The aim of this critical review is to provide a broad but digestible overview of mechanochemical synthesis, i.e. reactions conducted by grinding solid reactants together with no or minimal solvent. Although mechanochemistry has historically been a sideline approach to synthesis it may soon move into the mainstream because it is increasingly apparent that it can be practical, and even advantageous, and because of the opportunities it provides for developing more sustainable methods. Concentrating on recent advances, this article covers industrial aspects, inorganic materials, organic synthesis, cocrystallisation, pharmaceutical aspects, metal complexes (including metal–organic frameworks), supramolecular aspects and characterization methods. The historical development, mechanistic aspects, limitations and opportunities are also discussed (314 references).

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Mechanochemistry: opportunities for new and cleaner synthesis

인공고관절의 세라믹 볼 헤드의 기계적 안정성 평가를 위한 3 차원 유한요소 해석

Interpretation of X-ray Powder Diffraction Patterns . By H. Lipson and H. Steeple. Pp. viii + 335 + 3 plates. (Mac-millan: London; St Martins Press: New York, May 1970.) £4.

X-Ray Diffraction

Preceramic polymers were proposed over 30 years ago as precursors for the fabrication of mainly Si-based advanced ceramics, generally denoted as polymer-derived ceramics (PDCs). The polymer to ceramic transformation process enabled significant technological breakthroughs in ceramic science and technology, such as the development of ceramic fibers, coatings, or ceramics stable at ultrahigh temperatures (up to 2000°C) with respect to decomposition, crystallization, phase separation, and creep. In recent years, several important advances have been achieved such as the discovery of a variety of functional properties associated with PDCs. Moreover, novel insights into their structure at the nanoscale level have contributed to the fundamental understanding of the various useful and unique features of PDCs related to their high chemical durability or high creep resistance or semiconducting behavior. From the processing point of view, preceramic polymers have been used as reactive binders to produce technical ceramics, they have been manipulated to allow for the formation of ordered pores in the meso-range, they have been tested for joining advanced ceramic components, and have been processed into bulk or macroporous components. Consequently, possible fields of applications of PDCs have been extended significantly by the recent research and development activities. Several key engineering fields suitable for application of PDCs include high-temperature-resistant materials (energy materials, automotive, aerospace, etc.), hard materials, chemical engineering (catalyst support, food- and biotechnology, etc.), or functional materials in electrical engineering as well as in micro/nanoelectronics. The science and technological development of PDCs are highly interdisciplinary, at the forefront of micro- and nanoscience and technology, with expertise provided by chemists, physicists, mineralogists, and materials scientists, and engineers. Moreover, several specialized industries have already commercialized components based on PDCs, and the production and availability of the precursors used has dramatically increased over the past few years. In this feature article, we highlight the following scientific issues related to advanced PDCs research: (1) General synthesis procedures to produce silicon-based preceramic polymers.
(2) Special microstructural features of PDCs.
(3) Unusual materials properties of PDCs, that are related to their unique nanosized microstructure that makes preceramic polymers of great and topical interest to researchers across a wide spectrum of disciplines.
(4) Processing strategies to fabricate ceramic components from preceramic polymers.
(5) Discussion and presentation of several examples of possible real-life applications that take advantage of the special characteristics of preceramic polymers. Note: In the past, a wide range of specialized international symposia have been devoted to PDCs, in particular organized by the American Ceramic Society, the European Materials Society, and the Materials Research Society. Most of the reviews available on PDCs are either not up to date or deal with only a subset of preceramic polymers and ceramics (e.g., silazanes to produce SiCN-based ceramics). Thus, this review is focused on a large number of novel data and developments, and contains materials from the literature but also from sources that are not widely available.

Polymer-Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics

Metallurgical recovery of metals from electronic waste: a review.

Mechanochemical processing of sulphidic minerals

Covellite, CuS and chalcocite, Cu2S nanoparticles prepared in the explosive manner from elemental precursors were further ball-milled in order to observe additional changes caused by mechanical action. Three phases of chalcocite were interchanging during milling, monoclinic one being major at the equilibrium after 30 min. In the case of covellite synthesis, milling for 15 min brought about a significant diminishment in the content of digenite, Cu1.8S, impurity. Covellite powder exhibited finer character than chalcocite, as documented by crystallite size, grain size and specific surface area analysis. Finally, the effect of milling speed on the explosive character of the reaction and phase composition of chalcocite was investigated. The most drastic conditions favored the formation of the monoclinic phase with the lowest symmetry and the time and intensity of the explosion was found to depend on the milling speed. The whole process is mechanically driven.

Mechanochemistry of copper sulphides: phase interchanges during milling

Structural, surface and magnetic properties of chalcogenide Co9S8 nanoparticles prepared by mechanochemical synthesis

In recent years nanocrystalline semiconductors (QD) have attached much attention due to their great potential in technological applications. Electronic, optical and other properties of QD with respect to corresponding bulk materials are modified considerably, offering a number of potential applications in semiconductor and other industries. Nanophases have been synthesized by a number of techniques starting from vapour phase (i. e. inert gas condensation), liquid phase (i.e. rapid sodification) and solid state. The technique starting from solid state applies mechanochemical approach where synthesis is performed by solid state reactions in high-energy mills. We have developed the mechanochemical route to produce nanocrystalline semiconductors applying high-energy milling of metal acetates with sodium sulphide. The main advantage of this route is that it is “a quantity process” permitting kilogram quantities of nanomaterials to be produced at an ambient temperatures in a very short processing time. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Mechanochemistry in preparation of nanocrystalline semiconductors

PbS nanocrystals using surfactant assisted mechanochemical route has been successfully prepared. The methods of XRD, SEM, surface area and particle size measurements were used for nanocrystals characterization. The XRD patterns confirmed the presence of galena PbS (JCPDS 5–592) whatever treatment conditions were applied. The strong observable peaks indicate the highly crystalline nature in formation of PbS nanostructures where preferential crystal growth in the (200) direction after chelating agent (EDTANa2•2H2O) addition has been observed. The mean volume weighted crystallite size 4.9 nm and 35 nm has been calculated from XRD data using Williamson-Hall method for PbS synthesized without and/or with chelating agent, respectively corresponding with surface weighted crystallites sizes of 2.9 and 18.8 nm. The sample prepared without surfactant yields the smaller crystallites and the higher microstrain compared with surfactant assisted synthesis. The obtained results illustrate a possibility to manipulate crystal morphology by combining effect of milling and surfactant application.

https://www.degruyter.com/downloadpdf/j/chem.2009.7.issue-2/s11532-009-0005-3/s11532-009-0005-3.xml

Peter Baláž

Papers

Mechanochemical processing of sulphidic minerals

Mechanochemistry of copper sulphides: phase interchanges during milling

Structural, surface and magnetic properties of chalcogenide Co9S8 nanoparticles prepared by mechanochemical synthesis

Mechanochemistry in preparation of nanocrystalline semiconductors

PbS nanostructures synthesized via surfactant assisted mechanochemical route