Mechanochemical Activation Research Articles

Versatile Mechanochemical Reactions via Tailored Force Transmission in Mechanophores

In polymer mechanochemistry, regulating the intrinsic mechanical reactivity of a mechanophore offers extensive opportunities in material science, enabling the development of hierarchical and multifunctional polymer‐based materials. Recent advances have focused on innovating various types of mechanophores with inherent reactivity (e.g. regioselectivity and stereoselectivity). However, little attention has been given to modulating their reactivity by tailoring force transmission within mechanophores. Here, we introduce a novel approach through the implementation of a cyclic pulling geometry into an anthracene‐maleimide (AM) mechanophore. This approach manipulates force transmission within the mechanophore and effectively regulates its reactivity from 0.0160 min‐1 to 0.00133 min‐1, achieving up to a 12‐fold change. Mechanochemical coupling analysis suggests that the split force transmission within the ring may suppress the sequential bond rupture mechanism in AM mechanophores under applied forces. By leveraging the distinct force transmission pathways within cyclic and linear AM mechanophores, we covalently integrate them with a spiropyran mechanophore to design tandem mechanophore systems for hierarchical mechanochemical activation. These findings highlight the efficacy and versatility of the cyclic pulling strategy in modulating mechanophore reactivity, providing valuable insights for the design of tunable multifunctional polymer‐based materials.

Versatile Mechanochemical Reactions via Tailored Force Transmission in Mechanophores

In polymer mechanochemistry, regulating the intrinsic mechanical reactivity of a mechanophore offers extensive opportunities in material science, enabling the development of hierarchical and multifunctional polymer‐based materials. Recent advances have focused on innovating various types of mechanophores with inherent reactivity (e.g. regioselectivity and stereoselectivity). However, little attention has been given to modulating their reactivity by tailoring force transmission within mechanophores. Here, we introduce a novel approach through the implementation of a cyclic pulling geometry into an anthracene‐maleimide (AM) mechanophore. This approach manipulates force transmission within the mechanophore and effectively regulates its reactivity from 0.0160 min‐1 to 0.00133 min‐1, achieving up to a 12‐fold change. Mechanochemical coupling analysis suggests that the split force transmission within the ring may suppress the sequential bond rupture mechanism in AM mechanophores under applied forces. By leveraging the distinct force transmission pathways within cyclic and linear AM mechanophores, we covalently integrate them with a spiropyran mechanophore to design tandem mechanophore systems for hierarchical mechanochemical activation. These findings highlight the efficacy and versatility of the cyclic pulling strategy in modulating mechanophore reactivity, providing valuable insights for the design of tunable multifunctional polymer‐based materials.

Synthesis of core-functionalised naphthalene diimides from naphthalenetetracarboxylic dianhydride using a vibratory ball mill: bromination, imidization and Heck-type reactions.

The synthesis of 9 core-functionalised naphthalene diimide (c-NDI) residues is reported via a 3-step solvent free synthesis from naphthalenetetracarboxylic dianhydride using only mechanochemical activation. Selective dibromination and subsequent dimidiation were achieved for the first time in a vibratory ball mill, resulting in the key structural intermediate, 2,6-dibromonaphthalenediimide (DBND), which is the basis for elaboration into a multitude of organic electronic materials. Our new synthesis of DBND is achieved in just 5 hours' reaction time over two steps compared to typical solution state times of 24 hours. Subsequent Heck-type cross coupling reactions, with a range of styrene residues, produced a series of c-NDIs in good yields. The Heck-type reactions are rapid (1.5 hours), require no additional heating or solvent and are tolerant of atmospheric moisture and air.

Modifiers for the preparation of starch composites under mechanochemical activation: An extended set of criteria

Modification of starch with synthetic polymers under mechanochemical activation is a convenient way to regulate the operational properties of composite materials. The widespread use of this approach is limited by the lack of data on the influence of synthetic polymer nature on the properties of starch and the absence of clear criteria for modifiers selection in the form of aqueous dispersions. To eliminate existing problems, the work proposes to use five integral criteria − polarity, hydrophilicity, and flexibility of synthetic modifiers, as well as particle size and ζ-potential of their aqueous dispersions. To achieve this goal, we studied the dielectric constant, contact angles, IR spectra, and dynamic mechanical properties of four acrylic copolymers and an aliphatic polyurethane. Using the mechanochemical activation, blends and composite films based on corn starch and synthetic modifiers (80:20) were manufactured. Methods of rotational viscometry, X-ray diffraction analysis, DMA, mechanical tests, and moisture permeability allowed us to reveal the influence of the modifier integral parameters on the rheological characteristics of the molding blends and the impact of joint mechanical activation on them, as well as on the crystal structure of the composites, their storage modulus, strength, and transport characteristics.

Efficient carburization of high-entropy alloys from polyethylene microplastics using a green mechanochemical process to obtain excellent wave absorbing performance

Polyethylene as a major white pollutant has a significant negative impact on the environment and the human health. Beneficial recycling of polyethylene through mechanochemical processes not only can eliminate environmental hazards, but also enable some beneficial industrial applications. In this work, polyethylene was used as the raw materials of carburization of FeCoNiMn high-entropy alloys (HEAs) by a green mechanochemical method. The phase structure, magnetic properties, high-temperature oxidation resistance, corrosion resistance and electromagnetic-wave absorbing performance of the obtained carburized HEAs were investigated in detail. The carburized-FeCoNiMn HEAs exhibited excellent corrosion resistance, suggesting great application potential for use in harsh environments. Besides, the impedance matching was optimized and the electromagnetic-wave absorption bandwidth was expanded by this carburization process. Specifically, the reflection loss of C10 (FeCoNiMnC0.1) at 8.88 GHz reached −65.07 dB at a thickness of 2.79 mm, and both the C50 (FeCoNiMnC0.5) and C90 (FeCoNiMnC0.9) exhibited a maximum absorption bandwidth of 5.45 GHz. This work provides a new concept of utilizing common microplastic pollutants to achieve efficient carburization of HEAs by a green mechanochemical process.

Mechanisms of Thermal Decomposition in Spent NCM Lithium-Ion Battery Cathode Materials with Carbon Defects and Oxygen Vacancies.

Resource recovery from retired electric vehicle lithium-ion batteries (LIBs) is a key to sustainable supply of technology-critical metals. However, the mainstream pyrometallurgical recycling approach requires high temperature and high energy consumption. Our study proposes a novel mechanochemical processing combined with hydrogen (H2) reduction strategy to accelerate the breakdown of ternary nickel cobalt manganese oxide (NCM) cathode materials at a significantly lower temperature (450 °C). Particle refinement, material amorphization, and internal energy storage are considered critical success factors for the accelerated decomposition of NCM cathode materials. In our proposed approach, NCM cathode materials can develop active sites with carbon defects (Cv) and oxygen vacancies (Ov), which improve the reduction and breakdown of H2. The adsorbed H2 on the surface of NCM decomposes into H* and combines with oxygen to form OH species, which can be facilitated by Ov via the enhanced charge transfer. The introduced Cv can enhance H2 cracking and generate *C-H species to promote the thermal decomposition of NCM. The presence of defects proves to foster the preferential reduction of Mn(IV) by H2, leading to a lower activation energy for the NCM decomposition (from 139 to 110 kJ/mol) with less H2 consumption. Life cycle assessment suggests a reduction of 4.42 kg CO2 eq for the recycling of every 1.0 kg of retired batteries. This study can promote material circularity and minimize the environmental burden of mining technology-critical metals for a low-carbon transition.

Study on selective green leaching of rare earth elements from coal gangue using mechanochemical activation

This study proposes a sustainable method for the selective leaching of rare earth elements (REEs) from coal gangue. By combining 600 °C calcination, the addition of 5 % Fe2(SO4)3, and one hour of mechanical-chemical activation, we achieved a leaching efficiency of 65 % for REEs. This method alters the surface and crystalline structure of coal gangue, facilitating the release of rare earth phosphate minerals and the formation of water-soluble compounds (rare earth sulfates). Fe2(SO4)3 transforms into insoluble iron oxide, which immobilizes impurities and promotes the selective leaching of rare earth elements. Notably, during the leaching process, the leaching rates of aluminum (Al) and iron (Fe) were only 0.37 % and 1.27 %, respectively. Kinetic analysis indicates that this process follows a mixed reaction-controlled shrinking core model. This method effectively reduces the environmental risks associated with traditional acidic reagents, providing a sustainable pathway for the recovery of rare earth elements.

Kinetic Study of Oxidation of Ag-Sn-Zn Solid Solution Powders via Hot Mechanochemical Processing.

Ag-based electrical contact materials are essential in low-voltage devices such as relays, switches, circuit breakers, and contactors. Historically, Ag-CdO composites have been preferred due to their superior electrical and thermal conductivities, resistance to arcing, and mechanical strength. However, the toxicity of Cd has led to increased restrictions on its use. With the aim of contributing to the development of a new environment-friendly, Ag-Zn2SnO4-based electrical contact material, the kinetics of the hot mechanochemical oxidation of a Ag-Sn-Zn solid solution obtained by mechanical alloying were investigated. The results indicated that the proposed synthesis route produces Ag-based composites with a homogeneous distribution of nanoscale Zn2SnO4 precipitates, which is unattainable through conventional material processing methods. This kinetic study established that the mechanochemical oxidation of the Ag-Sn-Zn solid solution follows the Johnson-Mehl-Avrami-Kolmogorov model. An analysis of the microstructure and the relationship between the activation energy "Ea" and the Avrami exponent "n" from experimental data fitting suggests that the primary mechanism for the oxidation of the Ag-Sn-Zn solid solution during the hot mechanochemical process is related to the three-dimensional oxide growth being limited by oxygen diffusion after its immediate initial nucleation.

Solvent assisted mechanochemical synthesis, antimicrobial and antioxidant studies of Ni2+, Mn2+, Cr<sup>2+</sup> , and Cu<sup>2+</sup> Metal complexes of some ligands derived from l-histidine and l-alanine

Mechanochemistry enables rapid, quantitative reactions to occur at or close to 27℃. It is a one-step process that allows for reactant homogenization, product nucleation, and particle growth. These processes use little or no solvent, making them less wasteful and more environmentally friendly than solvent-based reactions. Ni2+ , Mn2+, Cr2+and Cu2+ metal ions were synthesized by grinding in an agate mortar with pestle using ligands derived from amino acids (Histidine &Alanine) which were further synthesized to form complexes. The entire experiment was carried out by solvent solvent-assisted mechanochemical process and ethanol was used as liquid liquid-assisted solvent. The complexes were characterized by IR spectroscopy, U-V spectroscopy, X-ray analysis, melting point, solubility test, and conductivity measurement. The Solubility test showed that the complexes are soluble in DMSO, DMF, and ethanol and are insoluble in both hexane and tetrachloromethane. The molar conductivity values are in the range of (6.05-28.56) Ω-1cm2mol-1 ) indicating the complexes behave as non-electrolytes. IR analysis showed a vibrational frequency band observed at (1620-1625) cm-1 which is assigned to the ʋ(C=N) of the azomethine, also the new bands M=N, M=O indicate the coordination reaction between the metal and the ligands. The UV visible analysis shows various transitions, the metal complexes showed adsorption bands at λ of 420 and 575nm respectively because of the ligand-to-metal charge transfer (LMCT). The XRD analysis showed that there was a change in phase between the starting material and the product which indicate that a reaction occurred, also the nature of the spectra showed that the compounds are all crystalline. The Antimicrobial activity showed that both the complexes and the ligands have good activity against the bacterial isolates. Antioxidant activity was also tested and the compound appeared to have moderate scavenging activities compared to the reference used. The values indicated that the activities are more pronounced when coordinated with metal ions.

Calorimetric study of the pozzolanic potential developed by the mechanochemical activation of kaolin clay

Calorimetric study of the pozzolanic potential developed by the mechanochemical activation of kaolin clay

Polymer Mechanochemistry in Confined Spaces.

With the development of mechanophores, polymer mechanochemistry has emerged as a powerful tool for creating force-responsive materials with a variety of desired functions, ranging from color change to molecular release. However, it remains challenging to improve the efficiency of mechanochemical activation, especially for mechanophores embedded within polymer networks, which has profound implications for translating mechanochemical responses into materials-centered applications. The physical and chemical conditions under spatial confinement differ significantly from those in the surrounding bulk environment, offering opportunities to facilitate mechanochemical activation. In this Minireview, we discuss and summarize recent progress in polymer mechanochemistry within confined spaces including surfaces/interfaces, polymer assemblies, and other nanostructures, specifically focusing on the effects of spatial confinement on the enhancement of mechanophore activation. We envision that combining confinement effects with advances in molecular and materials engineering will further improve the activation efficiency, capitalizing more fully on the potential of mechanophores toward practical applications.

Mechanochemical processing of landfilled coal fly ash for enhanced CO₂ sequestration and heavy metal immobilization in sustainable hydraulic cements

ABSTRACT This study developed an energy-efficient, sustainable, and economical method for capturing carbon dioxide using landfilled coal fly ash. The innovative approach processes captured carbon dioxide with supplementary additives and alkali activators to produce a new class of hydraulic cement. A total of eight cement formulations incorporating varying proportions of landfilled coal fly ash, calcium-containing industrial byproducts, and alkali activators were produced and experimentally tested. The study achieved significant CO₂ uptakes, reaching up to 8.35% by weight of the raw materials. Up to 99.98% immobilization efficiency of heavy metal (copper) was recorded along with a significant increase in the total dissolved solids and conductivity. FTIR spectroscopy confirmed CO₂ incorporation with notable peaks at 1400 cm− 1 and 1063 cm− 1, indicating carbonate species. SEM and EDS analyses revealed varied morphologies, with dense, interconnected particle networks in some of the cement formulations. Compressive strength tests showed all formulations exceeded the EPA’s minimum requirement of 0.34 MPa, with the highest strength reaching 38 MPa at 28 days. The findings of this study point to the viability of the production of mechanochemically processed hydraulic cements in CO₂ environment with effective carbon sequestration capability, marked heavy metals immobilization characteristics, and enhanced physical and mechanical attributes.

Particle aggregation and the grinding limit in high energy ball mill

Dust aggregates — clusters of individual particles — are formed during mechanochemical processing of brown coal in a planetary ball mill. The aggregate structure can be identified by comparing the average sizes of aggregates and individual particles. We showed that dust aggregates are generally arranged in a regular way: the number of individual particles located along the aggregate coincides with the number of particles located across the aggregate. Power of power-law distribution of the monomers per aggregate revealed that individual particles stick together in extremely dense clusters. The average number of monomers per claster is ~104. In addition, it turned out that the dependence of the monomer's “stickiness” on applied energy dose has a kink simultaneously with other characteristics of the mechanochemical process (the monomer size and the chemical reaction depth). Speaking using mechanochemistry terms, it corresponds to transition from the brittle grinding mode to the plastic deformation mode after reaching the grinding limit.

Mechanism of tetracycline sorption on carbon-bentonite

Antibiotics increased industrial production is the reason of their occurrence in wastewater, soils, groundwater, and drinking water. In this regard, treating the environment for pharmaceuticals is one of the urgent environmental challenges. Synthesis of adsorbents using different types of raw materials by the methods of mechanochemical activation makes it possible to significantly increase their sorption capacity due to the accumulation of various kinds of defects in the crystal structure of the adsorbent. We obtained the bentonite-carbon composite using roller-ring vibratory mill with coal-bentonite ratio of 30 : 70 and 50 : 50. However, the nature of the interaction between carbon and bentonite correlates with changes of surface area and porosity. The porous structure parameters of the samples show the mechanochemical activation of the mixture involves their components interactions. The authors studied the structural and chemical changes during the modification of bentonite with activated carbon by analysing the vibrational spectra of carbon, initial, and modified aluminosilicate samples. According to infrared spectroscopy of adsorbents, absorption bands characteristic of Si-O-C bond vibrations occurred. The paper investigates the sorption capacity of mechanochemically modified natural clay mineral Dash-Salakhli bentonite towards tetracycline hydrochloride. Research investigates the kinetics of the process and rapid sorption of tetracycline. The paper provides possible mechanisms of chemisorption due to donor-acceptor interaction and ion-exchange processes.

Aspects of Spodumene Lithium Extraction Techniques

Lithium (Li), a leading cathode material in rechargeable Li-ion batteries, is vital to modern energy storage technology, establishing it as one of the most impactful and strategical elements. Given the surge in the electric car market, it is crucial to improve lithium recovery from its rich mineral deposits using the most effective extraction technique. In recent years, both industry and academia have shown significant interest in Li recovery from various Li-bearing minerals. Of these, only extraction from spodumene has established a reliable industrial production of Li salts. The current approaches for cracking of the naturally occurring, stable α-spodumene structure into a more open structure—β-spodumene—involve the so-called decrepitation process that takes place at extreme temperatures of ~1100 °C. This conversion is necessary, as β-spodumene is more susceptible to chemical attacks facilitating Li extraction. In the last several decades, many techniques have been demonstrated and patented to process hard-rock mineral spodumene. The objective of this review is to present a thorough analysis of significant findings and the enhancement of process flowsheets over time that can be useful for both research endeavors and industrial process improvements. The review focuses on the following techniques: acid methods, alkali methods, carbonate roasting/autoclaving methods, sulfuric acid roasting/autoclaving methods, chlorinating methods, and mechanochemical activation. Recently, microwaves (MWs), as an energy source, have been employed to transform α-spodumene into β-spodumene. Considering its energy-efficient and short-duration aspects, the review discusses the interaction mechanism of MWs with solids, MW-assisted decrepitation, and Li extraction efficiencies. Finally, the merits and/or disadvantages, challenges, and prospects of the processes are summarized.

Mechanochemical Thioglycolate Modification of Microscale Zero‐Valent Iron for Superior Heavy Metal Removal

Microscale zero‐valent iron (mZVI) is widely used for water pollutant control and environmental remediation, yet its reactivity is still constrained by the inert oxide shell. Herein, we demonstrate that mechanochemical thioglycolate (TG) modification can dramatically enhance heavy metal (NiII, CrVI, CdII, PbII, HgII, and SbIII) removal rates of mZVI by times of 16.7 to 88.0. Compared with conventional impregnation (wet chemical process), this dry mechanochemical process could construct more robust covalent bonding between TG and the inert oxide shell of mZVI through its electron‐withdrawing carboxylate group to accelerate the electron release from the iron core, and more effectively strengthen the surface heavy metal adsorption through metal(d)‐sulfur(p) orbital hybridization between its thiol group and heavy metal ions. Impressively, this mechanochemically TG‐modified mZVI exhibited an unprecedented NiII removal capacity of 580.4 mg Ni g−1 Fe, 17.1 and 9.5 times those of mZVI and wet chemically TG‐modified mZVI, respectively. Its application potential was further validated by more than 10 days of stable groundwater NiII removal in a column flow reactor. This study offers a promising strategy to enhance the reactivity of mZVI, and also emphasizes the importance of the modification strategy in optimizing its performance for environmental applications.

Swelling and Degrafting of Poly(3-sulfopropyl methacrylate) Brushes.

Upon exposure to a good solvent, polymer brushes prepared via surface-initiated polymerization can undergo degrafting via cleavage of bonds that anchor the polymer tethers to the underlying substrate. As polymer brushes are often used in a solvent swollen state, this has implications for the longevity of these polymer coatings. Improving the fundamental understanding of this process is thus also of practical importance. It is believed that degrafting is the consequence of tension amplification at the bonds that anchor the polymer grafts, which is driven by swelling of the polymer brush film. Taking advantage of the sensitivity of the swelling behavior of poly(3-sulfopropyl methacrylate) (PSPMA) brushes toward changes in ionic strength, this study has investigated the degrafting behavior of these brushes in aqueous media at different LiCl and NaCl concentrations. The aim of these experiments was to investigate whether the rate constant of the degrafting process was correlated with the swelling ratio of the PSPMA brushes. The experiments show that in aqueous LiCl solutions, the initial rate constant of the degrafting process is correlated with the swelling ratio of the PSPMA brush. This observation represents a first example of the correlation between these two parameters for hydrophilic polymer brushes in aqueous media and supports the idea that degrafting is a mechanochemical process driven by a swelling-induced tension at the polymer-substrate interface.

Mechanochemical Thioglycolate Modification of Microscale Zero-Valent Iron for Superior Heavy Metal Removal.

Microscale zero-valent iron (mZVI) is widely used for water pollutant control and environmental remediation, yet its reactivity is still constrained by the inert oxide shell. Herein, we demonstrate that mechanochemical thioglycolate (TG) modification can dramatically enhance heavy metal (NiII, CrVI, CdII, PbII, HgII, and SbIII) removal rates of mZVI by times of 16.7 to 88.0. Compared with conventional impregnation (wet chemical process), this dry mechanochemical process could construct more robust covalent bonding between TG and the inert oxide shell of mZVI through its electron-withdrawing carboxylate group to accelerate the electron release from the iron core, and more effectively strengthen the surface heavy metal adsorption through metal(d)-sulfur(p) orbital hybridization between its thiol group and heavy metal ions. Impressively, this mechanochemically TG-modified mZVI exhibited an unprecedented NiII removal capacity of 580.4 mg Ni g-1 Fe, 17.1 and 9.5 times those of mZVI and wet chemically TG-modified mZVI, respectively. Its application potential was further validated by more than 10 days of stable groundwater NiII removal in a column flow reactor. This study offers a promising strategy to enhance the reactivity of mZVI, and also emphasizes the importance of the modification strategy in optimizing its performance for environmental applications.

INFLUENCE OF MECHANICAL ACTIVATION ON THE PROPERTIES OF CEMENT-WATER COMPOSITIONS WITH THE ADDITION OF GROUND LIMESTONE

The paper considers the issue related to determining the effect of mechanical activation of a mineral binder on the properties of both hardening and hardened cement-water compositions. The mechanical activation of cement in combination with the consumption of ground limestone, the amount of which was adjusted in the range from 0 to 40 % of the cement mass, is relevant for this study. The effect of mechanical chemical activation of Portland cement only and Portland cement with the addition of 20 and 40 % ground limestone on changing the water-solid ratio of equiviscous compositions was studied. It was shown that mechanical and chemical activation of a cement-water composition has a positive effect on reducing the W/S ratio of equiviscous compositions from 0.42 (no activation) to 0.38 (activation period 180 sec). The obtained experimental results indicate the presence of an induction period of heating of the cement paste both on Portland cement not subject to mechanical activation (this period is approximately 6 hours from the moment of interaction of cement with water) and on Portland cement subject to mechanical activation. In this case, the induction period was no more than 2 hours. Joint mechanical activation of an aqueous mixture of Portland cement and ground limestone ensures acceleration of the hydration processes of the binder, which is confirmed by the intensification of the exothermic heating of the filled cement-mixing compositions. The positive role of mechanical activation is also reflected in the acceleration of the thickening rate of the compositions, which was recorded by the kinetics of the decrease in the diameter of their spread over time. The positive role of mechanical activation in reducing the effective viscosity of cement-containing compositions is confirmed, which ensures a decrease in their water-solid ratio by an average of ‒ 8 ... 10 %. A positive effect of mechanochemical activation of Portland cement with the addition of ground limestone on the strength of cement stone at the age of 3 days has been revealed. Experimental studies indicate that only due to mechanical activation the strength of samples made of cement stone with the addition of ground limestone can be increased by almost 25...30 %.

Agrotechnology based on the bioorganic preparation HUMIN PLUS

The article is dedicated to the development and implementation of innovative agricultural technology in agriculture field. We give definitions of humic preparations of lake sapropel, we give brief theoretical aspects of the action mechanism of humic preparations on plants. We describe methods for obtaining humic-containing products at a high level - the technology of mechanochemical activation. We present the results of the practical application of nano and biophysical agricultural technologies on the example of seed and plant processing, crops in Kazakhstan.