Non-steady State Research Articles

Non-steady state validation of kinetic models for ethylene epoxidation over silver catalysts

A two-site kinetic model for ethylene epoxidation most accurately recreates the selectivity trends observed during transient pressure pulse experiments of ethylene over oxidized silver.

Analysis of electromechanical coupling vibration characteristics of motor-gear system based on bond graph theory

In recent years, there has been a growing demand in the field of engineering systems for research on the vibration response of motor-gear systems under non-steady state conditions. However, conventional modeling and simulation techniques are primarily restricted to systems within a single energy domain. When dealing with intricate electromechanical coupling systems, the modeling process becomes increasingly intricate. Consequently, this study adopts bond graph theory as the foundation for analyzing the vibration characteristics of motor-gear coupling systems. In addressing the vibration issue of the motor-gear transmission system, a nonlinear bond graph model is established that takes into account the time-varying mesh stiffness, static errors, and tooth surface friction, among other nonlinear factors. Then, according to the coupling relationship between motor mechanical systems and electrical systems, the electromechanical coupling dynamic model of the motor-gear system is established using the method of bond graph. In addition, the state equation of the system is derived based on the bond graph model. Finally, the system is simulated using 20-sim software, and the electromechanical coupled vibration characteristics of the simulation results are analyzed. This article lays the foundation for the design and analysis of motor-gear coupling systems and multi-energy domain complex systems.

A Non-Steady State NMR Effect Based Time-Varying Magnetic Field Measurement Method and Experimental Apparatus

A Non-Steady State NMR Effect Based Time-Varying Magnetic Field Measurement Method and Experimental Apparatus

Cross Relaxation Enables Spatiotemporal Color-Switchable Upconversion in a Single Sandwich Nanoparticle for Information Security.

Smart control of ionic interaction dynamics offers new possibilities for tuning and editing luminescence properties of lanthanide-based materials. However, it remains a daunting challenge to achieve the dynamic control of cross relaxation mediated photon upconversion, and in particular the involved intrinsic photophysics is still unclear. Herein, this work reports a conceptual model to realize the color-switchable upconversion of Tm3+ through spatiotemporal control of cross relaxation in the design of NaYF4:Gd@NaYbF4:Tm@NaYF4 sandwich nanostructure. It shows that cross relaxation plays a key role in modulating upconversion dynamics and tuning emission colors of Tm3+. Interestingly, it is found that there is a short temporal delay for the occurrence of cross relaxation in contrast to the spontaneous emission as a result of the slight energy mismatch between relevant energy levels. This further enables a fine emission color tuning upon non-steady state excitation. Moreover, a characteristic quenching time is proposed to describe the temporal evolution of cross relaxation quantitatively. These findings present a deep insight into the physics of ionic interactions in heavy doping systems, and also show great promise in frontier applications including information security, anti-counterfeiting and nanophotonics.

Carbon and silica fluxes during a declining North Atlantic spring bloom as part of the EXPORTS program

The goal of NASA's EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) project is to develop a predictive understanding of the fate of global ocean primary productivity and export of carbon from the surface to the deep ocean. Thorium-234 (234Th, t1/2 = 24.1 d) was used to measure sinking particle export from an anticyclonic eddy during the EXPORTS North Atlantic cruise (May 2021) at the Porcupine Abyssal Plain. The four-week sampling period was broken into three time periods (“epochs”) where 800 234Th seawater samples were collected from over 50 CTD casts with high depth resolution over the upper 500 m. Size-fractioned particulate samples were collected to determine particulate organic carbon (POC) and biogenic silica (bSi) to 234Th ratios using in situ McLane pumps. A 234Th non-steady state model shows an eddy center epoch average progression of increasing 234Th export (∼2800 ± 300 (Epoch 1; standard deviation) to 4500 ± 700 (Epoch 3) dpm m−2 d−1) out of the top 110 m of the water column over the course of the cruise (29 d). This translates into an epoch average progression of ∼11 ± 1 to 14 ± 2 mmol C m−2 d−1 of sinking POC flux, and ∼ 3 ± 1 to 6 ± 1 mmol bSi m−2 d−1 of sinking bSi flux to deeper waters at 110 m. The overall efficiency of the biological carbon pump (amount of net primary production reaching 100 m below the euphotic zone) increases from ∼10% to ∼30% throughout the sampling period. The temporal trends discussed extensively in this paper show that POC and bSi export increase during diatom bloom evolution.

Analytical solution and its application for the dynamic characteristics of a heat recovery steam generator in gas–steam combined cycle

This paper presents a study from the perspective of analytical solutions to analyze the dynamic characteristics of a Heat Recovery Steam Generator (HRSG) and explore its practical applications. The study employs the lumped parameter method to simplify the metal heat storage and temperature changes within HRSGs. Differential equations, based on the principles of mass and energy conservation, are formulated to describe the heating surfaces within HRSGs. Analytical solutions are derived, and the essential parameters in these expressions are discussed for their physical significance. Using these analytical solutions, the dynamic heat transfer processes for heating surfaces in a typical HRSG under various starting conditions are investigated. The findings reveal that a larger heat transfer factor or a smaller heat capacity factor of HRSG metal (or a larger ratio of these factors) results in a faster thermal equilibrium during the heat transfer process. Additionally, a dynamic forecasting model is developed based on these analytical solutions. The Particle Swarm Optimization (PSO) algorithm is applied as a parameter identification technique to fine-tune the model's initial parameters, which may be incomplete in real start-up processes. To validate the model, real-time on-site measurement data from a cold start-up of a non-supplementary fired HRSG is used. The results demonstrate the model's strong predictive capabilities, with an average absolute error ranging from 0.5 °C to 2 ℃, highlighting its high accuracy. Comparing the model with a thermal equilibrium model, it is evident that during the cold start-up of an HRSG, the heating surfaces exhibit dynamic characteristics, transitioning from a non-steady state in the first 3000 s to a quasi-steady state between 3000 and 7000 s.

Characteristics of temperature-dependent shear flow in an ultrasonicated ferrofluid

The rheological effect of manganese zinc (Mn-Zn) ferrite ferrofluid was studied and the impact of temperature on the magnetoviscosity and viscoelastic system of manganese-zinc ferrite ferrofluid generated by co-precipitation process is investigated. At 25 ◦C, a ferrofluid structure that is both hard and elastic is produced. As the temperature rises, the fluid structure loses its elasticity and becomes semi-rigid. When a low relaxation modulus is applied, the fluid behavior, which is temperature-dependent, exhibits the development of linear stress relaxation and steady state flow. When a greater relaxation modulus is used, non-steady state flow results. At a high temperature of 50 ◦C, steady state flow is quickly obtained, whereas at a low temperature, equilibrium or steady state is attained more slowly. At low temperatures, the fluid exhibits a solid-like structure, whereas at high temperatures, a liquid-like structure forms as the fluid’s viscosity decreases. With the creation of yield stress in the region with high shear rates, shear stress increases with temperature, and yield stress increases with temperature. The viscoelastic system is underdamped, and the amount of fluid deflected at 25 ◦C is small, which prevents the disruption of the fluid’s rheology. This develops as a result of the presence of a small deflection angle, which facilitates the development of high magnetoviscosity at low temperature. High viscous effect forms at low temperatures due to the creation of low shear stress and low deflection angle at temperature 25 ◦C. The sample has a single phase and FCC structure, which X-ray diffraction research has verified.

Diffusion, Separation, and Buffering of Non-Steady-State VOCs Flow on Activated Carbon

In this study, the diffusion, separation, and buffering of volatile organic compounds emitted in a non-steady state on activated carbon were studied. Ethanol and xylene, which have large differences in adsorption capacity and diffusion rate, were selected as the representative target pollutants of volatile organic compounds. In this paper, activated carbon with a certain intake concentration and adsorption equilibrium was chosen as the research object. The buffering effect of pulse load was studied. The buffering effect and influencing factors were analyzed. The Bangham equation proved to be a more effective tool in describing the dynamic processes of ethanol and xylene adsorption on activated carbon, indicating that pore diffusion was the rate-determining step in the adsorption process. R3 emerged as a more suitable criterion for evaluating non-steady-state emissions. Factors such as pulse time and pulse multiplier were influenced by Empty Bed Contact Time (EBCT), which collaborated with EBCT to impact the buffering performance of activated carbon. An EBCT of 4 cm was identified as the optimal bed height, with R3 reaching 1.48. Non-polar VOCs with chemically symmetric structures exhibited slower mass transfer rates compared to polar VOCs, resulting in larger adsorption capacities on activated carbon and better buffering performance.

Heat transfer characteristics and thermal insulation optimization of buried ductile iron heat-supply pipeline

ABSTRACT This study investigates heat transfer in a ductile iron heat-supply pipeline and develops a mathematical model through a comparative assessment of different techniques. The goal is to accurately describe non-steady state heat transfer in buried pipelines. A high-precision model is established by considering assumptions, equations, boundary conditions, calculation domain, geometry, and grid number. Calculation time is reduced, and accuracy is improved, providing a foundation for optimizing the thermal insulation layer. ANSYS software is used to simulate and optimize the thermal insulation of the pipeline. Results show a maximum error range of 1.20% to 10.20% with consistent temperature trends, verifying the model’s accuracy. The heat-affected zone of the thermal bridge is evaluated and optimized, and preventive measures are proposed to reduce the impact of heat bridges in joint areas. The study also compares nodular cast iron pipes with conventional steel thermal pipes under the same conditions. It reveals that the economic thickness of the thermal insulation layer for nodular cast iron pipes increases from 31 mm to 39 mm due to the thermal bridge effect, which is significant.

Pulsed Electrolysis Promotes CO2 Reduction to Ethanol on Heterostructured Cu2O/Ag Catalysts.

The electrochemical conversion of carbon dioxide (CO2)into ethanol with high added value has attracted increasing attention. Here, an efficient catalyst with abundant Cu2O/Ag interfaces for ethanol production under pulsed CO2 electrolysis is reported, which is composed of Cu2O hollow nanospheres loaded with Ag nanoparticles (named as se-Cu2O/Ag). The CO2-to-ethanol Faradaic efficiency is prominently improved to 46.3% at a partial current density up to 417mAcm-2 under pulsed electrolysis conditions in a neutral flow cell, notably outperforming conventional Cu catalysts during static electrolysis. In situ spectroscopy reveals the stabilized Cu+ species of se-Cu2O/Ag during pulsed electrolysis and the enhanced adsorbed CO intermediate(*CO)coverage on the heterostructured catalyst. Density functional theory (DFT) calculations further confirm that the Cu2O/Ag heterostructure stabilizes the *CO intermediate and promotes the coupling of *CO and adsorbed CH intermediate (*CH). Meanwhile, the stable Cu+ species under pulsed electrolysis favor the hydrogenation of adsorbed HCCOH intermediate (*HCCOH) to adsorbed HCCHOH intermediate (*HCCHOH) on the pathway to ethanol. The synergistic effect between the enhanced generation of *CO on Cu2O/Ag and regenerated Cu+ species under pulsed electrolysis steers the reaction pathway toward ethanol. This work provides some insights into selective ethanol production from CO2 electroreduction via combined catalyst design and non-steady state electrolysis.

Design and Optimization of Low Impact Shift Control Strategy for Aviation Transmission Power System Based on Response Surface Methodology

The utilization of a variable-speed power system significantly improves the forward flight speed and cruising range of the helicopter. Nevertheless, the shock of speed and torque during the shift process brings stability and safety problems that cannot be ignored. Thus, swift and stable shift control is a key issue in the research on aviation power systems. This study focuses on the design and optimization of low-impact shift control strategies for a variable-speed power system, which involves multiple control variables, long adjustment times, and uncontrollable risks due to the nonsteady state. A comprehensive power system model that integrates the engine, a two-speed dual-clutch transmission system, and the main rotor was proposed. By selecting the engine fuel flow, friction clutch hydraulic pressure, and rotor pitch angle as input signals, regression fitting models between the input signals’ starting time points and speed or torque shock were obtained using Response Surface Methodology (RMS). The interaction effect of multiple time series was analyzed, and four kinds of low-impact nonlinear programming multi-objective optimized models for speed or torque are proposed. The results indicate that the P values of the RMS fitting models at upshift and downshift are less than 0.0001 and 0.05, respectively, which are highly significant and can effectively predict the shift dynamic response; under the optimized upshift and downshift control strategy, the speed and torque shock are reduced by 5–10%.

Quantifying non-steady state natural gas leakage from the pipelines using an innovative sensor network and model for subsurface emissions - InSENSE

Detecting and quantifying subsurface leaks remains a challenge due to the complex nature and extent of belowground leak scenarios. To address these scenarios, monitoring and evaluating changes in gas leakage behavior over space and time are crucial for ensuring safe and efficient responses to known or potential gas leaks. This study demonstrates the capability of linking environmental and gas concentration data obtained using a low-cost, near real-time methane (CH4) detector network and an inverse gas migration model to capture and quantify non-steady state belowground natural gas (NG) leaks. The Estimating Surface Concentration Above Pipeline Emission (ESCAPE) model was modified to incorporate the impact of soil properties on gas migration. Field-scale controlled NG experiments with leakage rates ranging from 37 to 121 g/h indicate that elevated belowground near-surface (BNS) gas concentrations persist long before elevated surface concentrations are observed. On average, BNS CH4 concentrations were 20%–486% higher than surface CH4 concentrations within the monitoring radius of 4 m from the leak location. An increase in the BNS CH4 concentration was observed within 3 h as the leak rate increased from 37 to 89 g/h. However, due to the atmospheric fluctuations, any changes in surface CH4 concentrations could not be confirmed within this period. The plume area of the BNS CH4 extended approximately two times farther than that of the surface CH4 as the gas leak rate increased from 37 to 121 g/h. The estimated NG leak rates by the modified ESCAPE model agreed well with the experimental NG leak rates (m = 0.99 and R2 = 0.77), demonstrating that including soil characteristics and BNS CH4 measurements can advance estimations of non-steady NG leak rates in low and moderate NG leak rate scenarios. The CH4 detector network and model show potential as an innovative tool to improve operators' risk assessment and NG leakage response.

Dual-FBG arrays hybrid measurement technology for mechanical strain, temperature, and thermal strain on composite materials

The response measurement of spacecraft during reentry is very important for designing the base composite structure. This paper proposes a hybrid measurement method to measure the mechanical strain, the temperature, and the thermal strain using dual fiber Bragg grating (FBG) arrays. The decoupling of temperature and stain is illustrated by a three-step process such that triple physical variables are measured simultaneously. For the base composite structure, four heating scenarios with thermal steady and non-steady states encountered during the lifting re-entry were designed to illustrate the feasibility of the proposed method. Under the thermal non-steady state, the average absolute error of the temperature measured by the dual-FBG and the thermocouple did not exceed 2.799 K. Meanwhile, the dual FBG-based thermal strain was compared with the thermally measured strain with an average relative error of no more than 2.913%. A finite element model at different temperatures was developed to calculate mechanical responses and was compared with the results obtained by FBG. The results show significant agreement between the measurement and the simulation, with a maximum error of 3.61%.

Implications of the steady-state assumption for the global vegetation carbon turnover

Vegetation carbon turnover time (τ) is a central ecosystem property to quantify the global vegetation carbon dynamics. However, our understanding of vegetation dynamics is hampered by the lack of long-term observations of the changes in vegetation biomass. Here we challenge the steady state assumption of τ by using annual changes in vegetation biomass that derived from remote-sensing observations. We evaluate the changes in magnitude, spatial patterns, and uncertainties in vegetation carbon turnover times from 1992 to 2016. We found the robustness in the steady state assumption for forest ecosystems at large spatial scales, contrasting with local larger differences at the grid cell level between τ under steady state and τ under non-steady state conditions. The observation that terrestrial ecosystems are not in a steady state locally is deemed crucial when studying vegetation dynamics and the potential response of biomass to disturbance and climatic changes.

Dynamic rate analysis for low frequency operation of chemical reactors

Periodic operation of chemical reactors can enhance reactant conversion and product selectivity. It is desirable to identify reaction kinetics and networks that may benefit from non-steady state operation and to quantify the extent of that enhancement without extensive computations. In this study, we describe a simple method to establish approximate functional dependencies of isothermal point reaction enhancement on dynamic and kinetic parameters during low frequency operation. Low frequency operation permits the use of steady state as opposed to transient conservation equations to identify limits of fractional rate enhancement. By approximating local dynamic rates as square waves modulating between two steady states, an analytical function can be derived from global rate expressions. The function relates fractional rate enhancement to concentration wave amplitudes, phase shifts, cyclic averages, duty cycles and reaction orders for one or more dynamically-fed reactants. We show that the method may be applied to predict integral conversion enhancement for ideal reactors. During integral operation, nonstoichiometric concentration waves may change phase through disproportionate consumption of reactants at wave maxima and minima, hence inverting waves out-of-phase (180°) from their initial waveform. This may cause local rate enhancement to transition to rate diminishment. Three experimental examples involving catalytic oxidations are described that illustrate selected theoretical aspects of the study.

Non-Steady-State Symmetry Breaking Growth of Multilayered SnSe2 Nanoplates.

The use of non-equilibrium growth modes with non-steady dynamics is extensively explored in bulk materials such as amorphous and polycrystalline materials. Yet, research into the non-steady-state (NSS) growth of two-dimensional (2D) materials is still in its infancy. In this study, multilayered tin selenide (SnSe2 ) nanoplates are grown by chemical vapor deposition under NSS conditions (modulating carrier gas flow and temperature). Given the facile diffusion and inherent instability of SnSe2 , it proves to be an apt candidate for nucleation and growth in NSS scenarios. This leads to the emergence of SnSe2 nanoplates with distinct features (self-growth twisting, symmetry transformation, interlayer decoupling, homojunction, and large-area 2D domain), exhibiting pronounced second harmonic generation. The authors' findings shed light on the growth dynamics of 2D materials, broadening their potential applications in various fields.

Three-dimensional Budyko framework incorporating terrestrial water storage: Unraveling water-energy dynamics, vegetation, and ocean-atmosphere interactions

The two-dimensional steady-state Budyko framework, widely used to study water-energy dynamics in landscapes, primarily focused on the partitioning of precipitation into evapotranspiration (ET) and water yield. Though this framework has been extended by incorporating water storage changes into precipitation input for non-steady state conditions, the interactions among water-energy dynamics, vegetation covers, and ocean-atmosphere oscillations within the Budyko framework at finer spatial and temporal scales have been unexplored. This study aims to investigate the interactions of regional hydroclimatic conditions, vegetation, and climate teleconnections over the Indo-China Peninsula (ICP), a region highly vulnerable to climate change. To achieve the objective, we propose a three-dimensional Budyko framework that incorporates the ratio of Gravity Recovery and Climate Experiment (GRACE)-based terrestrial water storage (TWS) or its changes (TWSC) to precipitation (SI/SCI) as the third dimension alongside the traditional two-dimensional Budyko framework. Our findings reveal that TWS has a significant impact on the Budyko framework, particularly during the dry season. The dryness index (DI)/evaporative index (EI) and SI/SCI exhibit positive (strongly negative) linear relationships in the wet (dry) season, respectively. Vegetation covers strongly influence the three-dimensional Budyko framework, with poor performance observed in highly vegetated regions due to high ET demand. Through relative importance analysis, we identify the Silk Road Pattern (SRP) as the most influential climate teleconnection among nine different teleconnections, affecting hydroclimatic conditions over the ICP. Positive (negative) phases of SRP encourage water-limited (energy-limited) ET conditions. This demonstrates that the Budyko parameter is influenced not only by landscapes but also by climate teleconnections, offering potential benefits for Budyko parameter estimation. Furthermore, the linear relationships between DI/EI and SI/SCI in three-dimensional Budyko framework can provide a promising alternative method for evapotranspiration and groundwater estimation.

Durability assessment of industrial by-product and marine resource-based ultra-high-performance concrete

The increasing demand for concrete and the associated environmental impacts such as depletion of natural resources (e.g., fresh water, river sand, and coarse aggregates) have prompted the development of seawater and sea-sand concrete (SWSSC). On the other hand, incorporating industrial by-products in concrete as supplementary cementitious materials (SCMs) can offset the cement carbon footprint. Utilizing seawater, sea sand, and industrial wastes in ultra-high-performance concrete (UHPC) fabrication can lead to a sustainable as well as durable construction material, especially suited for marine infrastructure development. This experimental work investigates the durability properties of ultra-high-performance seawater and sea-sand concrete (UHP-SWSSC) with partial substitution of cement by ground granulated blast furnace slag and silica fume as SCMs. Five mixes were developed with varying proportions of SCMs as cement replacement (0% as control mix, 25% and 50% by mass) and water-to-binder ratio (0.15, 0.2 and 0.25). In addition to mechanical behaviour through standard axial compression tests on cube specimens, several durability indicators such as water absorption, sorptivity, the permeability of chloride ions, and volume of permeable voids were measured over time. Results reveal that the incorporation of SCMs in UHP-SWSSC although improves the mechanical properties marginally, significantly enhances the durability performance. In comparison to the control mix, 53%, 75%, and 95% reductions in the volume of permeable voids, rate of water absorption and non-steady state chloride migration coefficient were observed in a 50% SCM replaced mix, respectively. Addition of ground slag and silica fume induced a relatively compact matrix through refinement of the microstructure, which made the resulting concrete nearly impermeable to ion movements. An optimum water-to-binder ratio of 0.2 was established, below which neither the strength nor the durability characteristics improved further.

Creep failure characteristics and characterization of constitutive behaviors of jointed sandstone under multi-level loading of seepage pressure

To study creep failure behaviors of jointed rock mass with seepage pressure as the main damage driving force, creep tests under multi-level loading of seepage pressure were conducted on sandstone with different joint dip angles. In addition, a memory-dependent nonlinear seepage–creep model was established for jointed sandstone. The results show that jointed sandstone experiences three creep stages (initial, steady-state, and accelerated creep stages) in creep tests under multi-level loading paths of seepage pressure. Jointed sandstone with joint dip angles of 30° and 60° undergoes shear failure, while that with the joint dip angle of 45° is subject to tensile–shear failure. Under the same seepage pressure, the sandstone with the joint dip angle of 45° has a greater creep rate in the steady-state creep stage than that with joint dip angles of 30° and 60°. In the volumetric compression stage, the permeability increases at the instant of applying each level of seepage pressure, followed by gradual reduction and stabilization of permeability. In the volumetric dilation stage, the permeability gradually rises. The theory of memory-dependent derivative reflecting the time memory effect was introduced to establish the memory-dependent nonlinear viscoelastic–plastic seepage–creep model for jointed sandstone. The results obtained using the theoretical model conform to the test data. Moreover, the creep failure criterion of the rock was proposed. The creep acceleration starts to increase from 0 and the critical steady state transitions to a non-steady state, suggesting that the rock will soon be damaged. The calculation formula for critical time corresponding to the critical steady state of creep was also deduced. The critical time to onset of creep can serve as an early warning of the creep failure of rocks.

Data repeatability for the Cosmed K4 b2 portable metabolic cart during non-steady state exercise

BACKGROUND: Portable metabolic carts are a popular tool to assess aerobic capacity and affirm many cardiorespiratory conditions. They may also measure strength training performance. Given their popularity and increased usage to assess strength training performance; their data accuracy and consistency are important to determine. OBJECTIVE: Measure Cosmed K4 b2 portable metabolic cart data repeatability from consecutive seated calf press workouts. METHODS: Fifteen women and twelve men did two workouts that began with a stationary cycling warm-up followed by calf presses. Gases were measured before the calf press portion of workouts to establish baseline VO2 and VCO2 values, as well as continually throughout and after the calf press protocol. Subjects were detached from the cart once gas values returned to baseline after workouts concluded. In addition to VO2 and VCO2, repeatability was quantified for: breaths per minute, tidal volume, ventilation, O2 uptake relative to body mass, expired O2 and CO2 fractions, percent fat and carbohydrate utilization, METS and total energy cost. Mean and peak values per variable were analyzed. Repeatability was assessed separately for male and female data, as well as with values pooled, by the following: intraclass correlation coefficients, eta squared, limits of agreement, coefficient of variation and smallest real difference percent. RESULTS: Per variable, repeatability values across workouts were low. Female intraclass correlation coefficient mean values were more repeatable for variables related to gas measurements, yet male data were generally more repeatable for those related to substrate usage. CONCLUSIONS: Results for some repeatability indices were influenced by measurement magnitude. Peak values were predictably less repeatable than those for mean values. Most smallest real differences percent scores are so high they were rendered irrelevant or meaningless to determine true differences among paired values. Results suggest low data repeatability that are likely appropriate and realistic for the exercise protocol, hardware and intensity examined.