Two-step Kinetic Model Research Articles

Non-linear kinetic model of coke deactivation in methanol-to-gasoline conversion: Effects of nano and micro ZSM-5 crystals

Methanol-to-gasoline conversion over ZSM-5 catalysts, a non-petroleum carbon fuel process, is significantly impacted by coke deposition, which deactivates the catalyst by blocking zeolite pores during the reaction and diffusion process. This study investigated the differences in coke species development and deactivation using a non-linear kinetic model, comparing microcrystalline ZSM-5 with longer pore lengths to nanocrystalline ZSM-5 with shorter pores, both tested at 350°C. Catalyst and coke were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature-programmed oxidation (TPO), thermogravimetric analysis (TGA), and an elemental analyzer. Micro ZSM-5 initially achieved 99 % conversion but rapidly dropped to 61 % due to coke buildup, while nano ZSM-5 maintained over 98 % conversion for 24 hours before declining, highlighting the superior catalytic durability of shorter pores. Micro ZSM-5 showed faster coking, accumulating 7.19 % coke with higher temperature-resistant graphitic coke, whereas nano ZSM-5 exhibited a lower coke buildup of 4.56 %, forming primarily amorphous coke. A two-step non-linear kinetic model for soft and hard coke oxidation was applied, with the second-order model providing the highest correlation coefficient. The activation energy for coke decomposition was influenced by pore length, revealing distinct kinetic behaviors for hydrogen-deficient graphitic coke and amorphous coke. This study underscores the importance of zeolite pore structure on coke formation, deposition patterns, and catalytic durability, offering deeper insights into the methanol-to-gasoline conversion process.

Unlocking the potential of biochar: an iron-phosphorus-based composite modified adsorbent for adsorption of Pb(II) and Cd(II) in aqueous environments and response surface optimization of adsorption conditions.

In this work, iron-phosphorus based composite biochar (FPBC) was prepared by modification with potassium phosphate and iron oxides for the removal of heavy metal ions from single and mixed heavy metal (Pb and Cd) solutions. FTIR and XPS characterization experiments showed that the novel modified biochar had a greater number of surface functional groups compared to the pristine biochar. The maximum adsorption capacities of FPBC for Pb(II) and Cd(II) were 211.66mg·g-1 and 94.08mg·g-1 at 293K. The adsorption of Pb(II) and Cd(II) by FPBC followed the proposed two-step adsorption kinetic model and the Freundlich isothermal adsorption model, suggesting that the mechanism of adsorption of Pb(II) and Cd(II) by FPBC involved chemical adsorption of multiple layers. Mechanistic studies showed that the introduction of -PO4 and -PO3 chemisorbed with Pb(II) and Cd(II), and the introduction of -Fe-O increased the ion exchange with Pb(II) and Cd(II) during the adsorption process and produced precipitates such as Pb3Fe(PO4)3 and Cd5Fe2(P2O7)4. Additionally, the abundant -OH and -COOH groups also participated in the removal of Pb(II) and Cd(II). In addition, FPBC demonstrated strong selective adsorption of Pb(II) in mixed heavy metal solutions. The Response Surface Methodology(RSM) analysis determined the optimal adsorption conditions for FPBC as pH 5.31, temperature 26.01°C, and Pb(II) concentration 306.30mg·L-1 for Pb(II). Similarly, the optimal adsorption conditions for Cd(II) were found to be pH 5.66, temperature 39.34°C, and Cd(II) concentration 267.68mg·L-1. Therefore, FPBC has the potential for application as a composite-modified adsorbent for the adsorption of multiple heavy metal ions.

Photorelease of Nitric Oxide (NO) in Mono- and Bimetallic Ruthenium Nitrosyl Complexes: A Photokinetic Investigation with a Two-Step Model.

Two monometallic and three bimetallic ruthenium acetonitrile (RuMeCN) complexes are presented and fully characterized. All of them are built from the same skeleton [FTRu(bpy)(MeCN)]2+, in which FT is a fluorenyl-substituted terpyridine ligand and bpy is the 2,2'-bipyridine. The crystal structure of [FTRu(bpy)(MeCN)](PF6)2 is presented. A careful spectroscopic analysis allows establishing that these 5 RuMeCN complexes can be identified as the product of the photoreaction of 5 related RuNO complexes, investigated as efficient nitric oxide (NO) donors. Based on this set of complexes, the mechanism of the NO photorelease of the bimetallic complexes has been established through a complete investigation under irradiations performed at 365, 400, 455, and 490 nm wavelength. A two-step (A → B → C) kinetic model specially designed for this purpose provides a good description of the mechanism, with quantum yields of photorelease in the range 0.001-0.029, depending on the irradiation wavelength. In the first step of release, the quantum yields (ϕAB) are always found to be larger than those of the second step (ϕBC), at any irradiation wavelengths.

Small-scale superadiabatic combustors with a two-step chain-branching chemistry model: Asymptotic models and the effect of two-dimensionality on lean mixtures burning

Small-sized super-adiabatic combustion devices consisting of countercurrent channels with heat-exchange segments are investigated for their ability to burn ultra-lean mixtures. The study is carried out numerically using a two-step chain-branching kinetic model in which the flammability limit appears explicitly. Various asymptotic approximations for modeling the process are considered, together with the solution of the two-dimensional conservation equations for species and temperature in the gas and the solid walls. The influence of the width of the channels and the separating walls properties on the efficiency of the device in burning mixtures below the flammability limit is investigated. The main goal of the study is to determine the applicability of the considered asymptotic models for the effective prediction of the operation of such combustion devices. Novelty and significance statementThe study contains a demonstration of the possibility of burning ultra-lean mixtures in counterflow type combustion devices consisting of a system of parallel channels, using a two-step chain-branching kinetic model. A number of model asymptotic approximations and areas of their applicability are investigated. In particular, the present study considers finite width for the channels and the separating walls and the results are compared satisfactorily to previous papers of the same authors were the one-dimensional narrow channel approximation was used, validating in this way this approximation. The results of the study may be of importance for the design of small-scale combustion devices used for generating energy in remote conditions.

Kinetics of Flavonoid Degradation and Controlled Release from Functionalized Magnetic Nanoparticles.

Flavonoids are naturally occurring antioxidants that have been shown to protect cell membranes from oxidative stress and have a potential use in photodynamic cancer treatment. However, they degrade at physiological pH values, which is often neglected in drug release studies. Kinetic study of flavonoid oxidation can help to understand the mechanism of degradation and to correctly analyze flavonoid release data. Additionally, the incorporation of flavonoids into magnetic nanocarriers can be utilized to mitigate degradation and overcome their low solubility, while the release can be controlled using magnetic fields (MFs). An approach that combines alternating least squares (ALS) and multilinear regression to consider flavonoid autoxidation in release studies is presented. This approach can be used in general cases to account for the degradation of unstable drugs released from nanoparticles. The oxidation of quercetin, myricetin (MCE), and myricitrin (MCI) was studied in PBS buffer (pH = 7.4) using UV-vis spectrophotometry. ALS was used to determine the kinetic profiles and characteristic spectra, which were used to analyze UV-vis data of release from functionalized magnetic nanoparticles (MNPs). MNPs were selected for their unique magnetic properties, which can be exploited for both targeted drug delivery and control over the drug release. MNPs were prepared and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, superconducting quantum interference device magnetometer, and electrophoretic mobility measurements. Autoxidation of all three flavonoids follows a two-step first-order kinetic model. MCE showed the fastest degradation, while the oxidation of MCI was the slowest. The flavonoids were successfully loaded into the prepared MNPs, and the drug release was described by the first-order and Korsmeyer-Peppas models. External MFs were utilized to control the release mechanism and the cumulative mass of the flavonoids released.

Kinetics of Single-Wall Carbon Nanotube Coating Displacement by Single-Stranded DNA Depends on Nanotube Structure.

Time-resolved fluorescence spectroscopy has been used to study the displacement of adsorbed sodium dodecyl sulfate (SDS) from the surface of single-wall carbon nanotubes (SWCNTs) by short strands of single-stranded DNA. Intensity changes in near-infrared emission peaks of various SWCNT structures were analyzed following the addition of six different (GT)n oligomers (n from 3 to 20) to SDS-coated nanotube samples. There is a strong kinetic dependence on the oligomer length, with (GT)3 giving an initial rate more than 300 times greater than that of (GT)20. For shorter oligos in the (GT)n series, we observe an inverse dependence of the displacement rate on the SWCNT diameter, with SDS displaced from (6,5) more than twice as fast as from (8,7). However, this diameter dependence is reversed for oligos with more than six (GT) units. There is also a systematic dependence of the displacement rate on the nanotube chiral angle that is strongest for (GT)5, leading to a factor of ∼3 initial rate difference between (9,1) and (6,5) despite their identical diameters. To account for these findings, we propose a simple two-step kinetic model in which disruption of the original SDS coating is followed by conformational relaxation of ssDNA on the nanotube surface. The relaxation is relatively fast for ssDNA oligos shorter than 12 bp, making the first step rate-determining. Conversely, relaxation of the longer oligomers is slow enough that the second step becomes rate-determining.

(Invited) Kinetics of SWCNT Coating Displacement By ssDNA Depends on SWCNT Structure

Non-covalent hybrids formed by suspending single-wall carbon nanotubes (SWCNTs) in single-stranded DNA (ssDNA) present novel phenomena and suggest potential applications in biomedicine and nanotube sorting. Although the structures of these hybrids have been simulated using molecular dynamics calculations, much more experimental research is needed to understand their properties. In this study, selective interactions between SWCNTs and ssDNA are probed by measuring the kinetics by which ssDNA displaces SDS (sodium dodecyl sulfate) coatings on the nanotube surfaces. We used samples initially suspended in a low concentration of SDS to allow the coating displacement to occur and to suppress formation of free SDS micelles. The displacement process was monitored by time-dependent measurements of SWCNT fluorescence intensities and wavelengths. Our experiments showed very smooth decreases in fluorescence intensity and red-shifts in fluorescence wavelengths during the displacement process. Through a series of measurements, we found that ssDNA sequences with repeated guanine (G) and thymine (T) bases showed systematic patterns in the coating displacement kinetics. One result is that SDS displacement depends strongly on oligo length, with (GT)3 showing an initial rate constant 500 times greater than that of (GT)20. For shorter oligos in the (GT) n series, we observe an inverse dependence of initial rate constant on SWCNT diameter, with SDS displacement from (6,5) more than twice as fast as from (8,7). However, this diameter dependence is not present for (GT) n oligos with n greater than 6. We also find a distinct and systematic dependence of initial rate constant on nanotube chiral angle for (GT)5 and (GT)6. This effect gives a factor of ~3 difference between (9,1) and (6,5) despite their identical diameters. We empirically find these initial rate constants to vary as (SWCNT diameter)-4(cos 3θ)-y with y = -1/2 for (GT)5 and -1 for (GT)6. In addition, the full displacement kinetic traces are well fitted by double exponential kinetics, with rate constants and amplitudes dependent on SWCNT diameter. A two-step kinetic model for the displacement process will be presented to account for these findings.

Coupling effects of heating pelleting and torrefaction on black pellets production from microalga Nannochloropsis Oceanica residues

Microalga Mannochloropsis Oceanica residues (MNOR) are a potential bioenergy source that can become fossil fuel substitute. Its low density, high moisture and content of carbon and oxygen content hinder its wide application. Heating pelleting coupled with torrefaction is an effective approach to update MNOR. In this study, the effects of compression time, compression load and mold temperature were investigated in self-made heating pelleting device. The cost-effective combination for pelleting were 30 s, 1.0 MPa and 75 °C, where the pellets had high shatter resistance and relaxation density. The results of torrefaction experiments in tubular furnace showed that CO2 was main gas product released from MNOR pellet. Two kinds of acid with high-value were detected from tar by GCMS. FTIR and XPS analyses confirmed that the torrefaction enhanced the carbonation of the MNOR pellets, where the relative content of C- (C, H) increased and the relative content of C = O(–OH) decreased. The two-step first-order kinetic model was used to reveal the mechanisms of MNOR torrefaction, with activation energies ranging from 4.98 to 74.95 kJ/mol for powder and from 5.83 to 77.71 kJ/mol for pellet.

Experimental and numerical investigation on a solar-driven torrefaction reactor using woody waste (Ashe Juniper)

In this work, designs a novel solar-driven thermochemical conversion reactor to torrefy biomass waste (Ashe Juniper) for further pyrolysis applications. The effect of torrefaction temperature and residence time on the properties of biomass waste was investigated and results showed that torrefaction temperature dominates the properties of product compared to the effect of residence time. The highest energy yield (over 90%) was obtained at 210 ℃ while the highest energy densification (∼1.51) was achieved at 360 ℃. In addition, a two-step kinetic numerical model was used to analyze and predict the experimental process (kinetic rates) and results (C, H, and O contents) based on the experimental results. The analysis results showed that the predicted results are in good agreement with the practical results after torrefaction, indicating the feasibility of this numerical model for torrefaction and pyrolysis applications. The carbon footprint analysis showed that reduction effect of 1.3 ∼ 1.6 tCO2/ton-AJ can be obtained by torrefaction of Ashe Juniper. Finally, the prospects for future industrial applications of solar-driven torrefaction reactors discussed as one of affordable and clean energy.

Characteristics of reattached oblique detonation induced by a double wedge

The stationary characteristics of the oblique detonation wave (ODW) induced by the double wedge with an expansion corner are investigated using two-dimensional Navier–Stokes equations along with a two-step induction-exothermic kinetic model. The results show that the detached ODW can be reattached by expansion waves induced by the double wedge so that the standing window of ODW can be expanded. The re-standing position of ODW depends on the location and strength of the expansion waves, which are governed by the first wedge length L and the corner angle between the first and second wedge surface θC. There is a critical angle reattachment that determines whether the ODW can be reattached by expansion waves, and this critical angle increases as wedge length increases. However, the detached ODW cannot be reattached when the wedge length is increased to a critical value regardless of the wedge corner. The re-standing position moves downstream with the increment of θC until the last Mach wave tangent to the subsonic zone behind the strong overdriven ODW because no more Mach waves interact with the initiation zone. Moreover, the comparison of viscous and inviscid fields demonstrates that a shorter wedge length is necessary for the viscous field to reattach the ODW because the recirculation zone forms a gas wedge that extends the first wedge surface.

A numerical study on the influence of increased instability of quasi-detonation on the critical tube diameter phenomenon

At critical conditions, the effect of instability plays a prominent role in the gaseous detonation transmission from a tube into an unconfined space. This study aims to clarify such an effect by investigating the critical tube diameter of quasi-detonations, i.e., detonations under the influence of minor perturbations along the tube walls. The strategy is to conduct two-dimensional numerical simulations using the reactive Euler equations with a two-step induction-reaction kinetic model. The chemical kinetic parameters were adapted to model the detonation wave in the stoichiometric hydrogen-oxygen mixture at 20 kPa and 300 K. The quasi-detonations are obtained in channels with obstacles (attached to the boundaries) of different sizes to mimic wall roughness, σ, which is defined as the ratio between the obstacle size δ and half of the channel width D1/2. Below a critical value of σ, the rough wall creates only minor perturbations to the intrinsic cellular detonation. Apart from the velocity deficit, the degree of instability and cellular irregularity increases with roughness, resulting in a broader spectrum in the probability density function of the pressure and induction rate. For σ≳ 0.24, the intrinsic propagation dynamics are more significantly altered—the cellular structure vanishes locally or small cells re-appear from new re-initiation points. Detonations in these more significantly obstructed channels are not considered quasi-detonations subjected to minor boundary perturbations. The influence of small values of roughness on the critical tube diameter phenomenon is then examined. A shot-to-shot variation in cellular dynamics of quasi-detonations is considered by performing multiple simulations for each value of roughness to assess the probability of successful transmission into an unconfined space. For quasi-detonation diffraction at the sub-critical condition, despite a velocity deficit, increasingly higher instabilities resulting from a rough-walled geometry promote the re-initiation of a detonation in the open area. However, if the roughness increases beyond 0.24, both the velocity deficit and different propagation modes in a significantly obstructed channel lead to a lower probability of successful transmission.

Analysis of the performance and products in the torrefaction of sugarcane bagasse with different particle sizes

The torrefaction of sugarcane bagasse particles was evaluated using standard thermogravimetric equipment (TGA) and in a torrefaction reactor explicitly designed for this work. Different particle sizes (fine, large, and unground bagasse) were torrefied to examine any potential effect of particle type and size on the devolatilization process. The custom-designed reactor allowed measurement of the mass and temperature of the particle and the condensable volatiles captured through a condensation unit held at −12 °C during torrefaction. Final products of the process (liquids, solids, and gases) were measured and characterized to understand and analyze the processes occurring in the sugarcane biomass during torrefaction. A two-step kinetic model was fitted to experimental data on fine particles to get the kinetic parameters. A particle model was developed to understand the dynamics of biomass heating and conversion under isothermal conditions. Results of tests for large particles show an effect of particle size on the process of decomposition of the biomass. The large unground biomass showed the lowest mass loss among evaluated particles. The torrefaction process resulted in significant thermal impact for fine particles, having the highest center temperatures, devolatilization, and changes in the O-H group with FTIR tests.

The re-initiation of cellular detonations downstream of an inert layer

The current work aims to examine how the nature of cellular instabilities controls the re-initiation capability and dynamics of a gaseous detonation transmitting across a layer of inert (or non-detonable) gases. This canonical problem is tackled via computational analysis based on the two-dimensional, reactive Euler equations. Two different chemical kinetic models were used, a simplified two-step induction-reaction model and a detailed model for hydrogen-air. For the two-step model, cases with relatively high and low activation energies, representing highly and weakly unstable cellular detonations, respectively, are considered. For the weakly unstable case, two distinct types of re-initiation mechanisms were observed. (1) For thin inert layers, at the exit of the layer the detonation wave front has not fully decayed and thus the transverse waves are still relatively strong. Detonation re-initiation in the reactive gas downstream of the inert layer occurs at the gas compressed by the collision of the transverse waves, and thus is referred to as a cellular-instability-controlled re-initiation. (2) If an inert layer is sufficiently thick, the detonation wave front has fully decayed to a planar shock when it exits the inert layer, and re-initiation still occurs downstream as a result of planar shock compression only, which is thus referred to as a planar-shock-induced re-initiation. Between these two regimes there is a transition region where the wave front is not yet fully planar, and thus perturbations by the transverse waves still play a role in the re-initiation. For the highly unstable case, re-initiation only occurs via the cellular-instability-controlled mechanisms below a critical thickness of the inert layer. Additional simulations considering detailed chemical kinetics demonstrate that the critical re-initiation behaviors of an unstable stoichiometric mixture of hydrogen-air at 1 atm and 295 K are consistent with the finding from the two-step kinetic model for a highly unstable reactive mixture.

2D heterogeneous model of a polytropic methanation reactor

The paper presents a heterogeneous 2D model of a polytropic fixed bed methanation reactor for Co-SOEC syngas. The reactor with 80 mm inner diameter is operated without active cooling. Lab-scale experiments were used for model validation under variation of gas hourly space velocity (GHSV) (2000 h-1, 4000 h-1, 6000 h-1 and 8000 h-1) and pressure (1 bar, 2 bar, 4 bar, 6 bar, 8 bar, 10 bar). The conversion of Co-SOEC syngas containing a mixture of H2, CO and CO2 was calculated based on a two-step methanation kinetic model. Effective methanation kinetics was implemented based on a novel approximation of two different reaction efficiency approaches. The catalytic efficiency approximation combines conventional power law related and a Langmuir-Hinshelwood type reaction efficiency correlation by Roberts and Satterfield. It was found that mass transfer limitation is substantial for highly temperature sensitive polytropic methanation reactor modelling. Despite high exothermic behaviour without active cooling, a stable model set-up was managed entirely without parameter fitting to experimental data for a naturally cooled methanation reactor with highly reactive and undiluted syngas feed. The modelled results of Co-SOEC syngas methanation agree well with the experiments over a wide variety of pressure and GHSV. The interaction and limiting factors of mass diffusion, reaction heat removal, kinetics and thermodynamics can be thoroughly analysed based on the established model, which is a key step for developing highly efficient methanation reactor systems in industrial scale.

Reactive burn model calibration using high-throughput initiation experiments at sub-millimeter length scales

A first-of-its-kind model calibration was performed using Sandia National Laboratories’ high-throughput initiation (HTI) experiment for two types of vapor-deposited explosive films consisting of hexanitrostilbene (HNS) or pentaerythritol tetranitrate (PETN). These films exhibit prompt initiation, and they reach steady detonation at sub-millimeter length scales. Following prior work on HNS, we test the hypothesis of approximating these explosive films as fine-grained homogeneous solids with simple Arrhenius kinetics burn models. The model calibration process is described herein using a single-step as well as a two-step Arrhenius rate law, and it consists of systematic parameter sampling leading to a reduction in the model degrees of freedom. Multiple local minima are observed; results are given for seven different optimized parameter sets. Each model set is further evaluated in a two-dimensional simulation of the critical failure thickness for a sustained detonation. Overall, the two-step Arrhenius kinetics model captures the observed behavior for HNS; however, neither model produces a good fit to the PETN data. We hypothesize that the HTI results for PETN correspond to a heterogeneous response, owing to the smaller reaction zone of PETN compared to HNS (i.e., it does not homogenize the fine-grained hot spots as well). Future work should consider using the ignition and growth model for PETN, as well as other reactive burn models such as xHVRB, AWSD, PiSURF, and CREST.

Oblique detonation wave triggered by a double wedge in hypersonic flow

Pressure-gain combustion has gained attention for airbreathing ramjet engine applications owing to its better thermodynamic efficiency and fuel consumption rate. In contrast with traditional detonation induced by a single wedge, the present study considers oblique shock interactions attached to double wedges in a hypersonic combustible flow. The temperature/pressure increases sharply across the interaction zone that initiates an exothermic reaction, finally resulting in an Oblique Detonation Wave (ODW). Compared with the case for a single-wedge ODW, the double-wedge geometry has great potential to control the initiation of the ODW. As a tentative study, two-dimensional compressible Euler equations with a two-step induction-reaction kinetic model are used to solve the detonation dynamics triggered by a double wedge. The effects of the wedge angles and wedge corner locations on the initiation structures are investigated numerically. The results show an ODW complex comprising three Oblique Shock Waves (OSWs), an induction zone, a curved detonation front, and an unburned/low-temperature gas belt close to the surface of the second wedge. Both the increasing wedge angle and downstream wedge corner location lead to an abrupt OSW–ODW transition type, whereas the former corresponds to the shock–shock interaction and the later has a greater effect on the exothermic chemical process. Analysis of the shock polar and flow scale confirms that the OSW–ODW initiation structure mainly depends on the coupling of shocks and heat release in a confined initiation zone.

Predictive modeling for assessing the long-term thermal stability of a new fully-liquid quadrivalent meningococcal tetanus toxoid conjugated vaccine

Establishing product stability is critical for pharmaceuticals. We used a modeling approach to predict the thermal stability of a fully-liquid quadrivalent meningococcal (serogroups A, C, W, Y) conjugate vaccine (MenACYW-TT; MenQuadfi®) at potential transportation and storage temperatures. Vaccine degradation was determined by measuring the rate of hydrolysis through an increase of free polysaccharide (de-conjugated or unconjugated polysaccharide) content during six months storage at 25 °C, 45 °C and 56 °C. A procedure combining advanced kinetics and statistics was used to screen and compare kinetic models describing observed free polysaccharide increase as a function of time and temperature for each serogroup. Statistical analyses were used to quantify prediction accuracy. A two-step kinetic model described the increase in free polysaccharide content for serogroup A; whereas, one-step kinetic models were found suitable to describe the other serogroups. The models were used to predict free polysaccharide increases for each serogroup during long-term storage under recommended conditions (2–8 °C), and during temperature excursions to 25 °C or 40 °C. In both cases, serogroup-specific simulations accurately predict the respective observed experimental data. Experimental data collected to 48 months at 5 °C were within 99% predictive bands. The models described here can be used with confidence to establish shelf-life for this fully-liquid quadrivalent meningococcal conjugate vaccine; as well as, monitor in real-time free polysaccharide increase for vaccines experiencing temperature excursions during shipment/storage.

Near-field relaxation subsequent to the onset of oblique detonations with a two-step kinetic model

Initiation of an oblique detonation wave (ODW) results in a near-field region of curved detonation wave surface, which cannot be predicted by the detonation polar theory and lacks in-depth work on its features. In this study, Euler equations coupled with a two-step kinetic model are used to simulate ODW dynamics, and then the flow structures are analyzed by examining the asymptotic decay of local surface angle. The flow/reaction coupling is quantified by a non-dimensional Damköhler number Das that is defined as the ratio of the characteristic flow and chemical reaction length along streamlines. The results demonstrate a spectrum of local strong solutions forms, which always happens when the ODW transition pattern is abrupt, but the strong solutions deviate from the isolated strong solution predicted by the polar theory. Furthermore, the abrupt transition leads to a strong peak of Das, while the smooth one leads to a bump. Various simulated cases indicate that the transition pattern becomes abrupt and the local strong solution arises when the maximum Das reaches a critical range.

Low-fouling properties in serum of carboxylic-oligo(ethylene glycol)-based interfaces

In the present work we evaluated the low-fouling feature of a carboxylic-oligo(ethylene glycol) self-assembled monolayer (carboxylic-OEG-SAM) interface using a quartz crystal microbalance with dissipation monitoring (QCM-D). QCM-D measurements allowed us to estimate the amount of protein loading in two different serum dilutions at two different interfaces: bare gold and carboxylic-OEG. The observed amount of protein adsorbed onto bare gold is about twice higher that of carboxylic OEG interface, confirming the low-fouling characteristics of OEG-modified surfaces. Additionally, QCM-D results demonstrated the existence of two protein adsorption regimes, a faster and a slower, with distinct dissipation energies which was modelled by a two-step kinetic model. The faster regime was attributed to the adsorption of proteins into free sites of the carboxylic-OEG-SAM in a rigid binding process, followed by a slower and more viscoelastic adsorption process ascribed to structural conformational changes; this slower step conforms with the filling of remaining free sites associated with the steric hindrance in which protein-protein interactions defines the slower rate constant for the adsorption.

Numerical Study of Disturbance Resistance of Oblique Detonation Waves

The stability of oblique detonation waves (ODWs) is a fundamental problem, and resistance of ODWs against disturbances is crucial for oblique detonation engines in high-speed propulsion. In this work, numerical studies on ODW stability in disturbed flows are conducted using the two-dimensional reactive Euler equations with a two-step induction-reaction kinetic model. Two kinds of flow disturbances are, respectively, introduced into the steady flow field to assess ODW stability, including upstream transient high-pressure disturbance (UTHD) and downstream jet flow disturbance (DJFD) with different durations. Generally, an ODW is susceptible to disturbances at larger wedge angles and stable at smaller wedge angles. In the unstable wedge angle range, different ODW structures and transition patterns are obtained after disturbances, including different locations of the primary triple points, different numbers of the steady triple points on the wave surface, and different transition patterns from the leading oblique shock wave to the ODW. It is found that the primary triple point tends to move upstream for the disturbances that can form a local strong detached bow shock wave near the wedge tip. In contrast, the wave surface and the transition pattern are susceptible to all of the disturbances introduced in this study. Despite the unstable responses of the ODWs to the disturbances, the ODWs can keep standing stability after disturbances, which is beneficial to the propulsion application of ODWs.