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At least 901 records · Page 50

Structural Characterization of Loblolly Pine Derived Biochar by X-ray Diffraction and Electron Energy Loss Spectroscopy

Biochar from lignocellulosic biomass is emerging as a sustainable material with versatile applications, but its detailed properties are poorly understood because of its structural complexity. We propose a biochar structural development model based on experimental results including composition analysis, surface area and pore analysis, X-ray diffraction analysis, electron microscopy imaging, and electron energy loss spectroscopy. Loblolly pine derived biochars were produced at different carbonization temperatures between 300 to 1000 °C. Fixed carbon, sp 2 content, and number of graphene layers increased with increased carbonization temperature. Alternating average C–C bond length, interlayer spacing distance, and layer coherence length were observed. Bulk plasmon excitation energy was correlated to the average C–C bond length, and it serves as a good indicator of the carbon structure development when compared to the perfect graphitic carbon structure. On the basis of the experimental results, four different structural development phases are identified, which provide a comprehensive understanding of biochar nanocarbon crystallite development. Unlike previous biochar structure models, which proposed radially growing polyaromatic carbon crystallite, we propose a lengthwise growing polyaromatic carbon crystallite model. Furthermore, this experiment-based biochar model should be helpful when determining the structure of unknown biomass-derived carbon materials and disordered pyrolytic carbon materials.

Biomass carbonization↗

Characterization of particulate matter deposited in diesel particulate filters: Visual and analytical approach in macro-, micro- and nano-scales

Multi-scale analytical investigations of particulate matter (soot and ash) of two loaded diesel particulate filters (DPF) from (a) a truck (DPF1) and (b) a passenger car (DPF2) reveal the following: in DPF1 (without fuel-borne additives), soot aggregates form an approximately 130-270 {mu}m thick, homogeneous porous cake with pronounced orientation. Soot aggregates consist of 15-30 nm large individual particles exhibiting relatively mature internal nanostructures, however, far from being graphite. Ash aggregates largely accumulate at the outlet part of DPF1, while minor amounts are deposited directly on the channel walls all along the filter length. They consist of crystalline phases with individual particles of sizes down to the nanoscale range. Chemically, the ash consists mainly of Mg, S, Ca, Zn and P, elements encountered in lubricating oil additives. In the passenger car DPF2 (with fuel-borne additives), soot aggregates form an approximately 200-500 {mu}m thick, inhomogeneous porous cake consisting of several superposed layers corresponding to different soot generations. The largest part of the soot cake is composed of unburned, oriented soot aggregates left behind despite repeated regenerations, while a small part constitutes a loose layer with randomly oriented aggregates, which was deposited last and has not seen any regeneration. Fe-oxide particles of micro- to nano-scale sizes, originating from the fuel-borne additive, are often dispersed within the part of the soot cake composed of the unburned soot leftovers. The individual soot nanoparticles in DPF2 are approximately 15-40 nm large and generally less mature than in the truck DPF1. The presence of soot leftovers in DPF2 indicates that the addition of fuel-borne material does not fully compensate for the temperatures needed for complete soot removal. Ash in DPF2 is filling up more than half of the filter volume (at the downstream part) and is dominated by Fe-oxide aggregates, due to the Fe-based fuel-borne additive, but otherwise its chemical composition reflects compounds of lubricating oil additives. (author)

02 PETROLEUM↗

Method of preparing graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

A method of preparing a graphene-sulfur nanocomposite for a cathode in a rechargeable lithium-sulfur battery comprising thermally expanding graphite oxide to yield graphene layers, mixing the graphene layers with a first solution comprising sulfur and carbon disulfide, evaporating the carbon disulfide to yield a solid nanocomposite, and grinding the solid nanocomposite to yield the graphene-sulfur nanocomposite. Rechargeable-lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter of less than 50 nm.

25 ENERGY STORAGE↗

Enhancing isotope mixing in U-10Mo downblend castings with electromagnetic stirring

Uranium alloyed with 10 wt percent molybdenum (U-10Mo) is the proposed fuel for use in the United States’ high-performance research reactors. The U-10Mo fuel is fabricated by a two-step casting process that downblends highly enriched uranium with depleted uranium (DU) and/or natural uranium (NU) and subsequently alloys the resulting high-assay low-enriched uranium (HALEU) with Mo. Currently, a two-step casting process is needed to meet the ingots’ U-235 enrichment homogeneity specifications. This work demonstrates the ability to provide more homogeneous U-235 distributions during downblend casting by using zirconia for crucibles rather than graphite. When graphite is used as a crucible, the electromagnetic field produced by the induction heater couples directly with the graphite. Zirconia is nonconducting in this study, and therefore does not couple with the field. The induction field couples directly with the metal, and causes electromagnetic stirring (EMS) in the molten metal pool. Eight downblend casting experiments were carried out in this work. Four were performed with zirconia crucibles and four with graphite crucibles. The U-235 enrichment was measured at nine discrete points in each casting using laser ablation multi-collector inductively coupled mass spectrometry (LA-MC-ICP-MS). The enrichment homogeneity was approximately eight times better in zirconia crucible castings than in graphite crucible castings as measured by the plate enrichment range and enrichment coefficient of variation. The results show a single casting step could be used to meet USHPRR enrichment specifications if electromagnetic stirring is present during casting. A related investigation was carried out to determine whether it is appropriate to measure enrichment on as-cast ingots or whether heat treated specimens should be used to accurately characterize enrichment. The results show that the as-cast microstructure plays a significant role in enrichment homogeneity. It is recommended that all enrichment measurements be done after the homogenization heat treatment typical of U-10Mo processing.

36 MATERIALS SCIENCE↗

Nanowire-Based Materials as Coke-Resistant Catalyst Supports for Dry Methane Reforming

In this paper, nanowire-supported catalysts loaded with nickel are shown to be coke resistant compared to nanoparticle-supported catalysts. Specifically, Ni-loaded titania-based nanowire catalysts were tested with the dry methane reforming process in a laboratory-scale continuous packed-bed atmospheric reactor. The CO 2 conversion rate stayed above 90% for over 30 h on stream under coke-promoting conditions, such as high flow rates, low temperatures, and a high ratio of CH 4 to CO 2 . The coke (C x H y , x>>y) on the spent catalyst surface for both nanowire- and nanoparticle-supported catalysts was characterized by TGA, temperature-programmed reduction (TPR), and electron microscopy (SEM/TEM/EDS), and it was revealed that the types of carbon species present and their distribution over the morphology-enhanced materials played a major role in the deactivation. The CO 2 conversion activity of Ni supported on titania nanoparticles was reduced from ~80% to less than 72% in 30 h due to the formation of a graphitic coke formation. On the other hand, Ni particles supported on nanowires exhibited cube-octahedral morphologies, with a high density of non- (111) surface sites responsible for the increased activity and reduced graphitic coke deposition, giving a sustained and stable catalytic activity during a long time-on-stream experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanical behavior and fracture characteristics of off-axis fiber composites. 1: Experimental investigation

The mechanical behavior, fracture surfaces, and fracture modes of unidirectional high-modulus graphite-fiber/epoxy composites subjected to off-axis tensile loads were investigated experimentally. The investigation included the generation of stress-strain-to-fracture data and scanning electron microscope studies of the fractured surfaces. The results led to the identification of fracture modes and distinct fracture surface characteristics for off-axis tensile loading. The results also led to the formulation of critical for identifying and characterizing these fracture modes and their associated fracture surfaces. The results presented and discussed herein were used in the theoretical investigation and comparisons described in Part 2. These results should also provide a good foundation for identifying, characterizing, and quantifying fracture modes in both off-axis and angle-plied laminates.

Sinclair, J. H.↗

Quantitative thermal characterization of thin plates

The principles of quantitative thermal testing of the mechanical integrity of platelike structures are discussed. In this technique, a scanned laser pulse is used to inject a thermal pattern in a sample, and a thermal IR imager is used to document the evolution of the pattern subsequent to injection. The measurements are remote, noncontacting, and one-sided, and the algorithms used to obtain diffusivity are all emissivity-independent. The results yielded by application of the three analytical techniques, used to obtain diffusivity values from the image data on stainless steel, a graphite-epoxy composite, brass, and aluminum 2024 samples, are presented.

Welch, C. S.↗

Effects of Ball Milling on the Electrochemical Capacity and Interfacial Stability of Li 2 MnO 3 Cathode Materials

The cycling mechanism of Li 2 MnO 3 cathode materials synthesized by conventional solid-state methods at high temperatures (800-900 °C) has been intensively investigated. Previous studies showed that CO 2 and O 2 gas evolution accounts for most of the charge capacity, followed by some Mn reduction during discharge. In this work, we analyze the effects of ball milling on the structure, surface contaminant, and electrochemical capacity of Li 2 MnO 3 cathode material, with or without a graphitic fluoride (C-F) additive. At the same time, C-F is added to form a protective coating layer that reduces unwanted reactions with the electrolyte during later electrochemical cycling. We find that the C-F ball-milled material shows Li 2 MnO 3 /LiMnO 2 composite phases, while the purely ball-milled material shows a single Li 2 MnO 3 phase. Furthermore, we characterize surface species and gas evolution during the first cycle, which reveals the decomposition of Li 2 CO 3 and the carbonate electrolyte during the first charge, especially during the high potential region (>4.4 V), and the electrochemical reduction of only a small fraction of the evolved gas on the first discharge (<2.75 V). The appearance further demonstrates the repetitive nature of this process during charge and disappearance during discharge of Mn 2p 3/2 X-ray photoelectron spectroscopy (XPS) spectra signals during the first two cycles. These processes result in first discharge specific capacities of only 155 and 170 mAh/g after first charge specific capacities of 210 and 320 mAh/g for the pure ball-milled and ball-milled with C-F materials, respectively. These studies demonstrate the interfacial instability introduced by ball milling. However, the electrochemical capacity is significantly increased, necessitating further investigation to determine whether ball milling can activate Mn-containing cathode materials.

25 ENERGY STORAGE↗

Surface analysis of model systems: From a metal-graphite interface to an intermetallic catalyst

This thesis summarizes research completed on two different model systems. In the first system, we investigate the deposition of the elemental metal dysprosium on highlyoriented pyrolytic graphite (HOPG) and its resulting nucleation and growth. The goal of this research is to better understand the metal-carbon interactions that occur on HOPG and to apply those to an array of other carbon surfaces. This insight may prove beneficial to developing and using new materials for electronic applications, magnetic applications and catalysis. In the second system, we investigate the intermetallic single crystal NaAu2. We conducted a characterization of the clean (111) surface along with a determination of the effects of gas exposures on the surface. No surfaces of bulk NaAu2 have been previously characterized, although the closely related system of Na films on Au(111) has been investigated. NaAu2 is an active catalyst for CO oxidation. To better understand the catalytic reaction occurring, we studied the NaAu2 surface after exposure to O 2 ,g, CO g , CO 2,g ,and H 2 O g . The goal of this research is to find a possible alternative for supported gold catalysts by utilizing an Au-rich intermetallic compound and to determine how its catalytic reaction proceeds. This insight may be valuable in determining other catalytic alternatives as well as helping understand catalytic reactions that occur with other intermetallic compounds. In order to characterize and examine these systems, we utilized several ultrahigh vacuum (UHV) techniques, including scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon Nanotubes Growth by CVD on Graphite Fibers

Due to the superior electrical and mechanical properties of carbon nanotubes (CNT), synthesizing CNT on various substances for electronics devices and reinforced composites have been engaged in many efforts for applications. This presentation will illustrate CNT synthesized on graphite fibers by thermal CVD. On the fiber surface, iron nanoparticles as catalysts for CNT growth are coated. The growth temperature ranges from 600 to 1000 C and the pressure ranges from 100 Torr to one atmosphere. Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than or equal to 900 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in the rough fiber surface without any CNT grown on it. When the growth temperature is relative low (650-800 C), CNT with catalytic particles on the nanotube top ends are fabricated on the graphite surface. (Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis.) (By measuring the samples) Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT (MWCNT), depending on growth concentrations, are found. Morphology, length and diameter of these MWCNT are determined by scanning electron microscopy and Raman spectroscopy. The detailed results of syntheses and characterizations will be discussed in the presentation.

Zhu, Shen↗

Electrical and structural characterization of nano-carbon–aluminum composites fabricated by electro-charging-assisted process

Incorporating nano-carbon phases into metal-matrix composites is a promising strategy for simultaneously enhancing electrical conductivity and mechanical properties of metals. Here, we describe the manufacture of novel nano-carbonaluminum composites by an electro-charge-assisted process (EAP) that show 5.6% ± 1.7% increase in electrical conductivity compared to the base metal alloy. The source of nano-carbon that we used in this study is activated carbon with particle size less than 100 nm. The enhancement is attributed to nano-graphitic structures that extend through the lattice of the metal. Through electron transfer from the metal to the nanostructures the electron density at the interface of nano-crystalline graphite and the metal lattice increases thereby enhancing the bulk electrical conductivity. We identify the important fabrication parameters of the EAP for a reaction system employing a tapered graphite cathode. Here, a high current density of 100 A/cm 2 causes ionization and crystallization of the carbon in the liquid metal. The increase in electrical conductivity of the composite are directly related to the incorporation of the nanocrystalline carbon in the metal lattice. The superior performance of these nano-carbon aluminum composites makes them promising candidates for power transmission lines and other applications.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively. Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.

36 MATERIALS SCIENCE↗

Artificial intelligence inferred microstructural properties from voltage–capacity curves

Abstract The quantification of microstructural properties to optimize battery design and performance, to maintain product quality, or to track the degradation of LIBs remains expensive and slow when performed through currently used characterization approaches. In this paper, a convolution neural network-based deep learning approach (CNN) is reported to infer electrode microstructural properties from the inexpensive, easy to measure cell voltage versus capacity data. The developed framework combines two CNN models to balance the bias and variance of the overall predictions. As an example application, the method was demonstrated against porous electrode theory-generated voltage versus capacity plots. For the graphite|LiMn $$_2$$ 2 O $$_4$$ 4 chemistry, each voltage curve was parameterized as a function of the cathode microstructure tortuosity and area density, delivering CNN predictions of Bruggeman’s exponent and shape factor with 0.97 $$R^2$$ R 2 score within 2 s each, enabling to distinguish between different types of particle morphologies, anisotropies, and particle alignments. The developed neural network model can readily accelerate the processing-properties-performance and degradation characteristics of the existing and emerging LIB chemistries.

25 ENERGY STORAGE↗

Electrical bending actuation of gold-films with nanotextured surfaces

An actuating material system comprising a gold-film with nanotextured surface was fabricated. Using electroless gold plating onto a substrate of porous anodized aluminum oxide, a thin film of gold with a high density of short gold nanofibers on its surface was made. When one end of such a film was connected to an ion generator, bending was achieved upon electrical charging in air. Experiments showed that the free end of an 8 mm film could be displaced by more than 1.6 mm with a bending strain of 0.08%. In contrast with other types of thin-film artificial muscle materials, the present Au-film did not require any electrolyte to function. With the relatively easy fabrication method, this nanotextured film shows promising actuation behavior in air. Actuation systems based on a number of mechanisms have been developed in the last few decades, including electric, ionic, photonic, pneumatic, and thermal. As discussed in detail in Madden et al. and Brochu and Pei,11 the weaknesses of these materials include bulkiness, low stress or strain generation, low strain rate, long response time, short cycle life, and low energy efficiency. Recent developments have involved the possibilities to use the unique properties of nanostructures to produce actuation, such as in nanostructured carbon, nanoporous gold or platinum, V 2 O 5 nanofibre sheet, electroactive nanostructured polymers, hybrid carbon nanotube yarn, niobium nanowire yarn, and anodized aluminum oxide (AAO). Here, we introduce a nanostructured material system comprising a gold film with a high density of short gold-nanofibers attached to one side, which can bend to produce a large displacement (~1.6 mm) upon electrical charging through an ion generator. In addition to the displacement, the functionality without the need of an electrolyte is another advantage for using this material system as actuators. We discuss the fabrication and characterization methods, the morphology, and the actuating properties of this system here. To achieve a metal film with a nanotextured surface, electroless gold-plating was performed on substrates of AAO with a characteristic nano-honeycomb structure consisting of >10 10 pores per cm 2 . The fabrication of the AAO substrates followed the procedures described in Cheng and Ngan. The anodization condition for the AAO was 40 V against graphite electrode in saturated oxalic acid at 18 °C for 2 h. The pore diameter observed was 50 ± 5 nm. By using an electroless gold-plating method described by Kohli et al.,22 gold in short nanofiber form was deposited into the pores of the AAO template. As shown in Figs. 1(a) and 1(b), in addition to partially filling the pores with gold, the top surface of the AAO template was coated with a thin gold film (~100 nm) of Au. A ~30 μm layer of lacquer was then painted on the top of the thin gold film to serve as a supporting layer.

42 ENGINEERING↗

HRTEM low dose: the unfold of the morphed graphene, from amorphous carbon to morphed graphenes

We present experimental evidence under low-dose conditions transmission electron microscopy for the unfolding of the evolving changes in carbon soot during mechanical milling. The milled soot shows evolving changes as a function of the milling severity or time. Those changes are responsible for the transformation from amorphous carbon to graphenes, graphitic carbon, and highly ordered structures such as morphed graphenes, namely Rh6 and Rh6-II. The morphed graphenes are corrugated layers of carbon with cross-linked covalently nature and sp2 - or sp3 -type allotropes. Electron microscopy and numerical simulations are excellent complementary tools to identify those phases. Furthermore, the TEAM 05 microscope is an outstanding tool to resolve the microstructure and prevent any damage to the sample. Other characterization techniques such as XRD, Raman, and XPS fade to convey a true identification of those phases because the samples are usually blends or mixes of the mentioned phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An endochronic theory for transversely isotropic fibrous composites

A rational methodology of modelling both nonlinear and elastic dissipative response of transversely isotropic fibrous composites is developed and illustrated with the aid of the observed response of graphite-polyimide off-axis coupons. The methodology is based on the internal variable formalism employed within the text of classical irreversible thermodynamics and entails extension of Valanis' endochronic theory to transversely isotropic media. Applicability of the theory to prediction of various response characteristics of fibrous composites is illustrated by accurately modelling such often observed phenomena as: stiffening reversible behavior along fiber direction; dissipative response in shear and transverse tension characterized by power-laws with different hardening exponents; permanent strain accumulation; nonlinear unloading and reloading; and stress-interaction effects.

Pindera, M. J.↗

An endochronic model for the response of unidirectional composites under off-axis tensile load

A methodology of modelling both nonlinear elastic and dissipative response of transversely isotropic fibrous composites is developed and illustrated with the aid of the observed response of graphite-polyimide off-axis coupons. The methodology is based on the internal variable formalism employed within the text of classical irreversible thermodynamics and entails extension of Valanis' endochronic theory to transversely isotropic media. Applicability of the theory to prediction of various response characteristics of fibrous composites is illustrated by accurately modelling such often observed phenomena as: stiffening reversible behavior along fiber direction; dissipative response in shear and transverse tension characterized by power-laws with different hardening exponents; permanent strain accumulation; nonlinear unloading and reloading; and stress-interaction effects.

Pindera, M. J.↗

The Use of Pristine and Intercalated Graphite Fiber Composites as Buss Bars in Lead-Acid Batteries

This study was conducted as a part of the Firefly Energy Space Act Agreement project to investigate the possible use of composite materials in lead acid batteries. Specifically, it examined the use of intercalated graphite composites as buss bars. Currently, buss bars of these batteries are made of lead, a material that is problematic for several reasons. Over time, the lead is subject to both corrosion at the positive plate and sulfation at the negative plate, resulting in decreased battery life. In addition, the weight and size of the lead buss bars make for a heavy and cumbersome battery that is undesirable. Functionality and practicality of lead buss bars is adequate at best; consequently, investigation of more efficient composite materials would be advantageous. Practically speaking, graphite composites have a low density that is nearly one fourth that of its lead counterpart. A battery made of less dense materials would be more attractive to the consumer and the producer because it would be light and convenient. More importantly, low weight would be especially beneficial because it would result in greater overall power density of the battery. In addition to power density, use of graphite composite materials can also increase the life of the battery. From a functional standpoint, corrosion and sulfation at the positive and negative plates are major obstacles when considering how to extend battery life. Neither of these reactions are a factor when graphite composites replace lead parts because graphite is chemically non-reactive with the electrolyte within the battery. Without the problem of corrosion or sulfation, battery life expectancy can be almost doubled. The replacement of lead battery parts with composite materials is also more environmentally favorable because of easy disposal of organic materials. For this study, both pristine and bromine intercalated single-ply graphite fiber composites were created. The composites were fabricated in such a way as to facilitate their use in a 3" x 1/2" buss bar test cell. The prime objective of this investigation was to examine the effectiveness of a variety of graphite composite materials to act as buss bars and carry the current to and from the positive and negative battery plates. This energy transfer can be maximized by use of materials with high conductivity to minimize the buss resistance. Electrical conductivity of composites was measured using both a contactless eddy current probe and a four point measurement. In addition, the stability of these materials at battery-use conditions was characterized.

Opaluch, Amanda M.↗