Mechanochemical Applications of Reactive Extrusion from Organic Synthesis to Catalytic and Active Materials

In the past, the use of mechanochemical methods in organic synthesis was reported as somewhat of a curiosity. However, perceptions have changed over the last two decades, and this technology is now being appreciated as a greener and more efficient synthetic method. The qualified “offer” of ball mills that make use of different set-ups, materials, and dimensions has allowed this technology to mature. Nevertheless, the intrinsic batch nature of mechanochemical methods hinders industrial scale-ups. New studies have found, in reactive extrusion, a powerful technique with which to activate chemical reactions with mechanical forces in a continuous flow. This new environmentally friendly mechanochemical synthetic method may be able to miniaturize production plants with outstanding process intensifications by removing organic solvents and working in a flow mode. Compared to conventional processes, reactive extrusions display high simplicity, safety, and cleanliness, which can be exploited in a variety of applications. This paper presents perspective examples in the better-known areas of reactive extrusions, including oxidation reactions, polymer processing, and biomass conversion. This work should stimulate further developments, as it highlights the versatility of reactive extrusion and the huge potential of solid-phase flow chemistry.

Kinetic Energy Dose as a Unified Metric for Comparing Ball Mills in the Mechanocatalytic Depolymerization of Lignocellulose

Mechanochemistry utilizes mechanical forces to activate chemical bonds. It offers environmentally benign routes for both (bio) organic and inorganic syntheses. However, direct comparison of mechanochemistry results is often very challenging. In mechanochemical synthetic protocols, ball mill setup (mechanical design and grinding vessel geometry) in addition to experimental parameters (milling frequency, duration, ball count and size) vary broadly. This fact poses a severe issue to further progress in this exciting research area because ball mill setup and experimental parameters govern how much kinetic energy is transferred to a chemical reaction. In this work, we address the challenge of comparing mechanochemical reaction results by taking the energy dose provided by ball mills as a unified metric into account. In this quest, we applied kinematic modeling to two ball mills functioning under distinct working principles to express the energy dose as a mathematical function of the experimental parameters. By examining the effect of energy dose on the extent of the mechanocatalytic depolymerization (MCD) of lignocellulosic biomass (beechwood), we found linear correlations between yield of water-soluble products (WSP) and energy dose for both ball mills. Interestingly, when a substrate layer is formed on the grinding jar wall and/or grinding medium, a weak non-linear correlation between water-soluble products yield and energy dose is identified. We demonstrate that the chemical reaction’s best utilization of kinetic energy is achieved in the linear regime, which presents improved WSP yields for given energy doses. In the broader context, the current analysis outlines the usefulness of the energy dose as a unified metric in mechanochemistry to further the understanding of reaction results obtained from different ball mills operating under varied experimental conditions.

A guide to direct mechanocatalysis

Direct mechanocatalysis (DM) describes catalytic reactions in mechanochemical reactors such as ball mills with the distinctive feature that the milling equipment itself is the catalyst.

Influence of Powder Milling and Annealing Parameters on the Formation of Cubic Li7La3Zr2O12 Compound

Li-ion batteries are widely used as energy storage devices due to their excellent electrochemical performance. The cubic Li7La3Zr2O12 (c-LLZO) compound is regarded as a promising candidate as a solid-state electrolyte for lithium-ion batteries due to its high bulk Li-ion conductivity, excellent thermal performance, and chemical stability. The standard manufacturing procedure involves the high-temperature and lengthy annealing of powders. However, the formation of the tetragonal modification of LLZO and other undesired side phases results in the deterioration of electrochemical properties. The mechanical milling of precursor powders can enhance the powders’ reactivity and can result in an easier formation of c-LLZO. The aim of this work was to study the influence of selected milling and annealing parameters on c-LLZO compound formation. The starting powders of La(OH)3, Li2CO3, and ZrO2 were subjected to milling in various ball mills, under different milling conditions. The powders were then annealed at various temperatures for different lengths of times. These studies showed that the phase transformation processes of the powders were not very sensitive to the milling parameters. On the other hand, the final phase composition and microstructure strongly depended on heat treatment conditions. Low temperature annealing (750 °C) for 3 h produced 90% of c-LLZO in the powder structure.

A Review of the Milestones Reached by the Attainable Region Optimisation Technique in Particle Size Reduction

The attainable region (AR) is an optimization method adopted for use in comminution to achieve different objective functions, which all converge to optimising the production of the desired particle size distributions for downstream processes. The technique has so far mostly been used to optimise the breakage of particles in tumbling mills. It achieved the desired purpose by unveiling all possible outcomes derived from a combination of operational parameters that are bound by trajectories showing the limitations of a system. The technique has given the scientific community lenses to see the behaviour of different parameters in ball mills otherwise known as the black boxes due to their concealing nature. Since its inception, the AR technique has been applied to data obtained from the laboratory tests and simulated industrial mills and the results sometimes contradict or confirm the conventional milling practices in the industry. This makes the already conservative mining industry sceptical about its adoption. This review thus assesses the milestone covered as far as the AR development in comminution is concerned. It also helps to clarify the sources of the discrepancies between the AR results and the conventional knowledge concerning the optimisation of ball mill operational parameters.

Morphology and wear of high chromium and austempered ductile iron balls as grinding media in ball mills

High chromium balls are recognized as better grinding media in terms of wear rates than forged steel balls, which are conventional grinding media in the milling process of iron ore. In this research work, the wear rate of high chromium balls and austempered ductile iron (ADI) balls as crushing media in a ball mill are compared. ADI are prepared by austenitizing the spheroidal graphite (SG) iron balls at 920 °C for one hour, and step austempering heat treatments were given, which includes the first step austenitizing at 300 °C for 15 min, followed by a second step austenitizing at 400 °C for 60 min. The wear rates were estimated when both balls were used separately by maintaining the same machining conditions and when the balls are mixed. The grinding wear conduct of both materials is evaluated for wear loss in wet grinding conditions. The experimental results reveal that the performance of ADI balls is better than high chromium balls when tested separately and mixed. Results also indicate that the wear rates/revolutions will decrease when the operating period increases.

Increase of activation efficiency of hardening backfilling mixture components by application mining and metallurgical wastes

The main operation associated with the preparation of mining and metallurgical wastes for use as a hardening mixture and backfilling of mined-out space is their crushing and activation. Improving the activation processes is an urgent task, since their use can significantly increase the strength of the filling mass or reduce the consumption of the binder while maintaining its strength characteristics. For the efficient operation of mining enterprises, including ferrous metallurgy mines, it is necessary to provide highquality binders for the preparation of hardening mixtures for filling man-made voids formed during underground mining of solid mineral deposits. It has been established that the use of vibration, mechanical and electrical activation of the components of the hardening backfill mixture at mining enterprises leads to an increase in the activity of substandard materials by up to 10–40% for each apparatus. In particular, the enrichment of inert materials on a vibrating screen ГВ-1,2/3,2, Ukraine, increases the activity by 15– 20%. It has been substantiated that the activation of binders (blast-furnace granular slags) in a vertical vibrating mill МВВ-0,7, Ukraine, and a disintegrator ДУ-65 company “Disintegrator”, Estonia, increases the activity of the binder by 20–25%, when the active class of fractions 0.074 mm – by 55% is released versus 40% in ball mills. The recommended vibratory conveying installations increase the activity of the components of the hardening backfill mixture by 10–15%. The use of vibro-gravity transport installations ensures the supply of the filling mixture at a distance 15–20 times higher than the height of the vertical stack.