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Preliminary Characterization and Evaluation on FFF Manufactured 316H and ODS Steels

The Advanced Materials and Manufacturing Technology (AMMT) program develops cross-cutting technologies in support of a broad range of nuclear reactor technologies and maintains U.S. leadership in materials and manufacturing technologies for nuclear energy applications. The overarching vision of AMMT is to accelerate the development, qualification, demonstration, and deployment of advanced materials and manufacturing technologies to enable reliable and economical nuclear energy. Solid-state advanced manufacturing techniques can overcome some of the challenges in liquid-based additive manufacturing (AM) processes and should therefore be considered in material design and manufacturing as well. The work presented in this report forms part of a study on solid-state AM techniques of 316 stainless steels (SS) and oxide dispersion strengthened (ODS) steel components and supports the vision and goals of the AMMT program relevant to accelerate the development and deployment of advanced manufacturing processes. Achieving this can provide a safety improvement through larger safety margins, economic benefit for higher efficiency during operation, and a cost reduction through more effective manufacturing processes and less waste. This study provides preliminary information on development of the fused-filament fabrication (FFF) process using different powder types to demonstrate the sensitivity, and therefore the characterization of these sample components. The full solid-state manufacturing feasibility study will be completed and reported in a final feasibility evaluation during 2025. The study investigation used two 14YWT ODS powder batches, which provided information and the effect of different powder morphologies on manufacturability. The two 316SS powders demonstrated the effect of powder size on the manufacturability using FFF. Two product forms, namely a honeycomb structure and flat samples, were manufactured to demonstrate the flexibility of product form.

36 MATERIALS SCIENCE↗

Data for Rewiring Yeast Metabolism for Producing 2,3-Butanediol and Two Downstream Applications: Techno-Economic Analysis and Life Cycle Assessment of Methyl Ethyl Ketone (MEK) and Agricultural Biostimulant Production

Rising concerns for sustainability and global climate change have driven the development of sustainable production pathways for biofuels and chemicals from lignocellulosic biomass via integrated biological and chemical processes. We constructed an engineered Saccharomyces cerevisiae capable of producing 2,3-butanediol (2,3-BDO) from glucose without accumulating ethanol and glycerol, which hinder downstream processing of 2,3-BDO, through extensive metabolic reprogramming. Specifically, we introduced heterologous 2,3-BDO biosynthetic enzymes and deleted the major isozymes of ethanol and glycerol biosynthetic enzymes. In addition, we introduced an NAD+ regenerating Pyruvate-Malate (PM) cycle and enhanced the NAD+ regenerating capability of the PM cycle to resolve the redox imbalance from the deletion of ethanol and glycerol production pathways. The resulting engineered yeast produced 109.9 g/L of 2,3-BDO with a productivity of 1.0 g/L/h and a yield of 0.36 g/g glucose in a fed-batch fermentation. We also conducted techno-economic analysis (TEA) and life cycle assessment (LCA) of the production of methyl ethyl ketone (MEK) through catalytic dehydration of 2,3-BDO. A TEA based on the experimental results indicated that the minimum product selling price (MPSP) was estimated to be $1.90/kg. Regarding cradle-to-grave LCA, 100-year global warming potential (GWP100) and fossil energy consumption (FEC) were found to be 0.37 kg CO2 eq/kg and 3.1 MJ/kg, respectively. These results demonstrated the feasibility of cost-competitive and sustainable bio-based MEK production via yeast fermentation. In addition, we explored the possibility of using the fermentation broth containing 2,3-BDO as a biostimulant inducing drought tolerance in plants. As a result, the yeast 2,3-BDO fermentation broth can induce drought tolerance in Arabidopsis thaliana without a complicated purification process.

Economics↗

On the Efficient Evaluation of the Exchange Correlation Potential on Graphics Processing Unit Clusters

The predominance of Kohn–Sham density functional theory (KS-DFT) for the theoretical treatment of large experimentally relevant systems in molecular chemistry and materials science relies primarily on the existence of efficient software implementations which are capable of leveraging the latest advances in modern high-performance computing (HPC). With recent trends in HPC leading toward increasing reliance on heterogeneous accelerator-based architectures such as graphics processing units (GPU), existing code bases must embrace these architectural advances to maintain the high levels of performance that have come to be expected for these methods. In this work, we purpose a three-level parallelism scheme for the distributed numerical integration of the exchange-correlation (XC) potential in the Gaussian basis set discretization of the Kohn–Sham equations on large computing clusters consisting of multiple GPUs per compute node. In addition, we purpose and demonstrate the efficacy of the use of batched kernels, including batched level-3 BLAS operations, in achieving high levels of performance on the GPU. We demonstrate the performance and scalability of the implementation of the purposed method in the NWChemEx software package by comparing to the existing scalable CPU XC integration in NWChem.

97 MATHEMATICS AND COMPUTING↗

Phosphate amendments for chemical immobilization of uranium in contaminated soil

Uranium (U) contamination is a major environmental problem associated with the mining and processing of nuclear materials for both weapons and power production. When possible, in situ soil remediation techniques are preferable for reducing the risk associated with diffuse low-level U contamination. Uranium is known to form sparingly soluble phosphate compounds that persist in the environment. Therefore, batch experiments were performed to evaluate the efficacy of three phosphate amendments, hydroxyapatite (HA), sodium phytate (IP6) and sodium tripolyphosphate (TPP), to immobilize U in contaminated sediments. The amendments were added at equivalent phosphorus (P) concentrations and then equilibrated under a range of test conditions, with changes in soluble U and Ptotal monitored at pre-set time intervals. Only HA was effective at reducing the soluble U soil fraction when compared to the control, with IP6 and TPP increasing the soluble U soil fraction. After equilibration, changes in contaminant partitioning in the amended sediments were evaluated using operational extraction methods. Sequential extraction results for HA generally indicated a transfer of U from labile to more recalcitrant phases, while the results for IP6 and TPP were more ambiguous.

Uranyl↗

Synthesis of mesoscale, crumpled, reduced graphene oxide roses by water-in-oil emulsion approach

Mesoscale crumpled graphene oxide roses (GO roses) were synthesized by using colloidal graphene oxide (GO) variants as precursors for a hybrid emulsification-rapid evaporation approach. This process produced rose-like, spherical, reduced mesostructures of colloidal GO sheets, with corrugated surfaces and particle sizes tunable in the range of ~800 nm to 15 μm. Excellent reproducibility for particle size distribution is shown for each selected speed of homogenizer rotor among different sample batches. The morphology and chemical structure of these produced GO roses was investigated using electron microscopy and spectroscopy techniques. In conclusion, the proposed synthesis route provides control over particle size, morphology and chemical properties of the synthesized GO roses.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mixing Study for the Modification of H-Canyon Tank 31 and 32 Recirculation Lines Via M-Star®

As a part of the Accelerated Basin De-Inventory (ABD) program Tanks 31 or 32 will be re-purposed to support increasing the number of annual Material Test Reactor (MTR) and High Flux Isotope Reactor (HFIR) dissolutions. The proposed plan will allow Tanks 31 or 32 to be used as the dissolver cold chemical solution makeup tank and storage tank. The dissolver cold chemicals are 50% nitric acid, process water, mercuric nitrate, and gadolinium nitrate. Tanks 31 and 32 are 9 ft. (outer diameter) x 36 ft, horizontal, and can hold approximately 56,000 liters (15,000 gallons) each. One full volume of Tanks 31 or 32 can support 4 HFIR 6.4D equivalent batches. Both tanks are equipped with liquid level instrumentation. Tank 31 is equipped with 1 pump used for transfer and recirculation while Tank 32 is equipped with two pumps, one for transfer and the other for recirculation. Each of the pumps is equipped with sample taps. The tanks do not have specific gravity instrumentation, an agitator, or a sampler. Piping modifications will also be performed to supply the tank with cold chemicals. The current dissolver chemical composition is 5.0 -8.5M HNO3 and ~0.2 g Gd/L. The recirculating pump connected to Tank 31 is rated for a flowrate 175 gpm while the pump connected to Tank 32 is rated for a flowrate 50 gpm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Assessing Impact of Reactor Scaling on Carbohydrate and Lipid Yields from Saline and Fresh Water Algae

Effective deconstruction of algal biomass is a major challenge associated with algal biofuels/bioproduct production. Improving biomass conversion requires understanding how reaction parameters affect the scale-up of bench scale processes to move to cost-effective conversion. Pretreatment of both aquatic and terrestrial feedstocks, using similar reaction conditions, identical feedstock and pretreatment chemistries have reported wide ranges in total sugar yields. This has been attributed to differences in reactor size or scale, type of operation (batch vs continuous), method of heating, reactor geometry and solids loading (w/w). These factors can impact both mass and heat transfer affecting both yield and reaction kinetics. To understand how total sugar yields in algal biomass are affected by different dilute acid pretreatment configurations we evaluated total sugar and lipid release at three reactor scales ranging from 4 ml to 300 ml, operated under mixed and non-mixed regimes.

09 BIOMASS FUELS↗

Full-Scale Vessel Testing of the Standard High-Solids Vessel for the Hanford Waste Treatment Plant Pretreatment Facility - 17282

Concerns over the mixing performance of the planned pulse-jet mixed (PJM) vessels for high solids applications in the Hanford Waste Treatment and Immobilization Plant (WTP) Pretreatment (PT) Facility, led to the development of a standard high-solids vessel (SHSV) design and full-scale vessel testing. The SHSV is intended as a potential replacement for several high-level waste feed receipt and lag storage vessels, ultrafiltration feed preparation vessels, and plant wash vessels. The SHSV design concept uses multiple smaller vessels (60 500 to 79 500 liters nominal batch size) to replace larger vessels, providing redundancy, improved mixing (PJM design and spargers), monitoring (multi-level bubblers), reduced material at risk, and improved structural features. The SHSV also requires qualification of a single vessel design for high solids Newtonian and non-Newtonian slurry processing, rather than earlier multiple vessel designs. Qualification of the SHSV design for mixing will be achieved through full-scale vessel testing (FSVT) with a prototypic SHSV under a set of most adverse design conditions in conjunction with additional engineering analyses. An Integrated Technical Team consisting of the U.S. Department of Energy (DOE), Bechtel National, Inc. (BNI), and independent experts was established to accelerate and provide oversight and direction to the test program and SHSV qualification. This paper will present an overview of the SHSV, full-scale vessel test and qualification program, and the management program to achieve closure of technical issues associated with PJM vessel mixing and control systems. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solvent hold tank sample results for MCU-17-150-152 (July 2017) and MCU-17-153-155 (August 2017): Quarterly report

A trend summary that includes the last two Solvent Hold Tank (SHT) monthly samples is shown; MCU- 17-150-152 (July SHT) and MCU-17-153-155 (August SHT). Since the last SHT sample sent for analysis was the August sample the chemical state of the solvent is best approximated by the chemical analysis of the August SHT sample (MCU-17-153-155). This report mainly focused on the chemical analysis of the August SHT sample. The analysis data from the July SHT sample are presented in the “trend” plots of this report. Analysis of the August SHT sample (MCU-17-153-155) indicated that the modifier (CS-7SB) was 2% below but the extractant (MaxCalix) concentration was at its nominal recommended level (169,000 mg/L and 46,400 mg/L respectively). The suppressor (TiDG) level has decreased since the last measurement taken while the Modular Caustic-Side Solvent Extraction unit (MCU) was operating in January 2017, but has remained steady in the range of 666 (observed in April) to 715 mg/L (observed in the August 2017 sample) since February 2017, well above the minimum recommended level (479 mg/L), but below the nominal level. The “flat” trends observed in the TiDG, MaxCalix, modifier, and Gamma measurement are consistent with the solvent being idle since January 10, 2017. A strong correlation between density and modifier concentration in the solvent continues to be observed in the SHT samples. This analysis confirms the Isopar™L addition to the solvent in January 2017. This analysis also indicates the solvent did not require further additions. Based on the current monthly sample, the levels of TiDG, Isopar™L, MaxCalix, and modifier are sufficient for continuing operation but are expected to decrease with time if the Modular Caustic-Side Solvent Extraction Unit (MCU) returns to processing radioactive liquid waste. Otherwise, the levels of these components will remain steady. A future Isopar™L trimming addition to the solvent is recommended when MCU resumes processing waste. Two unknown impurities related to the modifier (but not sec-butyl phenol: a modifier degradation product observed before) at the 290 and 110 mg/L levels were observed in the August SHT sample by the Gas - Chromatography-Mass Spectrometry (GC-MS) method. They were observed in a second GC-MS re-run with a new column. Their identification can’t be ascertained at this time. No impurities were observed in the Hydrogen Nuclear Magnetic Resonance (HNMR). Another impurity observed in the samples was mercury. Based on the August SHT sample, up to 23 ± 5 micrograms of mercury per mL of solvent was detected (the average of the Cold Vapor-Atomic Adsorption [CV-AA] and X-Ray Fluorescence [XRF] methods). The higher mercury concentration in the solvent (as determined in the last three-monthly samples) is possibly due to either a higher mercury concentration in Salt Batches 8 and 9 (Tank 49H) . The gamma level (~ 2.0E4 dpm/mL) measured in the August SHT samples was one order of magnitude lower than the gamma levels observed in the December 2016 and January 2017 SHT samples. A similar level was observed in the July SHT sample (MCU-SHT-150-152). The gamma level has remained consistently steady since January 10, 2017 when MCU stopped processing radioactive liquid waste. The laboratory will continue to monitor the quality of the solvent in particularly for any new impurities or degradation of the solvent components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Solvolytic extraction of lignin from biomass is a critical step in lignin-first biorefining, including the reductive catalytic fractionation (RCF) process. Key to optimal RCF processing is the ability to rapidly extract lignin from biomass at high delignification extents and transfer the lignin molecules to a catalyst surface in a time frame that minimizes lignin condensation reactions. Here, we use a flow-through reactor to study the effects of temperature (175–250 °C), residence time (9 to 36 min), and solvent composition (methanol and methanol–water) on lignin extraction and condensation. We evaluated three metrics at each condition: total delignification, delignification rate, and extent of condensation, the latter measured by a decrease in monomer yield for batch hydrogenolysis reactions of solvolysis liquor compared to batch RCF reactions. We observe that delignification is predominantly determined by temperature, while residence time dictates the lignin condensation extent. Moreover, the extent of both extraction and condensation increased in the methanol–water solvent system compared to that in the methanol system. Lignin extracted in methanol is stable up to 18-min residence times at or below 225 °C, while a majority of the lignin extracted in methanol–water is condensed with a 9-min residence time at 200 °C. These results can inform reactor designs and solvent selection for lignin-first biorefining processes that aim to physically separate the biomass and catalyst.

biorefining↗

Investigation of a Wedge Adhesion Test for Edge Seals

Many photovoltaic (PV) technologies have been found to be sensitive to moisture that diffuses into a PV package. Even with the use of impermeable frontsheets and backsheets, moisture can penetrate from the edges of a module. To limit this moisture ingress pathway from occurring, manufacturers often use a low permeability polyisobutylene (PIB) based edge seal filled with desiccant to further restrict moisture ingress. Moisture ingress studies have shown that these materials are capable of blocking moisture for the 25-year life of a module; but to do so, they must remain well-adhered and free of cracks. This work focuses on adapting the Boeing Wedge test for use with edge seals laminated using glass substrates as part of a strategy to assess the long-term durability of edge seals. The advantage of this method is that it duplicates the residual stresses and strains that a glass/glass module may have when the lamination process results in some residual glass bending that puts the perimeter in tension. Additionally, this method allows one to simultaneously expose the material to thermal stress, humidity, mechanical stress, and ultraviolet radiation. The disadvantage of this method generally is that we are limited by the fracture toughness of the glass substrates that the edge seal is adhered to. However, the low toughness of typical uncrosslinked or sparsely crosslinked PIB makes them suitable for this technique. We present data obtained during the development of the wedge test for use with PV edge seal materials. This includes development of the measuring techniques and evaluation of the test method with relevant materials. We find consistent data within a given experiment, along with the theoretical independence of fracture toughness measurements with wedge thickness. This indicates that the test methodology is reproducible. However, even though individual experimental sets are consistent, the reproducibility between experimental sets is poor. We believe this may be due to inconsistencies in sample history, sample batch, or small changes in sample preparation/assembly from one month to the next. Because the fracture strength of typical edge seal materials is so low, they cannot be relied upon for mechanical strength. A small stress or strain on the edge seal is capable of promoting delamination or tearing causing the edge seal to fail. Because of this, edge seals are very dependent on the processing and construction parameters in the full size PV module such that any long term evaluation of their durability must be conducted on full size modules to be accurate.

14 SOLAR ENERGY↗

Study of an ammonia-based wet scrubbing process in a continuous flow system

A continuous gas and liquid flow, regenerative scrubbing process for CO{sub 2} capture was demonstrated at the bench-scale level. An aqueous ammonia-based solution captures CO{sub 2} from simulated flue gas in an absorber and releases a nearly pure stream of CO{sub 2} in the regenerator. After the regeneration, the solution of ammonium compounds is recycled to the absorber. The design of a continuous flow unit was based on earlier exploratory results from a semi-batch reactor, where a CO{sub 2} and N{sub 2} simulated flue gas mixture flowed through a well-mixed batch of ammonia-based solution. During the semi-batch tests, the solution was cycled between absorption and regeneration steps to measure the carrying capacity of the solution at various initial ammonia concentrations and temperatures. Consequentially, a series of tests were conducted on the continuous unit to observe the effect of various parameters on CO{sub 2} removal efficiency and regenerator effectiveness within the flow system. The parameters that were studied included absorber temperature, regenerator temperature, initial NH{sub 3} concentration, simulated flue gas flow rate, liquid solvent inventory in the flow system, and height of the packed-bed absorber. From this testing and subsequent testing, ammonia losses from both the absorption and regeneration steps were quantified, and attempts were made to maintain steady state during operations. Implications of experimental results with respect to process design are discussed.

54 ENVIRONMENTAL SCIENCES↗

Experimental investigation of wood combustion in a fixed bed with hot air

Highlights: • Upward combustion is a new combustion concept with ignition by hot primary air. • Upward combustion has three stages: short drying, rapid devolatilization and char combustion. • Variation of fuel moisture and inert content have little influence on the combustion. • Experimental comparison between conventional and upward combustion is presented. - Abstract: Waste combustion on a grate with energy recovery is an important pillar of municipal solid waste (MSW) management in the Netherlands. In MSW incinerators fresh waste stacked on a grate enters the combustion chamber, heats up by radiation from the flame above the layer and ignition occurs. Typically, the reaction zone starts at the top of the waste layer and propagates downwards, producing heat for drying and devolatilization of the fresh waste below it until the ignition front reaches the grate. The control of this process is mainly based on empiricism. MSW is a highly inhomogeneous fuel with continuous fluctuating moisture content, heating value and chemical composition. The resulting process fluctuations may cause process control difficulties, fouling and corrosion issues, extra maintenance, and unplanned stops. In the new concept the fuel layer is ignited by means of preheated air (T > 220 °C) from below without any external ignition source. As a result a combustion front will be formed close to the grate and will propagate upwards. That is why this approach is denoted by upward combustion. Experimental research has been carried out in a batch reactor with height of 4.55 m, an inner diameter of 200 mm and a fuel layer height up to 1 m. Due to a high quality two-layer insulation adiabatic conditions can be assumed. The primary air can be preheated up to 350 °C, and the secondary air is distributed via nozzles above the waste layer. During the experiments, temperatures along the height of the reactor, gas composition and total weight decrease are continuously monitored. The influence of the primary air speed, fuel moisture and inert content on the combustion characteristics (ignition rate, combustion rate, ignition front speed and temperature of the reaction zone) is evaluated. The upward combustion concept decouples the drying, devolatilization and burnout phase. In this way the moisture and inert content of the waste have almost no influence on the combustion process. In this paper an experimental comparison between conventional and reversed combustion is presented.

09 BIOMASS FUELS↗

Ultra-fast Boriding for Improved Energy Efficiency and Reduced Emissions in Materials Processing Industries (Final Report)

High-temperature treatment processes (such as nitriding, carburizing, and boronizing) are well-established and used widely by numerous industrial sectors to achieve superior mechanical and tribological properties on all kinds of engineering components made out of ferrous materials. Unfortunately, these traditional processes are very slow and energy intensive, and they produce large amounts of CO 2 emissions and liquid/solid wastes to deal with during and after each process run. From economic and environmental points of views, it is highly desirable to develop and implement novel surface treatment technologies that are quick, cheap, clean, and energy efficient. The main objective of this project was to develop an industrial-scale ultra-fast boriding process that realizes all of these desirable attributes. The other objectives of the project were to demonstrate the superior performance, properties, and durability of borided surfaces under relevant test conditions and to transfer optimized technology to industry for large-scale practice. Major research activities included process design, modeling, product optimization, and scale-up. This project has achieved all of its stated objectives, and the industrial-scale boriding process has been successfully transferred to industry. Specifically, all of the original tasks have been completed, and the milestones have been met by scaling up from a small proof-of-concept system (which could only handle about 0.25 kg melt) to a commercial-scale boriding unit that can handle up to 4,000 kg melt. Mechanical and tribological testing of borided test samples and industrial parts has also been carried out, and their superior performance over a broad range of test conditions has been validated. With the large-scale, ultra-fast boriding process, we could achieve thick, hard, and uniform boride layers on all kinds of steel components, even after only 5 min of treatment time. We could also attain excellent uniformity in thickness over the entire exposed surfaces — even in the very sharp corners or interior sections of odd-shaped workpieces. Boriding of numerous nonferrous materials was also demonstrated, and thick boride layers (up to 300 µm in thickness) were achieved on their outer surfaces. With the use of a large-scale boriding unit at Argonne National Laboratory, our research team has successfully treated large numbers of industrial components in a batch-to-batch operation without creating any in-house gaseous emissions or producing solid and/or liquid wastes. With the use of this large unit, our team achieved surface hardness values of 15 to 45 GPa, depending on the type of metal or alloy being treated. The thick boride layers attained on steel components consisted of FeB, Fe 2 B, and Fe 3 B phases, and their hardness values ranged from 16 to 22 GPa. Layers consisting of Fe 2 B phase alone are also possible with this process, and in the case of nonferrous materials. Overall, because of the much superior property and performance improvements in treated products, much lower energy consumption, and nearly zero environmental waste and emissions, the demonstrated boriding technology may find broad applications in many cross-cutting industries. Mechanical wear, abrasion, erosion, corrosion, and scuffing are often life-limiting factors in mechanical systems that are used in manufacturing, transportation, aerospace, agricultural, earth-moving, and mining equipment; but the machine components treated by ultra-fast boriding can effectively prevent such degradations. In this project, the ultra-fast boriding was proven to be most ideal for the treatment of iron and many other ferrous alloys, like stainless steel. We have shown through our experimental studies that our method can also be used for the treatment of many nonferrous metals and alloys. In the case of superalloys and Ni 3 Al intermetallic materials, more than a 300-µm thick boride layer can be achieved with our boriding furnace within 15 to 30 min (which results in five times the hardness of the base materials). Pre-carburized steels and nonferrous alloys can also be treated by the new boriding technique. Overall, very thick (more than a quarter millimeter) and hard surface layers produced by ultra-fast boriding are expected to have a positive impact on the performance and durability of all types of machine components that are subject to corrosive, erosive, abrasive, and adhesive wear. Since the focus of our project was primarily on the large-scale boriding of ferrous materials, in this report, we will broadly cover the results from various ferrous materials that were used in our experiments. Another transformational feature of ultra-fast boriding is that it does not create any greenhouse gas emissions or solid and/or liquid wastes to deal with during or after the treatment; hence, it is an ultra-green technology (no need for expensive waste disposal and/or treatment facilities). It may eliminate the use of natural gas and other carbon-based fuels as the primary energy source in the heat treatment industry (which is the most common practice at present), thus, minimizing the CO 2 , NO x , CO, and SO x emissions that are generated in large quantities by current heat treatment practices. The main ingredient used during boriding is borax, which is a natural mineral. Our demonstrated and scaled-up technology can now be used in a wide range of manufacturing and transportation applications. It can deliver thick and uniform boride layers of more than 200 µm in steels, if needed, over the entire exposed surfaces — even in the very sharp corners or interior sections of workpieces (which are typical of gears, tools, pipes, and other components). Beneath the distinct boride layers is an equally-thick boron diffusion layer or zone, which is comparable to the diffusion zones achieved by carburizing and nitriding processes. In the cases of traditional boriding, nitriding, and/or carburizing methods, achieving such layer thickness and case depths would have taken several hours, and these surfaces would not have achieved the same levels of hardness and other desirable properties as they do with ultra-fast boriding. Some of the key stakeholders of ultra-fast boriding technology include companies that are active in heat-treatment, thermal-diffusion, and hard-coating processes; metal-forming, machining, and other manufacturing processes; and technologies related to transportation (including original equipment manufacturers for autos), mining and oil exploration, agricultural and heavy equipment. Bodycote Thermal Processing was the cost-sharing industrial partner and licensee in this project. They also provided test components and technical and commercial information pertaining to industrial components that are most suitable for ultra-fast boriding. Bodycote also coordinated some of the field tests and metallurgical examinations. Overall, ultra-fast boriding is a transformational technology that can complement, if not replace, many of the energy- and carbon-intensive surface treatment processes that are in use today, such as conventional boriding, carburizing, nitriding, carbo-nitriding, and physical and chemical vapor deposition. In our project, the developed technology was scaled-up and proven to be an ultra-green, ultra-efficient process that can drastically reduce costs, increase productivity, and improve the performance and reliability of machine components used in cross-cutting industrial applications.

Erdemir, Ali↗

Sample Results From Routine Salt Batch 7 Samples

Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the “microbatches” of Integrated Salt Disposition Project (ISDP) Salt Batch (“Macrobatch”) 7B have been analyzed for 238 Pu, 90 Sr, 137 Cs, cations (Inductively Coupled Plasma Emission Spectroscopy - ICPES), and anions (Ion Chromatography Anions - IC-A). The analytical results from the current microbatch samples are similar to those from previous macrobatch samples. The Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU) continue to show more than adequate Pu and Sr removal, and there is a distinct positive trend in Cs removal (increasing cesium decontamination), due to the use of the Next Generation Solvent (NGS). The bulk chemistry of the DSSHT and SEHT samples do not show any signs of unusual behavior.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analytical Results from Routine DSSHT and SEHT Monthly Samples

Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the “microbatches” of Integrated Salt Disposition Project (ISDP) Salt Batch (“Macrobatch”) 8B have been analyzed for 238 Pu, 90 Sr, 137 Cs, cations (Inductively Coupled Plasma Emission Spectroscopy - ICPES), and anions (Ion Chromatography Anions - IC-A). The analytical results from the current microbatch samples are similar to those from previous macrobatch samples. The Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU) continue to show more than adequate Pu and Sr removal for times when monosodium titanate (MST) is used. Even with no MST strike being performed there exists some small Pu and Sr removal, likely from filtration of fines containing these elements. The Cs removal continues to be excellent, with decontamination factors (DF) averaging 16,400. The bulk chemistry of the DSSHT and SEHT samples do not show any signs of unusual behavior. SRNL recommends that a sample of the strip feed be analyzed for cation and anion content if a further decline in boron concentration is noted in future SEHT samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preliminary Report on Compositional Specification for Printed 316SS

The Advanced Materials and Manufacturing Technologies Program is focused on accelerating the development and deployment of advanced materials and components fabricated via additive manufacturing (AM). A key challenge for the widespread adoption of AM is the variability in material properties, which can originate from powder feedstock, process parameters, geometry, and the machine. AM powder feedstock compositions are based on those developed for conventional manufacturing. However, the smaller melt pools combined with multiple melt cycles over the course of a build can have substantial effects on the local phase selection resulting from minor batch-to-batch feedstock variability. Therefore, this report focuses on coupling CALPHAD calculations with data mining and visualization to aid the development of compositional specifications for stainless steel 316, an important alloy for nuclear applications and suitable for AM. This work reports that δ-ferrite formation has a stronger dependence on the amount of nickel in the alloy despite nickel being an austenite stabilizer. These findings show the need for exercising a tighter control on the amount of nickel in the alloy compared with the amount of chromium, which is a ferrite stabilizer.

36 MATERIALS SCIENCE↗

Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Solvolytic extraction of lignin from biomass is a critical step in lignin-first biorefining, including the reductive catalytic fractionation (RCF) process. Key to optimal RCF processing is the ability to rapidly extract lignin from biomass at high delignification extents and transfer the lignin molecules to a catalyst surface in a time frame that minimizes lignin condensation reactions. Here, we use a flow-through reactor to study the effects of temperature (175-250 °C), residence time (9 to 36 min), and solvent composition (methanol and methanol-water) on lignin extraction and condensation. We evaluated three metrics at each condition: total delignification, delignification rate, and extent of condensation, the latter measured by a decrease in monomer yield for batch hydrogenolysis reactions of solvolysis liquor compared to batch RCF reactions. We observe that delignification is predominantly determined by temperature, while residence time dictates the lignin condensation extent. Moreover, the extent of both extraction and condensation increased in the methanol-water solvent system compared to that in the methanol system. Lignin extracted in methanol is stable up to 18-min residence times at or below 225 °C, while a majority of the lignin extracted in methanol-water is condensed with a 9-min residence time at 200 °C. These results can inform reactor designs and solvent selection for lignin-first biorefining processes that aim to physically separate the biomass and catalyst.

09 BIOMASS FUELS↗