CNM-based AM are provided to address ongoing challenges.

36 MATERIALS SCIENCE↗

Surface-Mediated Interconnections of Nanoparticles in Cellulosic Fibrous Materials toward 3D Sensors

Fibrous materials serve as an intriguing class of 3D materials to meet the growing demands for flexible, foldable, biocompatible, biodegradable, dis- posable, inexpensive, and wearable sensors and the rising desires for higher sensitivity, greater miniaturization, lower cost, and better wearability. The use of such materials for the creation of a fibrous sensor substrate that interfaces with a sensing film in 3D with the transducing electronics is however difficult by conventional photolithographic methods. Here, a highly effective pathway featuring surface-mediated interconnection (SMI) of metal nanoclusters (NCs) and nanoparticles (NPs) in fibrous materials at ambient conditions is demon- strated for fabricating fibrous sensor substrates or platforms. Bimodally distrib- uted gold–copper alloy NCs and NPs are used as a model system to demonstrate the semiconductive-to-metallic conductivity transition, quantized capacitive charging, and anisotropic conductivity characteristics. Upon coupling SMI of NCs/NPs as electrically conductive microelectrodes and surface-mediated assembly (SMA) of the NCs/NPs as chemically sensitive interfaces, the resulting fibrous chemiresistors function as sensitive and selective sensors for gaseous and vaporous analytes. Finally, this new SMI–SMA strategy has significant implications for manufacturing high-performance fibrous platforms to meet the growing demands of the advanced multifunctional sensors and biosensors.

36 MATERIALS SCIENCE↗

The preparation and characterization of chemically deuterium incorporated cotton fibers

Preparation of deuterium incorporated cellulose is a vital tool to investigate cellulose internal structure and to expand the application fields of cellulose materials. In this study, cellulosic cotton fibers with anti-rehydration (exchange-resistant) deuterium incorporated in cellulose were prepared by chemical hydrogen–deuterium exchange treatment. The chemical hydrogen–deuterium exchange process, along with exchange time, were characterized by nuclear magnetic resonance hydrogen spectroscopy (1H-NMR). The anti-rehydration deuterium incorporation was determined by Fourier Transform infrared spectroscopy (FTIR) and Stable Isotope Ratio Mass Spectrometer (IRSM). Here, the effect of the deuterium hydroxyl substitution on cotton fiber’s spectral data, microstructure, crystalline information, degree of polymerization, as well as it’s thermogravimetric analysis (charcoalization and combustion) are explored. Analysis of the chemical exchange process indicated that the hydrogen–deuterium exchange occurred preferentially in the amorphous cellulose component over the first several minutes. Deuterium exchange in the anti-rehydration crystalline phase took several hours. Increasing the treatment time, enhanced exchange-resistant deuterium incorporation to as high as about 60% of the cotton fibers’ cellulose hydroxyl groups was achieved. The characterization of FTIR, Fourier transform Raman (FT-Raman), and near-infrared spectra (NIR) all exhibited the deuterium spectral isotope effect on cellulose hydroxl groups. While, apart from the effect of reaction temperature, deuterium incorporation isotope effect did not affect the cellulose microstructure, crystalline index and the degree of polymerization properties. Furthermore, the thermogravimetric analysis of deuterated cotton fibers under N 2 and air atmosphere were both altered due to the thermodynamic isotope effect. These observations revealed the hydrogen–deuterium exchange treatment process and impacts on cellulose fiber properties, which helped us to better understand the cellulose internal structure and may facilitate the potential utilization of deuterated cellulosic materials.

59 BASIC BIOLOGICAL SCIENCES↗

Recent Advances in Functional Materials through Cellulose Nanofiber Templating

Advanced templating techniques have enabled delicate control of both nano- and microscale structures and have helped thrust functional materials into the forefront of society. Cellulose nanomaterials are derived from natural polymers and show promise as a templating source for advanced materials. Use of cellulose nanomaterials in templating combines nanoscale property control with sustainability, an attribute often lacking in other templating techniques. Use of cellulose nanofibers for templating has shown great promise in recent years, but previous reviews on cellulose nanomaterial templating techniques have not provided extensive analysis of cellulose nanofiber templating. Cellulose nanofibers display several unique properties, including mechanical strength, porosity, high water retention, high surface functionality, and an entangled fibrous network, all of which can dictate distinctive aspects in the final templated materials. Many applications exploit the unique aspects of templating with cellulose nanofibers that help control the final properties of the material, including, but not limited to, applications in catalysis, batteries, supercapacitors, electrodes, building materials, biomaterials, and membranes. A detailed analysis on the use of cellulose nanofibers templating is provided, addressing specifically how careful selection of templating mechanisms and methodologies, combined toward goal applications, can be used to directly benefit chosen applications in advanced functional materials.

36 MATERIALS SCIENCE↗

Characterization of CNC Nanoparticles Prepared via Ultrasonic-Assisted Spray Drying and Their Application in Composite Films

The ultrasonic-assisted spray dryer, also known as a nano spray dryer and predominantly used on a lab scale in the pharmaceutical and food industries, enables the production of nanometer-sized particles. In this study, the nano spray dryer was applied to cellulosic materials, such as cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). CNC suspensions were successfully dried, while the CNF suspensions could not be dried, attributable to their longer fibril lengths. The nano spray drying process was performed under different drying conditions, including nebulizer hole sizes, solid concentrations, and gas flow rates. It was confirmed that the individual particle size of nano spray-dried CNCs (nano SDCNCs) decreased as the nebulizer hole sizes and solid contents of the suspensions decreased. The production rate of the nano spray dryer increased with higher solid contents and lower gas flow rates. The resulting nano SDCNCs were added to a polyvinyl alcohol (PVA) matrix as a reinforcing material to evaluate their reinforcement behavior in a plastic matrix using solvent casting. After incorporating the 20 wt.% nano SDCNCs into the PVA matrix, the tensile strength and tensile modulus elasticity of the neat PVA nanocomposite film increased by 22% and 32%, respectively, while preserving the transparency of the films.

36 MATERIALS SCIENCE↗

Relative toxicity of pyrolysis products of some synthetic polymers

Nineteen samples of synthetic polymers were evaluated for relative toxicity in the course of characterizing materials intended for aircraft interior applications. The generic polymers included ABS, chlorinated PVC, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyaryl sulfone, polyether sulfone, polybismaleimide, and polyvinyl fluoride. Test results are presented, and compared in relative rankings with similar results on cellulosic materials and other synthetic polymers. Under these test conditions, the samples of synthetic polymers were either comparable to or significantly less toxic than the samples of commercial cellulosic materials.

Hilado, C. J.↗

Enhanced thermal reliability and performance of calcium chloride hexahydrate phase change material using cellulose nanofibril and graphene nanoplatelet

In recent years, thermal energy storage (TES) has gained attention for its role in enhancing renewable energy solutions and sustainable energy consumption. The usage of strontium chloride hexahydrate (SCH), graphene nanoplatelet (GNP), and cellulose nanofibril (CNF) additives were investigated to enhance the performance of calcium chloride hexahydrate (CCH) based on the melting/solidification behavior for TES applications. In this work, we develop a promising phase-change-material (PCM) formulation by introducing these additives that reduce supercooling, improve the thermal conductivity and stabilizing the energy storage capacity of CCH. Rheological characterizations demonstrated that the addition of 1 wt% of CNF into CCH produced the required improvement in viscosity and boosted solid-like rheological behavior. Structural characterizations show a physical mixing of the materials within the PCM composites. Our observations show that the amphiphilicity of CNF enables the surface attachment to GNP via hydrophobic interactions providing effective dispersion of GNP throughout the PCM composite. The addition of a nucleating agent, SCH decreased the degree of supercooling of ~20 g of CCH from >20 °C to 3 °C at a cooling rate of 5 °C/min. Thermal characterization showed the resulting PCM composite has a latent heat of melting of 186 Jg -1 , phase change temperature of 32 °C, and stable thermal properties after being subjected to 70 melt-freeze cycles. Adding CNF and GNP to pure CCH increased its thermal conductivity by 76 %. The high thermal conductivity of GNP and its effective dispersion by CNF is responsible for this enhancement. The study highlights the use of biodegradable nanocellulose for the preparation of sustainable PCM composites with improved performance. In conclusion, these PCM composites are scalable, they have potential to increase energy efficiency and revolutionalize the heating/cooling applications in buildings and other TES systems.

25 ENERGY STORAGE↗

Pyrolysis of polymeric materials. I - Effect of chemical structure, temperature, heating rate, and air flow on char yield and toxicity

Various polymeric materials, including synthetic polymers and cellulosic materials, were evaluated at different temperatures, heating rates and air flow rates for thermophysical and toxicological responses. It is shown that char yields appeared to be a function of air access as much as of the chemical structure of the material. It is stated that the sensitivity of the apparent thermal stability of some materials to air access is so marked that thermogravimetric studies in oxygen-free atmospheres may be a consistently misleading approach to comparing synthetic polymers intended to increase fire safety. Toxicity also appeared to be a function of temperature and air access as much as of the chemical structure of the material. Toxicity of the gases evolved seemed to increase with increasing char yield for some polymers.

Hilado, C. J.↗