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.

A pristine colusite Cu26V2Sn6S32 was successfully synthesised on a 100 g scale via a mechanochemical reaction in an industrial eccentric vibratory ball mill followed by spark plasma sintering (SPS) at 873 K. The milling of elemental precursors from 1 up to 12 hours was performed and the prepared samples were investigated in detail by X-ray powder diffraction, Mossbauer spectroscopy, scanning electron microscopy, and thermoelectric property measurements. The results point to the formation of a high purity and high crystallinity non-exsoluted colusite phase after the SPS process (P3n, a = 10.7614(1) A) in the case of a 12 h milled sample. In comparison, samples milled for 1–6 h displayed small quantities of binary Cu–S phases and vanadium core–shell inclusions, leading to a V-poor/Sn-rich colusite with a higher degree of structural disorder. These samples exhibit lower electrical conductivity and Seebeck coefficient while an increase in the total thermal conductivity is observed. This phenomenon is explained by a higher reactivity and grain size reduction upon prolonged milling and by a weak evolution of the chemical composition from a partly disordered V-poor/Sn-rich colusite phase to a well-ordered stoichiometric Cu26V2Sn6S32 colusite, which leads to a decrease in carrier concentration. For all samples, the calculated PF values, around 0.7–0.8 mW m−1 K−2 at 700 K, are comparable to the values previously achieved for mechanochemically synthesised Cu26V2Sn6S32 in laboratory mills. This approach thus serves as an example of scaling-up possibility for sulphur-based TE materials and supports their future large-scale deployment.

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Promoted crystallisation and cationic ordering in thermoelectric Cu26V2Sn6S32 colusite by eccentric vibratory ball milling

The mechanochemical reduction of lead sulphide with elemental iron in a high-energy mill was studied. X-ray photoelectron spectroscopy was used for characterization of obtained products of reduction. Elemental lead as well as its divalent forms were identified in the surface layer of products of mechanochemical reduction. The mechanochemical reduction of lead sulphide with elemental iron on the surface is a complicated reaction and the identification of compounds formed in the surface layer is not unambiguous. However, only 23% of elemental lead on the surface is produced. The degree of mechanochemical transformation in the surface layer is not very high under chosen conditions. Higher power input is needed for further progress of the reaction.

A study of mechanochemical reduction of lead sulphide by elemental iron on the surface by X-ray photoelectron spectroscopy

Nanocrystalline Sb2S3 particles have been synthesized from Sb and S powders by high-energy milling in a planetary mill using argon protective atmosphere. X-ray di raction, particle size analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, electron di raction, high resolution transmission electron microscopy, UV-VIS, and di erential scanning calorimetry methods for characterization of the prepared particles were applied. The powder X-ray di raction pattern shows that Sb2S3 nanocrystals belong to the orthorhombic phase with calculated crystallite size of about 36 nm. The nanocrystalline Sb2S3 particles are constituted by randomly distributed crystalline nanodomains (20 nm) and then these particles are forming aggregates. The monomodal distribution of Sb2S3 particles with the average hydrodynamic parameter 210 nm was obtained. The quanti cation of energy dispersive X-ray spectroscopy analysis peaks give an atomic ratio of 2:3 for Sb:S. The optical band gap determined from the absorption spectrum is 4.9 eV, indicating a considerable blue shift relative to the bulk Sb2S3. Di erential scanning calorimetry curves exhibit a broad exothermic peak between 200 and 300 ◦C, suggesting recovery processes. This interpretation is supported by X-ray di raction measurements that indicate a 23-fold increase of the crystallite size to about 827 nm as a consequence of application of high temperature process. The controlled mechanochemical synthesis of Sb2S3 nanoparticles at ambient temperature and atmospheric pressure remains a great challenge.

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Mechanochemically synthesized nanocrystalline Sb2S3 particles

Mossbauer spectroscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, electron paramagnetic resonance and X-ray diffraction were used to identify changes of surface, structure and spectroscopic properties of sulfide minerals produced by mechanical activation. In the present study we report the results of chalcopyrite (CuFeS 2 ), pyrite (FeS 2 ), cinnabar (HgS), bornite (Cu 5 FeS 4 ) and zinc sulfide (ZnS). The influence of energy input to the mill and the nature of grinding environment have been investigated upon the Fe contamination of the materials.

Peter Baláž

Papers

Promoted crystallisation and cationic ordering in thermoelectric Cu26V2Sn6S32 colusite by eccentric vibratory ball milling

A study of mechanochemical reduction of lead sulphide by elemental iron on the surface by X-ray photoelectron spectroscopy

Mechanochemically synthesized nanocrystalline Sb2S3 particles

Influence of mechanical activation on the Mossbauer spectra of the sulfides

Non-stoichiometric niobium sulphide synthesized by mechanochemical route