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115 records · Page 7

Graphite-Embedded High-Performance Insulated Metal Substrate for Wide-Bandgap Power Modules

Emerging wide-bandgap (WBG) semiconductor devices such as silicon carbide (SiC) metal–oxide semiconductor field-effect transistors (MOSFETs) and gallium nitride high-electron-mobility transistors can handle high power in reduced semiconductor areas better than conventional Si-based devices owing to superior material properties. With increased power loss density in a WBG-based converter and reduced die size in power modules, thermal management of power devices must be optimized for high performance. Here, we present a graphite-embedded insulated metal substrate (thermally-annealed-pyrolytic-graphite-embedded insulated metal substrate—IMSwTPG) designed for WBG power modules. Theoretical thermal performance analysis of graphite-embedded metal cores is presented, with design details for IMSwTPG with embedded graphite to replace a direct-bonded copper (DBC) substrate. The proposed IMSwTPG is compared with an aluminum nitride-based DBC substrate using finite-element thermal analysis for steady-state and transient thermal performance. The solutions’ thermal performances are compared under different coolant temperature and thermal loading conditions, and the proposed substrate's electrical performance is validated with static and dynamic characterization. Using graphite-embedded substrates, junction-to-case thermal resistance of SiC MOSFETs can be reduced up to 17%, and device current density can be increased by 10%, regardless of the thermal management strategy used to cool the substrate. Reduced transient thermal impedance of up to 40% of dies owing to increased heat capacity is validated in transient thermal simulations and experiments. The half-bridge power module's electrical performance is evaluated for on -state resistance, switching performance, and switching loss at three junction temperature conditions. The proposed substrate solution has minimal impact on conduction and switching performance of SiC MOSFETs.

42 ENGINEERING↗

Development of Ti 3 SiC 2 MAX phase tubular structures for solar receiver applications

Solar receiver tubes are key components of concentrating solar-thermal power (CSP) systems that harvest solar energy. For better efficiency, the Gen3 CSP receivers, which collect heat into a heat transfer fluid, require a temperature exceeding 700 °C during operation and need to perform under extreme conditions of high temperature and high thermal stress. Operators are seeking CSP designs using new high-temperature structural materials with high thermal conductivity and high creep resistance to achieve a design life of 30 years and thus help recover the plant capital cost sooner. MAX phase materials, which consist of an early transition metal element, an A-group element, and carbon or nitrogen, are expected to exhibit high creep resistance as well as high fracture toughness. Here, in this paper, we describe fabricating both (1) dense Ti 3 SiC 2 MAX phase disks and (2) short-length tubes using field-assisted sintering technology (FAST). First, the disk samples that we fabricated are fully dense and contain ≈90 % Ti 3 SiC 2 MAX phase materials and ≈10 % TiC phase materials. We determined a flexure strength of 519 ± 32 MPa by conducting a four-point bending test at room temperature with rectangular bar samples of ≈100 % density. The thermal conductivity of the Ti 3 SiC 2 MAX phase samples, measured by light flashing analysis, decreases linearly from a value of 41 W . m -1 . K -1 at room temperature to a value of 36 W . m -1 . K -1 at 650 °C. A solar reflectance measurement of the Ti 3 SiC 2 MAX phase revealed that, temperature increases from 400 to 1400 °C, thermal emittance increases from 0.39 to 0.49, while selectivity decreases from 1.8 to 1.4, respectively. Whereas the surface oxidized MAX phase samples after 100 h exposure to air at 1000 °C exhibit that of SiC. Next, we discuss fabrication of the crack-free Ti 3 SiC 2 MAX phase tubular structures accomplished by using FAST processing in graphite bedding. A Ti 3 SiC 2 MAX phase content of > 95 % with traceable ≈3% remaining TiC phase and ≈15 % porosity were demonstrated after high-temperature annealing. An average fracture strength of ≈250 MPa was determined with Ti 3 SiC 2 MAX phase tubes of ≈85 % density by diametral compression testing at room temperature. Our work demonstrated that using FAST processing to produce Ti 3 SiC 2 MAX phase tubular structures for CSP receiver applications is a viable approach.

14 SOLAR ENERGY↗

Synergetic effect of Ti 3+ and oxygen doping on enhancing photoelectrochemical and photocatalytic properties of TiO 2 /g-C 3 N 4 heterojunctions

To improve the utilization of visible light and reduce photogenerated electron/hole recombination, Ti 3+ self-doped TiO 2 /oxygen-doped graphitic carbon nitride (Ti 3+ -TiO 2 /O-g-C 3 N 4 ) heterojunctions were prepared via hydrothermal treatment of a mixture of g-C 3 N 4 and titanium oxohydride sol obtained from the reaction of TiH 2 with H 2 O 2 . In this way, exfoliated O-g-C 3 N 4 and Ti 3+ -TiO 2 nanoparticles were obtained. Simultaneously, strong bonding was formed between Ti 3+ -TiO 2 nanoparticles and exfoliated O-g-C 3 N 4 during the hydrothermal process. Charge transfer and recombination processes were characterized by transient photocurrent responses, electrochemical impedance test, and photoluminescence spectroscopy. The photocatalytic performances were investigated through rhodamine B degradation test under an irradiation source based on 30 W cold visible-light-emitting diode. The highest visible-light photoelectrochemical and photocatalytic activities were observed from the heterojunction with 1:2 mass ratio of Ti 3+ -TiO 2 to O-g-C 3 N 4 . The photodegradation reaction rate constant based on this heterojuction is 0.0356 min -1 , which is 3.87 and 4.56 times higher than those of pristine Ti 3+ -TiO 2 and pure g-C 3 N 4 , respectively. Here, the remarkably high photoelectrochemical and photocatalytic performances of the heterojunctions are mainly attributed to the synergetic effect of efficient photogenerated electron-hole separation, decreased electron transfer resistance from interfacial chemical hydroxy residue bonds, and oxidizing groups originating from Ti 3+ -TiO 2 and O-g-C 3 N 4 .

25 ENERGY STORAGE↗

The Characterization of the Selected Materials for Space Shuttle

The harsh conditions to which the Space Shuttles are exposed during flight required the development and use of many unique materials. These materials were specially designed to withstand extreme temperatures, in some cases over 1600 C, while other material must withstand the cryogenic conditions of -253 C, and others must operate while under extreme loads. All of these materials must not only operate in the harsh condition but they must be light weight as well. The Space Shuttle is composed of three major components when configured for launch, Figure 1; the Shuttle, solid rocket boosters, and external tank (ET). The different heat shields of the Shuttle make up the thermal protection system (TPS); this system consists of many different types of components designed to operate on various parts of the vehicle. The body of the Shuttle and ET are composed mainly of aluminum alloy and graphite epoxy. The TPS consists of reinforced carbon-carbon (RCC) used on the wing leading edges and nose cap areas while the upper forward fuselage areas, the entire underside of the Shuttle, the Orbiter maneuvering system, and reaction control system utilize blacc high temperature reusable surface insulation (HRSI) tiles, Figure 2. Other areas of the Orbiter are protected by fibrous refractory composite insulation (FRCI) tiles. Areas where the temperature stays below 649 C, such as the forward fuselage, mid-fuselage, aft fuselage, vertical tail, and upper wing, are protected by other material such as, white low temperature reusable surface insulation (LRSI) tiles, advanced flexible reusable surface insulation (AFRSI) blankets, and felt reusable surface insulation (FRSI) white blankets. The RCC is a pyrolized laminated carbon with the outer surface converted to silicon carbide to prevent oxidation. The FiRST tiles are made of a low-density, high purity silica 99.8-percent amorphous fiber insulation that is made rigid by ceramic bonding resulting in 90-percent void and 10-percent materials. The RCC and HRSI are used in areas where the temperature rises above 1260 T. The FRCI tiles are high strength tiles derived by adding alumina-bososilicate fiber to the pure silica tile slurry that welds the micron-sizes fibers of pure silica into a rigid structure during sintering. The FRCI is composed of 20-percent alumina-borosilicate fibers and 80-percent silica fibers, and provided improved strength, durability and resistance to coating cracking and weight reduction than HRSI.

Kim, Hae-Soo↗

Experimental Investigation of the Impact of Cathode Grade on Sludge Formation at the Cathode Block-Aluminum Interface of Hall–Héroult Cells

The presence of resistive sludge on the cathode surface in Hall–Héroult cells can increase the aluminum production costs and reduces cell lifetime. Modern cells with graphitized cathode blocks generally operate satisfactorily but some are exhibiting excessive deposit formation, thus lower performances. Little attention has ever been given to the role of the cathode grade and its properties on sludge formation. In this investigation, five graphitized industrial cathode grades with varying properties are tested on a bench scale aluminum electrolysis setup with cathodic current density of 0.9 A/cm{sup 2}, under a nitrogen atmosphere at 1233 K (960 °C) for 8 hours with initial bath composition of 10 pct alumina, cryolite ratio of 2.2, 5 pct CaF{sub 2} and no point feeding. Postmortem characterization includes Rietveld refinement of deposits, optical microscopy and SEM-EDS observations of the carbon-aluminum interface. Sludge located near the center of the cathode surface was generated during the experiments despite the absence of point feeding. The sludge profile was variable among grades and could be related to the horizontal and vertical thermal conductivities of the blocks. This study has pushed further the understanding of the mechanisms of sludge formation and dissolution concerning the cathode grade properties.

36 MATERIALS SCIENCE↗

Scalable and Cost-Effective Barrier Layer Coating to Improve Stability and Performance of SOFC Cathode

During this project, a dense GDC barrier layer was deposited on YSZ substrate to prevent chemical reaction between LSCF and YSZ by a cost-effective EPD method. PPy was used as the agent to make YSZ conductive. Highly compact GDC green layer was obtained by the EPD process in an ethanol-based suspension. The deposition rate on PPy coated YSZ is slower than that on graphite because the charge transfer process is the rate-determining step. The main resistance is from the ion accumulation/depletion zone. The H + ions reduced at the cathode consist of free H + ions and absorbed H + ions corresponding to the unavoidable electrochemical reaction and deposition, respectively. A factor f was introduced to reflects EPD efficiency and describe the competitive relationship between deposition and electrochemical reaction during EPD process. f is in the range from 0 to 0.5 which is determined by the amount ration between free H + ions and absorbed H + ions at the suspension/deposit interface and the conductivity of the cathode. f decreases with the increase of current density or applied voltage and the conductivity of the cathode. GDC thin layers formed by DC-EPD in a thickness range of 5-8 µm were successfully densified at as low as 1300 °C and the adhesion between GDC and YSZ was good. The densification temperature can be further reduced to 1250 °C when AC-EPD was used to replace DC-EPD. The deposition rate increases with the increase of duty cycle and voltage ratio. The deposition rate increases with the increase of frequency from 10 Hz to 500 Hz, while decrease when the frequency increases from 500 Hz to 5000 Hz. Desorption of absorbed charge carrier is easy and irreversible. The deposition rate is independent on the conductivity of the cathode when the electrochemical reaction can be ignored with a high frequency. Inter-diffusion of cation ions between the electrolyte and barrier layer has been systematically characterized via 3-D atom probe, TEM, and other techniques. No measurable Sr transport occurs across the GDC layer with a thickness of 1.5 – 6 μm at a LSCF processing temperature of 1000 °C. However, Sr transport does occur across GDC layer with a thickness of 1.5 or 3 μm at a higher LSCF sintering temperature (1000 °C or 1200 °C). The primary pathway are open pores or grain boundaries in the GDC. The observed zirconate layer is discontinuous even for the most extreme conditions (1.5 μm GDC, 1200 °C LSCF sintering temperature). Increasing the thickness of GDC to 4.5 μm can effectively suppress any zirconate formation measurable by SEM-EDX. Cobalt is observed at grain boundaries within the GDC, suggesting some depletion of Co from the LSCF layer that may ultimately impact electrode performance.

08 HYDROGEN↗

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗