A feedback control framework for safe and economically‐optimal operation of nonlinear processes

Maintaining safe operation of chemical processes and meeting environmental constraints are issues of paramount importance in the area of process systems and control engineering, and are ideally achieved while maximizing economic profit. It has long been argued that process safety is fundamentally a process control problem, yet few research efforts have been directed toward integrating the rather disparate domains of process safety and process control. Economic model predictive control (EMPC) has attracted significant attention recently due to its ability to optimize process operation accounting directly for process economics considerations. However, there is very limited work on the problem of integrating safety considerations in EMPC to ensure simultaneous safe operation and maximization of process profit. Motivated by the above considerations, this work develops three EMPC schemes that adjust in real‐time the size of the safety sets in which the process state should reside to ensure safe process operation and feedback control of the process state while optimizing economics via time‐varying process operation. Recursive feasibility and closed‐loop stability are established for a sufficiently small EMPC sampling period. The proposed schemes, which effectively integrate feedback control, process economics, and safety considerations, are demonstrated with a chemical process example. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2391–2409, 2016     

Charge transport mechanisms and memory effects in amorphous TaNx thin films

Amorphous semiconducting materials have unique electrical properties that may be beneficial in nanoelectronics, such as low leakage current, charge memory effects, and hysteresis functionality. However, electrical characteristics between different or neighboring regions in the same amorphous nanostructure may differ greatly. In this work, the bulk and surface local charge carrier transport properties of a-TaN_x amorphous thin films deposited in two different substrates are investigated by conductive atomic force microscopy. The nitride films are grown either on Au (100) or Si [100] substrates by pulsed laser deposition at 157 nm in nitrogen environment. For the a-TaN_x films deposited on Au, it is found that they display a negligible leakage current until a high bias voltage is reached. On the contrary, a much lower threshold voltage for the leakage current and a lower total resistance is observed for the a-TaN_x film deposited on the Si substrate. Furthermore, I-V characteristics of the a-TaN_x film deposited on Au show significant hysteresis effects for both polarities of bias voltage, while for the film deposited on Si hysteresis, effects appear only for positive bias voltage, suggesting that with the usage of the appropriate substrate, the a-TaN_x nanodomains may have potential use as charge memory devices.     

Proactive fault‐tolerant model predictive control

Fault‐tolerant control methods have been extensively researched over the last 10 years in the context of chemical process control applications, and provide a natural framework for integrating process monitoring and control aspects in a way that not only fault detection and isolation but also control system reconfiguration is achieved in the event of a process or actuator fault. But almost all the efforts are focused on the reactive fault‐tolerant control. As another way for fault‐tolerant control, proactive fault‐tolerant control has been a popular topic in the communication systems and aerospace control systems communities for the last 10 years. At this point, no work has been done on proactive fault‐tolerant control within the context of chemical process control. Motivated by this, a proactive fault‐tolerant Lyapunov‐based model predictive controller (LMPC) that can effectively deal with an incipient control actuator fault is proposed. This approach to proactive fault‐tolerant control combines the unique stability and robustness properties of LMPC as well as explicitly accounting for incipient control actuator faults in the formulation of the MPC. Our theoretical results are applied to a chemical process example, and different scenaria were simulated to demonstrate that the proposed proactive fault‐tolerant model predictive control method can achieve practical stability and efficiently deal with a control actuator fault. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2810–2820, 2013     

High‐solids mar resistant clearcoats prepared from an isophthalate‐based oligoester and a melamine resin. Study and characterization of mar resistance with scanning probe microscopy method

A new series of high‐solids [low‐VOC (volatile organic compound)content] mar resistant clearcoats (CL‐series) were prepared upon crosslinking of a new‐synthesized hydroxyl‐terminated isophthalate‐based liquid oligoester (L‐311) with an hexakis(methoxymethylol)melamine (HMMM) resin, via an acid‐catalyzed etherification reaction. The chemical, physical, and mechanical properties of the CL‐clearcoats were compared to those of a reference clearcoat (CRO). An attempt was made to investigate the effect that the amounts of catalyst and melamine resin had on the clearcoats' physical, chemical, and mechanical properties, and moreover, to correlate these properties to the films chemical structures. The new‐formulated high‐solids clearcoats (CL‐series) presented enhanced processability and higher NVW values (lower VOC content) than the reference clearcoat CRO, and their properties (pencil hardness, knoop hardness, adhesion, impact resistance, solvent and gasoline resistance, mar resistance, and flexibility) were better or comparable to those of the CRO. More specifically, the mar resistance of the CL‐clearcoats series was investigated by applying both the crockmeter test and a novel method that employed a modified scanning probe microscope. In addition, we identified and characterized the different responses of the CRO and certain CL‐clearcoats to marring stress. The experimental data regarding the mar resistance of the new‐formulated clearcoats fully justified our polymer design strategy, verifying our expectations for the possibility of preparing glossy, high‐solids mar‐resistant clearcoats that could present enhanced processability and solvent resistance, relatively high pencil hardness, and at the same time very good elastic recovery to marring stress. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1317–1333, 2002     

Development and Evaluation of a High-Volume Aerosol-into-Liquid Collector for Fine and Ultrafine Particulate Matter

This study presents a novel high-volume aerosol-into-liquid collector, developed to provide concentrated slurries of fine and/or ultrafine particulate matter (PM) to be used for unattended, in situ measurements of PM chemistry and toxicity. This system operates at 200 liters per minute (L/min) flow and utilizes the saturation–condensation, particle-to-droplet growth component of the versatile aerosol concentration enrichment system (VACES), growing fine or ultrafine PM to 3–4-μm droplets, in conjunction with a newly designed impactor, in which grown particles are collected gradually forming highly concentrated slurries. Laboratory evaluation results indicated an excellent overall system collection efficiency (over 90%) for both monodisperse and polydisperse particles in the range of 0.01 to 2 μm. Field evaluations illustrated that overall a very good agreement was obtained for most PM_2.5 species between the new aerosol collection system and the VACES/BioSampler tandem as well as filter samplers operating in parallel. Very good agreement between the new system and the VACES/BioSampler was also observed for reactive oxygen species (ROS) in ambient PM_2.5 samples, whereas lower ROS values were obtained from the water extracts of the filter, likely due to incomplete extraction of water insoluble redox active species collected on the filter substrate. Moreover, the field tests indicated that the new aerosol collection system could achieve continuous and unattended collection of concentrated suspensions for at least 2 to 3 days without any obvious shortcomings in its operation. Both laboratory and field evaluations of the high-volume aerosol-into-liquid collector suggest that this system is an effective technology for collection and characterization of ambient aerosols.

Copyright 2013 American Association for Aerosol Research     

Development and Evaluation of a Continuous Ambient PM2.5 Mass Monitor

A Continuous Ambient Mass Monitor (CAMM) for fine particle mass (PM_2.5) has recently been developed at the Harvard School of Public Health. The principle of this method is based on the measurement of the increase in pressure drop across a membrane filter (Fluoropore^TM) during particle sampling. The monitor consists of a conventional impactor inlet to remove particles larger than 2.5 mu m, a diffusion dryer to remove particle-bound water, a filter tape to collect particles, a filter tape transportation system to allow unassisted sampling, and a data acquisition and control unit. For each sampling period (typically 30- 60 min), a new segment of the filter tape is exposed so that particles remain close to equilibrium with the sample air during their collection. This results in mini mization of volatilization and adsorption artifacts during sampling. Furthermore, since the required flow rate for the fine particle mass monitoring channel is only 0.3 L / min, the relative humidity of the air sample can be easily reduced to 40% or less using a NafionTM diffusion dryer to remove particle-bound water. The CAMM has a detection limit of > 5 mu g / m³ for PM_2.5 concentrations averaged over 1 h. The performance of the newly developed monitor was investigated through laboratory and field studies. Laboratory tests included a calibration of the CAMM using polystyrene latex (PSL) and silica particles. A series of field studies were conducted in 7 cities with presumably different PM_2.5 chemical composition. The 24 1-h CAMM measurements were averaged and compared to Harvard Impactor (HI) 24 h PM_2.5 integrated measurements. Based on 211 valid sampling days, the measurements obtained from the Harvard Impactor and the CAMM were highly correlated (r² = 0.90). The average CAMM-to-HI concentration ratio was 1.07 (+- 0.18).     

Proton interactions in chemical-electrochemical and physical systems

The repulsive Coulombic forces exerted between proton wave particles in electrochemical and physical systems are examined, together with the attractive ion-induced dipole forces between protons and neighboring neutral particles, e.g. neutrons in the case of physical systems (nuclei). It is shown that when protons and neutrons are treated as harmonic oscillators with the same kinetic and potential energy, then two roots exist for their vibrational velocity. One root corresponds to negligible relativistic corrections (v/c?1) and unstable nuclei, the other to significant relativistic corrections (v/c≈1) and to formation of stable nuclei. It is shown that the first root corresponds to protons in chemical-electrochemical systems and the second (relativistic) root corresponds to protons in nuclei. In the latter case the formation of stable nuclei is due to the attractive ion-induced dipole forces and to the pronounced increase in mass and gravitational forces. The latter, together with the ion-induced dipole forces, counterbalance the strong repulsive Coulombic forces. This leads to the analytical computation of the energy of formation of the ⁴He and ²H nuclei and of the gravitational constant. All three computed values are in quantitative agreement with experiment.     

Gender stereotyping over instant messenger: The effects of gender and context

Researchers have observed that contrary to the high expectations for online communications, gender stereotyping has not disappeared in this medium, and is sometimes even accentuated. This study aimed to understand the effect of gender over instant messenger, a relatively new and unexplored medium. Instant messenger was chosen because it is a medium that is used most by youth who have grown up communicating online. Participants were interviewed over instant messenger about a potential online support service and were then asked to judge the effectiveness of their interviewer. The interviewer was identified only by a masculine or feminine name and was computer-simulated so as to remove any bias. The topic of discussion was stereotypically masculine or stereotypically feminine. Male participants were found to employ a male superiority heuristic, whereby they judged the male interviewer as more competent, regardless of the context. Female participants were hypothesized to judge the female interviewer as more competent in the feminine context, and the male interviewer as more competent in the masculine context (the context-gender match heuristic), but this hypothesis was not supported. The findings are discussed in the context of previous research on gender stereotyping in online communication.     

Determination of pesticide residues in olive oils with protected geographical indication or designation of origin

Seventy olive oil samples with protected geographical indication (PGI) or designation of origin (PDO) were analysed for fifty‐one target pesticides by means of gas chromatography coupled to mass spectrometry. The highest detection rates were observed for penconazole (n = 20), α‐endosulfan (n = 18), β‐endosulfan (n = 16) and flufenoxuron (n = 12). Four of the seventy investigated samples contained pesticide residues in levels exceeding MRLs. However, the investigated samples showed decreased occurrence and levels of pesticides residues in comparison with previous studies concerning samples from Greek conventional and organic cultivations. According to Spearman matrix, powerful correlations were obtained between α‐endosulfan and β‐endosulfan, detected as pair in thirteen samples and between flufenoxuron and penconazole detected as pair in eleven samples. Among Greek olive oil samples, the Cretan ones showed the lower detection rates and the lowest average number of detected pesticides per sample (1.75) in the case of pesticides positive samples.