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At least 1,747 records · Page 97

The Influence of Galvanizing Parameters on the Structural Development of Zn-Al-Based Coatings

The evolution of some layers’ characteristics, deposited by galvanization, was monitored according to the technological parameters of the process. Two types of alloys from the Zn-Al and Zn-Al-Ti-B systems were used for deposition. The structure of the deposited layers was analyzed by optical and electron microscopy. The chemical composition, phases and compounds in the structures were identified. The mechanical properties of the structural constituents of the layers were determined by nanoindentation. These techniques highlighted the typical non-uniformities in terms of composition and properties in the layers, mainly due to the diffusion and distribution of iron from the steel substrate in the deposited layers. The evaluation of iron diffusion in the deposited layer was done by differential thermal analysis. The values of the critical temperatures (melting temperature, eutectic temperature and solidification temperature) were correlated with the parameters used during deposition. It was observed that the structure of the coatings is layered, with a specific order from the steel substrate to the edge. In these layers, the constituents are mixtures of soft solid solutions of Al in Zn (η and β) and hard intermetallic compounds. Moreover, increasing the immersion time in the galvanizing bath and the bath temperature leads to an increase in iron diffusion in the coating layer, which contributes to lower coating thickness, thus reducing its durability in operation.

36 MATERIALS SCIENCE↗

Effect of Deposition Pressure, Nitrogen Content and Substrate Temperature on Optical and Mechanical Behavior of Nanocomposite Al-Si-N Hard Coatings for Solar Thermal Applications

Hard and optically transparent nanocomposite Al-Si-N thin films were deposited using DC magnetron sputtering at different process parameters. There was a significant effect of these parameters on the film properties affecting its mechanical and optical behavior. The nitrogen content or pressure, deposition pressure and substrate temperature strongly influence the phase formation which governs the hardness and optical transparency of the coating. Hardness was measured between 18 and 30 GPa. The band gap could be varied in the range of 3.8-4.2 eV by varying nitrogen pressures in the chamber during deposition. The films showed (0-80)% transparency in UV and visible region depending on the sputtering conditions.

36 MATERIALS SCIENCE↗

Corrosion and Fatigue Behavior of High-Strength Steel Treated with a Zn-Alloy Thermo-diffusion Coating

High and low cycle fatigue tests were conducted on high-strength steel using four-point bending. The materials tested were ASTM A723 steel in the as-machined condition, grit-blasted condition, MIL-DTL-16232 heavy manganese phosphate-coated condition, and ASTM A1059 Zn-alloy thermo-diffusion coated (Zn-TDC). The ASTM A723 steel base material exhibits a yield strength of ~1000 MPa. The effects of the surface treatments versus uncoated steel were examined. The fatigue life of the Zn-TDC specimens was generally reduced on as-coated specimens versus uncoated or phosphate-coated specimens. Several mechanisms are examined including the role of compressive residual stress relief with the Zn-TDC process as well as fatigue crack initiation from the hardened Zn-Fe alloy surface layer produced in the gas-metal reaction. Additionally, the effects of corrosion pitting on the fatigue life of coated specimens are explored as the Zn-TDC specimens exhibit significantly improved corrosion resistance over phosphate-coated and oiled specimens.

36 MATERIALS SCIENCE↗

Hybrid Chemo-Mechanical Plastics Recycling: Solvent-free, High-speed Reactive Extrusion of Low-Density Polyethylene

Low-Density Polyethylene (LDPE) is ubiquitous in the packaging industry due to its flexibility, toughness, and low cost. However, it is typically contaminated with other materials, seriously limiting options for mechanical recycling. Interest in chemical recycling techniques such as pyrolysis and hydrothermal liquefaction is growing, but most of these processes face technoeconomic challenges that have limited commercial deployment. We present a hybrid chemo-mechanical approach using reactive twin-screw extrusion (TSE) for tailoring the molecular weight and chain structure of reclaimed LDPE. Two types of zeolite catalysts at several loading levels were evaluated over a range of processing conditions. Structural, thermal, and rheological properties of the extruded samples were investigated and compared to virgin LDPE and LDPE extruded without the catalyst. A nuclear magnetic resonance spectroscopic technique was used to investigate changes in the structure of the polymer. LDPE extruded with microporous y-zeolite showed lower degradation temperature and increased short chain branching. Mesoporous MCM-41 also induced increased branching but had no effect on degradation temperature. The theoretical mechanical energy input for the chemical modification was calculated using process modeling. The demonstrated hybrid reactive extrusion process provides a potential low-cost, simple approach for repurposing LDPE-based flexible packaging as coatings and adhesives.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, Processing and Properties of Calcium- and Nickel-Doped Yttrium Chromates(III) Y{sub 0.8}Ca{sub 0.2}Cr{sub 1−x}Ni{sub x}O{sub 3} (x = 0-0.3) and Studies on Their Potential Application as Coatings for SOFC Interconnects

In the present study, a calcium- and nickel-doped yttrium chromates (YCCN)-based, conductive–protective layers for metallic interconnects used in the intermediate-temperature solid oxide fuel cells (IT-SOFCs) were investigated. Synthesis of Y{sub 0.8}Ca{sub 0.2}Cr{sub 1−x}Ni{sub x}O{sub 3} (x = 0; 0.15 and 0.3) powders was performed using a wet chemistry method with two different complexing agents: ethylenediaminetetraacetic acid and glycine. Based on the result of thermal analysis of obtained precursors, optimal conditions of the calcination process were determined. Powders were then milled, compacted and sintered at different temperatures using free sintering method, into series of dense, polycrystalline sinters. The use of glycine precursor allowed obtaining a single-phase material in all cases. Based on the electrical and sintering properties, the Y{sub 0.8}Ca{sub 0.2}Cr{sub 0.85}Ni{sub 0.15}O{sub 3} material was selected for further studies. It was deposited using cost-effective screen-printing method on the Crofer 22APU ferritic stainless steel. To investigate properties and suitability of the resulting layer/steel system for IT-SOFCs applications, the high-temperature, dual-atmosphere studies were carried out for the first time for ceramic/metallic system, in conditions as close as possible to actual working conditions of the fuel cell. The layer exhibited high stability and good protective properties. The area-specific resistance of the studied ceramic layer/metallic substrate composite was determined, with the obtained value of 0.0366 Ω cm{sup 2} being within the arbitrary limit set for these materials (0.1 Ω cm{sup 2}). The results show that the investigated materials are suitable for the projected application.

36 MATERIALS SCIENCE↗

A Process for Preparing 1,3-Diamino-5-Pentafluorosulfanylbenzene and Polymers Therefrom

Diamines have shown their utility in the formation of many polymers. Examples of these polymers include polyimides, polyamides, and epoxies. The properties of these polymers are often dependent on the diamine which is used to make the polymer. By the present invention, a process was developed to make a diamine containing pentafluorosulfanylbenzene moiety. This process involves two steps: the preparation of a dinitro precursor and the reduction of the dinitro compound to form the diamine. This diamine was then reacted with various dianhydrides, diacidchlorides, and epoxy resins to yield the corresponding polyimide, polyamide, and epoxy polymers. These polymers were then used to make films, a wire coating enamel, and a semi-permeable membrane. The novelty of this invention resides in the process to make the diamine. Traditionally, dinitro compounds are reduced with hydrazine or a catalyst such as palladium on charcoal. The catalyst which is used in this invention is platinum oxide. When this catalyst is used, it makes it possible to form a polymer-grade diamine.

St.clair, Anne K.↗

Uncertainties in the effects of organic aerosol coatings on polycyclic aromatic hydrocarbon concentrations and their estimated health effects

We used the CAM5 model to examine how different particle-bound polycyclic aromatic hydrocarbon (PAH) degradation approaches affect the spatial distribution of benzo(a)pyrene (BaP). Three approaches were evaluated: NOA (no effect of OA coatings state on BaP), shielded (viscous OA coatings shield BaP from oxidation under cool and dry conditions) and ROI-T (viscous OA coatings slow BaP oxidation in response to temperature and humidity). Results show that BaP concentrations vary seasonally, influenced by emissions, deposition, transport and degradation approach, all of which are influenced by meteorological conditions. All simulations predict higher population-weighted global average (PWGA) fresh BaP concentrations during December–January–February (DJF) compared to June–July–August (JJA), due to increased emissions from household activities and reduced removal processes during colder months. The shielded and ROI-T approaches, which account for OA coatings, result in 2–6 times higher BaP concentrations in DJF compared to NOA. The shielded simulation predicts the highest PWGA fresh BaP concentration (1.3 ng m −3 ), with 90 % of BaP protected from oxidation. In contrast, the ROI-T approach forecasts lower concentrations in middle to low latitudes, as it assumes less effective OA coatings under warmer, more humid conditions. Evaluations against observed BaP concentrations show the shielded approach performs best, with a normalized mean bias (NMB) within ± 20 %. The combined incremental lifetime cancer risk (ILCR) for both fresh and oxidized PAHs is similar across simulations, emphasizing the importance of considering both forms in health risk assessments. This study highlights the critical role of accurate degradation approaches in PAH modeling.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Investigation of Ga 2 O 3 as a new transparent conductive oxide for photovoltaics applications

This small innovation project intended to leverage recent activity and advances in ultrawide-bandgap oxide power electronics toward the investigation of Ga 2 O 3 as a transparent conductive oxide (TCO) for use in photovoltaics (PV). Ga 2 O 3 ’s theoretical advantage over incumbent TCOs is its very large bandgap of 4.8 eV, ensuring optical transparency of photons with λ ≥ 260 nm, effectively the full terrestrial solar spectrum. At the time of proposal writing, literature on Ga 2 O 3 as a TCO/optical material was relatively sparse — what little existed was focused on for UV sensors and/or emitters, with none related to PV. As such, this project was intended to help determine the potential of Ga 2 O 3 as a PV-oriented TCO by investigating its deposition using tools common to the PV and electronics industries — atomic layer deposition (ALD) and RF sputtering (RS), both of which are already used in PV manufacturing — and its resultant optical and electronic properties. Final project goals were to test its application to Si and III-V solar cells. Controllable film thickness and excellent uniformity was established for both methods deposition methods, with ALD providing higher precision for thinner films and RS more effective for growing thicker films. The as-deposited films were found to be amorphous in nature. Spectroscopic ellipsometry (SE) confirmed bandgaps of at least 4.8 eV and non-parasitic absorption across both AM0 and AM1.5G spectra; a refractive index approaching the expected value of 1.8 was also observed, with some degree of tunability based on process parameters. Using this initial optical data, a transfer matrix model, which interfaces with in-house EQE and LIV models, was developed to simulate Ga 2 O 3 optical effects on various solar cells, included potential in antireflection coatings (ARCs). Despite promising optical properties, the resultant resistivity / conductivity metrics did not meet expectations, regardless of deposition process. Although thick RS-deposited films, using both undoped and 1 at% Ge (n-type) doped sintered targets — demonstrated high net carrier concentrations (via C-V), and low specific resistance Ohmic contacts were demonstrated, transmission line measurements (TLM) showed very high resistivity. Further analysis indicated high vertical film conductivity, but very low lateral conductivity. Deeper characterization revealed a relatively high density of nano/microcrystalline inclusions that were ostensibly the source of the vertical conductivity, with the amorphous matrix serving as an effective insulator (likely due to high concentrations of electronic trap states). Despite extensive work to increase film polycrystallinity — demonstrated via high temperature annealing — sufficient lateral conductivity for TCO use was not achieved. The final phase of the project shifted focus toward investigation of ALD-deposited Ga 2 O 3 ’s potential as a passivant and/or passivating contact for both Si and III-V solar cells, with expectation of performance similar to Al 2 O 3 . However, initial rounds of testing using our baseline ALD process yielded minimal (but not quite zero) passivation of both GaInP and Si surfaces. Dielectric passivation is well-known to be highly process sensitive; given the unoptimized nature of the process used, this work was deemed inconclusive. The final outlook with respect to feasibility of Ga 2 O 3 as a PV-oriented TCO is, ultimately, still uncertain. The work performed in this project confirmed the optical properties and deposition methods, but the achieved electrical properties do not meet technological needs; literature reports in recent years are somewhat inconsistent and potentially untrustworthy, but generally appear to be in line with our results. At the very least it is clear that, should Ga 2 O 3 still be under consideration for PV TCO and/or selective contact applications, a significant amount of optimization and study is still needed.

14 SOLAR ENERGY↗

Tailored emitter, low-resistivity, ion-implanted silicon solar cells

Open-circuit voltages as high as 0.645 V (AM0, 25 C) have been obtained by a new process developed for low-resistivity silicon. The process utilizes high-dose phosphorus implantation followed by furnace annealing and simultaneous oxide growth. The effect of the thermally grown oxide is a reduction of surface recombination velocity; the oxide also acts as a moderately efficient antireflection (AR) coating. Boron-doped, float-zone silicon with resistivities from 0.1 to 1.0 (omega)(cm) has been processed according to this sequence; results show that the highest open-circuit voltage is obtained with 0.1(omega)(cm) starting material. The effects of Auger recombination and bandgap narrowing caused by high doping concentrations in the n(+)junction region have been investigated by implanting phosphorus over a wide range of dose levels. The effects of emitter-phosphorus concentrations tailored to optimize electric fields in the emitter have also been investigated.

Minnucci, J. A.↗

Corrosion-resistant polyurethane coatings from structure-homogenized biorefinery lignin through fractionation and oxypropylation

Using lignin for polyurethane (PU) synthesis is challenging because of its heterogeneous structure, i.e., broad molecule weight (MW) distribution and diverse hydroxyl (OH) functionality. This complexity influences the crosslinking reaction between lignin and isocyanate and affects the quality of PU products. Here, we propose a two-step strategy for lignin structure homogenization by lowering its MW and uniforming OH functionality (step 2). Step 1 involves a bioethanol fractionation process, yielding fractionated lignin with one order lower MW than the raw lignin while exhibiting better processability for the subsequent process. Step 2 is performed by an oxyalkylation process using fractionated lignin that converts phenolic and carboxylic OHs to aliphatic OHs. As a result, we obtained structure-homogenized lignin with good compatibility and crosslinking with hexamethylene diisocyanate for PU coating synthesis. Moreover, PU coatings prepared from structure-homogenized lignin display a defect-free microscopic structure and show better corrosion resistance than coatings fabricated from its raw lignin alternative. Overall, the structure homogenization process is a beneficial way of using lignin as biopolyol in PU synthesis toward the application-oriented design of corrosion-resistant lignin-based PU coatings.

36 MATERIALS SCIENCE↗

Process for application of powder particles to filamentary materials

This invention is a process for the uniform application of polymer powder particles to a filamentary material in a continuous manner to form a uniform composite prepreg material. A tow of the filamentary material is fed under carefully controlled tension into a spreading unit, where it is spread pneumatically into an even band. The spread filamentary tow is then coated with polymer particles from a fluidized bed, after which the coated filamentary tow is fused before take-up on a package for subsequent utilization. This process produces a composite prepreg uniformly without imposing severe stress on the filamentary material, and without requiring long, high temperature residence times for the polymer.

Baucom, Robert M.↗

Electrodeposition and analysis of thick bismuth films

Due to its unique physical and chemical properties, bismuth is an attractive candidate for a wide range of applications such as battery anodes, radiation shielding, and semiconductors, to name a few. This work presents the electrodeposition of mechanically stable and homogenous bismuth films at micron-scale thicknesses. A simple one-step electrodeposition process using either a pulse/reverse or direct current source yielded thick, homogenous, and mechanically stable bismuth films. Morphology, electrochemical behavior, adhesion, and mechanical stability of bismuth coatings plated with varying parameters were characterized via optical profilometry, cyclic voltammetry, electron microscopy, and tribology. Scratch testing on thick electroplated coatings (> 100 µm) revealed similar wear resistance properties between the pulse/reverse plated and direct current electroplated films. This study presents a versatile bismuth electroplating process with the possibility to replace lead in radiation shields with an inexpensive, non-toxic metal, or to make industrially relevant electrocatalytic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing the Dynamics of Platinum Nanoparticle Catalysts on Carbon in Oxygen and Water Using Environmental TEM

Deactivation of supported metal nanoparticle catalysts, especially in relevant gas condition, is a critical challenge for many technological applications, including heterogeneous catalysis, electrocatalysis, fuel cells, biomedical imaging and drug delivery. It has been far more commonly realized that deactivation of catalysts stems from surface area loss due to particle coarsening, however, for which the mechanism remains largely unclear. Herein, we use aberration corrected environmental transmission electron microscopy, at atomic level, to in-situ observe the dynamics of Pt catalyst in fuel cell relevant gas conditions. Particles migration and coalescence is observed to be the dominant coarsening process. As compared with the case of H2O, O2 promotes Pt nanoparticle migration on carbon surface. Surprisingly, coating Pt/carbon with a nanofilm of electrolyte (Nafion ionomer) leads to a faster migration of Pt in H2O than in O2, a consequence of Nafion-carbon interface water “lubrication” effect. Atomically, the particles coalescence is featured by re-orientation of particles towards lattice matching, a process driven by orientation dependent van der Waals force. These results provide direct observations of dynamics of metal nanoparticles at critical surface/interface under relevant conditions and yield significant insights into the multi-phase interaction in related technological processes.

atomic scale↗

Thin film studies toward improving the performance of accelerator electron sources

Future electron accelerators require DC high voltage photoguns to operate beyond the present state of the art to conduct new experiments that require ultra-bright electron beams with high average current and higher bunch charge. To meet these demands, the accelerators must demonstrate improvements in a number of photogun areas including vacuum, field emission elimination in high voltage electrodes, and photocathodes. This dissertation illustrates how these improvements can be achieved by the application of suitable thin-films to the photogun structure for producing ultra-bright electron beams. This work is composed of three complementary studies. First, the outgassing rates of three nominally identical 304L stainless steel vacuum chambers were studied to determine the effects of chamber coatings (silicon and titanium nitride) and heat treatments. For an uncoated stainless steel chamber, the diffusion limited outgassing was taken over by the recombination limited process as soon as a low outgassing rate of ~1.79(±0.05) x 10- 13 Torr L s -1 cm -2 was achieved. An amorphous silicon coating on the stainless steel chambers exhibited recombination limited behavior and any heat treatment became ineffective in reducing the outgassing rate. A TiN coated chamber yielded the smallest apparent outgassing rate of all the chambers: 6.44(±0.05) x 10 -13 Torr L s -1 cm -2 following an initial 90 °C bake and 2(±20) x 10 -16 Torr L s -1 cm -2 following the final bake in the series. This perceived low outgassing rate was attributed to the small pumping nature of TiN coating itself. Second, the high voltage performance of three TiN-coated aluminum electrodes, before and after gas conditioning with helium, were compared to that of bare aluminum electrodes and electrodes manufactured from titanium alloy (Ti-6Al-4V). This study suggests that aluminum electrodes, coated with TiN, could simplify the task of implementing photocathode cooling, which is required for future high current electron beam applications. The best performing TiN-coated aluminum electrode demonstrated less than 15 pA of field emission current at -- 175 kV for a 10 mm cathode/anode gap, which corresponds to a field strength of 22.5 MV/m. Third, the effect of antimony thickness on the performance of bialkali-antimonide photocathodes was studied. The high-capacity effusion source enabled us to successfully manufacture photocathodes having a maximum QE around 10% and extended low voltage 1/e lifetime (> 90 days) at 532 nm via the co-deposition method, with relatively thick layers of antimony (≥ 300 nm). We speculate that alkali co-deposition provides optimized stoichiometry for photocathodes manufactured using thick Sb layers, which could serve as a reservoir for the alkali. In summary, this research examined the effectiveness of thin films applied on photogun chamber components to achieve an extremely high vacuum, to eliminate high voltage induced field emission from electrodes, and to generate photocurrent with high quantum yield with an extended operational lifetime. Simultaneous implementation of these findings can meet the challenges of future ultra-bright photoguns.

42 ENGINEERING↗

Production of LEU fully ceramic microencapsulated fuel for irradiation testing

The Advanced Fuels Campaign of the US DOE Fuel Cycle Research/Development program is currently engaged in production of FCM fuel for irradiation testing in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL). FCM fuel production is a serial process with 3 major steps namely kernel, TRISO, and compact production. The first step in the kernel process is production of air-dried UO{sub 3} gel spheres with suspended carbon particles. These spheres, roughly 2 mm in size, are then calcined to produce a mixture of UO{sub 2} and carbon. This calcination step may be performed in either argon, hydrogen, or mixtures of these gases. Once the calcination step is complete, temperature is increased (>1400 Celsius degrees) to convert this mixture to UO{sub 2} + UC{sub x}. Once dense oxide-carbide kernels are available, the inert environment is switched to a nitrogen containing one to facilitate carbothermic reduction of kernels and production of UN. Essentially, the oxygen and carbon in the oxide-carbide kernels react with one another to produce CO and are replaced with nitrogen inside the lattice. The TRISO step in fuel production is incorporation of a porous carbon buffer layer, a dense inner pyrolytic carbon layer (IPyC), a SiC layer, and finally and outer pyrolytic carbon layer (OPyC) onto the UN kernels. The coating layer deposition step is carried out inside a graphite furnace using a fluidized bed chemical vapor deposition (CVD) process. In essence, a mixture of reactant and inert gasses flow from the bottom through a bed of particles that are in turn fluidized by the gas stream. The particles undergo CVD and once a different coating layer is to be incorporated, the furnace temperature is adjusted and the reactant gases are changed. The final step in the series of fuel production activities is the consolidation of UN TRISO particles inside the SiC matrix to produce cylindrical pellets. It entails 3 critical areas: SiC powder mixing, over-coating of particles, and high-temperature densification. Optimal execution of the powder mixing step is vital to achieve a fully dense SiC matrix at the end of the process. The SiC matrix is consolidated using a special form of liquid phase sintering (LPS) involving nano-powder feedstock that is designated as the NITE process. The SiC nano-powder slurry is sprayed directly onto the particle surface using a piezoelectric nozzle. Once the over-coated particles are available, final consolidation step at high temperatures (1875 Celsius degrees) is carried out.

36 MATERIALS SCIENCE↗

Fabrication of magnetic core PEI-silica shell particles

Highlights: • PEI-silica shell fabrication was developed for iron-carbonyl core material. • Magnetic separation of core-free by-product of the fabrication proved successful. • Varying fabrication method/concentration successfully tuned shell characteristics. • Sonication methods produced smooth coatings with a trend towards multicore particles. • Raspberry-like coatings were made by the slow addition, one- and two-pot methods. - Abstract: Magnetic core-silica shell particles combine the physico-chemical properties of the silica shell with the magnetic properties of the core. Seven possible particle coating methods utilizing the biomimetic polyamine polyethyleneimine (PEI) as the silication catalyst, have been identified and the objective of this study was to link the properties of the final PEI-silica coating with the methodology. The PEI-silica coated carbonyl iron particles were characterized via scanning electron microscopy, energy dispersive X-ray spectroscopy and Fourier transfer infrared spectroscopy. Varying the fabrication method and silane concentration successfully tuned the shell characteristics. Methods using sonication produced smooth more evenly distributed coatings with a tendency towards multicore particles. In contrast, raspberry-like coatings were produced via the slow addition, one- and two-pot methods. The magnetic separation process after synthesis achieved a degree of purification that makes these core–shell particles useful for potential applications that require specific surface interactions and the ease of magnetic separation.

36 MATERIALS SCIENCE↗

Development of Advanced Low Conductivity Thermal Barrier Coatings

Advanced multi-component, low conductivity oxide thermal barrier coatings have been developed using an approach that emphasizes real-time monitoring of thermal conductivity under conditions that are engine-like in terms of temperatures and heat fluxes. This is in contrast to the traditional approach where coatings are initially optimized in terms of furnace and burner rig durability with subsequent measurement in the as-processed or furnace-sintered condition. The present work establishes a laser high-heat-flux test as the basis for evaluating advanced plasma-sprayed and electron beam-physical vapor deposited (EB-PVD) thermal barrier coatings under the NASA Ultra-Efficient Engine Technology (UEET) Program. The candidate coating materials for this program are novel thermal barrier coatings that are found to have significantly reduced thermal conductivities and improved thermal stability due to an oxide-defect-cluster design. Critical issues for designing advanced low conductivity coatings with improved coating durability are also discussed.

Zhu, Dong-Ming↗