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At least 1,225 records · Page 68

Screening of alkali-assisted storage conditions to define the operational window of deacetylation within storage systems in the bioenergy supply chain

Overcoming biomass heterogeneity and associated recalcitrance to thermal, chemical, and enzymatic depolymerization is a necessary but challenging aspect of valorizing lignocellulosic biomass to fuels and chemicals. Here, this study explores how this recalcitrance can be reduced during the supply chain unit operation of storage, which is required for seasonally harvested agricultural residues to maintain constant throughput at a biorefinery. In this work, partial alkali pretreatment was performed just prior to corn stover entering storage, which had the benefit of providing a high pH environment entering storage such that soluble sugars were preserved and saponified acetyl groups in hemicellulose. This work investigated a range of viable conditions where saponification and preservation occur simultaneously by varying the moisture content (40% and 60%) and concentrations of sodium hydroxide (low and high) during aerobic and anaerobic storage. Anaerobic conditions preserved overall dry matter below 5% in the three scenarios evaluated, and the highest alkali loading solubilized up to 15% lignin, 18% xylan, and 50% of acetate, meanwhile doubling the extractable components. Scanning electron microscopy images highlighted potential physical impacts including cell-wall disruption near vascular bundles, pitting within parenchyma cells, and cell-wall distortion. Techno-economic assessment indicated that this storage approach and associated logistics system is economically competitive with a conventional approach using low-moisture bales.

09 BIOMASS FUELS↗

Influence of Air and Ethanol Dehydration on Structure, Behavior, and Function of Type I Collagen Scaffolds

Ethanol dehydration is a common step in both scaffold manufacturing and tissue processing, yet the influence of ethanol on collagen is not well understood. This study examined the effects of dehydration, via ethanol treatment and air drying, on collagen structure, behavior, mechanics, and rehydration capacity. Multiple material characterization methods were used including Fourier Transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy, thermogravimetric analysis, small/medium angle x‐ray scattering, volumetric swelling analysis, and tensile testing. Ethanol dehydration removed bulk water from scaffolds, making them stronger and stiffer, but also showed loss of molecular water. This molecular water appears to act as a collagen stabilizer, resulting in less thermally stable scaffolds. The loss of molecular water is also evident in the molecular d‐spacing. Secondary structure of scaffolds was also altered by ethanol, resulting in significantly enhanced rehydration capacity. Bulk water, both before and after rehydration, largely determined mechanical properties, which did not correlate with other structural measures such as FTIR. While rehydration largely returned collagen spacing to pre‐ethanol treated state, structural alterations seen in FTIR cannot be recovered. These results have implications for not only collagen scaffolds, but in many tissue engineering and processing applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Influence of Water, Vacuum, and Temperature on Surface Conditions of a Zeolite‐based Molecular Sieve

Molecular sieves such as zeolite-based materials are ubiquitous in industrial separation processes. However, there is a significant gap in understanding the surface properties and adsorption mechanisms for commercial zeolites, as most research focuses on pure zeolite powders rather than industrially relevant forms. Here, this work addresses this gap in understanding by employing advanced characterization techniques, including positron annihilation spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, liquid nitrogen sorption, and Fourier-transform infrared spectroscopy, to investigate the adsorption and desorption behavior of water in commercial zeolite 13X. Our research reveals insights into the pore-filling mechanisms, the impact of material binders on adsorption properties, and the dynamics of hydration and drying processes for zeolites. Monitoring changes on a minute scale allowed the distinction between fast and slow processes leading to sample drying. The identification of positronium bound to Na + ions indicated that water molecules remain in the vicinity of Na + ions after air-drying zeolite 13X. These findings highlight the importance of various environmental conditions in restoring zeolite properties to baseline after hydration, with significant implications for optimizing industrial processes. This work sets the direction for further research aimed at developing more efficient and robust separation techniques.

Beads Binder↗

Photoexcitation of Fe 3 O Nodes in MOF Drives Water Oxidation at pH=1 When Ru Catalyst Is Present

Abstract Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco‐friendly solar fuels. However, systems with light‐driven water oxidation reaction (WOR) at pH=1 are rare. Broadly used [Ru(bpy) 3 ] 2+ (bpy=2,2’‐bipyridine) photosensitizer has a fixed +1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe 2 O 3 , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe‐based metal–organic framework (MOF) water oxidation photoelectrocatalysts active at pH=1 are presented. Fe‐MIL‐126 and Fe MOF‐dcbpy structures were formed with 4,4’‐biphenyl dicarboxylate (bpdc), 2,2’‐bipyridine‐5,5’‐dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metal‐based catalysts via coordination to 2,2’‐bipyridine fragments. Fe‐based MOFs were doped with Ru‐based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H 2 O) 2 ] 2+ WOC. Materials were analyzed with X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra‐red (FTIR) spectroscopy, resonance Raman, X‐ray absorption spectroscopy, fs optical pump‐probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, Fe III and Ru III oxidation states are present, indicating rate‐limiting electron transfer in MOF. Fe 3 O nodes emerge as photosensitizers able to drive prolonged O 2 evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru‐WOC modification for faster WOC catalysis, or Ru‐WOC substitution to 3d metal‐based systems. The findings give further insight for development of light‐driven water splitting systems based on Earth‐abundant metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical and Electrochemical Characterization of Hot–Pressed Li 6 PS 5 Cl Solid State Electrolyte: Operating Pressure–Invariant High Ionic Conductivity

Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li 6 PS 5 X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10 –2 S cm –1 ) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250°C. Furthermore, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa.

25 ENERGY STORAGE↗

Fabrication of hybrid tin oxide‐cellulose nanocomposite as the flexible and thin supercapacitor

Abstract Microfibrillated cellulose (MFC) with reinforcing effects is a useful building block in the fabrication of flexible and thin supercapacitors. Herein, a hybrid tin oxide‐cellulose nanocomposite was hydrothermally produced and coated on MFC thin films to form a supercapacitor. The hybrid tin oxide‐cellulose thin films were structurally analyzed using scanning electrode microscopy, Fourier transform infrared spectroscopy and x‐ray diffraction. The cellulose thin film with the highest loading of hybrid tin oxide‐cellulose nanocomposite exhibited a specific capacitance of 225.88 F g −1 at 100 mV s −1 and 486.38 F g −1 at 20 mV s −1 in the three‐electrode electrochemical system. In addition, it revealed good cyclic stability up to 40 cycles run continuously with 95% cyclic retention. The high specific capacitance and superior cyclic stability could be related to the enhanced charge mobility and ion diffusion between the solid and electrolyte interface. The cellulose thin film coated with flower‐like hybrid nanocomposite showed great potential in energy storage.

Letchumanan, Iswary↗

Evolution of eggshell structure in relation to nesting ecology in non-avian reptiles

Amniotic eggs are multifunctional structures that enabled early tetrapods to colonize the land millions of years ago, and are now the reproductive mode of over 70% of all terrestrial amniotes. Eggshell morphology is at the core of animal survival, mediating the interactions between embryos and their environment, and has evolved into a massive diversity of forms and functions in modern reptiles. These functions are critical to embryonic survival and may serve as models for new antimicrobial and/or breathable membranes. However, we still lack critical data on the basic structural and functional properties of eggs, particularly of reptiles. Here, we first characterized egg shape, shell thickness, porosity, and mineralization of eggs from 91 reptile species using optical images, scanning electron microscopy, and micro computed tomography, and collected data on nesting ecology from the literature. We then used comparative analyses to test hypotheses on the selective pressures driving their evolution. We hypothesized that eggshell morphology has evolved to protect shells from physical damage and desiccation, and, in support, found a positive relationship between thickness and precipitation, and a negative relationship between porosity and temperature. Although mineralization varied extensively, it was not correlated with nesting ecology variables. Ancestral state reconstructions show thinning and increased porosity over evolutionary time in squamates, but the opposite in turtles and crocodilians. Egg shape, size, porosity and calcification were correlated, suggesting potential structural or developmental tradeoffs. This study provides new data and insights into the morphology and evolution of reptile eggs, and raises numerous questions for additional research.

59 BASIC BIOLOGICAL SCIENCES↗

Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy

Here, the structure and dynamics of polystyrene (PS)-b-poly(ethylene oxide) block copolymers (BCPs) are studied. The BCPs exhibit microphase-separated cylindrical and lamellar morphologies. Structural dynamics are measured with X-ray photon correlation spectroscopy in the small-angle regime. Morphologies and domain sizes are evaluated using small-angle X-ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions are investigated. Grain sizes evaluated using SAXS are found to depend on processing only for the rubbery majority BCP. The structural relaxation times are examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (T g ) of PS, all samples exhibit stretched autocorrelation decays and diffusive dynamics. Near T g of PS, the dynamics of all samples are anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurs at 153 °C or 1.13 T g of PS. In the diffusive regime (at high temperature), structural relaxation times are dependent on the processing method. Near PS T g (at low temperature), structural relaxation times scale with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out-of-equilibrium state of PS dominates the structural dynamics of these strongly phase-segregated BCPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data‐Driven Engineering of Thermostable Collagen‐Mimetic Peptoid Triple Helices

Collagen-mimetic peptides (CMPs) are engineered molecules designed to replicate the triple-helical structure of natural collagen. A repeating x–y-Gly sequence is the defining motif of CMPs and is critical to their triple-helical structure and stability. Substitutions to the residues occupying the x and y positions present a means to modulate the CMP structure and properties. Peptoid residues—N-substituted glycine derivatives—present an attractive potential substitution due to their thermal stability, proteolytic resistance, biocompatibility, and diverse palette of non-natural side chains, but also tend to introduce a high degree of backbone flexibility that can diminish the stability of the triple helix. In this work, we report a computational active learning cycle comprising molecular dynamics simulation, Gaussian process regression, and Bayesian optimization to computationally identify a number of promising peptoid substitutions predicted to stabilize the desired quaternary structure through side chain interactions and produce stable peptoid-based collagen-like triple helices. To experimentally test the computational predictions, a top candidate identified by the screen was synthesized and imaged using scanning electron microscopy to resolve fibril-like bundles consistent with collagen-like triple helices. This work predicts a number of CMP peptoid substitutions capable of forming stable triple-helical structures, presents a generalizable design strategy for engineering desired peptoid structures, and opens new avenues for the design of peptoid-based biomimetic materials.

active learning↗

Fabrication of diatomite‐based microencapsulated flame retardant and its improved fire safety of unsaturated polyester resin

To achive excellent fire resistance, new microcapsule flame retardants (DMCAD and DMPPD) were prepared using 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide combined with melamine cyanurate or melamine polyphosphate as the shell material and diatomite as the core material. The successful assembly of DMCAD and DMPPD was detailed characterized by Fourier transform infrared (FT‐IR) spectra, X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Meanwhile, the flame retardancy and thermal stability of the unsaturated polyester resin (UPR)/DMCAD and UPR/DMPPD composites were also studied. The addition of DMCAD and DMPPD effectively improves the flame retardance properties of UPR, and the effect of DMPPD was better. The limiting oxygen index (LOI) of UPR/DMPPD‐3 increased by 11.6% when compared with that of UPR, and the sample achieved V‐0 rating. Moreover, the peak heat release rate (pHRR) and the total heat release (THR) rate of UPR/DMPPD‐3 were reduced by 67% and 26%, respectively. Under nitrogen condition and air condition, UPR/DMPPD showed better thermal stability and char‐forming ability from the thermogravimetric (TG) results. Residual char of the UPR composites was systematically analyzed with SEM and XPS. Finally, the flame retardant mechanism of DMPPD was proposed.

Chen, Gang↗

Surface modification of bamboo fiber with sodium hydroxide and graphene oxide in epoxy composites

Bamboo fibers (BFs) have high mechanical properties and are candidate reinforcement for epoxy matrix composites. However, to improve performance, good fiber-matrix interaction is required. In this work, unidirectional long BF reinforced epoxy composites at fiber volume content of 22%, 40%, and 50% were made by compression molding. The 40 v% untreated BF reinforced composites exhibited 107% and 439% increase for flexural strength and modulus, respectively, compared to neat epoxy. Sodium hydroxide (NaOH) treatment was used to modify the surface of the BFs, and then the NaOH modified BFs were coated with graphene oxide (GO). The 40 v% NaOH modified BF composites showed an improvement from 259.9 to 327.5 MPa for flexural strength and from 16.7 to 21.5 GPa for flexural modulus, compared to 40 v% untreated BF composites. Slight improvement in properties up to 334.6 MPa for flexural strength and up to 23.8 GPa for flexural modulus was achieved for composites made of 40 v% NaOH/GO modified BF. Surface modification of BF after the NaOH and NaOH/GO treatment was confirmed by X-ray photoelectron spectroscopy and by scanning electron microscopy, which showed differences on the fiber surface morphology and on the composite fracture surface. This BF surface modification approach with GO has potential to impart other properties beyond mechanical to produce multifunctional composite and lead to the use of sustainable plant fibers as alternatives to synthetic fibers.

36 MATERIALS SCIENCE↗

Synthesis and characterization of porous polydimethylsiloxane structures with adjustable porosity and pore morphology using emulsion templating technique

Abstract Porous polydimethylsiloxane (PDMS) framework with adjustable pore structures has been fabricated by polymerization of the continuous phase in the emulsion templates. Different types of surfactants, including nonionic (Triton X‐100), cationic (Benzalkonium chloride), anionic (sodium dodecyl sulfate), and silicone‐based block copolymer were used to stabilize the water‐in‐oil emulsion system. Deionized water with a wide range of internal phases varying from 10% to 60% by weight was employed to make the low internal phase emulsion and medium internal phase emulsion. The effect of surfactant type, surfactant concentration, and the internal phase volume on the stability of the emulsion, pore morphology, and pore size distribution was explored. The stability of the emulsion was investigated by comparing the pore morphology of the cured sample at different set times, such as 0, 6, and 72 h. Scanning electron microscopy was employed for the characterization of the porous structures. The image analysis was conducted, and the pore size distribution, porosity, and open‐cell ratio of each sample were calculated. Interconnected pores have been seen in the porous PDMS made from emulsions with an internal phase larger than 30%. The results demonstrated that the frequency of open‐cell pores and the pore size is dependent on the surfactant types.

Abshirini, Mohammad↗

Microstructure changes during failure of PVDF-based photovoltaic backsheets

The backsheet layer of a solar module provides a safety and environmental barrier to the high voltages running through the photovoltaic (PV) cells and electrical contacts within the core of the module. However, in the past decade, backsheet cracking has become one of the most observed failure modes in PV module field surveys. In this work, the degradation of polyvinylidene fluoride (PVDF)-based backsheets is explored. Backsheet samples are either exposed to accelerated laboratory aging (UV light, heat, and moisture) or collected from the field. Fourier transform infrared and Raman spectroscopy, fragmentation testing, atomic force and scanning electron microscopy, and small-angle neutron scattering are combined to develop an understanding of how chemistry and microstructure evolve during aging. Chemical degradation, surface pitting, polymer phase changes, and anisotropic polymer domains are all observed in aged backsheet samples. The results provide insight into the degradation mechanisms that lead to cracking and field failure of PVDF-based backsheets. The comparison of aged PVDF-based backsheets helps to lay the groundwork for limiting polymer-based failure modes in PV modules.

PVDF↗

Positron annihilation lifetime spectroscopy study of polyvinylpyrrolidone‐added polyvinylidene fluoride membranes: Investigation of free volume and permeation relationships

ABSTRACT Polyvinylidene fluoride (PVDF) membranes were prepared via the phase inversion method from casting solutions containing PVDF, dimethylformamide (DMF), and polyvinylpyrrolidone (PVP) as pore former. PVP was used in the casting solution in a range of 0–5 wt % and extracted. The effect on membranes of using PVP in the casting process was analyzed by X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, viscosity, and water permeability techniques. With an increase of PVP from 0 to 5 wt %, the PVDF casting solution viscosities increased from 858 to 1148 cP; the resulting PVDF membrane thickness increased; and the crystallinity of PVDF membranes decreased from 40.0 to 33.3%, which indicates that the addition of PVP inhibits the degree of crystallization in the PVDF membranes. SEM results revealed the shape and size of macropores in the membranes; these macropores changed after PVP addition to the casting solutions. The impact of structural changes on free‐volume properties was evaluated using positron annihilation lifetime spectroscopy (PALS) studies. PALS analysis indicated no effect on the average radius (~3.4 Å) of membrane free‐volume holes from the addition of PVP to the casting solution. However, the percentage of o ‐Ps pick‐off annihilation intensity, I 3 , increased from 1.7 to 5.1% with increased PVP content. Further, increasing the PVP content from 0.5 to 5% resulted in an increased final pure water permeability flux. For instance, the 210 min flux for a 14% PVDF + 0.5% PVP membrane was found to be 3.3 times greater than a control membrane having the same PVDF concentration. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 589–598

Eren, Bilge↗

Development of Parameters for the Particle Size Distribution of TATB

Laser light scattering (LLS), manual counting of scanning electron microscopy (SEM) images, and reduction of SEM images using ImageJ (open source program) to determine Feret (caliper) diameters were applied to determine particle size distribution (PSD) of four preparations of 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) and yttria‐stabilized zirconia (YSZ), an SEM certified standard. Mie theory was used to reduce the LLS data. The spherical nature of the YSZ made it a good candidate for LLS. Variations in n , the refractive index, and iκ, the imaginary component, produced very little change in the PSD. However, changing the carrier liquid from H 2 O to a 40% aqueous sucrose solution, thereby changing the carrier refractive index, n 0 , substantially affected the PSD. The Mie complex refractive indices for the YSZ were n = 2.200, iκ = 0.100, with a 40% aqueous sucrose solution, n 0 = 1.400. The triclinic crystal structure of TATB made refractive index determinations more difficult, so a study was conducted varying Mie parameters and comparing them to the same data reduced using the Fraunhofer theory. Changing the n and κ parameters produced PSD with a small concentration of particles less than 1 µm in size or none in this range. SEM images, Feret data, manual counting, and Fraunhofer data reduction indicate particles less than 1 µm are probably < 5% in concentration. The final selection of Mie parameters for TATB was n = 2.283, iκ = 0.1, and suspension medium, n 0 = 1.330. Finally, computations, using density functional theory produced similar parameters.

Feret diameter↗

Mitigating Heavy Ion Irradiation‐Induced Degradation in p‐type SnO Thin‐Film Transistors at Room Temperature

The study investigates the mitigation of radiation damage on p‐type SnO thin‐film transistors (TFTs) with a fast, room‐temperature annealing process. Atomic layer deposition is utilized to fabricate bottom‐gate TFTs of high‐quality p‐type SnO layers. After 2.8 MeV Au 4+ irradiation at a fluence level of 5.2 × 10 12 ions cm −2 , the output drain current and on/off current ratio ( I on / I off ) decrease by more than one order of magnitude, field‐effect mobility ( μ FE ) reduces more than four times, and subthreshold swing (SS) increases more than four times along with a negative shift in threshold voltage. The observed degradation is attributed to increased surface roughness and defect density, as confirmed by scanning electron microscopy (SEM), high‐resolution micro‐Raman, and transmission electron microscopy (TEM) with geometric phase analysis (GPA). A technique is demonstrated to recover the device performance at room temperature and in less than a minute, using the electron wind force (EWF) obtained from low‐duty‐cycle high‐density pulsed current. At a pulsed current density of 4.0 × 10 5 A cm −2 , approximately four times increase in I on / I off is observed, 41% increase in μ FE , and 20% decrease in the SS of the irradiated TFTs, suggesting effectiveness of the new annealing technique.

Al-Mamun, Nahid Sultan↗

Influence of Protection Layers on Thermal Stability of Nitride Thin Films

Nitrides are commonly studied for their properties relevant to numerous coating applications, and have been recently used to synthesize newly predicted materials in thin film form. However, thermodynamic stability of such nitride materials is difficult to experimentally evaluate, due to limited thermal budget of thin films. Here we show that thermal stability of nitride films can be extended using protection layers. Specifically, we find that zirconium nitride (ZrN) thin films are stable up to at least 1200°C annealing temperature in N2 atmosphere, if aluminum nitride (AlN) diffusion barriers and capping layers are used. X-ray diffraction (XRD) measurements show the expected thermodynamically stable rocksalt structure of ZrN, and scanning electron microscopy (SEM) confirms compact microstructure of these ZrN films. Without such protection layers, transient bixbyite Zr2ON2 phase and high-temperature ZrSi2 phase are observed after annealing by XRD, SEM, and auger electron spectroscopy (AES), due to side reaction with native surface oxide (ZrOx) and substrate (Si) respectively. These results demonstrate that protection layers are beneficial to increase the thermal budget of nitride thin films, for evaluating thermodynamic stability of new nitride materials, for capturing transient metastable phases during crystallization, and for using functional nitride coatings in extreme environments.

36 MATERIALS SCIENCE↗