Mobility in granular materials upon cyclic loading

We investigate the ability to move of large objects—referred to as intruders—embedded in a granular material and subjected to cyclic loadings. A discrete element method is used to simulate the dynamics response of intruders subjected to a vertical uplift cyclic force, exploring a wide range of loading magnitudes and frequencies. The analysis of the intruder and grains displacements over many cycles reveals three mobility regimes. In the first two regimes, called confined and failure the intruder either do not significantly move or consistently moves upward after each cycles. We introduce a physically based model considering an inertial drag force to rationalise the existence of these regimes depending on the loading frequency and magnitude. We further evidence a third intermediate regime of creep, where intruder trajectories exhibit long periods of confinement punctuated by shorter periods of sustained uplift motion. Finally, we observe unexpected failures at low loading magnitudes and specific frequencies, which we attribute to a process of elasto-inertial resonance. These results highlight the important differences in the mobility of intruders upon constant and cyclic loadings.     

Resolving force indeterminacy in contact dynamics using compatibility conditions

Contact dynamics (CD) is a powerful method to solve the dynamics of large systems of colliding rigid bodies. CD can be computationally more efficient than classical penalty-based discrete element methods (DEM) for simulating contact between stiff materials such as rock, glass, or engineering metals. However, by idealizing bodies as perfectly rigid, contact forces computed by CD can be non-unique due to indeterminacy in the contact network, which is a common occurence in dense granular flows. We propose a frictionless CD method that is designed to identify only the unique set of contact forces that would be predicted by a soft particle method, such as DEM, in the limit of large stiffness. The method involves applying an elastic compatibility condition to the contact forces, which maintains no-penetration constraints but filters out force distributions that could not have arisen from stiff elastic contacts. The method can be used as a post-processing step that could be integrated into existing CD codes with minimal effort. We demonstrate its efficacy in a variety of indeterminate problems, including some involving multiple materials, non-spherical shapes, and nonlinear contact constitutive laws.     

K–La–MgO as heterogeneous catalyst for synthesis of 3-(2-hydroxyethyl)-1,3-oxazolidin-2-one from diethanol amine and carbon dioxide

Cost-effective valorization of carbon dioxide into bulk and specialty chemicals using catalysis will be attractive in the foreseeable future. 1,3-Oxazolidin-2-one derivatives are one of the important classes of heterocyclic compounds which have wide applications in pharmaceutical industries due to their biological activities such as antibacterial, antimicrobial, antiseptic. Various synthetic routes are employed to prepare these compounds which include phosgenation, oxidative carbonylation, etc., which make use of polluting chemicals and homogeneous catalysts. The heterogeneous catalytic processes to synthesize these derivatives are quite limited. Thus, developing a green route which is environmental friendly is highly desirable. The current work deals with development of a heterogeneous reusable catalyst and its application to synthesize 1,3-oxazolidin-2-one derivatives using carbon dioxide as a C1 source. The fact that no use of promoter or organic co-catalyst is made in the current process makes the synthesis route more favorable. Pure La–MgO and K–La–MgO with different K loading (1, 3, 5, and 7 wt%) synthesized by combustion route were screened for carbonylation of diethanol amine. 5% K–La–MgO was found to be the best catalyst. The catalyst was well characterized in virgin form and after use by various analytical techniques like TEM, SEM, XRD, CO₂ and NH₃-TPD, BET surface area analysis. With 5% K–La/MgO, 72% conversion of diethanol amine was achieved with 100% selectivity of the desired product at optimum conditions, i.e., 150 °C, 5 wt% K–La/MgO catalyst loading of 0.02 g/cm³ and 2.0 MPa CO₂ pressure. Reaction mechanism was proposed and kinetic model developed. The apparent activation energy was calculated as 18.76 kcal/mol. The catalyst was robust and recyclable. The process is clean and green.     

Delignification kinetics of empty fruit bunch (EFB): a sustainable and green pretreatment approach using malic acid-based solvents

Recently, the development of efficient and environmentally benign solvents has received great attention to replace current harsh organic solvents. In this context, low-transition-temperature mixtures (LTTMs) have emerged as favorable green solvents for biomass delignification. Palm oil biomass, empty fruit bunch (EFB) was pretreated with commercial l-malic acid and microwave hydrothermally extracted cactus malic acid-derived LTTMs at 60, 80, and 100 °C. The LTTMs applied in this study were derived from malic acid–choline chloride–water and malic acid–monosodium glutamate–water with a molar ratio of 2:4:2 and 3:1:5, respectively. Three first-order reactions were used to express the delignification kinetic model of EFB. The first term was based on the initial stage and assigned as infinite due to the fast rate of delignification which could not be detected. The second and third terms were proportional to bulk and residual delignification stages. A good agreement was obtained between the kinetic model and the experimental data obtained in this study with R²?≥?0.91. The activation energies for the delignification reactions using l-malic acid and cactus malic acid-based LTTMs in the bulk and residual stages were approximated as 36–56 and 19–26 kJ/mol and 34–90 and 47–87 kJ/mol, respectively.     

Valorisation of mango seed via extraction of starch: preliminary techno-economic analysis

Reducing environmental impacts and obtaining economic benefits based on utilisation of waste materials are drivers for the implementation of cleaner production policies and technologies in food processing industries. Starch is a very versatile material with a wide range of applications in the food, pharmaceutical, textile, paper, cosmetic and construction industries. In Ethiopia, starch is widely used in the textile industry. To meet the starch demand, the country imports approximately 45% of the starch used in the country. Consequently, it is imperative to find additional sources of starch that could substitute for the amount of starch that is currently being imported. Mango seeds, a waste material that is disposed of after consumption of mangos, were studied for potential use as an alternative resource for starch production. The results showed that starch extraction from mango seeds was facile and a good quality product was obtained. The present study is concerned with a techno-economic analysis for industrial production of starch from mango seeds. The study shows that extraction of starch from waste mango seeds is feasible: the project is financially viable with an accounting rate of return of 83% and a break-even analysis of 78% with a payback period of 2 years.     

Graphene quantum dots derived from hollow carbon nano-onions

Herein, carbon nano-onions (CNOs) with different structures have been investigated as precursors for the synthesis of graphene quantum dots (GQDs). It was found that hollow CNOs yield GQDs with a uniform size distribution, whereas metal encapsulation in the CNO structure is disadvantageous for the same. Furthermore, the hollow CNOs are also advantageous for the synthesis of GQDs with a yellow-green hybrid luminescence and long-ranged excitation wavelength (λ _ex)-independent photoluminescent (PL) behavior, in which the λ _ex upper limit was 480 nm. These features enable safe sensing and cell tracking applications with a longer excitation wavelength in the visible light region. The potential applications of the synthesized GQDs as fluorescent sensing probes for detecting Cu(II) ions and non-toxic cell imaging under visible light excitation have been demonstrated. This means that sensing and bioimaging can be accomplished in the natural environment with no need for UV excitation. This work provides a reference to researchers in tailoring CNO structures in terms of their inner space to synthesize GQDs with the desired luminescence behavior.

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Facile growth of homogeneous Ni(OH)<Subscript>2</Subscript> coating on carbon nanosheets for high-performance asymmetric supercapacitor applications

The growth of a Ni(OH)₂ coating on conductive carbon substrates is an efficient way to address issues related to their poor conductivity in electrochemical capacitor applications. However, the direct growth of nickel hydroxide coatings on a carbon substrate is challenging, because the surfaces of these systems are not compatible and a preoxidation treatment of the conductive carbon substrate is usually required. Herein, we present a facile preoxidation-free approach to fabricate a uniform Ni(OH)₂ coating on carbon nanosheets (CNs) by an ion-exchange reaction to achieve the in situ transformation of a MgO/C composite to a Ni(OH)₂/C one. The obtained Ni(OH)₂/CNs hybrids possess nanosheet morphology, a large surface area (278 m²/g), and homogeneous elemental distributions. When employed as supercapacitors in a three-electrode configuration, the Ni(OH)₂/CNs hybrid achieves a large capacitance of 2,218 F/g at a current density of 1.0 A/g. Moreover, asymmetric supercapacitors fabricated with the Ni(OH)₂/CNs hybrid exhibit superior supercapacitive performances, with a large capacity of 198 F/g, and high energy density of 56.7 Wh/kg at a power density of 4.0 kW/kg. They show excellent cycling stability with 93% capacity retention after 10,000 cycles, making the Ni(OH)₂/CNs hybrid a promising candidate for practical applications in supercapacitor devices.

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