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Synergistic Effects of Inexpensive Mixed Metal Oxides for Catalytic Hydrothermal Liquefaction of Food Wastes
Industrial wastes and natural mixed oxide materials were evaluated as inexpensive heterogeneous catalysts for catalytic hydrothermal liquefaction (CHTL) of food wastes. Red mud and red clay achieved biocrude carbon yields of 47.0 and 39.5% with higher heating values (HHVs) of 40.2 and 37.7 MJ kg –1 , respectively, which were much greater than those without the catalyst (biocrude carbon yield of 19.7% and HHV of 36.1 MJ kg –1 ). Biocrude characterization revealed that similar families of molecules were formed in the presence and absence of catalysts, implying that the main role of the catalyst is to promote rates of thermal reactions, leading to biocrude production without opening new pathways. The crystalline structures of inexpensive mixed oxides were stable under hydrothermal conditions, with modest calcium leaching (7.5%) and trace leaching of other metals. Using red clay or red mud resulted in >40% recovery of the energy in food waste as biocrude, greater than that obtained under noncatalytic conditions (18%) or from any individual constituent oxide (19–27%). The improved CHTL performance of the mixed metal oxides compared with single-metal oxides was attributed to the synergistic effects of base and acid sites present on catalyst surfaces; mixed oxides presented balanced densities of acids and bases, whereas the constituent oxides were either primarily acidic or primarily basic. Lastly, the percent of energy recovered as biocrude oil was strongly correlated with the base-to-acid site density ratio, providing an important performance predictor for CHTL conversion of food waste to bioenergy.
Innovative, Inexpensive Etching Technique Developed for Polymer Electro- Optical Structures
Electro-optic, polymer-based integrated optic devices for high-speed communication and computing applications offer potentially significant advantages over conventional inorganic electro-optic crystals. One key area of integrated optical technology--primary processing and fabrication--may particularly benefit from the use of polymer materials. However, as efforts concentrate on the miniaturization of electro-integrated circuit pattern geometries, the ability to etch fine features and smoothly sloped sidewalls is essential to make polymers useful for electro-integrated circuit applications. There are many existing processes available to etch polymer materials, but they all yield nearly vertical sidewalls. Vertical sidewalls are too difficult to reliably cover with a metal layer, and incomplete metalization degrades microwave performance, particularly at high frequency. However, obtaining a very sloped sidewall greatly improves the deposition of metal on the sidewall, leading to low-loss characteristics, which are essential to integrating these devices in highspeed electro-optic modulators. The NASA Lewis Research Center has developed in-house an inexpensive etching technique that uses a photolithography method followed by a simple, wet chemical etching process to etch through polymer layers. In addition to being simpler and inexpensive, this process can be used to fabricate smoothly sloped sidewalls by using a commercial none rodible mask: Spin-On-Glass. A commercial transparent material, Spin-On-Glass, uses processes and equipment similar to that for photoresist techniques.
Metal–Nitrogen–Carbon Cluster–Decorated Titanium Carbide is a Durable and Inexpensive Oxygen Reduction Reaction Electrocatalyst
Clusters of nitrogen- and carbon-coordinated transition metals dispersed in a carbon matrix (e. g., Fe-N-C) have emerged as an inexpensive class of electrocatalysts for the oxygen reduction reaction (ORR). In this work, it was shown that optimizing the interaction between the nitrogen-coordinated transition metal clusters embedded in a more stable and corrosion-resistant carbide matrix yielded an ORR electrocatalyst with enhanced activity and stability compared to Fe-N-C catalysts. Utilizing first-principles calculations, an electrostatics-based descriptor of catalytic activity was identified, and nitrogen-coordinated iron (FeN 4 ) clusters embedded in a TiC matrix were predicted to be an efficient platinum-group metal (PGM)-free ORR electrocatalyst. Guided by theory, selected catalyst formulations were synthesized, and it was demonstrated that the experimentally observed trends in activity fell exactly in line with the descriptor-derived theoretical predictions. The Fe-N-TiC catalyst exhibited enhanced activity (20 %) and durability (3.5-fold improvement) compared to a traditional Fe-N-C catalyst. It was posited that the electrostatics-based descriptor provides a powerful platform for the design of active and stable PGM-free electrocatalysts and heterogenous single-atom catalysts for other electrochemical reactions.
Computationally inexpensive part-scale thermal history of additive friction-stir deposition
This study presents an analytical model for steady-state power generation and tool heat loss in additive friction-stir deposition (AFSD), developed to enable part-scale thermal simulation while remaining computationally inexpensive. The model predicts total generated power, yielding 3.7–4.7 kW across deposition temperature setpoints of 400–460 °C for the deposition of AA6061 with a Be-Cu tool. This corresponds to 90–95% of the reported spindle power. Tool heat loss is experimentally determined by calibrating a steady-state energy balance between the generated power, the substrate-deposition thermal gradient, and a temperature dependent tool heat loss term: q tool (T) = a + b (T - 400°C) with a = 2.7 x 10 6 Wm -2 and b = 9.5 x 10 3 Wm -2 K -1 . The calibration indicates that about 69% of the generated heat is conducted into the tool for this configuration, which is much higher than previously reported. The calibrated heat-source is implemented in finite element software (Adamantine) to simulate the transient thermal history of a 100 cm 3 representative build in 8 min on a standard desktop (at 0.635 mm build-height resolution). For the first three layers, the substrate temperatures between simulation and experiment are within 10% mean absolute percentage error. Sensitivity analysis indicates that uncertainties in average deposition temperature and deformation localization (stir-zone geometry, depth, and spatial dependance of strain-rate and flow stress) dominate model variance, motivating additional experimental verification.
Preparation of Porous Nanofibers from Electrospun Polyacrylonitrile/Polyvinylidene Fluoride Composite Nanofibers by Inexpensive Salt Using for Dye Adsorption
The high surface area of porous nanofibers enhances their performance for many applications. The present study investigated electrospinning and dye adsorption properties of polymeric nanofibers which were porous by various types of salts. The salt/polyacrylonitrile/polyvinylidene fluoride composite nanofibers were electrospun, and the inexpensive salts such as sodium chloride (NaCl), sodium bicarbonate (NaHCO{sub 3}), or calcium chloride (CaCl{sub 2}) was used to manufacture the porous fibers. Subsequently, the salt was removed by a selective dissolution, and salt extraction of nanofibers was performed with the solution of hydrochloric acid (10 wt%). Salt/PVDF/PAN and porous PVDF/PAN composite nanofibers have been applied to dye adsorption of solution. The characteristics of nanofibers were studied by Fourier transform infrared microscopy (FTIR) and scanning electron microscopy (SEM) analysis. FTIR showed that the salt was extracted from PVDF/PAN nanofibers successfully, and SEM indicated that many pores were aligned with the nanofibers. The adsorption capacity of salt nanofibers webs and porous nanofibers webs for Basic Blue 41 were compared with each other, and porous fibers were obtained from NaHCO{sub 3} having the highest dye adsorption value. Adsorption of dyes follows the Langmuir isotherm and pseudo-second order kinetics.
Chapter 12 - Addressing Groundwater Fluoride Contamination Using Inexpensively Processed Bauxite
Globally, 200 million people are at risk of adverse health effects from drinking groundwater contaminated with high fluoride concentrations that exceed the World Health Organization's maximum contaminant limit (WHO MCL=1.5ppmF-). Although many defluoridation technologies have been demonstrated to work in lab, most have proven inappropriate for impoverished rural regions of developing countries because they are cost-prohibitive, require skilled labor, or are difficult to scale. The authors submit evidence for the use of bauxite, an aluminum-rich ore, as a potentially inexpensive, effective, and scalable defluoridation technology. Specifically, we present results from experimental studies that characterize globally diverse bauxite ores, elucidate fluoride removal mechanisms, and establish proof of concept that mildly processed bauxite can cost-effectively remediate field-relevant fluoride concentrations in synthetic and real groundwater matrices at field-relevant kinetics. We discuss practical implications of these research findings and highlight remaining challenges and unknowns that need to be further studied before implementing the proposed defluoridation process in the field.
Intrinsically sodiophilic, mesoporous metal-free wetting layers based on inexpensive carbon black for sodium-metal batteries
In this article, elevated temperature molten Na batteries are seeing a resurgence of interest for low-cost electrochemical energy storage for the grid. Of the many recent innovations in this battery concept, new methods focused on intermediate temperature operation (e.g. 110–190 °C) have gained prominence as a way to enable comparable performance with less thermal energy loss and lower-cost materials of construction. However, the poor wettability of molten Na on suitable solid-electrolyte separators such as sodium Beta Alumina Solid-Electrolyte (Na-β”-Al 2 O 3 , ‘BASE’) requires continued innovation in interface engineering to promote full utilization of the solid-electrolyte surface area and minimize cell resistance. There have been many successful approaches to improve Na-wettability to-date including heat treatment in an inert atmosphere to remove adsorbed surface species, deposition of alloying metals such as Pb, Sn, or Bi, and use of carbon-based interfacial layers. However, these approaches either lack the ability to provide good wetting at very low temperatures (near the melting point of Na) or rely on non-scalable processes and/or toxic/expensive metals. To solve these issues, a new carbon-based sodiophilic treatment is demonstrated, which utilizes inexpensive components to form a meso/macroporous sodiophilic layer, is easily applied via drop-casting or spray-coating, provides excellent wetting as low as 110 °C, and is completely metal-free. It is found that the good sodium wetting can be attributed to the wider range of pore sizes in the carbon layers demonstrated in this study. Na wetting may occur as surface tension is initially broken by larger pores, followed by the intrusion of molten Na into smaller pores due to the apparent intrinsic affinity of Na-metal for carbon surfaces, in conjunction with the capillarity effect. Low cell-level area specific resistances of 20–30 and 13–15 Ω·cm 2 are demonstrated at 110 and 140 °C respectively. Finally, the utility of this metal-free wetting layer for solid-Na anodes is explored, showing that the metal-free wetting layer can reach a critical current density of 1.88 mA·cm -2 at 30 °C.
High-precision vapor pressure measurement apparatus with facile and inexpensive construction
This study describes an apparatus for high-precision variable temperature measurement of liquid vapor pressure. The apparatus can be used to measure the vapor pressure using only 0.5 ml of the liquid sample. To evaluate the accuracy of the device measurement, water and 2-propanol are utilized as standard liquids, and their vapor pressure is measured with a maximum uncertainty of ~1%. This apparatus can be replicated using inexpensive and commonly used laboratory fittings and fixtures, making it an indispensable tool for synthetic chemists and chemical engineers involved in the iterative synthesis of compounds, targeting different vapor–liquid equilibrium regimes.
High Efficiency, Inexpensive Thin Film III-V Photovoltaics using Single-Crystalline-Like, Flexible Substrates
An innovative, non-mainstream approach has been developed to fabricate inexpensive GaAs solar cells directly on epi-ready flexible metal substrates. Using templates made by ion beam assisted deposition (IBAD) and epitaxial germanium films made by Plasma Enhanced Chemical Vapor Deposition (PECVD), epitaxial GaAs films with high opto-electronic and structural quality have been grown on metal substrates using metal organic chemical vapor deposition (MOCVD). Crystallographic out-of-plane and in-plane texture spread less than 1 degree full-width-at-half-maximum (FWHM) was achieved in undoped, n-type and p-type GaAs films as well as in AlGaAs films on metal substrates. Electron mobility of >1300 cm 2 /V-s was attained in GaAs:Si n-type films. Also, hole mobility of >100 cm 2 /V-s was measured in GaAs:Zn films. Consistent doping was obtained in GaAs:Si (10 15 -10 18 cm -3 ), and GaAs:Zn films (10 17 -10 19 cm -3 ), necessary for the active device layers of a GaAs solar cell. Defect reduction techniques (thermal cycling, superlattice structures) were implemented to reduce defect density in GaAs films from 1 × 10 9 cm -2 to 9 × 10 7 cm -2 . Lifetime of 2.3 ns was obtained in AlGaAs/GaAs double-heterostructure device. Solar cells were fabricated based on designs using 1-dimensional and 2-dimensional simulations tailored to the specific properties of the GaAs films on metal substrates. All device fabrication processes (lithography, anti-reflection coating (ARC), device isolation and mesa formation and ohmic metal electrode formation) suitable for III-V solar cell fabrication on metal substrates were fully developed. A bi-layered ARC using ZnS and MgF 2 was used to minimize the reflection over wide range of spectrum. When this ARC was applied after removal of the parasitic absorption layer, the conversion efficiencies were improved up to 11.1% with V oc = ~0.621 V, J sc = ~24.5 mA/cm 2 , and FF = ~0.735. Yet another accomplishment in this project was the development of all electrically-conducting architecture for GaAs solar cells on metal substrates. Biaxial-texture was successfully achieved in all electrically-conducting buffer layer on metal substrate in structure based on IBAD TiN instead of IBAD MgO. The all electrically-conducting Ge/NiSi 2 /TiN/IBAD-TiN/Hastelloy substrate was used to fabricate back contacts for vertically conducting solar cell structures on metal substrates. A metallic resistivity as low as 4.17 μΩ•cm was obtained. A significant improvement of the texture of the Ge template was achieved using a Ag buffer layer between the TiN films. Epitaxial GaAs was successfully grown on the all-electrically-conducting buffer architecture. A Liquid Phase Epitaxy (LPE) method to drastically increase grain size of epitaxial Ge while maintaining the single-crystalline-like texture. Grain size up to 35 µm was achieved in LPE Ge grown on sputtered Ge with a grain size of ~ 1 µm on IBAD template on metal substrate. Epitaxial GaAs was grown on LPE Ge, with an out-of-plane texture of 0.34° compared to 0.98° in GaAs grown on sputter deposited Ge. A model was developed to simulate the effect of grain boundaries as a function of grain size of GaAs films on metal substrates. This model showed that even the very low angle grain boundaries (<1º misorientation) of our GaAs films led to decrease in Voc. Hydrogen plasma passivation treatment is being developed to improve open circuit voltage and the conversion efficiency of GaAs solar cells on flexible substrate.
Novel Epitaxial Lift-Off for Flexible, Inexpensive GaAs Solar Cells
Novel Epitaxial Lift-Off for Flexible, Inexpensive GaAs Solar Cells
Advancing insulation retrofits from flexible inexpensive lucid materials (AIR FILMs) for single-pane windows
This project focused on Advancing Insulation Retrofits from Flexible Inexpensive Lucid Materials (AIR FILMs) for Single-Pane Windows. The team developed innovative porous materials that can improve the energy efficiency of existing single-pane windows in commercial and residential buildings in two technical product categories: (1) retrofits that can be applied onto existing windowpanes and (2) manufactured windowpanes that can be installed into the existing window sash.
Surface Acoustic Wave Sensors for Refrigerant Leak Detection: Compact, Inexpensive, Selective and Sensitive Sensors
Pacific Northwest National Laboratory (PNNL), in collaboration with Parker and Hannifin, is developing a compact, inexpensive, and highly sensitive and selective surface acoustic wave sensor coated with fluorophillic sorbent for detecting fluorocarbon leaks from HVAC systems. Having a highly effective sorbent sensitive to fluorocarbon refrigerant vapors provides a means to develop a sensing device for leak detection. Surface acoustic wave (SAW) sensors with a gas sensing film deposited between the delay lines or on the interdigital transducer have been used to detect gas and vapor molecules in harsh environments with high sensitivity. As part of this project, PNNL screened several sorbent materials that are shown to be selective towards fluorocarbon refrigerant (R32) molecule. The identified sorbent materials were synthesized, characterized, and tested towards R32 using various spectroscopic technique. Next, the sorbent material was coated on a SAW sensor as a thin film using vapor deposition and drop coating methods. The coated thin film was further characterized and tested towards the detection of pure R32 and R32 in ambient air at room temperature to demonstrate the SAW response towards R32 in presence of other competing gases and vapors in air.
Characterization of inexpensive metal oxide sensor performance for trace methane detection
Abstract. Methane, a major contributor to climate change, is emitted by a variety of natural and anthropogenic sources. Commercially available lab-grade instruments for sensing trace methane are expensive, and previous efforts to develop inexpensive, field-deployable trace methane sensors have had mixed results. Industrial and commercial metal oxide (MOx) methane sensors, which are intended for leak detection and safety monitoring, can potentially be repurposed and adapted for low-concentration sensing. As an initial step towards developing a low-cost sensing system, we characterize the performance of five off-the-shelf MOx sensors for 2–10 ppm methane detection in a laboratory setting (Figaro Engineering TGS2600, TGS2602, TGS2611-C00, TGS2611-E00, and Henan Hanwei Electronics MQ4). We identify TGS2611-C00, TGS2611-E00, and MQ4 as promising for trace methane sensing but show that variations in ambient humidity and temperature pose a challenge for the sensors in this application.
Development of an inexpensive matrix-assisted laser desorption—time of flight mass spectrometry method for the identification of endophytes and rhizobacteria cultured from the microbiome associated with maize
Many endophytes and rhizobacteria associated with plants support the growth and health of their hosts. The vast majority of these potentially beneficial bacteria have yet to be characterized, in part because of the cost of identifying bacterial isolates. Matrix-assisted laser desorption-time of flight (MALDI-TOF) has enabled culturomic studies of host-associated microbiomes but analysis of mass spectra generated from plant-associated bacteria requires optimization. In this study, we aligned mass spectra generated from endophytes and rhizobacteria isolated from heritage and sweet varieties of Zea mays. Multiple iterations of alignment attempts identified a set of parameters that sorted 114 isolates into 60 coherent MALDI-TOF taxonomic units (MTUs). These MTUs corresponded to strains with practically identical (>99%) 16S rRNA gene sequences. Mass spectra were used to train a machine learning algorithm that classified 100% of the isolates into 60 MTUs. These MTUs provided >70% coverage of aerobic, heterotrophic bacteria readily cultured with nutrient rich media from the maize microbiome and allowed prediction of the total diversity recoverable with that particular cultivation method. Acidovorax sp., Pseudomonas sp. and Cellulosimicrobium sp. dominated the library generated from the rhizoplane. Relative to the sweet variety, the heritage variety contained a high number of MTUs. The ability to detect these differences in libraries, suggests a rapid and inexpensive method of describing the diversity of bacteria cultured from the endosphere and rhizosphere of maize.
Inexpensive, stable circuit measures heart rate
Inexpensive transistorized circuit provides reliable analog indications of heart rate in response to preamplified electrocardiograph signal applied to its input.
Inexpensive electrical connector is moisture and corrosion-proof
Compression-sealed electrical connector made principally of plastic components is used in a corrosive atmosphere. This inexpensive and moistureproof connector can be modified to provide a multiple-pin connector.
Inexpensive infrared source improvised from flashlight
Inexpensive hand-held source of infrared energy is provided by a flashlight bulb coated with a paint which filters out the visible light emitted by the bulb and transmits only infrared radiation. This device can be used for checking infrared sensors and for experimental purposes.