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.

The phenomenon of positron–electron annihilation in lifetime measuring mode is considered as a tool to study nanostructurization in solids possessing mixed positron and positronium (Ps) trapping. Structural inhomogeneities due to guest nanoparticles in such solids are described in terms of substitution trapping in positron- and Ps-related sites within the same host matrix. The developed approach allows estimation of interfacial free-volume voids as being responsible for positron trapping and defect-free bulk positron lifetimes of nanoparticle-modified solids. For the example of arsenic sulfide, As4S4 nanoparticles embedded in polyvinylpyrrolidone (PVP) environment under high-energy ball milling, an alternative algorithm to parameterize these structural imperfections is justified. Interfacial free-volume voids between neighboring nanoparticles filled with loosely packed As4S4 crystallites are considered as the most probable positron trapping sites. The observed variations in mixed positron–Ps trapping modes under nanostructurization are adequately defined with respect to the chemistry of guest nanoparticles. Direct evidence for this algorithm is provided as the basis of experimental three-term decomposed positron lifetime spectra for As4S4–PVP nanocomposites parameterized with respect to different fitting protocols.

Positron annihilation lifetime study of atomic imperfections in nanostructurized solids: On the parameterized trapping in wet-milled arsenic sulfides As4S4

Thermoanalytical study of mechanically activated cinnabar

Simultaneous valorization of polyvinyl chloride and eggshell wastes by a semi-industrial mechanochemical approach.

Combined chemical and bacterial leaching of ultrafine ground chalcopyrite

At present mechanochemistry of sulphides appears to be a science with a sound theoretical foundation exhibiting a wide range effectiveness in different areas of science and technology. For traditional application mechanochemistry is of exceptional importance in extractive metallurgy of sulphidic ores where many technological processes have been developed. Metal sulphides can be also utilized in emerging nanotechnology with application as advanced luminescence, optoelectronic, magnetic and catalytic materials.

Peter Baláž

Papers

Positron annihilation lifetime study of atomic imperfections in nanostructurized solids: On the parameterized trapping in wet-milled arsenic sulfides As4S4

Thermoanalytical study of mechanically activated cinnabar

Simultaneous valorization of polyvinyl chloride and eggshell wastes by a semi-industrial mechanochemical approach.

Combined chemical and bacterial leaching of ultrafine ground chalcopyrite

Mechanochemistry of sulphides