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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanofabrication and Nanomanufacturing".

Deadline for manuscript submissions: closed (18 December 2021) | Viewed by 30585

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Dr. Marcela Achimovičová

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Institute of geotechnics, Slovak Academy of Sciences, Košice, Slovakia
Interests: mechanochemical synthesis; kinetics; ball milling; chalcogenides–metal sulphides; selenides; selenospinels; nanostructured semiconductors; surfactant-assisted milling; surface-modified nanoparticles; industrial milling; physicochemical and optical properties
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Special Issue Information

Dear Colleagues,

Mechanochemistry dealing with mechanochemical reactions that are induced by mechanical energy-milling has made significant progress in recent years. The identified hallmarks of this branch of chemistry include:

Influencing reactivity by creating interphases in composite and multi/phase systems, by defects in solids and by the existence of relaxation phenomena;
Creating well-crystallized cores of nanoparticles with disordered near-surface shell regions;
Performing simple, dry, time-convenient one-step syntheses;
Preparing nanomaterials, nanocomposites with properties set in advance;
Scaling up to industrial production; and
Feasibility of manufacturing under environmentally friendly and essentially waste-free conditions.

This Special Issue aims to collect scientific knowledge and examinations of all the “mechanochemists” conducting investigations in the field of Mechanochemistry and Nanotechnology covering all aspects from inorganic and organic mechanochemical synthesis, elucidation of the mechanism of the mechanochemical reactions, metal–organic frameworks, nano-structured semiconductors and advanced synthesis of nanomaterials for solar cells, thermoelectrics, energy, hydrogen storage, biological and environmental applications, crystal engineering, industrial application of mechanochemistry in nanotechnology, and development of new approaches and methodologies.

Dr. Marcela Achimovičová
Guest Editor

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Keywords

mechanochemical synthesis
milling
nanomaterials
nanostructured materials
structural, morphological, and physicochemical characterization
industrial milling
new applications for nanotechnology

Published Papers (10 papers)

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Research

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18 pages, 81421 KiB

Open AccessArticle

Phase Transformations from Nanocrystalline to Amorphous (Zr₇₀Ni₂₅Al₅)_100-xW_x (x; 0, 2, 10, 20, 35 at. %) and Subsequent Consolidation

by M. Sherif El-Eskandarany, Naser Ali, Fahad Al-Ajmi and Mohammad Banyan

Nanomaterials 2021, 11(11), 2952; https://doi.org/10.3390/nano11112952 - 3 Nov 2021

Cited by 3 | Viewed by 1632

Abstract

Glasses, which date back to about 2500 BC, originated in Mesopotamia and were later brought to Egypt in approximately 1450 BC. In contrast to the long-range order materials (crystalline materials), the atoms and molecules of glasses, which are noncrystalline materials (short-range order) are not organized in a definite lattice pattern. Metallic glassy materials with amorphous structure, which are rather new members of the advanced materials family, were discovered in 1960. Due to their amorphous structure, metallic glassy alloys, particularly in the supercooled liquid region, behave differently when compared with crystalline alloys. They reveal unique and unusual mechanical, physical, and chemical characteristics that make them desirable materials for many advanced applications. Although metallic glasses can be produced using different techniques, many of these methods cannot be utilized to produce amorphous alloys when the system has high-melting temperature alloys (above 1500 °C) and/or is immiscible. As a result, such constraints may limit the ability to fabricate high-thermal stable metallic glassy families. The purpose of this research is to fabricate metallic glassy (Zr₇₀Ni₂₅Al₅)_100-xW_x (x; 0, 2, 10, 20, and 35 at. %) by cold rolling the constituent powders and then mechanically alloying them in a high-energy ball mill. The as-prepared metallic glassy powders demonstrated high-thermal stability and glass forming ability, as evidenced by a broad supercooled liquid region and a high crystallization temperature. The glassy powders were then consolidated into full-dense bulk metallic glasses using a spark plasma sintering technique. This consolidation method did not result in the crystallization of the materials, as the consolidated buttons retained their short-range order fashion. Additionally, the current work demonstrated the capability of fabricating very large bulk metallic glassy buttons with diameters ranging from 20 to 50 mm. The results indicated that the microhardness of the synthesized metallic glassy alloys increased as the W concentration increased. As far as the authors are aware, this is the first time this metallic glassy system has been reported. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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14 pages, 2483 KiB

Open AccessArticle

Mechanochemical Synthesis of Rosin-Modified Montmorillonite: A Breakthrough Approach to the Next Generation of OMMT/Rubber Nanocomposites

by Elaheh Esmaeili, Seyyed Amin Rounaghi and Jürgen Eckert

Nanomaterials 2021, 11(8), 1974; https://doi.org/10.3390/nano11081974 - 31 Jul 2021

Cited by 7 | Viewed by 2017

Abstract

The current investigation presents a green mechanochemical procedure for the synthesis of a special kind of rubber-compatible organo-montmorillonite (OMMT) for use in the inner liner compound of tires. The compatibility character of the OMMT arises from the mechanochemical reaction of the raw bentonite mineral and gum rosin as some of the organic constituents of the inner liner composition. The monitoring of OMMT synthesis by various characterization techniques reveals that gum rosin gradually intercalates into the montmorillonite (MMT) galleries during milling and increases the interlayer spacing to 41.1 ± 0.5 Å. The findings confirm the simultaneous formation of single- or few-layered OMMT platelets with average sizes from the sub-micron range up to several micrometers during the milling process. The mechanical properties of the OMMT/rubber nanocomposite, such as tensile strength, tear resistance and elongation, present a good enhancement in comparison to the un-modified material. Moreover, the organo-modification of the inner liner composition also leads to a property improvement of about 50%. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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14 pages, 4610 KiB

Open AccessArticle

Solvent-Free Mechanochemical Synthesis and Characterization of Nickel Tellurides with Various Stoichiometries: NiTe, NiTe₂ and Ni₂Te₃

by Matjaž Kristl, Sašo Gyergyek, Srečo D. Škapin and Janja Kristl

Nanomaterials 2021, 11(8), 1959; https://doi.org/10.3390/nano11081959 - 29 Jul 2021

Cited by 7 | Viewed by 2603

Abstract

The paper reports the synthesis of nickel tellurides via a mechanochemical method from elemental precursors. NiTe, NiTe₂, and Ni₂Te₃ were prepared by milling in stainless steel vials under nitrogen, using milling times from 1 h to 12 h. The products were characterized by powder X-ray diffraction (pXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), vibrating sample magnetometer (VSM), UV-VIS spectrometry, and thermal analysis (TGA and DSC). The products were obtained in the form of aggregates, several hundreds of nanometers in size, consisting of smaller nanosized crystallites. The magnetic measurements revealed a ferromagnetic behavior at room temperature. The band gap energies calculated using Tauc plots for NiTe, NiTe₂, and Ni₂Te₃ were 3.59, 3.94, and 3.70 eV, respectively. The mechanochemical process has proved to be a simple and successful method for the preparation of binary nickel tellurides, avoiding the use of solvents, toxic precursors, and energy-consuming reaction conditions. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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8 pages, 1550 KiB

Open AccessArticle

Effect of Nano-Y₂O₃ Content on Microstructure and Mechanical Properties of Fe18Cr Films Fabricated by RF Magnetron Sputtering

by Bang-Lei Zhao, Le Wang, Li-Feng Zhang, Jian-Gang Ke, Zhuo-Ming Xie, Jun-Feng Yang, Xian-Ping Wang, Ting Hao, Chang-Song Liu and Xue-Bang Wu

Nanomaterials 2021, 11(7), 1754; https://doi.org/10.3390/nano11071754 - 5 Jul 2021

Cited by 1 | Viewed by 1851

Abstract

In this work, FeCr-based films with different Y₂O₃ contents were fabricated using radio frequency (RF) magnetron sputtering. The effects of Y₂O₃ content on their microstructure and mechanical properties were investigated through scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductive coupled plasma emission spectrometer (ICP) and a nanoindenter. It was found that the Y₂O₃-doped FeCr films exhibited a nanocomposite structure with nanosized Y₂O₃ particles uniformly distributed into a FeCr matrix. With the increase of Y₂O₃ content from 0 to 1.97 wt.%, the average grain size of the FeCr films decreased from 12.65 nm to 7.34 nm, demonstrating a grain refining effect of Y₂O₃. Furthermore, the hardness of the Y₂O₃-doped FeCr films showed an increasing trend with Y₂O₃ concentration, owing to the synergetic effect of dispersion strengthening and grain refinement strengthening. This work provides a beneficial guidance on the development and research of composite materials of nanocrystalline metal with a rare earth oxide dispersion phase. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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10 pages, 1412 KiB

Open AccessArticle

Covalent Positioning of Single DNA Molecules for Nanopatterning

by Eung-Sam Kim, Jung Sook Kim, Nishan Chakrabarty and Chul-Ho Yun

Nanomaterials 2021, 11(7), 1725; https://doi.org/10.3390/nano11071725 - 30 Jun 2021

Viewed by 1706

Abstract

Bottom-up micropatterning or nanopatterning can be viewed as the localization of target molecules to the desired area of a surface. A majority of these processes rely on the physical adsorption of ink-like molecules to the paper-like surface, resulting in unstable immobilization of the target molecules owing to their noncovalent linkage to the surface. Herein, successive single nick-sealing facilitated the covalent immobilization of individual DNA molecules at defined positions on a dendron-coated silicon surface using atomic force microscopy. The covalently-patterned ssDNA was visualized when the streptavidin-coated gold nanoparticles bound to the biotinylated DNA. The successive covalent positioning of the target DNA under ambient conditions may facilitate the bottom-up construction of DNA-based durable nanostructures, nanorobots, or memory system. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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11 pages, 34508 KiB

Open AccessArticle

Mechanochemical Preparation of Magnetically Separable Fe and Cu-Based Bimetallic Nanocatalysts for Vanillin Production

by Paulette Gómez-López, Claudia Espro, Daily Rodríguez-Padrón, Alina M. Balu, Francisco Ivars-Barceló, Olvido Irrazábal Moreda, Clemente G. Alvarado-Beltrán and Rafael Luque

Nanomaterials 2021, 11(4), 1050; https://doi.org/10.3390/nano11041050 - 20 Apr 2021

Cited by 3 | Viewed by 2455

Abstract

A highly sustainable method for the preparation of supported iron oxide and copper nanoparticles (NPs) on a biomass-derived carbon by solvent-free mechanochemical process is reported. In-situ mechanochemically obtained extracts from orange peel could behave as a green reducing agent, allowing the formation of Cu metal nanoparticles as well as generating a magnetic phase (magnetite) in the systems via partial Fe³⁺ reduction. At the same time, orange peel residues also served as template and carbon source, adding oxygen functionalities, which were found to benefit the catalytic performance of mechanochemically synthesized nanomaterials. The series of magnetic Cu-Fe@OP were tested in the oxidation of trans-ferulic acid towards vanillin, remarkably revealing a maximum vanillin yield of 82% for the sample treated at 200 °C. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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19 pages, 4368 KiB

Open AccessArticle

SDS-Stabilized CuInSe₂/ZnS Multinanocomposites Prepared by Mechanochemical Synthesis for Advanced Biomedical Application

by Erika Dutková, Zdenka Lukáčová Bujňáková, Oleh Sphotyuk, Jana Jakubíková, Danka Cholujová, Viera Šišková, Nina Daneu, Matej Baláž, Jaroslav Kováč, Jaroslav Kováč, Jr., Jaroslav Briančin and Pavlo Demchenko

Nanomaterials 2021, 11(1), 69; https://doi.org/10.3390/nano11010069 - 30 Dec 2020

Cited by 5 | Viewed by 2555

Abstract

The CuInSe₂/ZnS multiparticulate nanocomposites were first synthesized employing two-step mechanochemical synthesis. In the first step, tetragonal CuInSe₂ crystals prepared from copper, indium and selenium precursors were co-milled with zinc acetate dihydrate and sodium sulfide nonahydrate as precursors for ZnS in different molar ratios by mechanochemical route in a planetary mill. In the second step, the prepared CuInSe₂/ZnS nanocrystals were further milled in a circulation mill in sodium dodecyl sulphate (SDS) solution (0.5 wt.%) to stabilize the synthesized nanoparticles. The sodium dodecyl sulphate capped CuInSe₂/ZnS 5:0-SDS nanosuspension was shown to be stable for 20 weeks, whereas the CuInSe₂/ZnS 4:1-SDS one was stable for about 11 weeks. After sodium dodecyl sulphate capping, unimodal particle size distribution was obtained with particle size medians approaching, respectively, 123 nm and 188 nm for CuInSe₂/ZnS 5:0-SDS and CuInSe₂/ZnS 4:1-SDS nanocomposites. Successful stabilization of the prepared nanosuspensions due to sodium dodecyl sulphate covering the surface of the nanocomposite particles was confirmed by zeta potential measurements. The prepared CuInSe₂/ZnS 5:0-SDS and CuInSe₂/ZnS 4:1-SDS nanosuspensions possessed anti-myeloma sensitizing potential assessed by significantly reduced viability of multiple myeloma cell lines, with efficient fluorescence inside viable cells and higher cytotoxic efficacy in CuInSe₂/ZnS 4:1-SDS nanosuspension. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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17 pages, 4096 KiB

Open AccessArticle

Sustainable One-Step Solid-State Synthesis of Antibacterially Active Silver Nanoparticles Using Mechanochemistry

by Mária Kováčová, Nina Daneu, Ľudmila Tkáčiková, Radovan Búreš, Erika Dutková, Martin Stahorský, Zdenka Lukáčová Bujňáková and Matej Baláž

Nanomaterials 2020, 10(11), 2119; https://doi.org/10.3390/nano10112119 - 25 Oct 2020

Cited by 10 | Viewed by 2435

Abstract

A combination of solid-state mechanochemical and green approaches for the synthesis of silver nanoparticles (AgNPs) is explored in this study. Thymus serpyllum L. (SER), Sambucus nigra L. (SAM) and Thymus vulgaris L. (TYM) plants were successfully applied to reduce AgNO₃ to AgNPs, as confirmed by X-ray diffraction analysis, with SER being the best reducing agent, and TYM being the worst. The experiments were performed via a one-step planetary milling process, where various AgNO₃:plant mass ratios (1:1, 1:10, 1:50 and 1:100) were investigated. Atomic absorption spectrometry indicated that the stability of the mechanochemically produced AgNPs increased markedly when a sufficiently large quantity of the reducing plant was used. Furthermore, when larger quantities of plant material were employed, the crystallite size of the AgNPs decreased. TEM analysis revealed that all AgNPs produced from both AgNO₃:plant ratios 1:1 and 1:10 exhibit the bimodal size distribution with the larger fraction with size in tens of nm and the smaller one below 10 nm in size. The antibacterial activity of the produced AgNPs was observed only for AgNO₃:plant ratio 1:1, with the AgNPs prepared using SER showing the greatest antibacterial properties. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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13 pages, 7792 KiB

Open AccessArticle

Comparative Study of Nanostructured CuSe Semiconductor Synthesized in a Planetary and Vibratory Mill

by Marcela Achimovičová, Matej Baláž, Vladimír Girman, Juraj Kurimský, Jaroslav Briančin, Erika Dutková and Katarína Gáborová

Nanomaterials 2020, 10(10), 2038; https://doi.org/10.3390/nano10102038 - 15 Oct 2020

Cited by 13 | Viewed by 2310

Abstract

Copper(II) selenide, CuSe was prepared from Cu and Se powders in a stoichiometric ratio by a rapid, and convenient one-step mechanochemical synthesis, after 5 and 10 min of milling in a planetary, and an industrial vibratory, mill. The kinetics of the synthesis, and the structural, morphological, optical, and electrical properties of CuSe products prepared in the two types of mill were studied. Their crystal structure, physical properties, and morphology were characterized by X-ray diffraction, specific surface area measurements, particle size distribution, scanning, and transmission electron microscopy. The products crystallized in a hexagonal crystal structure. However, a small amount of orthorhombic phase was also identified. The scanning electron microscopy revealed that both products consist of agglomerated particles of irregular shape, forming clusters with a size ~50 μm. Transmission electron microscopy proved the nanocrystalline character of the CuSe particles. The optical properties were studied using UV–Vis and photoluminescence spectroscopy. The determined band gap energies of 1.6 and 1.8 eV for the planetary- and vibratory-milled product, respectively, were blue-shifted relative to the bulk CuSe. CuSe prepared in the vibratory mill had lower resistivity and higher conductivity, which corresponds to its larger crystallite size in comparison with CuSe prepared in the planetary mill. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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Review

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35 pages, 16166 KiB

Open AccessReview

Mechanical Milling: A Superior Nanotechnological Tool for Fabrication of Nanocrystalline and Nanocomposite Materials

by M. Sherif El-Eskandarany, Abdulsalam Al-Hazza, Latifa A. Al-Hajji, Naser Ali, Ahmed A. Al-Duweesh, Mohammad Banyan and Fahad Al-Ajmi

Nanomaterials 2021, 11(10), 2484; https://doi.org/10.3390/nano11102484 - 24 Sep 2021

Cited by 41 | Viewed by 9698

Abstract

Throughout human history, any society’s capacity to fabricate and refine new materials to satisfy its demands has resulted in advances to its performance and worldwide standing. Life in the twenty-first century cannot be predicated on tiny groupings of materials; rather, it must be predicated on huge families of novel elements dubbed “advanced materials”. While there are several approaches and strategies for fabricating advanced materials, mechanical milling (MM) and mechanochemistry have garnered much interest and consideration as novel ways for synthesizing a diverse range of new materials that cannot be synthesized by conventional means. Equilibrium, nonequilibrium, and nanocomposite materials can be easily obtained by MM. This review article has been addressed in part to present a brief history of ball milling’s application in the manufacture of a diverse variety of complex and innovative materials during the last 50 years. Furthermore, the mechanism of the MM process will be discussed, as well as the factors affecting the milling process. Typical examples of some systems developed at the Nanotechnology and Applications Program of the Kuwait Institute for Scientific Research during the last five years will be presented in this articles. Nanodiamonds, nanocrystalline hard materials (e.g., WC), metal-matrix and ceramic matrix nanocomposites, and nanocrystalline titanium nitride will be presented and discussed. The authors hope that the article will benefit readers and act as a primer for engineers and researchers beginning on material production projects using mechanical milling. Full article

(This article belongs to the Special Issue Mechanochemistry and Nanotechnology)

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