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At least 1,783 records · Page 99

Influences of horizontal hypokinesia on performance and circadian physiological rhythms in female humans

Eight females from 35-45 yr of age were subjected to seven days of ambulatory control, seven days of bed rest, and a five day recovery period, with 30 min of centrifugation on day seven of bedrest to determine the effects of weightlessness on the circadian rhythms of females in that age group. Heart rate and rectal temperature (RT) were monitored and each subject was tested in a flight simulator twice a day in conditions of varying levels of turbulence. The flight simulations were run during the morning and acrophase of the circadian RT and performance errors wery monitored for 6 min. No significant differences were detected in the group performance data pre-, during, and post-bedrest, although better performance in the simulator was observed after the centrifuge exposure. An RT phase shift was statistically significant between pre- and during bedrest stages.

Winget, C. M.↗

Spatiotemporal Distribution of {sup 241}Am in the Vicinity of the Waste Isolation Pilot Plant - 19543

Environmental monitoring around nuclear facilities is essential for characterizing the baseline conditions that are critical for identifying releases and quantifying their effects, should they occur, and for assessing post-closure performance. The spatiotemporal distribution and transport behavior of {sup 241}Am in the vicinity of a deep geologic repository for transuranic waste were assessed using data spanning the pre-operational phase to the present, including an accidental radionuclide release in 2014. The {sup 241}Am background values of 0.027±0.109 μBq/m{sup 3} (aerosols), and 0.061±0.065 Bq/kg (soil), as well as the {sup 241}Am/{sup 239+240}Pu ratios of 0.41±0.06 (aerosols) and 0.38±0.04 (soil), are similar to global fallout values. Pre-operations concentrations of {sup 241}Am show a strong seasonal dependence, attributed to resuspension of soils contaminated by global fallout, with no contribution from the upwind Project Gnome site ({sup 241}Am/{sup 239+240}Pu =0.24±0.08). During the 2014 accidental release, aerosol concentrations of {sup 241}Am briefly increased to 115.2 μBq/m{sup 3} at an onsite monitoring station, and 81.4 μBq/m{sup 3} at a station ∼1 km downwind of the exhaust shaft, changing the {sup 241}Am/{sup 239+240}Pu from ∼0.37 to ∼10. However, some four years later, conditions have returned to background. Almost 90% of the {sup 241}Am inventory is the 0-5 cm soil layer and there is no evidence of concentrations above regulatory standards, or that can be attributed to waste disposal operations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Excerpt from Oxygen Monitor Clean Testing Report Performed in 2010

The Rosemount X-STREAM Series X2GP is a paramagnetic oxygen analyzer with a 0-25% oxygen measurement range. It claims a drift less than 2% of span (0.10% volume oxygen) per week, and a response time of less than 5 seconds (for the analyzer to report 90% of a step change). Our test equipment was set-up such that the same gas was running through each oxygen analyzer at the same time. This allowed Calibration Error, Calibration Drift, and Loss of Power Testing to be run on all monitors at the same time, eliminating any variability between the analyzers from tolerances in the gas cylinder, ambient temperature, ambient pressure, test duration, etc. An APTech pressure regulator was placed on the gas cylinder manifold and a 23 psia Paroscientific pressure transducer measured the regulator’s outlet pressure. This did not give the inlet pressure on any one analyzer but outlet pressure from the manifold before the stream was split. The APTech pressure regulator was used to keep operating conditions consistent. A DWYER rotameter was installed on each oxygen monitor’s outlet piping. With the exception of Variation of Flow Rate Testing, the rotameter was left fully open for all testing. The flow rate through each oxygen monitor was controlled by a Swagelok needle valve that was installed on each analyzer’s inlet piping. Additionally, a filter was installed in the each monitor’s inlet piping to keep particles from the measurement cells and a Swagelok ball valve was installed on each monitor’s outlet piping to isolate each monitor between tests. No pumps were installed. Each of the cylinders used was at a pressure greater than ambient room barometric pressure. This pressure differential was used to move gas through the testing equipment. The flow rate through each analyzer was controlled by the Swagelok needle valve installed on each analyzer’s inlet piping. Finally, for all tests, a Paroscientific Digiquartz Barometer was used to measure ambient room barometric pressure and a Fluke Thermo-hygrometer was used to measure ambient room temperature.

47 OTHER INSTRUMENTATION↗

Division of attention as a function of the number of steps, visual shifts, and memory load

The effects on divided attention of visual shifts and long-term memory retrieval during a monitoring task are considered. A concurrent vigilance task was standardized under all experimental conditions. The results show that subjects can perform nearly perfectly on all of the time-shared tasks if long-term memory retrieval is not required for monitoring. With the requirement of memory retrieval, however, there was a large decrease in accuracy for all of the time-shared activities. It was concluded that the attentional demand of longterm memory retrieval is appreciable (even for a well-learned motor sequence), and thus memory retrieval results in a sizable reduction in the capability of subjects to divide their attention. A selected bibliography on the divided attention literature is provided.

Chechile, R. A.↗

Mid-latitude ionospheric response to active experiments

Understanding the ion chemistry and conditions leading to the formation of ionospheric depletions (ionospheric holes) was an important objective of the NASA active ionospheric experiment program. Millstone Hill radar observations were used to monitor the magnitude and temporal extent of the plasma holes produced under varying conditions. The major objective of the completed project was to provide radar diagnostic support for individual NASA rocket campaigns flown from Wallops Island. Two rocket programs, NICARE and REDAIR 2, were selected by NASA for radar support during the proposal period and pre-launch and in-flight radar observations were provided for each as well as basic reduction of the acquired data for scientific analysis. Radar operations and analysis for both of these experiments were performed as proposed and the work on these projects at M.I.T. was completed.

Foster, John C.↗

Monitoring with Data Automata

We present a form of automaton, referred to as data automata, suited for monitoring sequences of data-carrying events, for example emitted by an executing software system. This form of automata allows states to be parameterized with data, forming named records, which are stored in an efficiently indexed data structure, a form of database. This very explicit approach differs from other automaton-based monitoring approaches. Data automata are also characterized by allowing transition conditions to refer to other parameterized states, and by allowing transitions sequences. The presented automaton concept is inspired by rule-based systems, especially the Rete algorithm, which is one of the well-established algorithms for executing rule-based systems. We present an optimized external DSL for data automata, as well as a comparable unoptimized internal DSL (API) in the Scala programming language, in order to compare the two solutions. An evaluation compares these two solutions to several other monitoring systems.

log analysis↗

The role of space borne imaging radars in environmental monitoring: Some shuttle imaging radar results in Asia

The synoptic view afforded by orbiting Earth sensors can be extremely valuable for resource evaluation, environmental monitoring and development planning. For many regions of the world, however, cloud cover has prevented the acquisition of remotely sensed data during the most environmentally stressful periods of the year. This paper discusses how synthetic aperture imaging radar can be used to provide valuable data about the condition of the Earth's surface during periods of bad weather. Examples are given of applications using data from the Shuttle Imaging Radars (SIR) A and B for agriculture land use and crop condition assessment, monsoon flood boundary and flood damage assessment, water resource monitoring and terrain modeling, coastal forest mapping and vegetation penetration, and coastal development monitoring. Recent SIR-B results in Bangladesh are emphasized, radar system basics are reviewed and future SAR systems discussed.

Imhoff, M.↗

Clearing a Path to Commercialization of Marine Renewable Energy Technologies Through Public–Private Collaboration

Governments are increasingly turning toward public–private partnerships to bring industry support to improving public assets or services. Here, we describe a unique public–private collaboration where a government entity has developed mechanisms to support public and private sector advancement and commercialization of monitoring technologies for marine renewable energy. These support mechanisms include access to a range of skilled personnel and test facilities that promote rapid innovation, prove reliability, and inspire creativity in technology development as innovations move from concept to practice. The ability to iteratively test hardware and software components, sensors, and systems can accelerate adoption of new methods and instrumentation designs. As a case study, we present the development of passive acoustic monitoring technologies customized for operation in energetic waves and currents. We discuss the value of testing different systems together, under the same conditions, as well as the progression through different test locations. The outcome is multiple, complementary monitoring technologies that are well suited to addressing an area of high environmental uncertainty and reducing barriers to responsible deployment of low-carbon energy conversion systems, creating solutions for the future.

16 TIDAL AND WAVE POWER↗

Iodine Capture Studies of Copper- and Bismuth-Based Sorbents

The release of radioiodine, one of several radionuclides of concern when recycling used nuclear fuel (UNF), is an important consideration in the fuel cycle. In this study, two sorbent materials, Cu 0 -polyacrylonitrile (PAN) and Bi 0 -PAN, were tested as solid sorbent candidates for iodine capture. Experiments using a thin bed of sorbent material were exposed to vaporized iodine for over 300 hours (~2 weeks) under varied conditions in a dynamic flow environment. The overall performance was monitored in real-time using thermogravimetric analysis, and the materials were subsequently characterized for surface and bulk analysis using scanning electron microscopy – energy-dispersive spectroscopy (SEM-EDS) and powder x-ray diffraction (pXRD), respectively. Iodine (in the form of I 2 ) is expected to be released primarily in the dissolver off-gas (DOG) stream; therefore, this study demonstrates the effects of elemental iodine (I 2 ), water vapor (H 2 O), and nitrogen dioxide (NO 2 ). When exposed to ‘ideal’ conditions (in which I 2 is carried by dry air), Cu 0 -PAN and Bi 0 -PAN behave differently, with TGA analysis indicating that Cu 0 sorption performance is higher than that of Bi 0 , as evidenced by a larger mass change. Under ‘harsh’ conditions—such as a gaseous feed containing I 2 , H 2 O, and NO 2 vapors carried by air,—iodine capture performance for both Cu 0 - and Bi 0 -PAN are affected. SEM-EDS and pXRD analysis of these materials is discussed herein.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Intrinsic and environmental drivers of pairwise cohesion in wild Canis social groups

Animals within social groups respond to costs and benefits of sociality by adjusting the proportion of time they spend in close proximity to other individuals in the group (cohesion). Variation in cohesion between individuals, in turn, shapes important group-level processes such as subgroup formation and fission–fusion dynamics. Although critical to animal sociality, a comprehensive understanding of the factors influencing cohesion remains a gap in our knowledge of cooperative behavior in animals. We tracked 574 individuals from six species within the genus Canis in 15 countries on four continents with GPS telemetry to estimate the time that pairs of individuals within social groups spent in close proximity and test hypotheses regarding drivers of cohesion. Pairs of social canids (Canis spp.) varied widely in the proportion of time they spent together (5%–100%) during seasonal monitoring periods relative to both intrinsic characteristics and environmental conditions. The majority of our data came from three species of wolves (gray wolves, eastern wolves, and red wolves) and coyotes. For these species, cohesion within social groups was greatest between breeding pairs and varied seasonally as the nature of cooperative activities changed relative to annual life history patterns. Across species, wolves were more cohesive than coyotes. For wolves, pairs were less cohesive in larger groups, and when suitable, small prey was present reflecting the constraints of food resources and intragroup competition on social associations. Pair cohesion in wolves declined with increased anthropogenic modification of the landscape and greater climatic variability, underscoring challenges for conserving social top predators in a changing world. We show that pairwise cohesion in social groups varies strongly both within and across Canis species, as individuals respond to changing ecological context defined by resources, competition, and anthropogenic disturbance. Our work highlights that cohesion is a highly plastic component of animal sociality that holds significant promise for elucidating ecological and evolutionary mechanisms underlying cooperative behavior.

59 BASIC BIOLOGICAL SCIENCES↗

Safeguarding the Health of the NASA Astronaut Community: the Need for Expanded Medical Monitoring for Former NASA Astronauts Under the Astronaut Occupational Health Program

The astronaut community is unique, and may be disproportionately exposed to occupational hazards not commonly seen in other communities. The extent to which the demands of the astronaut occupation and exposure to spaceflight-related hazards affect the health of the astronaut population over the life course is not completely known. Provision of health screening services to active and former astronauts ensures individual, mission, and community health and safety. Currently, the NASA Johnson Space Center (JSC) Flight Medicine Clinic (FMC) provides extensive medical monitoring to active astronauts throughout their careers. Upon retirement, astronauts may voluntarily return to the JSC FMC for an annual preventive exam. However, current retiree monitoring includes only selected screening tests, representing an opportunity for augmentation. The potential latent health effects of spaceflight demand an expanded framework of testing for former astronauts. The need is two-fold: screening tests widely recommended for other aging communities are necessary for astronauts to rule out conditions resulting from the natural aging process (e.g., colonoscopy, mammography), as opposed to conditions resulting directly from the astronaut occupation; and increased breadth of monitoring services will improve the understanding of occupational health risks and longitudinal health of the astronaut community, past, present, and future. To meet this need, NASA has begun an extensive exploration of the overall approach, cost, and policy implications of expanding existing medical monitoring under the Astronaut Occupational Health program for former NASA astronauts.

Rossi, Meredith↗

Methods to Automate Assessing the Outage Risk and Technical Specification Compliance for Planned Work and Current Plant Conditions. Light Water Reactor Sustainability Program report

This research effort is a part of the Light Water Reactor Sustainability (LWRS) Program, which is a research and development (R&D) program sponsored by the Department of Energy. The LWRS Program is performed in close collaboration with industry R&D programs that provide the technical foundations for licensing and managing the long term, safe, and economical operation of current nuclear power plants (NPPs). The LWRS Program serves to help the United States (U.S.) nuclear industry adopt new technologies and engineering solutions that facilitate the continued safe operation of these NPPs and the extension of their current operating licenses. The Outage Risk Management Improvement Pilot Project seeks to improve the management of nuclear power plant outages. This is done through the development of tools to assist in evaluating pending activities against requirements to detect undesired interactions. Significant efforts are expended to manage the nuclear risk of an outage. The utilities conduct pre outage risk assessments, based on a very detailed review of the outage schedule, to identify where combinations of outage work and out of service equipment would result in degraded conditions with respect to nuclear safety or regulatory compliance. Probabilistic risk assessment studies are conducted to quantify incremental core damage frequency as a result of the outage activities and system unavailability. These studies are usually presented to site and fleet management, the site plant operational review committee, and the NPP’s independent Nuclear Safety Review Board for concurrence that the outage is planned safely and that reasonable measures have been taken to reduce the added risk of conducting the outage. During the outage, the plant configuration is monitored continuously to ensure that it conforms to the approved safety plan. Deviations must be assessed and approved by management committees and, in some cases, the plant operational review committee. In virtually all outage meetings and job briefings, the current nuclear safety status of the plant is communicated, including information on the specific equipment necessary to meet the requirements of the nuclear safety plan. In addition, the operations and outage organizations implement several layers of physical and administrative barriers to prevent unintended interaction with the systems and equipment credited for nuclear safety. In spite of all these efforts, nuclear safety challenges still occur too frequently during outages. While some of these are due to failures of equipment credited for safety, the majority occur because of human error. These typically involve some form of interaction between work activities and plant configuration changes. Some of them are very subtle and are extremely challenging to detect in advance. Nevertheless, they are not acceptable and represent clear opportunities to improve nuclear safety during outages. This particular report will provide a demonstration of the capabilities in the development of a predictive software platform for improving configuration control and accessing the plant risks associated with outage work protocols and illustrate how the software assists in strategies to minimize these interactions. In addition to maintaining nuclear safety, there are numerous administrative requirements that must be complied with during an outage. This report will discuss the use of logic modelling to monitor planned work against technical specification requirements for given plant conditions and to integrate these requirements with shutdown risk models, clearance order requirements and other plant condition requirements.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Resolution Enhancement of MODIS-Derived Water Indices for Studying Persistent Flooding

Monitoring coastal marshes for persistent flooding and salinity stress is a high priority issue in Louisiana. Remote sensing can identify environmental variables that can be indicators of marsh habitat conditions, and offer timely and relatively accurate information for aiding wetland vegetation management. Monitoring activity accuracy is often limited by mixed pixels which occur when areas represented by the pixel encompasses more than one cover type. Mixtures of marsh grasses and open water in 250m Moderate Resolution Imaging Spectroradiometer (MODIS) data can impede flood area estimation. Flood mapping of such mixtures requires finer spatial resolution data to better represent the cover type composition within 250m MODIS pixel. Fusion of MODIS and Landsat can improve both spectral and temporal resolution of time series products to resolve rapid changes from forcing mechanisms like hurricane winds and storm surge. For this study, using a method for estimating sub-pixel values from a MODIS time series of a Normalized Difference Water Index (NDWI), using temporal weighting, was implemented to map persistent flooding in Louisiana coastal marshes. Ordinarily NDWI computed from daily 250m MODIS pixels represents a mixture of fragmented marshes and water. Here, sub-pixel NDWI values were derived for MODIS data using Landsat 30-m data. Each MODIS pixel was disaggregated into a mixture of the eight cover types according to the classified image pixels falling inside the MODIS pixel. The Landsat pixel means for each cover type inside a MODIS pixel were computed for the Landsat data preceding the MODIS image in time and for the Landsat data succeeding the MODIS image. The Landsat data were then weighted exponentially according to closeness in date to the MODIS data. The reconstructed MODIS data were produced by summing the product of fractional cover type with estimated NDWI values within each cover type. A new daily time series was produced using both the reconstructed 250-m MODIS, with enhanced features, and the approximated daily 30-m high-resolution image based on Landsat data. The algorithm was developed and tested over the Calcasieu-Sabine Basin, which was heavily inundated by storm surge from Hurricane Ike to study the extent and duration of flooding following the storm. Time series for 2000-2009, covering flooding events by Hurricane Rita in 2005 and Hurricane Ike in 2008, were derived. High resolution images were formed for all days in 2008 between the first cloud free Landsat scene and the last cloud-free Landsat scene. To refine and validate flooding maps, each time series was compared to Louisiana Coastwide Reference Monitoring System (CRMS) station water levels adjusted to marsh to optimize thresholds for MODIS-derived time series of NDWI. Seasonal fluctuations were adjusted by subtracting ten year average NDWI for marshes, excluding the hurricane events. Results from different NDWI indices and a combination of indices were compared. Flooding persistence that was mapped with higher-resolution data showed some improvement over the original MODIS time series estimates. The advantage of this novel technique is that improved mapping of extent and duration of inundation can be provided.

Underwood, L. W.↗

Evaluation of Clamshell Current Coupler for Online Frequency Domain and Spread Spectrum Time Domain Reflectometry to Detect Anomalies in Energized Cables

This document describes adaptation and evaluation of a clamshell inductive current coupler for online reflectometry testing (both frequency domain reflectometry and spread spectrum time domain reflectometry) to evaluate cable insulation degradation and anomalies. Safety-critical nuclear power plant cables were initially qualified for 40 years. However, as plants extend their operating licenses to 60 and 80 years, justification for continued safe operation includes test and monitoring programs. These will become more important as the industry moves to condition based qualification programs. Cable test programs traditionally involve manual interventions to disconnect cables, perform one or several tests, then reconnect the systems, usually during refueling outages occurring only every 18 to 24 months. This poses an operational burden that can be minimized by online testing or periodic connection to a coupler that may remain on the cable of interest or be clamped onto the cable without de-termination. This work investigates the adaptation of a clamshell inductive current coupler for either frequency domain reflectometry or spread-spectrum time domain reflectometry. The reflectometry test instrument injects a broad-band chirp or pseudo-noise signal onto a cable conductor and monitors for a reflected signal indicative of an impedance change caused by a damage condition. The instrument maximum input signal levels are typically 10 to 30 volts or less and the instruments will be damaged if subjected to 60 Hz power line voltages of 110, 220, or 480 VAC. One commercial spread-spectrum time domain reflectometry system has circuitry suitable for voltages up to 1 kV, but typical reflectometry tests are performed on de-energized cables. The clamshell inductive coupler provides >60 dB of 60 Hz attenuation with less than 10 dB loss in the 1-500 MHz test bandwidth of interest. An energized cable was successfully tested up to 6.7 kVp-p and frequency response plots imply that the tests could be extended to 10 kV or higher energized levels.

36 MATERIALS SCIENCE↗

High-precision control of tracked field robots in the presence of unknown traction coefficients

Accurate steering through crop rows that avoids crop damage is one of the most important tasks for agricultural robots utilized in various field operations, such as monitoring, mechanical weeding, or spraying. In practice, varying soil conditions can result in off-track navigation due to unknown traction coefficients so that it can cause crop damage. To address this problem, this work presents the development, application, and experimental results of a real-time receding horizon estimation and control (RHEC) framework applied to a fully autonomous mobile robotic platform to increase its steering accuracy. Recent advances in cheap and fast microprocessors, as well as advances in solution methods for nonlinear optimization problems, have made nonlinear receding horizon control (RHC) and receding horizon estimation (RHE) methods suitable for field robots that require high-frequency (milliseconds) updates. A real-time RHEC framework is developed and applied to a fully autonomous mobile robotic platform designed by the authors for in-field phenotyping applications in sorghum fields. Nonlinear RHE is used to estimate constrained states and parameters, and nonlinear RHC is designed based on an adaptive system model that contains time-varying parameters. The capabilities of the real-time RHEC framework are verified experimentally, and the results show an accurate tracking performance on a bumpy and wet soil field. Finally, the mean values of the Euclidean error and required computation time of the RHEC framework are equal to 0.0423 m and 0.88 ms, respectively.

42 ENGINEERING↗

Reduction in the Number of Mg Acceptors with Al Concentration in Al x Ga 1-x N

High hole concentrations in Al x Ga 1-x N become increasingly difficult to obtain as the Al mole fraction increases. The problem is believed to be related to compensation, extended defects, and the band gap of the alloy. Whereas electrical measurements are commonly used to measure hole density, we used electron paramagnetic resonance (EPR) spectroscopy to investigate a defect related to the neutral Mg acceptor. The amount and symmetry of neutral Mg in MOCVD-grown Al x Ga 1-x N with x = 0 to 0.28 was monitored for films with different dislocation densities and surface conditions. EPR measurements indicated that the amount of neutral Mg decreased by 60% in 900°C-annealed Al x Ga 1-x N films for x = 0.18 and 0.28 as compared with x = 0.00 and 0.08. A decrease in the angular dependence of the EPR signal accompanied the increased x, suggesting a change in the local environment of the Mg. Neither dislocation density nor annealing conditions contribute to the reduced amount of neutral Mg in samples with the higher Al concentration. Rather, compensation is the simplest explanation of the observations, because a donor could both reduce the number of neutral acceptors and cause the variation in the angular dependence.

36 MATERIALS SCIENCE↗

Modeling of fluid injection-induced fault reactivation using coupled fluid flow and mechanical interface model

The present study is aimed at developing a numerical model to reproduce coupled hydro-mechanical processes associated with fault reactivation by fluid injection in low permeability rock, as part of the DECOVALEX-2019 project Task B. We proposed a modeling approach for simulating the processes using the TOUGH-FLAC simulator, and modeled a fault reactivation experiment conducted at Mont Terri Rock Laboratory in Switzerland. The first step of the study involved benchmark calculations considering a simplified fault plane and geometry. Fluid flow along a fault was modeled using elements of aperture-sized thickness on the basis of Darcy's law and the cubic law in TOUGH2, whereas the mechanical behavior of a single fault was represented by zero-thickness interface elements in FLAC3D upon which a slip and/or separation is allowed. A methodology to connect a TOUGH2 volume element to a FLAC3D interface element was developed for handling the hydro-mechanical interactions on the fault during fluid injection. Two different fault models for describing the evolutions of hydraulic aperture by elastic fracture opening and failure-induced aperture increase were considered in the benchmark calculations. In the coupling process, the changes in geometrical features and hydrological properties induced by mechanical deformation were continuously updated. The transient responses of the fault and host rock to stepwise pressurization were examined during the simulation. The hydro-mechanical behavior, including the injection flow rate, pressure distribution around the borehole, stress conditions, and displacements in normal and shear directions were monitored in the surrounding rock and along the fault. The results of benchmark calculations suggest that the developed model reasonably represents the hydro-mechanical behavior of a fault and the surrounding rock. This modeling approach was applied to the fault reactivation experiment of the Mont Terri Rock Laboratory. In this interpretive modeling, a parametric study was conducted to examine the effects of input parameters regarding in situ stress and fault properties on the hydro-mechanical responses of the fault to water injection. Then, an optimal parameter set to reproduce the field experiment results was chosen by trial-and-error. The injection flow rate and pressure response during fault reactivation closely matched those obtained at the site, which indicates the capability of the model to appropriately capture the progressive pathway evolution during fault reactivation tests at the site. Finally, the anchor displacements were overestimated by the model, but a fair agreement was obtained in terms of the order of magnitude and the variation tendency.

58 GEOSCIENCES↗

Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO 2 Adsorbents

The cationic ring-opening polymerization of azetidine to form branched poly(propylenimine) (PPI) is investigated for the purpose of evaluating the utility of PPI/silica composite adsorbents for CO 2 capture. The polymerization kinetics and primary:secondary:tertiary amine distribution are monitored with 1H NMR during reaction with varied synthesis conditions (i.e., reaction time 20–150 h), temperature (343–353 K), and monomer to acid initiator (here, HClO 4 ) ratio. It is found that primary amines are converted to tertiary amines with increased polymerization time, while the addition of monomer over the first 6 h of polymerization increases the primary amine content. This suggests a mechanism where the monomer is rapidly consumed, leaving dimers or small oligomers that still contain rings as key reaction centers. The synthesized polymer is neutralized with either NH 4 OH or a basic resin and impregnated into mesoporous silica (SBA-15). The CO 2 capture properties of these composite adsorbents are investigated, giving information about the effectiveness of the acid neutralization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗