SEARCH · Search NASA

Results for “Process Control”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 631 records · Page 35

All sources NASA NTRS DOE OSTI

DOE OSTI2020

Slag Management of Carbon Feedstock Used in Gasification FY17 TCF between Eastman Chemical and NETL (Final Report)

NETL, in collaboration with Eastman Chemical Corp (Kingsport, TN), targeted the joint evaluation and refinement of a slag management program developed by NETL (NETL IP, patent applied for) to control gasifier slag properties formed from ash in individual or combinations of different coal-based carbon feedstock materials and specific slag modifiers used in gasification. Slag forms from mineral or organic-metallic impurities in the carbon feedstock that melt at the high temperatures of gasification, coalescing to form a liquid (slag) that must flow from the gasifier. Slag additives, also known as slag modifiers, are often added to the carbon feedstock to modify the ash chemistry and achieve desired slag flow properties at target temperatures used in gasification. If slag does not flow from a gasifier, its buildup within the gasification chamber will cause either gasifier shutdown to physically remove the slag (consuming time and damaging the protective refractory lining), or the gasification temperature must be increased to lower slag viscosity so it can flow from the gasifier, leading to greater refractory wear/corrosion, along with increased fouling and downstream component wear. Because of these issues, gasification is typically targeted at the lowest temperature possible where slag will flow in a controlled manner (a temperature range called T100 for the lowest temperature, with T250 being the highest temperature where the slag has achieved the desired fluidity). That temperature range also needs to yield a desired syngas composition, highlighting the importance of knowing and being able to control carbon feedstock slag viscosity and the temperature of thermal breakdown of the carbon feedstock. Slag viscosity varies with changes in the gasification chamber temperature, oxygen partial pressure, and slag chemistry. The slag model work with Eastman Chemical targeted predicting and controlling molten coal ash slag behavior at specific gasification conditions. The final goal of the refined model was to develop/refine the NETL slag model so a gasifier operator would be able to predict slag behavior prior to purchasing or using a carbon feedstock and control slag properties once a carbon feedstock is being gasified, allowing a gasifier user to determine what mineral additives or blends of different carbon materials would be needed to achieve desired slag properties at targeted gasification conditions. For a given carbon feedstock and desired gasification condition, the actual gasification cost and slag behavior would be able to be predicted using the slag management program in advance of purchasing or using the carbon feedstock – allowing accurate control of slag ash behavior in real time. As part of the TCF project work with Eastman Chemical, the viscosity of several ash compositions of interest to them would be measured and used to populate the slag model, along with a large database of historical slag temperature, chemistry, and viscosity information they possess – information that would in-crease the predictive accuracy of the slag management model with slag ash chemistry of interest to them. As part of the model evaluation and refinement, the predictive model and its database will be installed on computers at Eastman Chemical and used to manage slag properties in a gasifier during real-time operation of their gasifier. In summary, success of the slag management program at Eastman Chemical would support its use by other gasifier operators to manage slag chemistry and properties over other desired gasification temperature ranges, allowing greater process control and efficiency of their carbon feedstock conversion during gasification.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2015

Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface

The hydrodeoxygenation of organic acids is often found to be a rate-controlling process during upgrading of biomass feedstocks into fuels. We developed a microkinetic model based on data obtained from density functional theory calculations for the decarboxylation and decarbonylation mechanisms of propanoic acid (CH 3 CH 2 COOH) over a Ru(0 0 0 1) model surface. The model predicts that the decarbonylation mechanism is two orders of magnitude faster than the decarboxylation mechanism. The most favorable decarbonylation pathway proceeds via removal of the acid –OH group to produce propanoyl (CH 3 CH 2 CO) followed by C–CO bond scission of propanoyl to produce CH 3 CH 2 and CO. Finally, CH 3 CH 2 is hydrogenated to CH 3 CH 3 . Dehydrogenation reactions that have been observed to be important over Pd catalysts play no role over Ru(0 0 0 1), and a sensitivity analysis indicates that removal of the acid –OH group is the rate-controlling step in the deoxygenation. Altogether, our results suggest that to improve the Ru catalyst performance for the decarbonylation of organic acids, the free site coverage needs to be increased by, for example, adding a catalyst promoter that decreases the hydrogen and CO adsorption strength (without significantly affecting the C–OH bond scission rate), or by raising the reaction temperature and operating at relatively low CO and H 2 partial pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Estimates of Acetonitrile Generation from Scale Melter Testing of LAW Simulants (VSL-19S4573-1, Rev A)

With high nitrate feeds, such as Hanford low activity waste (LAW) feeds, the addition of reductants is necessary in order to control foaming of the molten glass pool in the melter because such foaming can lead to extensive downtime. Sugar, which was used for this purpose at the West Valley Demonstration Project vitrification facility, has been selected as the baseline reductant for the Hanford Waste Treatment and Immobilization Plant (WTP). The amount of sugar required increases with the amount of nitrates present in the feed and decreases with the amount of waste organics present in the feed, which themselves act as reductants. Excessive additions of reductants can be deleterious, leading to over-reduction of the melt and formation of sulfides and molten metals. Consequently, the oxidants and reductants in the feed must be suitably balanced. The basis for achieving this balance was developed by VSL and Atkins for the vitrification of high-sodium-nitrate feeds at Savannah River's M-Area and has been successfully applied to the processing of a wide variety of simulated WTP feeds over many years and was ultimately incorporated into the WTP process control models. The reaction of sugar with nitrates and nitrites in the cold cap controls the redox state of the underlying melt, which prevents foaming, and also significantly decreases the amount of NOx produced. In addition, however, small amount of organics reaction products are formed. Extensive testing at VSL over the past more than 20 years has shown that acetonitrile is the most prevalent such organic species. That testing has also shown that a significant amount of acetonitrile is captured in the liquid scrubbers in the WTP off-gas treatment system and will therefore be present in the secondary liquid effluents. In particular, acetonitrile is prevalent in the submerged bed scrubber (SBS) and wet electrostatic precipitator (WESP) liquid effluents from WTP LAW off-gas treatment. When these liquids are concentrated in the WTP Effluent Management Facility (EMF) evaporator in the direct feed LAW (DFLAW) flow-sheet, VSL testing has shown that the majority of the acetonitrile partitions to the evaporator condensate. Since the evaporator condensate is directed to the Hanford Effluent Treatment Facility (ETF), this creates a potential issue with the ETF waste acceptance criteria. Consequently, there is a need to assess the available test data in order to develop projections of the likely concentrations of acetonitrile in the streams to ETF. The objective of the present report is to provide such an assessment in order to provide input to flow-sheet model projections.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Analysis of backwash settings to maximize net water production in an engineering-scale ultrafiltration system for water reuse

Ultrafiltration (UF) has been widely utilized as water pretreatment for different applications especially in water reuse. The UF system operation is characterized by a filtration phase, where particles accumulate on the membrane surface resulting in an increase in the transmembrane pressure (TMP) and a cleaning phase, where foulants are removed through cleaning cycles including physical backwash and chemical-enhanced backwash (CEB). In this study, data from an engineering-scale UF system treating reclaimed wastewater were used to assess the impact of backwashing on the filtration process. TMP backwash trigger, backwash duration, and CEB frequency were purposely varied for a cycle-by-cycle investigation on the net water production, water recovery, initial operating TMP, and filtration cycle duration. As the TMP backwash trigger was varied between 62 and 145kPa, the maximum net water production (63 m 3 /d) was achieved at 103kPa and water recovery remained relatively constant at approximately 92%. Backwash durations of 45, 65, and 85s were performed where both net water production and water recovery yielded similar results (~63 m 3 /d and ~ 91%) compared with 103kPa TMP backwash trigger. The CEB frequency was also lowered from one every three backwashes (1/3) to 1/6 and 1/12 and resulted in decreased net water production and water recovery while the initial TMP increased. Interestingly, the total number of CEBs remained approximately constant regardless of their frequency. In conclusion, results suggest that CEB is an important fouling control process to maximize water production.

42 ENGINEERING↗

DOE OSTI2026

Development of Data-Driven Models for Performance Prediction and Chemical Dosing of a Full-Scale Controlled Phosphorus Precipitation Reactor

This study evaluated the use of data-driven models to improve control of a struvite precipitation reactor that removes phosphorus from wastewater while producing a fertilizer product. The researchers developed predictive models for influent orthophosphate concentration, effluent orthophosphate concentration, and phosphorus removal using operational data from a full-scale MagPrex™ reactor at a water resource recovery facility in Denver, Colorado. Model predictions were used to recommend magnesium chloride dosing adjustments needed to achieve a target effluent phosphorus concentration. Several machine learning approaches were tested, with ridge regression providing the best predictions for influent orthophosphate concentration and phosphorus removal, and XGBoost providing the best predictions for effluent orthophosphate concentration. Simulation results indicated that the decision-support approach could correctly identify dosing adjustments in most cases and reduce chemical use. Full-scale implementation achieved lower accuracy due to changing operating conditions and limited historical data in some operating ranges. Here, the results demonstrate the potential of data-driven tools to support phosphorus recovery process control while also identifying practical limitations that affect deployment in full-scale systems.

42 ENGINEERING↗

DOE OSTI2021

Carbide Nanoparticle Dispersion Techniques for Metal Powder Metallurgy

Nanoparticles (NP) embedded into a matrix material have been shown to improve mechanical properties such as strength, hardness, and wear-resistance. However, the tendency of NPs to agglomerate in the powder mixing process is a major concern. This study investigates five different mechanochemical processing (MCP) routes to mitigate agglomeration to achieve a uniform dispersion of ZrC NPs in an Fe-based metal matrix composite. Our results suggest that MCP with only process controlling agents is ineffective in avoiding aggregation of these NPs. Instead, the uniformity of the carbide NP dispersion is achieved by pre-dispersing the NPs under ultrasonication using suitable surfactants followed by mechanically mixing of the NPs with iron powders in an alcohol solvent which is then dried. High-energy MCP is then used to embed the NPs within the powders. These collective steps resulted in a uniform dispersion of ZrC in the sintered (consolidated) Fe sample.

08 HYDROGEN↗

DOE OSTI2021

Novel estimation of aerosol processes with particle size distribution measurements: a case study with the TOMAS algorithm v1.0.0

Atmospheric aerosol microphysical processes are a significant source of uncertainty in predicting climate change. Specifically, aerosol nucleation, emissions, and growth rates, which are simulated in chemical transport models to predict the particle size distribution, are not understood well. However, long-term size distribution measurements made at several ground-based sites across Europe implicitly contain information about the processes that created those size distributions. This work aims to extract that information by developing and applying an inverse technique to constrain aerosol emissions as well as nucleation and growth rates based on hourly size distribution measurements. We developed an inverse method based upon process control theory into an online estimation technique to scale aerosol nucleation, emissions, and growth so that the model–measurement bias in three measured aerosol properties exponentially decays. The properties, which are calculated from the measured and predicted size distributions, used to constrain aerosol nucleation, emission, and growth rates are the number of particles with a diameter between 3 and 6 nm, the number with a diameter greater than 10 nm, and the total dry volume of aerosol ( N 3–6 , N 10 , V dry ), respectively. In this paper, we focus on developing and applying the estimation methodology in a zero-dimensional “box” model as a proof of concept before applying it to a three-dimensional simulation in subsequent work. The methodology is first tested on a dataset of synthetic and perfect measurements that span diverse environments in which the true particle emissions, growth, and nucleation rates are known. The inverse technique accurately estimates the aerosol microphysical process rates with an average and maximum error of 2 % and 13 %, respectively. Next, we investigate the effect that measurement noise has on the estimated rates. The method is robust to typical instrument noise in the aerosol properties as there is a negligible increase in the bias of the estimated process rates. Finally, the methodology is applied to long-term datasets of in situ size distribution measurements in western Europe from May 2006 through June 2007. At Melpitz, Germany, and Hyytiälä, Finland, the average diurnal profiles of estimated 3 nm particle formation rates are reasonable, having peaks near noon local time with average peak values of 1 and 0.15 cm –3 s –1 , respectively. The normalized absolute error in estimated N 3–6 , N 10 , and V dry at three European measurement sites is less than 15 %, showing that the estimation framework developed here has potential to decrease model–measurement bias while constraining uncertain aerosol microphysical processes.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

Ion-Exchange Interdiffusion Model with Potential Application to Long-Term Nuclear Waste Glass Performance

Ion exchange is an integral mechanism influencing the corrosion of glasses. Due to the formation of alteration layers in aqueous conditions, it is difficult to conclusively deconvolute the process of ion exchange from other processes, principally dissolution of the glass matrix. Therefore, we have developed a method to isolate alkali diffusion that involves contacting glass coupons with a solution of 6 LiCl dissolved in functionally inert dimethyl sulfoxide. Here, we employ the method at temperatures ranging from 25 to 150 °C with various glass formulations. Glass compositions include simulant nuclear waste glasses, such as SON68 and the international simple glass (ISG), glasses in which the nature of the alkali element was varied, and glasses that contained more than one alkali element. An interdiffusion model based on Fick’s second law was developed and applied to all experiments to extract diffusion coefficients. The model expands established models of interdiffusion to the case where multiple types of alkali sites are present in the glass. Activation energies for alkali ion exchange were calculated and the results are in agreement with those obtained in glass strengthening experiments but are nearly five times higher than values reported for diffusion-controlled processes in nuclear waste glass corrosion experiments. A discussion of the root causes for this apparent discrepancy is provided. The interdiffusion model derived from laboratory experiments is expected to be useful for modeling glass corrosion in a geological repository when the silicon concentration is high.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Advanced Control Architecture and Sensor Information Development for Process Automation, Optimization, and Imaging of Chemical Looping Systems

The Syngas Chemical Looping (SCL) process developed at The Ohio State University (OSU) uses an iron-based oxygen carrier to convert syngas into high-purity hydrogen while simultaneously capturing carbon dioxide that is readily sequestrable. A 25 kWth sub-pilot unit was successfully demonstrated multiple times on the OSU Clean Coal Research Facility, and a 250 kWth – 3 MWth pilot demonstration unit has been designed and constructed at the National Carbon Capture Center (NCCC) in Wilsonville, Alabama. The focus of this project is to develop multiple technologies to automate the startup and shutdown of chemical looping system. Success of this project will propel the advanced carbon capture method toward commercialization, hence be disruptive to the fossil fuel and power industries. Advanced process automation control architecture and imaging and optimization sensor software were developed for OSU chemical looping process. A high-level controller (HLC) consisting of decision-making and controller-selection logic integrated with sliding mode controllers (SMCs) were developed to perform chemical looping process startup and shutdown. Babcock & Wilcox Power Generation Group’s FocalPoint Optimization System was implemented to optimize the process operating conditions. The process automation controller and optimization information were realized and tested on OSU’s existing sub-pilot chemical looping test unit under atmospheric condition. The implemented control architecture was able to perform the complete process procedure from startup, steady-state reaction operation to shutdown with minimal operator intervention. The controller was also implemented on the pressurized syngas chemical looping (SCL) pilot test unit constructed at the National Carbon Capture Center (NCCC), demonstrating its pressure control capability with a designed transient state trajectory. An electrical capacitance volume tomography (ECVT) sensor device and its software were developed to image the packed moving bed and slugging fluidized bed of oxygen carriers in chemical looping systems at elevated temperatures. The ECVT device constructed was capable of tracking the subtle voidage variance along the moving bed axis as a feature for directly measuring the oxygen carrier particles’ linear velocity. Also, the high temperature ECVT device was used to study the fluidization characteristics of Geldart Group D particles.

08 HYDROGEN↗

DOE OSTI2016

Electrodeposition of Actinides on a Semiconductor Detector for Concentration Monitoring

Pyroprocessing is a promising technology for separation and recycle of actinides from spent nuclear fuel. It is being actively researched in the United States as well as the Republic of Korea for possible implementation into a closed nuclear fuel cycle. The features of the chemical technology behind pyro-processing, unfortunately, present difficulties for real time accounting of actinides. Development of optimal process monitoring technology and safeguards approaches are, thus, a high priority for completing the development of the overall process technology. Real time monitoring of actinide concentrations in the molten salt electro-refiners is particularly important to achieve because of the potential for multiple significant quantities of plutonium in the molten salt. To address this need, development of a semiconductor detector for real-time monitoring of actinides in molten chloride salt (LiCl-KCl) is being conducted. Towards this end, a novel alpha spectroscopy detection system is being developed using wide band-gap semiconductor material, such as GaN or SiC, with a Boron-Doped-Diamond (BDD) contact. The objective is to deposit a thin layer of actinides onto the BDD layer, which will be used to measure the alpha particle spectrum that will distinguish individual actinides and their concentration. In the first stage, the actinide electrodeposition onto a surrogate material for the detector has been undertaken. While this project is in its very early states, a couple of observations have been made. One is that the electrodeposition is a slow, diffusion-controlled process. Therefore the deposit should be as thin (≅1 m) as the alpha spectroscopy permits (the resolution gets inferior with lesser number of atoms). Also, applied potentials should not be too negative; otherwise the deposit does not adhere well to the surface. The application of this method to measuring actinides in molten salt appears to be feasible, and a considerable amount of further investigation is planned. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2015

Round-Robin Verification and Final Development of the IEC 62788-1-5 Encapsulation Size Change Test; NREL (National Renewable Energy Laboratory)

Polymeric encapsulation materials may a change size when processed at typical module lamination temperatures. The relief of residual strain, trapped during the manufacture of encapsulation sheet, can affect module performance and reliability. For example, displaced cells and interconnects threaten: cell fracture; broken interconnects (open circuits and ground faults); delamination at interfaces; and void formation. A standardized test for the characterization of change in linear dimensions of encapsulation sheet has been developed and verified. The IEC 62788-1-5 standard quantifies the maximum change in linear dimensions that may occur to allow for process control of size change. Developments incorporated into the Committee Draft (CD) of the standard as well as the assessment of the repeatability and reproducibility of the test method are described here. No pass/fail criteria are given in the standard, rather a repeatable protocol to quantify the change in dimension is provided to aid those working with encapsulation. The round-robin experiment described here identified that the repeatability and reproducibility of measurements is on the order of 1%. Recent refinements to the test procedure to improve repeatability and reproducibility include: the use of a convection oven to improve the thermal equilibration time constant and its uniformity; well-defined measurement locations reduce the effects of sampling size -and location- relative to the specimen edges; a standardized sand substrate may be readily obtained to reduce friction that would otherwise complicate the results; specimen sampling is defined, so that material is examined at known sites across the width and length of rolls; and encapsulation should be examined at the manufacturer’s recommended processing temperature, except when a cross-linking reaction may limit the size change. EVA, for example, should be examined 100 °C, between its melt transition (occurring up to 80 °C) and the onset of cross-linking (often at 100 °C).

14 SOLAR ENERGY↗

DOE OSTI2019

FastProNGS: fast preprocessing of next-generation sequencing reads

Background Next-generation sequencing technology is developing rapidly and the vast amount of data that is generated needs to be preprocessed for downstream analyses. Yet, until now, software that can efficiently make all the quality assessments and filtration of raw data is still lacking. Results We developed FastProNGS to integrate the quality control process with automatic adapter removal. Parallel processing was implemented to speed up the process by allocating multiple threads. Compared with similar up-to-date preprocessing tools, FastProNGS is by far the fastest. Read information before and after filtration can be output in plain-text, JSON, or HTML formats with user-friendly visualization. Conclusions FastProNGS is a rapid, standardized, and user-friendly tool for preprocessing next-generation sequencing data within minutes. It is an all-in-one software that is convenient for bulk data analysis. It is additionally very flexible and can implement different functions using different user-set parameter combinations.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2016

Comparison of the dose distribution obtained from dosimetric systems with intensity modulated radiotherapy planning system in the treatment of prostate cancer

The aim of this study is to compare Intensity Modulated Radiation Therapy (IMRT) plan of prostate cancer patients with different dose verification systems in dosimetric aspects and to compare these systems with each other in terms of reliability, applicability and application time. Dosimetric control processes of IMRT plan of three prostate cancer patients were carried out using thermoluminescent dosimeter (TLD), ion chamber (IC) and 2D Array detector systems. The difference between the dose values obtained from the dosimetric systems and treatment planning system (TPS) were found to be about % 5. For the measured (TLD) and calculated (TPS) doses %3 percentage differences were obtained for the points close to center while percentage differences increased at the field edges. It was found that TLD and IC measurements will increase the precision and reliability of the results of 2D Array.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

DOE OSTI2024

In situ x-ray imaging to understand subsurface behavior during continuous wave laser drilling

A limited understanding regarding the underlying dynamics and mechanisms of material removal during continuous wave laser drilling has presented significant challenges in achieving precision and process control. Here, to address this, we employed high-fidelity, in situ synchrotron x-ray imaging to reveal previously unknown material behaviors during continuous wave laser drilling with power modulation. Our findings highlight that high-aspect ratio drill holes are achieved when the laser modulation frequency falls within the range of 8–12 kHz, provided that the laser average power and modulation amplitude levels meet the specified limits. Under these conditions, we identified a material removal mechanism driven by incremental accumulation of recoil pressure that gradually pushes material upward from deep within the substrate to the surface. This mechanism manifested as a low-frequency fluctuation in the vapor depression depth, resulting in periodic instances of material ejection. Furthermore, our study underscores that rapid expansion of the melt pool and the widening of the drill hole opening can impede effective material removal by redirecting energy from material ejection to increasing the melt pool size. This investigation contributes essential insights into the subsurface dynamics involved in the drilling of high-aspect ratio holes, furthering our fundamental understanding of this intricate process.

47 OTHER INSTRUMENTATION↗

DOE OSTI2022

Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc 0.5 Ta 0.5 O 3 ) films

Lead scandium tantalate (PbSc 0.5 Ta 0.5 O 3 , PST), an order/disorder ferroelectric, is a potential candidate for electrocaloric cooling and pyroelectric infrared (IR) detector. In this work, we report the phase transformation kinetics from two series of samples containing pure amorphous and mixture of amorphous and pyrochlore to desired perovskite phase using postdeposition rapid thermal processing (RTP) as well as growth mechanism of RF sputtered PST thin films using excess lead target on platinized silicon (Pt/Ti/SiO 2 /Si) substrates. We find that small changes in the temperature ramp have a large effect on the degree of perovskite conversion (ferroelectric phase), orientation (crystallographic texture), and long-range order parameter (< S 111 >). Through isothermal annealing, we obtained optimal perovskite phase at ≥700°C temperature. The phase transformation is characterized by spontaneous formation of center-type in-plane radial rosette-like structures revealed by scanning electron microscopy. The PST perovskite crystallites were found to coexist with pyrochlore in RTP annealed films. The volume fractions for perovskite and pyrochlore phase were obtained from the analysis of “rosettes” and respective X-ray diffraction intensities which helped to determine various parameters associated with phase kinetics (n, k, and activation energy, Ea) and accompanying growth. The effective activation energies of perovskite transition and growth were found to be 332 ± 11 kJ/mol (345 ± 11 kJ/mol) and 114 ± 10 kJ/mol (122 ± 10 kJ/mol), respectively, for pure amorphous only (and mixed amorphous and pyrochlore) phase following nucleation-growth controlled Avrami's equation. A linear growth rate (n~1) for the perovskite phase indicates predominant interface-controlled process and diffusion-limited phenomena thus inhibiting rosette size owing to reactant depletion and soft impingement at the grain boundary. However, the growth behavior is isotropic in two-dimension parallel to the plane of the substrates for both sample series. Furthermore, lead loss was severe for in-situ growth and RTP combined with conventional furnace annealing than those of RTP only films, which were closer to stoichiometric albeit with excess lead and marginal oxygen vacancies (V o ).

36 MATERIALS SCIENCE↗

DOE OSTI2020

Functional metal–organic frameworks as effective sensors of gases and volatile compounds

Developing efficient sensor materials with superior performance for selective, fast and sensitive detection of gases and volatile organic compounds (VOCs) is essential for human health and environmental protection, through monitoring indoor and outdoor air pollutions, managing industrial processes, controlling food quality and assisting early diagnosis of diseases. Metal–organic frameworks (MOFs) are a unique type of crystalline and porous solid material constructed from metal nodes (metal ions or clusters) and functional organic ligands. They have been investigated extensively for possible use as high performance sensors for the detection of many different gases and VOCs in recent years, due to their large surface area, tunable pore size, functionalizable sites and intriguing properties, such as electrical conductivity, magnetism, ferroelectricity, luminescence and chromism. The high porosity of MOFs allows them to interact strongly with various analytes, including gases and VOCs, thus resulting in easily measurable responses to different physicochemical parameters. Although much of the recent work on MOF-based luminescent sensors have been summarized in several excellent reviews (up to 2018), a comprehensive overview of these materials for sensing gases and VOCs based on chemiresistive, magnetic, ferroelectric, and colorimertic mechanisms is missing. In this review, we highlight the most recent progress in developing MOF sensing and switching materials with an emphasis on sensing mechanisms based on electricity, magnetism, ferroelectricity and chromism. We provide a comprehensive analysis on the MOF–analyte interactions in these processes, which play a key role in the sensing performance of the MOF-based sensors and switches. We discuss in detail possible applications of MOF-based sensing and switching materials in detecting oxygen, water vapor, toxic industrial gases (such as hydrogen sulfide, ammonia, sulfur dioxide, nitrous oxide, carbon oxides and carbon disulfide) and VOCs (such as aromatic and aliphatic hydrocarbons, ketones, alcohols, aldehydes, chlorinated hydrocarbons and N,N'-dimethylformamide). Altogether, this review serves as a timely source of information and provides insight for the future development of advanced MOF materials as next-generation gas and VOC sensors.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Low Cost Electrochromic Film on Plastic for Net-Zero Energy Buildings

Over 4 Quads of energy are lost through windows annually. Passive coatings reduce wasted energy, but energy lost through windows would remain over 2 Quads with complete replacement of Low-E glass. Active control of transmitted light and solar heating with electrochromic (EC) windows can transform the efficiency of energy use within buildings, thereby reducing energy footprints and corresponding greenhouse emissions. High production, integration, and distribution cost limits adoption of current EC products. ITN aimed to utilize its proven heritage of efficiently transitioning technologies from rigid to flexible substrates employing roll-to-roll manufacturing to capture the emerging EC window market opportunity. The project focused on three main efforts (1) Transition Small Scale Prototypes To Limited 0.5 Meter Wide, Web Coater Production, (2) Satisfy Market Driven EC Performance Metrics on Plastic Substrates, and (3) Product Development and Commercialization. The overall goal was to substantially reduce investor risk to motivate private investment in a production facility to further transition and scale this promising technology. A 0.5 meter roll-to-roll web coater was designed, constructed, and commissioned at ITN to support EC development effort. With this tool, we were able to establish the feasibility of roll-to-roll production of EC devices. Individually layers were continuously produced at lengths up to 3 meters with good uniformity, both down web and cross web. Solid state devices were produced, and device performance was being enhanced through hardware modifications underway at the close of the project. When deployed in composite device structures, we were able to verify that individual layers were able to achieve a transmission range of 3-70% transmission average over the visible portion of the spectrum. Initial development of intelligent process controls led to verification of a 2-state controller employed during deposition of the electrochromic layer. The project also successfully increased device performance in line with market needs. Improved device materials provided increased transmission range to a 5-65% transmission over the visible spectrum and faster switching times for both small area batch parts and large area composite materials. We were able to demonstrate durable cycling over 10,000-20,000 cycles in a variety of architectures including suspended films in an IGU and films laminated to glass tested in open air representative of retrofit applications. Robust packaging techniques were identified and samples proved durable even in 40C and 100% relative humidity outside the IGU environment.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

Understanding the Spatiotemporal Variability of Tropical Orographic Rainfall Using Convective Plume Buoyancy

Abstract Mechanical forcing by orography affects precipitating convection across many tropical regions, but controls on the intensity and horizontal extent of the orographic precipitation peak and rain shadow remain poorly understood. A recent theory explains this control of precipitation as arising from modulation of lower-tropospheric temperature and moisture by orographic mechanical forcing, setting the distribution of convective rainfall by controlling parcel buoyancy. Using satellite and reanalysis data, we evaluate this theory by investigating spatiotemporal precipitation variations in six mountainous tropical regions spanning South and Southeast Asia, and the Maritime Continent. We show that a strong relationship holds in these regions between daily precipitation and a measure of convective plume buoyancy. This measure depends on boundary layer thermodynamic properties and lower-free-tropospheric moisture and temperature. Consistent with the theory, temporal variations in lower-free-tropospheric temperature are primarily modulated by orographic mechanical lifting through changes in cross-slope wind speed. However, winds directed along background horizontal moisture gradients also influence lower-tropospheric moisture variations in some regions. The buoyancy measure is also shown to explain many aspects of the spatial patterns of precipitation. Finally, we present a linear model with two horizontal dimensions that combines mountain wave dynamics with a linearized closure exploiting the relationship between precipitation and plume buoyancy. In some regions, this model skillfully captures the spatial structure and intensity of rainfall; it underestimates rainfall in regions where time-mean ascent in large-scale convergence zones shapes lower-tropospheric humidity. Overall, these results provide new understanding of fundamental processes controlling subseasonal and spatial variations in tropical orographic precipitation.

54 ENVIRONMENTAL SCIENCES↗