Reactive Mixture Research Articles

Roboticized AI-assisted microfluidic photocatalytic synthesis and screening up to 10,000 reactions per day

The current throughput of conventional organic chemical synthesis is usually a few experiments for each operator per day. We develop a robotic system for ultra-high-throughput chemical synthesis, online characterization, and large-scale condition screening of photocatalytic reactions, based on the liquid-core waveguide, microfluidic liquid-handling, and artificial intelligence techniques. The system is capable of performing automated reactant mixture preparation, changing, introduction, ultra-fast photocatalytic reactions in seconds, online spectroscopic detection of the reaction product, and screening of different reaction conditions. We apply the system in large-scale screening of 12,000 reaction conditions of a photocatalytic [2 + 2] cycloaddition reaction including multiple continuous and discrete variables, reaching an ultra-high throughput up to 10,000 reaction conditions per day. Based on the data, AI-assisted cross-substrate/photocatalyst prediction is conducted.

Effect of Cu incorporation on Fe-based catalysts for selective CO2 hydrogenation to olefins

The process of converting CO2 into sustainable chemical feedstock and fuels through reaction with renewable hydrogen has been regarded as a promising direction in energy research. The enhancement of CO2 hydrogenation efficiency to produce valuable hydrocarbons (specifically olefins) on Fe catalysts through Cu modification has been extensively researched. However, there is ongoing vigorous debate regarding the impact of these modifications on catalytic properties and the underlying mechanism. When compared to unprompted iron-based catalysts for CO2 hydrogenation, the choice of desired products, such as C2-C4 and C5+, is relatively low. So, promoters are frequently employed to customize and enhance product distribution. This study investigates how adding Cu to Fe-based supported catalysts affects their performance in converting CO2 to hydrocarbons, with a specific emphasis on the interaction between Fe and Cu. To achieve this goal, catalysts were created using co-precipitation methods, varying the distribution of Fe and Cu within them. A set of composite catalysts underwent testing in a fixed bed setup using a reactant gas mixture at 350 °C and 30 bar pressure. Analysis techniques such as XRD, SEM, TEM, NH3-TPD, H2-TPR, and N2 adsorption-desorption isotherms revealed the presence of iron-copper interaction within the composite catalysts. This interaction between the two components synergistically enhances the catalytic activity in CO2 hydrogenation.

Explosion risks: Variety of deflagration-to-detonation transition scenarios in smooth tubes

In the framework of comprehensive assessment of explosion risks on board of spacecrafts and on the facilities of launch places, the paper is focused on the detailed analysis of particular scenarios of deflagration-to-detonation transition taking place in smooth tubes filled with acetylene-oxygen mixtures of different compositions. By means of precise numerical simulation it is demonstrated that various scenarios of detonation onset can take place depending on the mixture composition and its initial thermodynamic state. It is demonstrated that independent on the particular scenario always the basic mechanism of detonation onset via the formation of strong enough shock wave takes place. In more reactive mixtures the strong shock originates from the self-sustained process of joint pressure build up and reaction intensification exactly at the flame front. In less reactive mixtures the transient flow behavior leads to the shock waves generation and interaction. As a result, a brand new reaction kernel could arise in the area of shock waves interaction. In number of cases, that leads to the coupling between the shock wave and the newborn reaction front and results in the strong shock formation and further detonation onset.

ASSESSMENT OF AGGREGATE MIXTURE REACTIVITY IN CONCRETE AT 60°C

Research on the durability of structural concrete requires careful selection of aggregates, particularly considering their reactivity to alkali-silica reaction (ASR). The Miniature Concrete Prism Test (MCPT) allows for shortened testing time and eliminates the need for aggregate crushing, making it a practical alternative to other methods. The aim of the research is to evaluate the reactivity of aggregate mixtures with varying mineral compositions. Research results confirm the significant impact of fine aggregates on concrete expansion in the MCPT method in NaOH solution at 60°C. The observed expansion correlates with a reduction in concrete’s elastic modulus.

Purification of a reactive dyes mixture solution by means of pre-hydrolysed coagulants in the standard tests and coagulating flow system

Reactive dyes, widely used in textiles, often leach into sewage due to incomplete bonding with fibers. Coagulation offers an effective solution, yet standard lab tests for coagulation efficiency lack realism and are significantly labour and time-consuming. To address this, a novel approach is proposed: optimizing coagulation through a prototype lab flow. This system automates solution flow, reagent dosing, coagulation, and sludge separation via sedimentation and filtration. Tests reveal effective coagulation of various reactive dyes with pre-polymerized Al coagulants, but limited efficacy with Fe(III) coagulant. The flow system demonstrates mostly better purification results than jar tests, achieving around 95% colour removal with Al coagulants. This study highlights the efficacy of coagulation and filtration in jar tests, offering a simplified yet efficient method for assessing coagulation performance.

Influence of the reactive gas mixture on the superconducting properties of nitrogen-doped aluminum thin films

We present a correlation between disorder and superconducting properties in nitrogen-doped aluminum thin films, ranging from a few nitrogen impurities to the insulating limit due to AlN formation. Samples were deposited via reactive sputtering on (100) silicon substrates with native oxide at room temperature. Our findings show that adding nitrogen increases the superconducting critical temperature (Tc) compared to pure metal films. By varying the nitrogen/argon ratio up to 6 %, we observed a dome-like Tc behavior: 2 K at low concentrations, peaking at 3.3 K at intermediate concentrations, and then dropping as the samples become insulating (≈ 4.4 %). Increasing nitrogen raises resistivity and shifts the material from metallic to semiconductor-like behavior. Disorder impacts the upper critical field, starting at 0.2 T for low nitrogen content and reaching up to 3.2 T for nitrogen-rich samples with Tc = 2.2 K. Current-voltage curves reveal typical vortex dissipation, as expected for type II superconductors.

Investigation into the Fuel Characteristics of Biodiesel Synthesized through the Transesterification of Palm Oil Using a TiO2/CH3ONa Nanocatalyst

Biodiesel is a renewable and sustainable alternative fuel to petrol-derived diesel. Decreasing the operating costs by improving the catalyst’s characteristics is an effective way to increase the competitiveness of biodiesel in the fuel market. An aqueous solution of sodium methoxide (CH3ONa), which is a traditional alkaline catalyst, was immersed in nanometer-sized particles of titanium dioxide (TiO2) powder to prepare the strong alkaline catalyst TiO2/CH3ONa. The immersion method was used to enhance the transesterification reaction. The mixture of TiO2 and CH3ONa was calcined in a high-temperature furnace in a range between 150 and 450 °C continuously for 4 h. The heterogeneous alkaline catalyst TiO2/CH3ONa was then used to catalyze the strong alkaline transesterification reaction of palm oil with methanol. The highest content of fatty acid methyl esters (FAMEs), which amounted to 95.9%, was produced when the molar ratio of methanol to palm oil was equal to 6, and 3 wt.% TiO2/CH3ONa was used, based on the weight of the palm oil. The FAMEs produced from the above conditions were also found to have the lowest kinematic viscosity of 4.17 mm2/s, an acid value of 0.32 mg KOH/g oil, and a water content of 0.031 wt.%, as well as the highest heating value of 40.02 MJ/kg and cetane index of 50.05. The lower catalyst amount of 1 wt.%, in contrast, resulted in the lowest cetane index of 49.31. The highest distillation temperature of 355 °C was found when 3 wt.% of the catalyst was added to the reactant mixture with a methanol/palm oil molar ratio of 6. The prepared catalyst is considered effective for improving the fuel characteristics of biodiesel.

Synthesis of near‐spherical BN powders by templated carbothermal reduction and nitridation

AbstractBoron nitride (BN) powders with near‐spherical particles of more than 10 µm were synthesized by templated carbothermal reduction and nitridation. The effects of processing factors, such as raw material mixing methods, C/B2O3 molar ratios, and carbon templates, were systematically studied, and the reaction mechanism was discussed. The experimental results showed that the integrity and morphology of the carbon templates was usually destroyed during ball milling or grinding, but preserved during magnetic stirring. The morphology of synthesized BN particles depended on the C/B2O3 molar ratio in starting reactant mixtures and gradually changed from sheet‐like to near‐spherical shape with decreasing C/B2O3 molar ratio. The morphology and size of synthesized BN particles agreed with that of the carbon templates, which means that the morphology and size of synthesized BN particles can be tailored by controlling that of the carbon template. The BN near‐spherical particles synthesized in this work may be used as thermally conductive fillers for electronic packaging.

Analysis of the behavior of a gas-generating system under runaway conditions in a closed vessel

In the event of a runaway reaction, emergency relief systems (ERS) act as the last line of defense against the vessel explosion. To date, ERS design for scenarios involving the runaway of chemical mixtures that generate gaseous reaction products remains very challenging as it requires the prediction of the gas generation rate under runaway conditions at large scale. Current methodologies for the assessment of the gas generation rate are based on pseudo-adiabatic calorimetric experiments at laboratory scale in which the temperature and pressure profiles resulting from the runaway are used to assess the gas generation rate using the ideal gas law. The gas generation rate needs to be further corrected for the thermal inertia (φ-factor), of the calorimetric cell used (φ>1) to predict large scale behavior (φ≈1). The work described in this paper focuses on evaluating the capability of this approach to accurately assess the gas generation rate. It uses a dynamic simulator tool based on rigorous thermodynamics to calculate the temperature, pressure, and the composition of each component in a closed vessel containing a gas generating reactive mixture (decomposition of 20 % w/w di-tert butyl peroxide in toluene) under runaway conditions over a range of initial vessel fill levels. The results were analyzed to develop a better understanding of the phenomena that govern the thermal behavior of the mixture, the overall pressurization of the vessel, rate of generation of the gaseous products and its distribution in the liquid and vapor phase of the vessel as the runaway reaction occurs. The simulated pressure, temperature and phase composition data rigorously calculated by the simulator were used to assess and highlight the limitations of using the temperature and pressure in a closed vessel and the ideal gas law to evaluate the gas generation rate. The simulations were also used to evaluate the validity of φ-factor correction methods currently available in the literature.

A Comparative Study of the Hydrogen Auto-Ignition Process in Oxygen–Nitrogen and Oxygen–Water Vapor Oxidizer: Numerical Investigations in Mixture Fraction Space and 3D Forced Homogeneous Isotropic Turbulent Flow Field

In this paper, we analyze the auto-ignition process of hydrogen in a hot oxidizer stream composed of oxygen–nitrogen and oxygen–water vapor with nitrogen/water vapor mass fractions in a range of 0.1–0.9. The temperature of the oxidizer varies from 1100 K to 1500 K and the temperature of hydrogen is assumed to be 300 K. The research is performed in 1D mixture fraction space and in a forced homogeneous isotropic turbulent (HIT) flow field. In the latter case, the Large Eddy Simulation (LES) method combined with the Eulerian Stochastic Field (ESF) combustion model is applied. The results obtained in mixture fraction space aim to determine the most reactive mixture fraction, maximum flame temperature, and dependence on the scalar dissipation rate. Among others, we found that the ignition in H2-O2-H2O mixtures occurs later than in H2-O2-N2 mixtures, especially at low oxidizer temperatures. On the other hand, for a high oxidizer temperature, the ignitability of H2-O2-H2O mixtures is extended, i.e., the ignition occurs for a larger content of H2O and takes place faster. The 3D LES-ESF results show that the ignition time is virtually independent of initial conditions, e.g., randomness of an initial flow field and turbulence intensity. The latter parameter, however, strongly affects the flame evolution. It is shown that the presence of water vapor decreases ignitability and makes flames more prone to extinction.

Influence of Solid Alkaline Photocatalysts Irradiated with UV Light on Fuel Properties of Palm Oil Biodiesel.

TiO2 nanoparticles are full of porosity that can be impregnated with a strong alkaline catalyst CH3ONa to form a TiO2/CH3ONa catalyst. TiO2 of the anatase phase, which is a semiconductor material, has been a prominent photocatalyst due to its excited photocatalyst activity, chemical and biological stability, and nontoxicity. The CH3ONa compound has been widely used as a catalyst for transesterification. Although the synthesized photocatalyst TiO2 powder with CH3ONa is anticipated to greatly enhance the transesterification efficiency, leading to improving biodiesel properties, relevant studies have not been found. After the photocatalyst was prepared, a reactant mixture of palm oil, methanol, and heterogeneous catalyst TiO2/CH3ONa was illuminated by ultraviolet (UV) light from light-emitting diode (LED) lamps. The experimental results revealed that the formation of fatty acid methyl esters was significantly increased to 98.4% with ultraviolet-light illumination for the molar ratio of methanol/palm oil equal to 6 and 3 wt % catalyst addition. The decrease of the catalyst amount to 2 wt % resulted in a slight decrease of the fatty acid methyl esters to 97.06 wt %. The lowest kinematic viscosity and acid value and the highest distillation temperature, heating value, and cetane index were observed under the above reaction conditions. The distillation temperature and cetane index were increased while the acid value was decreased under ultraviolet illumination on the reactant mixture. Consequently, the optimum preparing conditions for biodiesel production were 6 and 3 wt % for the molar ratio of methanol/palm oil and catalyst addition under UV-light irradiation.

Experimental study on the propagation mechanism of acetylene-air detonation waves in a unilaterally intermittently constrained channel

This study experimentally explores the propagation mechanisms of acetylene/air detonation waves within a channel intermittently constrained on one side, utilizing soot foil and high-speed schlieren photography to capture the cellular structure and shock-flame evolution. The experiments revealed that the detonation waves traverse the semi-enclosed channel with various discrete wall configurations on the side in three distinct propagation modes: (I) periodic detonation failure and re-initiation; (II) single extinction and re-initiation; (III) non-extinction. Mode I occurs exclusively when the open area ratio exceeds 0.85, while detonation tends to favour Mode II when the gaps between discrete walls exceed three times the cell size; otherwise, it tends towards Modes III. The re-initiation mechanism of detonation involves curvature shocks inducing local explosions of reactive mixtures through multiple Mach reflections off the discrete walls. The self-sustained propagation mechanism of the detonation wave is maintained by the interaction of strong transverse shocks reflected from discrete walls with the inherent transverse waves within the detonation structure, sustaining the instability of the cellular detonation.

Influence of fuel inhomogeneity on detonation wave propagation in a rotating detonation combustor

Rotating detonation combustor (RDC) is a form of pressure gain combustion, which is thermodynamically more efficient than the traditional constant-pressure combustors. In most RDCs, the fuel–air mixture is not perfectly premixed and results in inhomogeneous mixing within the domain. Due to discrete fuel injection locations, local pockets of rich and lean mixtures are formed in the refill region. The objective of the present work is to gain an understanding of the effects of reactant mixture inhomogeneity on detonation wave structure, wave velocity, and pressure profile. To study the effect of mixture inhomogeneity, probability density functions of fuel mass fractions are generated with varying standard deviations. These distributions of fuel mass fractions are incorporated in 2D reacting simulations as a spatially/temporally varying inlet boundary condition. Using this methodology, the effect of mixture inhomogeneity is independently investigated to determine the effects on detonation wave propagation and RDC performance. As mixture inhomogeneity is increased, detonation wave speed, detonation efficiency, and potential for pressure gain all decrease, ultimately leading to the separation of the reaction zone from the shock wave.

Understanding the thermodynamic effects of chemically reactive working fluids in the Stirling heat pump

Within the realm of sustainable heating technologies, this study examines the performance of a Stirling heat pump employing chemically reactive working fluids in contrast to conventional inert counterparts. Reactive working fluids are energy vectors that enable the conversion of not only thermal but also chemical energy within the heat pump. The investigation spans a wide range of theoretical reactive gaseous mixtures, leveraging the ideal gas mixture thermodynamic model. Each fluid is characterized by an equilibrated chemical reaction, denoted as A2(g)⇄2A(g), and distinguished by a set of reaction coordinates: the standard entropy change of reaction and standard enthalpy change of reaction. The chemical reaction evolution and thermodynamic properties are observed in each transformation, and the overall coefficient of performance (COP) of the system is evaluated and benchmarked against that of comparable inert working fluids. It is observed that the exothermic reaction during isothermal compression significantly increases the thermal energy supplied to the heat sink, as well as the thermal energy density per unit maximum volume, by up to 269 %, compared to an inert gas system. However, for the majority of reactive fluids studied, chemical reactions introduce irreversibility in the internal regenerator due to heat transfer across a finite temperature difference, contrary to the case of inert working fluids, penalizing the COP. Consequently, a reduction of up to 28 % in the COP is observed. Nevertheless, there exists a range of reactive fluids, characterized by reversible heat exchange in the internal regenerator, offering increased thermal energy transfer to the heat sink without compromising the COP.

Double flame dynamics in hotspot ignition

Hotspot ignition is a key problem in fundamental flame initiation, combustion control and prevention of abnormal combustion phenomena. Depending on the characteristics of the hotspot and the thermochemical condition of the reactive mixture, subsequent reaction front initiated from a hotspot can vary substantially. The current paper focus on the dynamics and chemistry for one of the most complicated scenarios - hotspot induced double flames, which include a cool and a hot flame segment. This work adopts a recently developed compressible reacting flow simulation code COGNAC to investigate the initiation and propagation of double flame dynamics from hotspot ignition in a one-dimensional spherical coordinate. The results have shown that under atmospheric pressure, double flame initiation is not feasible for sufficiently small hotspot. Under elevated pressures, double flame can be initiated within a much wider hotspot window, exhibiting complex flame dynamics, such as variations in cool and hot flame bifurcation behaviors and their initiation locations. Analysis on thermochemical structure and dynamics of double flame has shown that the interaction of cool and hot flames in a double flame structure is inherently intermutual, in that the leading cool flame enhances trailing hot flame speed through reform of the unburnt mixture, while the trailing hot flame initiation affects the leading cool flame via thermal expansion effects.

Atomic cluster expansion potential for large scale simulations of hydrocarbons under shock compression.

We present an Atomic Cluster Expansion (ACE) machine learned potential developed for high-fidelity atomistic simulations of hydrocarbons, targeting pressures and temperatures near and above supercritical fluid regimes for molecular fluids. A diverse set of stoichiometries were covered in training, including 1:0 (pure carbon), 1:4 (methane), and 1:1 (benzene), and rich bonding environments sampled at supercritical temperatures, hydrogen rich, reactive mixtures where metastable stoichiometries arise, including 1:2 (ethylene) and 1:3 (ethane). A high-fidelity training database was constructed by performing large-scale quantum molecular dynamic simulations [density functional theory (DFT) MD] of diamond, graphite, methane, and benzene. A novel approach to selecting structures from DFT MD is also presented, which allows for the rapid selection of unique DFT MD frames from complex trajectories. Comparisons to DFT and experimental data demonstrate that the presented ACE potential accurately reproduces isotherms, carbon melting curves, radial distribution functions, and shock Hugoniots for carbon and hydrocarbon systems for pressures up to 100GPa and temperatures up to 6000K for hydrocarbon systems and up to 9000K for pure carbon systems. This work delivers a potential that can be used for accurate, large-scale simulations of shocked hydrocarbons and demonstrates a methodology for fitting and validating machine learning interatomic potentials to complex molecular environments, which can be applied to energetic materials in future works.

Oxidation of Ethylene Glycol into Valuable Chemical Using BiVO4 Photoanode

Introduction Plastic photoreforming using photocatalysts is a solar-powered technology that facilitates the generation of hydrogen (H2) from water while simultaneously breaking down plastic waste into valuable organic products. While the focus in the past few decades has predominantly centered on enhancing the H2 production efficiency, recent attention has shifted towards selective plastic oxidation reactions (U. Nwosu, et al. Renew. Sust. Energ. Rev. , 2021, 148, 111266). However, the investigation of effective cocatalysts for selective oxidation of plastic compounds has not been well studied.The photoelectrochemical (PEC) system offers a promising approach by segregating the anodic and cathodic processes, thereby enabling a more concentrated focus on the oxidation reaction in the design of reactions. In this study, we evaluate the BiVO4 photoanode modified with various cocatalysts, for example, cobalt phosphate (Co-Pi) for the oxidation of ethylene glycol (EG), a crucial component in the formation of polyethylene terephthalate (PET). Additionally, we introduce acetonitrile (MeCN) into the reactant mixture to suppress the oxygen evolution reaction (OER), which otherwise competes with the ethylene glycol oxidation reaction (EGOR), creating a more conducive reaction environment for enhanced efficiency. Materials and Methods The BiVO4 photoanode on fluorine doped tin oxide (FTO) glass was fabricated as previously reported (V. Andrei, et al. Adv. Energy Mater , 2018, 8, 1801403). Briefly,BiOI precursor was electrochemically deposited on the FTO glass and then drop-casted a vanadyl acetylacetonate [VO(acac)2] solution onto the surface and heated at 723 K for 60 min. The deposition of the Co-Pi cocatalyst onto BiVO4 was achieved by photoassisted electrodeposition method. The obtained photoanodes were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). PEC measurements were carried out using a three-electrode configuration under simulated solar irradiation (100 mW cm− 2, AM 1.5G). The experiments were performed in various solutions containing 1 M EG: 0.5 M Na2SO4 in H2O, 0.1 M NaClO4 in MeCN, and the mixed solution of MeCN and H2O. Product analysis was performed using proton nuclear magnetic resonance (1H NMR). Results and discussion According to the XRD and SEM results, the formation of nanoporous BiVO4 film on FTO glass was confirmed. To assess the PEC performance for EGOR using BiVO4 electrode, we carried out the experiments under conditions with and without the EG substrate (Figure (a)). With the addition of EG, a notable shift of the onset potential from 0.6 VRHE to 0.5 VRHE was observed. In addition, the photocurrent density at 1.2 VRHE increased from 0.67 mA/cm2 to 0.92 mA/cm2. This result indicates that EGOR is more favorable on the BiVO4 surface compared to OER. The Co-Pi cocatalyst deposition on the BiVO4 notably increased the current under both conditions, with and without the EG substrate. Although Co-Pi is commonly recognized for its catalytic role in OER, our experiment surprisingly revealed its positive impact on EG performance as well. The Co-Pi/BiVO4 photoanode exhibited a negative shift of the onset potential to 0.3 VRHE and an enhancement of photocurrent density to 2.04 mA/cm2 at 1.2 VRHE for EGOR compared to bare BiVO4. Additionally, the Co-Pi/BiVO4 photoanode showed 16.9% and 2.7% faradaic efficiencies (FE) for formate and glyoxal production, respectively, while bare BiVO4 exhibited 10.6% FE for formate and no glyoxal production.Under aqueous conditions, the FE for EGOR is currently low due to the competition between OER and EGOR. To overcome this challenge and enhance the EGOR efficiency, we introduced MeCN into the aqueous solution because MeCN has higher (more positive) anodic oxidation potential than the aqueous medium (L. M. Reid, et al. Sustainable Energy Fuels , 2018, 2, 1905-1927). In the MeCN-water mixed solution (MeCN:water = 9:1), OER was effectively suppressed to 0.33 mA/cm2, while EGOR was significantly enhanced to 2.50 mA/cm2 at 1.2 VRHE potential (Figure (b)). This MeCN-water mixed solvent created a more favorable environment for EGOR on bare BiVO4, resulting in a notable increase in FE for formate to 19.8% and FE for glyoxal to 13.2%, which represents a 1.87 and 4.89 times improvement, respectively, compared to the pure aqueous condition. Conclusions The deposition of Co-Pi cocatalyst on the BiVO4 film improved the photocurrent density and FE for formate production. Moreover, the introduction of MeCN in the solvent created a more favolable reaction condition for EGOR, suppressing OER and increasing the EGOR activity. Figure 1

Kraft lignin-based polyurethanes: Bulk properties, stability and adhesion to native aluminum surfaces

Lignin as a byproduct from pulp and paper manufacturing has been extensively investigated as raw material for polymer developments. Although, fundamental topics related to the adhesion mechanisms of lignin-based reactive polyurethanes (LPU) still remain unclear. In this work, LPU thin films on native aluminum surface were prepared and characterized. Diluted in THF, employed as the solvent, reactive mixtures of 4,4′-methylene diphenyl isocyanate (4,4′-MDI) and the soluble fraction of three lignins (liquid hydroxypropylated Kraft lignin and two powder Kraft lignins with different pH) were used for LPU thin film deposition via spin coating on aluminum (PVD layer on silicon wafer). The resulting film thickness ranged from 8 nm to several micrometers. The chemical state of the three LPU compositions was assessed in bulk by infrared attenuated total reflectance (IR-ATR) and in the thin films by infrared external reflection absorption spectroscopy (IR-ERAS). Binding energies of 4,4′-methylene diphenyl diisocyanate with aliphatic and aromatic hydroxyl groups were estimated using Density Functional Theory (DFT) simulations. Thus, besides the elucidation of the bulk chemical state of LPUs, the relation to adhesion and stability of LPUs to a native aluminum surface was evaluated. In addition, film topography and homogeneity were monitored by SFM. All lignin types form uniform and homogeneous films. Results revealed a higher consumption of isocyanate groups (NCO) in the formulation with the alkaline Kraft lignin than with the acid one, despite its lower hydroxyl content. A gradient of unreacted NCO was observed in LPU thin films obtained with the powder Kraft lignin types. Residual NCO is also found in thicker films, while the thinnest films did not contain unreacted NCO anymore, indicating the activating effect of the native aluminum surface on LPU formation.

Effects of alkali-silica reaction on the fracture energy of mass concrete: Experimental investigations using the wedge splitting test

This work aims to study the effects of alkali-silica reaction (ASR) on the fracture energy of reactive mass concrete mixtures (maximum aggregate sizes of 38 mm and 76 mm), characteristic of an existing hydro-electric facility. More than 40 large concrete blocks were casted and stored in a controlled environmental chamber for more than 1100 days. The blocks as well as cylindrical reference cores were monitored in expansion. Wedge splitting (WS) tests with different notch to depth ratios, were performed at different ASR advancements to assess the evolution of mechanical and fracture parameters of concrete. Digital Image Correlation (DIC) technique was used to monitor the tests. Damage Rate Index (DRI) technique was also performed on cores extracted from the blocks, following the completion of the splitting tests. Important size and heterogeneity effects were observed on the assessed ASR expansion and fracture energy. By filtering these effects, it was possible to assess for the first time in literature the evolution of size-independent fracture energy with respect to intrinsic volumetric expansion of concrete. The findings suggest that fracture energy increases for moderate levels of expansion, due to crack branching within the splitting crack, interacting with pre-existing ASR-induced cracks. This phenomenon was not observed for the case of a few horizontally cast blocks where the splitting crack ran parallel to pre-existing ASR cracks, indicating an anisotropy in ASR damage effects on the fracture energy of concrete.

Controllability of Pre-Chamber Induced Homogeneous Charge Compression Ignition and Performance Comparison with Pre-Chamber Spark Ignition and Homogeneous Charge Compression Ignition

This paper presents an experimental and numerical evaluation of the pre-chamber induced HCCI combustion concept (PC-HCCI) in terms of engine performance, emissions, and controllability. In this concept, a spark-initiated combustion in the pre-chamber is utilized to trigger the kinetically controlled combustion of an ultra-lean mixture in the main combustion chamber. The experimental measurements were performed on a single-cylinder engine with a custom-made active pre-chamber. A high compression ratio of 17.5 was used, which limits the maximum achievable engine load due to high knocking tendency but enables both standard PCSI combustion (flame propagation) at very high dilution levels and HCCI combustion at reasonable intake temperatures. The analysis of combustion characteristics and the resulting performance is performed at indicated mean effective pressures (IMEPs) of 3.5 and 3.0 bars, and three different intake temperatures of 80 °C, 90 °C, and 100 °C. The variation in engine load was achieved by adjusting the excess air ratio in the main chamber. On each combination of intake temperature and engine load, a spark sweep and an injected PC fuel mass sweep were performed to obtain the highest indicated efficiency while satisfying the restrictions in terms of combustion stability and knock intensity. It was shown that, unlike in a conventional HCCI engine, the combustion phasing can be directly and reliably controlled by adjusting either spark timing or the reactivity of the pre-chamber mixture, ensuring adequate combustion stability and eliminating potential misfires. A similar indicated efficiency as with conventional HCCI combustion was obtained, while the NOx emissions, although slightly elevated, are still insignificant. Compared to PCSI combustion at the same engine load, a 4-percentage-point increase in indicated efficiency and two times lower NOx emissions were achieved. Compared to the most efficient PCSI operating point, it was 1 percentage point lower, indicating that efficiency was achieved, but the specific NOx emissions are reduced by approximately 70%. Most importantly, very similar performance was obtained with significant variations in intake temperature, proving the reliability and adaptability of this combustion concept.