Milling Treatment Research Articles

In-situ synthesis of Mn2SiO4 and MnxSi dual phases through solid-state reaction to improve the initial Coulombic efficiency of SiO anode for Lithium-Ion batteries

Silicon monoxide(SiO)-based anode materials have been extensively examined as high energy density for lithium-ion batteries, but still suffer from low initial Coulombic efficiency(ICE). Here, A novel SiO-MnO/Mn2SiO4-MnxSi anode material, prepared through scalable ball milling and heat treatment, is proposed for the first time, in which Mn2SiO4 and MnxSi alloy through solid-state reaction are embedded in the silicon oxide matrix to improve ICE. Half-cell testing shows that the ICE of pristine SiO increased from 52.5 % to 70.5 %, thanks to the solid-state reaction between SiO and MnO during the heat treatment, in which MnO consumed the SiO2 generated during the disproportionation of SiO, thereby reducing the first irreversible loss of Li+ during the lithiation process. In addition, the MnxSi alloy phase can improve lithium-ion diffusion ability to a certain extent. This report provides a new approach to alleviate the ICE performance of SiO-based anode materials.

Solvent-free ball milling activation of cellulose for efficient surface modification and pyrolysis

Due to the innate recalcitrancy caused by robust hydrogen bonding interaction, cellulose cannot be easily processed into high-valued materials or chemicals. Herein, a solvent-free ball milling treatment was conducted to activate microcrystalline cellulose (MCC). The research results demonstrated that ball milling treatment rapidly reduced the average particle size (Ð) and crystalline index (CrI) of MCC. Ball milling treatment for 1 h resulted in the Ð and CrI of MCC decreasing from 48 μm and 84.5 % to 23.3 μm and 25.4 %, respectively. Further prolonging the ball milling time from 1 h to 4 h slightly reduced the Ð and CrI of cellulose but led to the degradation of cellulose. Furthermore, the ball milling-activated cellulose (BMC) was chemically modified for preparing polylactic acid (PLA)/modified cellulose (m-BMC) composite films. Benefitting from the decreased Ð and valid surface modification of BMC, the tensile strength and elongation at break of the achieved PLA/m-BMC improved by 77.2 % and 189.3 % compared with the PLA/MCC, respectively. Besides, ball milling for 1 h improved the relative contents of saccharides in the pyrolysis products of cellulose from 33.2 % to 60.4 %. This work provided some basic understanding of ball milling activation of cellulose for further efficient surface modification and pyrolysis.

Using a seed impact mill to limit waterhemp (Amaranthus tuberculatus) seed inputs in Iowa soybean

Abstract Mounting cases of herbicide-resistant waterhemp [Amaranthus tuberculatus (Moq.) Sauer] in the U.S. Midwest have renewed the interest in nonchemical weed management strategies. Field experiments were conducted in 2021 and 2022 to quantify the effectiveness of a commercial combine equipped with a seed impact mill in preventing A. tuberculatus seed return to the soil seedbank in soybean [Glycine max (L.) Merr.]. Amaranthus tuberculatus seed shattering before crop harvest was quantified. Amaranthus tuberculatus started shattering seeds during the last week of August in both years. Overall, 51% of A. tuberculatus seeds were retained on the plant at harvest on October 23, 2021, compared with 61% at harvest on October 7, 2022. Viability of shattered A. tuberculatus seeds ranged from 84% to 94%. Additional seed shattering occurred when plants were disturbed by the combine header during soybean harvest, which caused 15% and 9% shattering in 2021 and 2022, respectively. Amaranthus tuberculatus seeds passed through the impact mill were grouped in three categories: no damage, moderate damage, and severe damage. In 2021, A. tuberculatus seeds with moderate damage had 26% lower germination and viability than seeds with no visible damage. In 2022, seed germination and viability of no-damage seeds did not differ from seeds with a moderate level of damage. No severely damaged seed germinated or tested viable in either year. Altogether, impact mill treatment reduced the number of germinable seeds by 87% compared with the no–impact mill treatment. These results indicate that seed impact mills can be a useful tool in Iowa soybean production to help manage multiple herbicide–resistant A. tuberculatus populations. However, A. tuberculatus seed shattering before crop harvest reduces the overall effectiveness of seed impact mills in preventing seedbank replenishments.

Enhancing quality and strength of recycled coarse and fine aggregates through high-temperature and ball milling treatments: mechanisms and cost-effective solutions

Enhancing quality and strength of recycled coarse and fine aggregates through high-temperature and ball milling treatments: mechanisms and cost-effective solutions

Two-ways regulation of the emulsion gel properties of curdlan by dry ball milling treatment and their relationships with the microstructures, emulsification characteristics and gel properties of ball milled curdlan

Ball milling treatment could affect the microstructures, improve the emulsification properties of curdlan (CL) and regulate the emulsion gel properties of CL based emulsion gel in two-ways. With increasing ball milling time (1 h–8 h), the particle size first decreased and then increased, the relative crystallinity decreased, and the contact angle increased. Ball milled curdlan (BMCL)-6 h showed the best emulsifying property and stability, which was the combined effects of decreased particle size and increased hydrophobic property. Ball milling 1 h and 2 h significantly improved the hardness and chewiness of CL-based emulsion gels, while, ball milling 4 h–8 h could make the emulsion gels much softer and ice cream-like. When the emulsion gels were heated twice consecutively, the visual appearance and texture properties did not change significantly, indicating the excellent thermal stability of these emulsion gels. The BMCL based emulsion gel with adjustable gel properties and good thermal stability has a wide range of uses in the food system.

Study on the formation and digestibility of starch-phenolic acid complexes under ball milling treatment

In this paper, complexes of corn starch (CS) with p-coumaric acid (p-CA) and caffeic acid (CA) were prepared using ball milling for various durations. The complexes' multiscale structure, digestibility, and intermolecular interaction were explored. The ball milling treatment disrupts the orderliness of the starch double helix. Increased milling time exposes more active sites, resulting in the formation of surface-coarse complexes. The physicochemical properties and structures of the complexes varied significantly depending on the functional group and milling duration. p-CA and CA interacted with CS through non-covalent bonding to form non-inclusion complexes. Hydrogen bonding is the main driving force, and -OH and -COOH are the active sites. Phenolic acid intercalated between starch chains while wrapping the residual granules, improving the short-range ordering, thermal stability, and peak viscosity of ball-milled starch. Regarding digestibility, both phenolic acids inhibited CS digestion. However, the complexes prepared with CA, having more hydroxyl groups and longer milling times, were more effective. This study provides a basis for developing low-digestibility foods.

Preparation and slow-release properties of nanocellulose composite hydrogels

Nanocellulose (CNF) was obtained from carrots using a combination of chemical treatment, mechanical milling, and ultrasonic treatment. Ultrafast preparation of maleic anhydride esterified nanocellulose was achieved by a hydrated hydrogen ion-driven dissociation, chemical cross-linking strategy based on a “one-pot” reaction method. Esterification modification with maleic anhydride reduced the crystallinity of nanocellulose and enhanced its thermal stability. High-strength drug-carrying hydrogels (MACNF/SA) with different drug loading capacities were prepared using cefixime (CFX) as a drug model and maleic anhydride esterified nanocellulose (MACNF) and sodium alginate (SA) as the main raw materials. The compressive strength of MACNF/SA hydrogels made from MACNF reached a maximum of 80.3 kPa when the mass ratio of CNF to MA was 2.5:12. Rheological property tests showed that the MACNF/SA hydrogels were pseudoplastic fluids with shear thinning. The drug release from the drug-carrying hydrogels followed non-Fickian diffusion.

Effects of peracetic acid delignification on hemicellulose extraction by dimethyl sulfoxide

Extracting high-purity and structurally intact hemicelluloses from lignocellulosic fibers is a prerequisite to reveal their structures and realize high-value utilization. Delignification is usually performed before hemicellulose extraction to break the covalent bonds between hemicelluloses and lignin for effective separations, but usually leads to toxic by-products and hemicellulose degradation. Peracetic acid (PAA) is an environmentally friendly oxidizing agent, which is more selective for delignification and has less effect on the primary structure of hemicelluloses. However, the yields and chemical structures of hemicelluloses extracted at different PAA delignification conditions are not clear, which greatly hinders its research and application. Consequently, the response surface methodology (RSM) was used in this study to optimize the process parameters of PAA delignification. With the increase of temperature or time, the yield of holocellulose decreases, and the hemicellulose yield increases first and then decreases. With the increase of delignification degree, the hemicellulose yield increases significantly. The degree of PAA delignification also has a significant effect on the chemical structures of extracted hemicelluloses; hemicellulose samples extracted from highly delignified holocelluloses have a higher xylose unit content, molecular weight (MW) and degree of substitution by acetyl groups (DSAc). The tert-butanol solvent exchange or ball milling treatments on holocelluloses significantly increase the hemicellulose yields, by avoiding the hornification and improving the accessibility of holocellulose. This study will provide theoretical and technical support for the efficient separation of hemicelluloses.

Facile preparation of heptazine-covered Fe2O3 and its synergistic effect on the enhanced flame retardance of silicone rubber composite

The flammability of silicone rubber (SR) significantly limits its broad use in areas that require high flame retardancy. In this study, heptazine-covered Fe2O3, which exhibits effective flame retardancy, was prepared using simple ball milling and heat treatment, which are advantageous for large-scale production. The prepared filler was incorporated into SR. The addition of 7.02 wt% FM filler increased the thermal degradation onset temperature at 5 % weight loss from 492.5 °C for neat SR to 502.7 °C (FM 1:1 composite). Moreover, the peak heat release rate and peak smoke production rate of the FM 1:1 composite significantly decreased by 43.15 % and 68.42 %, respectively, indicating a significant enhancement in the fire safety and smoke suppression of the FM composites. The chemical, morphological, and electronic structures of the FM fillers, pyrolysis gas production, and char residue were thoroughly investigated to reveal the possible flame-retarding mechanisms of the SR composites.

Effects of synergistic application of Viscozyme L–wet ball milling on structural, physicochemical and functional properties of insoluble dietary fiber from ginseng residue

Synergistic effect of Viscozyme L with wet ball milling treatment on structural, physicochemical and functional aspects of insoluble dietary fiber (IDF) from ginseng residue were examined. SEM examination showed that IDF extracted by Viscozyme L in conjunction with wet ball milling (WBE-IDF) exhibited loose microstructural arrangement, and particle size of WBE-IDF was much smaller than that of IDF extracted by Viscozyme L (E-IDF) and along IDF (untreated). The FTIR spectra demonstrated the variations in the peak intensities in three modified ginseng IDFs. Besides, the highest thermal stability and viscosity was displayed by WBE-IDF among examined samples. In addition, WBE-IDF has higher water and oil holding, water swelling, nitrite ion absorption, bile acid absorption, and glucose absorption capacities as compared to that of E-IDF and IDF. Overall results revealed that the Viscozyme L combined with wet ball milling extraction may change ginseng IDF structure, and improve its physicochemical and functional qualities, thereby providing a theoretical basis for food industry to produce good ginseng IDF.

Formic Acid Dehydration Using Mechanochemically Prepared TiO2‐Graphite Composites

AbstractCommercial high surface area graphite (HSAG300) and commercial TiO2 were used to produce composite materials through a simple mechanochemical method involving milling and ultrasonic treatments. The acid and basic sites exposed on the surfaces of these materials were characterized by temperature‐programmed desorption (TPD) of ammonia and carbon dioxide. The catalytic materials were tested in the dehydration reaction of formic acid to produce hydrogen‐free CO. While HSAG300 is practically inactive under reaction conditions (continuous gas flow at temperatures in the range of 100–250 °C), all samples containing TiO2 are active, exhibiting high selectivity to CO without significant deactivation at moderate reaction temperatures. It is demonstrated that the presence of graphite in the catalysts enhances the specific catalytic activity of TiO2. Assuming that the dehydration reaction is catalyzed by acid sites on the TiO2 surfaces, a comparative evaluation of the surface sites reveals that the graphite‐TiO2 interactions not only change the density of surface sites but also modify the strength of the acid centers of TiO2. In summary, the interaction of HSAG300 with TiO2 modulates the surface properties of the prepared composite catalysts, decreasing the total number of basic surface sites and increasing the strength of acidic sites compared to bare TiO2.

Microwave absorption performance of La1.5Sr0.5NiO4/SrFe12O19 composites with thin matching thickness

The global focus on electromagnetic interference and pollution is undeniable. To counter these challenges, high-performance microwave-absorbing materials (MAMs), typically composed of dielectric and magnetic components, offer effective solutions by ensuring favorable impedance matching. Leveraging these MAMs has proven beneficial across various sectors, including 5G technology, information security, energy harvesting, diminished radar cross-section, and advancements in military applications. We successfully synthesized composites of La1.5Sr0.5NiO4 (LSNO) and SrFe12O19 (SrM) composites through ball milling and heat treatment. With the escalation of SrM weight percentage in the composites, noticeable alteration in structural, morphological, and static magnetic characteristics was ensured.Moreover, the amalgamation of these components bolstered the EM properties, consequently yielding exceptional microwave absorption capabilities in the composites. The composites with 40, 60, and 80 wt% of SrM (named S4, S6, and S8) exhibited excellent microwave absorption performance with an absorption rate of over 99.9 % for a thin thickness. The S4 and S8 composites attained reflection loss (RL) values of −34.75 dB and −36.93 dB, with 2.0 and 1.6 mm thicknesses, respectively. Meanwhile, the S6 composite achieved an RL value of −44.24 dB with a thickness of 1.9 mm. These composites' outstanding microwave absorption performance can be attributed to their significant magnetic loss, remarkable dielectric loss, and synergistic effects.

Investigation on the hydrogen absorption and dissociation properties of ball milling CeMg12/Ni/NbF5 type alloy for emergency power supply of fuel cell for meteorological radar station

In this article, in order to investigate the mechanism of action of catalysis on the hydrogenation and dehydrogenation properties of CeMg12-type alloy, the catalysis Ni and NbF5 was been added to prepare the CeMg12/Ni/NbF5 composite materials during ball milling treatment. The results in term of microstructure indicate that part of NbF5 is transformed into low valence NbF4 and helpful for forming MgF2 phase after ball milling treatment, which is advantageous for ameliorating the hydriding and dehydriding performances of experimental alloy. The results of the study from the perspective of hydrogen absorption and desorption performance test show that the increasing NbF5 decreases the enthalpy-value for hydrogen release and the platform pressure for the process of hydrogen releasing of ball-milled alloy, which is good for improving the hydrogen release performance of the alloy. The addition of a certain amount of NbF5 can effectively upgrade the kinetics of hydrogen dissociation of CeMg12-type alloy treated through mechanical ball milling. The alloy with 6 wt.% NbF5 has the best kinetic performance of hydrogen release, corresponding to activation energy can be reduced from 90.86 kJ/mol (0 wt.% NbF5) to 86.41 kJ/mol(6 wt.% NbF5).

Instant Synthesis of Cu2O Nanoparticles by a Selective Ionic Exchange in Nanozeolite 4A

This study presents a novel method for synthesizing Cu2O nanoparticles by employing ion exchange within a modified nanozeolite 4A matrix. The nanoparticles had a consistent particle size, predominantly around 6[Formula: see text]nm, with a narrow distribution. Nanosizing of the zeolite was achieved through high-energy milling treatments, thereby enhancing the surface-to-volume ratio. A band close to 700[Formula: see text]cm[Formula: see text] was observed in the FTIR spectrum, potentially indicating that zeolite downsizing was related to symmetric stretching of the Si–O bond postmilling. Furthermore, a distinctive band corresponding to Cu(I)–O stretching vibrations was identified at approximately 600[Formula: see text]cm[Formula: see text]. Additionally, optical absorption analyses of the UV-Vis spectrum revealed two characteristic bands attributable to Cu2O nanoparticles at 370[Formula: see text]nm and 470[Formula: see text]nm. These findings have led to advancements in resource use and promoted sustainable and environmentally friendly production practices.

Indirect magneto-ionic effect in FeSi2/Si nanocomposite induced by electrochemical lithiation and delithiation

A nanocomposite consisting of iron disilicide nanocrystals embedded in a Si matrix was prepared from industry-grade ferrosilicon by ball milling and subsequent heat treatment. By tailoring the heat treatment temperature either the metallic α-FeSi2 or the semiconducting β-FeSi2 phase could be made the dominant one, as indicated by x-ray diffraction. Magnetization curve and zero-field cooled/field cooled measurements revealed that ferromagnetic and superparamagnetic centers are present in the nanocomposites, which could be attributed to Fe-rich defective regions at the surface of the iron disilicide nanocrystals. For both nanocomposites, containing either mainly the α or β phase, we could show that the magnetization can be varied by about 40% by electrochemical lithiation and delithiation of the surrounding Si matrix, with up to 6.5% of the magnetization change being reversible. These variations could be attributed to the formation of additional Fe-rich magnetic regions, induced by a local change of the Fe/Si fraction at the FeSi2/Si interfaces, and their subsequent partial elimination. Thus, this work demonstrates a new concept for how an ‘indirect magneto-ionic effect’ can be obtained in composite materials consisting of a phase prone to the electrochemical ion uptake (i.e. the Si matrix) and a magnetic phase (i.e. the FeSi2 nanocrystals).

Eco-friendly material extrusion 3D printing for fabricating W-Ni-Fe lattices with improved compressive resistance

Tungsten (W) and its alloys are prevalently utilized in many special fields, such as the military and nuclear industry, owing to their exceptional attributes, including superior hardness, high density, and remarkable resistance to high temperatures. However, there are still challenges to achieve easy preparation of porous W alloys and uncover the secrets of their mechanical behavior. In this work, a porous lattice made from W93Ni4.9Fe2.1 with uniform microstructure was designed using enhanced material extrusion (MEX) 3D printing technology, offering exceptional formability while ensuring safety and environmental friendliness. The W93Ni4.9Fe2.1 lattice, fabricated at an extrusion temperature of 150 °C and infill percentage of 60 % exhibits the optimal geometry and homogeneous sintering shrinkage. The W93Ni4.9Fe2.1 lattice, fabricated at an extrusion temperature of 170 °C and infill percentage of 60 % shows the best compressive properties with the ultimate compressive strength of 1442 MPa and plastic strain of 19.8 %. The study of rheological properties of designed slurry determines the viscous flow activation energy of 1.64 kJ·mol−1 for the smooth extrusion of slurry, which is crucial for the formability of W93Ni4.9Fe2.1 lattice 3D printing. The ball milling treatment significantly improves the sinterability of W93Ni4.9Fe2.1 powder, confirming the effectiveness of mechanical alloying. This work presents a novel approach for fabricating complex structured porous W alloy with high-performance in a low-cost and environmentally friendly manner.

Regulating sulfur vacancies formation on mechanochemically modified pyrite to steer non-radical molecular oxygen activation for water purification

Ubiquitous pyrite (FeS2) in the earth’s crust features strong reducing capacity, presenting a promising alternative for molecular oxygen (O2) activation to facilitate water purification, but the interfacial electron transfer efficiency was remarkably retarded due to the existed passivation layer and limited reactive sites on the surface of pristine pyrite. Herein, we proposed an effective mechanochemical approach to unlock the potential of pyrite for O2 activation and refractory pollutant degradation. Compared to the inert pristine one, the ball milling-treated pyrite (BMPs) could achieve efficient sulfamethoxazole (SMX) degradation with a rate constant of 0.23 h−1. By a combination of characterizations, batch experiments, and density function theory (DFT) calculations, a clear panorama delineated the consecutive O2 adsorption and activation processes was established. Ball milling treatment could import rich sulfur vacancies (SVs) on pyrite, which unshifted the p-band center of adjacent S for improved O2 adsorption, also narrowed the band gap of BMPs to promote the interfacial electron transfer rate for O2 activation. Singlet oxygen (1O2) was identified as the dominant reactive species for SMX degradation, such non-radical oxidation feature rendered the system with remarkable activity and environmental robustness. Our work lay a foundation for constructing robust pyrite towards stable and efficient environmental remediation applications.

Removal of lead ions onto potassium-type fine-grained zeolite prepared from dry or wet milling treatment

Potassium-type zeolite (KZ) was prepared from coal fly ash by hydrothermal activation treatment using potassium hydroxide solution and potassium-type fine-grained zeolite was prepared by dry milling (KZ-D) or wet milling (KZ-W). The effects of the different treatments on the Pb2+ adsorption performance were assessed. KZ-W resulted in a much smaller particle diameter (0.61 ± 0.12 µm) than KZ-D (1.4 ± 0.48 µm) and KZ (6.5 ± 0.49 µm). KZ-W also realized a higher pore volume, mean pore diameter, and specific surface area, than KZ-D and KZ. Additionally, KZ-W realized a greater Pb2+ adsorption capacity (242.6 mg/g) than KZ (195.3 mg/g) or KZ-D (188.9 mg/g). The adsorption phenomena were fitted to the Freundlich and Langmuir models to clarify the Pb2+ adsorption mechanism, and then both models showed a good fit to the experimental data (the correlation coefficients of 0.914–0.996 for Freundlich model and 0.897–0.981 for Langmuir model). Additionally, the ion exchange capability, elemental distribution, and binding energy before and after adsorption were analyzed. The results indicated that the physicochemical characteristics of the tested adsorbent surface affected the Pb2+ adsorption capacity in the aqueous phase. According to kinetics, the pseudo-second-order model matched the experimental data (the correlation coefficients of 0.996–0.999). The samples also demonstrated selective adsorption of Pb2+ in a binary solution. The results demonstrated that KZ-W can effectively remove Pb2+ from the aqueous phase and that it may be a useful tool for preventing contamination of water bodies.

Experimental conditions for room temperature ferromagnetism in Fe-doped SnO2 via mechanochemical milling and thermal treatment

Identifying optimal experimental conditions, preferably through a simple and cost-effective method, for the fabrication of oxide-diluted magnetic semiconductors, such as Fe-doped SnO2, holds great significance in the quest for spintronic materials operating at room temperature (RT). While mechanochemical milling is a well-established technique meeting these requirements, its numerous milling variables necessitate careful consideration of restricted experimental conditions. In this study, we present some experimental mechanochemical milling conditions to prepare impurity-free iron-doped tin dioxide nanoparticles exhibiting RT ferromagnetic signal. To achieve this, we investigated the effects of milling time, the choice of the starting Sn reactant, and iron concentration on the purity of Sn1−xFexO2 (x = 0, 0.03, and 0.05) nanopowders obtained through mechanochemical milling followed by thermal treatment. Characterization through XRD, XANES, and EXAFS at the Fe K-edge, RT Raman spectroscopy, 119Sn and 57Fe Mössbauer spectroscopies, and magnetic measurements was conducted. Among the experimental techniques, micro-Raman spectroscopy proved the most effective in detecting the formation of hematite as an impurity phase. Our results indicate that extending the milling time to 12 h, as opposed to 3 h, employing anhydrous SnCl2, instead of SnCl2·2H2O and using the low iron concentration of x = 0.03, results in proper conditions for producing impurity-free samples with a robust RT ferromagnetic signal. The oxidation states for iron and tin ions were determined to be 3+ and 4+, respectively, with both occupying octahedral sites, suggesting iron’s replacement of tin. Our findings propose that both the bound magnetic polaron and RKKY models offer potential explanations for the origin of the ferromagnetic signal observed at room temperature in Sn0.97Fe0.03O2 sample milled for 12 h.

A clean approach to high-strength fly ash-based geopolymers: Multi-granular screening with NaAlO2 enhancement

The limited application of fly ash-based geopolymers in large-scale construction is primarily due to the slow evolution of compressive strength and low early-stage compressive strength. Our research counters this by introducing a method that harnesses the innate reactivity of finer fly ash (FF), significantly enhancing the compressive strength. Experimental and characterization results suggest that the superior performance of FF-based geopolymer is attributable to its higher content of reactive silica-alumina components, an optimal ratio of soluble silica to alumina, and a greater specific surface area, which collectively facilitate the geopolymerization process. Adding just 15 wt% NaOH, the FF-based geopolymer attains a compressive strength of 58.81 MPa after 14 d and an additional 10 wt% NaAlO2 can increase compressive strength to 70.5 MPa, showcasing a method that circumvents the need for energy-intensive milling or activation treatments. For the coarser fractions, thermal activation at 550 °C for an hour markedly improves strength to 39.40 MPa, aligning it with traditionally processed fly ash. This breakthrough paves the way for cleaner, more energy-efficient, and more substantial geopolymer materials in modern construction.