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

Porous ceramics are now expected to be used for a wide variety of industrial applications from filtration, absorption, catalysts and catalyst supports to lightweight structural components. During the last decade, tremendous efforts have been devoted for the researches on innovative processing technologies of porous ceramics, resulting in better control of the porous structures and substantial improvements of the properties. This article intends to review these recent progresses of porous ceramics. Because of a vast amount of research works reported in this field these days, the review mainly focuses on macro-porous ceramics whose pore size is larger than 50 nm. Followed by giving a general classification of porous ceramics, a number of innovative processing routes developed for critical control of pores are described, along with some important properties. The processes are divided into four categories including (i) partial sintering, (ii) sacrificial fugitives, (iii) replica templates and (iv) dir...

Macro-porous ceramics: processing and properties

The major advances in the field of the designed construction of hierarchically structured porous inorganic or hybrid materials wherein multiscale texturation is obtained via the combination of aerosol or spray processing with sol-gel chemistry, self-assembly and multiple templating are the topic of this review. The available materials span a very large set of structures and chemical compositions (silicates, aluminates, transition metal oxides, nanocomposites including metallic or chalcogenides nanoparticles, hybrid organic-inorganic, biohybrids). The resulting materials are manifested as powders or smart coatings via aerosol-directed writing combine the intrinsic physical and chemical properties of the inorganic or hybrid matrices with defined multiscale porous networks having a tunable pore size and connectivity, high surface area and accessibility. Indeed the combination of soft chemical routes and spray processing provides "a wind of change" in the field of "advanced materials". These strategies give birth to a promising family of innovative materials with many actual and future potential applications in various domains such as catalysis, sensing, photonic and microelectronic devices, nano-ionics and energy, functional coatings, biomaterials, multifunctional therapeutic carriers, and microfluidics, among others.

Aerosol Route to Functional Nanostructured Inorganic and Hybrid Porous Materials

Ordered mesoporous inorganic non-oxide materials attract increasing interest due to their plenty of unique properties and functionalities and potential applications. Lots of achievements have been made on their synthesis and structural characterization, especially in the last five years. In this critical review, the ordered mesoporous non-oxide materials are categorized by compositions, including non-oxide ceramics, metal chalcogenides, metal nitrides, carbides and fluorides, and systematically summarized on the basis of their synthesis approaches and mechanisms, as well as properties. Two synthesis routes such as hard-templating (nanocasting) and soft-templating (surfactant assembly) routes are demonstrated. The principal issues in the nanocasting synthesis including the template composition and mesostructure, pore surface chemistry, precursor selection, processing and template removal are emphatically described. A great number of successful cases from the soft-templating method are focused on the surfactant liquid-crystal mesophases to synthesize mesostructured metal chalcogenide composites and the inorganic-block-organic copolymer self-assembly to obtain non-oxide ceramics (296 references).

Ordered mesoporous non-oxide materials.

Periodic Mesoporous Organosilica (PMO) nanomaterials are envisioned to be one of the most prolific subjects of research in the next decade. Similar to mesoporous silica nanoparticles (MSN), PMO nanoparticles (NPs) prepared from organo-bridged alkoxysilanes have tunable mesopores that could be utilized for many applications such as gas and molecule adsorption, catalysis, drug and gene delivery, electronics, and sensing; but unlike MSN, the diversity in chemical nature of the pore walls of such nanomaterials is theoretically unlimited. Thus, we expect that PMO NPs will attract considerable interest over the next decade. In this review, we will present a comprehensive overview of the synthetic strategies for the preparation of nanoscaled PMO materials, and then describe their applications in catalysis and nanomedicine. The remarkable assets of the PMO structure are also detailed, and insights are provided for the preparation of more complex PMO nanoplatforms.

Syntheses and applications of periodic mesoporous organosilica nanoparticles

A new strategy to obtain transparent, thermally stable, and formable photoluminescent materials for LED applications is presented. Starting from commercially available silicon-based polymers, luminescence properties are developed by means of simple heat treatment. Solid polymethylsilsesquioxane MK (Wacker-Besil®PMS MK) and liquid poly(ureamethylvinyl)silazane Ceraset (Kion Ceraset® PUVMS) were thermally treated between 200 and 700 °C for 2 h under Ar atmosphere. Photoluminescence properties were observed in all the samples. The structural rearrangements during thermal annealing were effective in order to red-shift the emission spectra of the untreated polymers to the visible range. The formation of dangling bonds and carbon sp2, associated with the annealing procedure and confirmed by means of Electron Paramagnetic Resonance (EPR) spectroscopy and solid state Magic Angle Spinning NMR (MAS-NMR) contribute to the red-shift of the photoluminescence emissions of the polymers. After heat treatment at low temperatures (200, 300, and 400 °C), both the polymers show fluorescence in the UV range. While the polysiloxane reveals white luminescence after annealing at 500 and 600 °C, the polysilazane heat-treated at 500 °C exhibits emission in the blue-green range and is transparent. At higher temperatures the presence of free carbon counteracts the luminescence properties.

Luminescence of heat-treated silicon-based polymers: promising materials for LED applications

SiOC glass monoliths possessing hierarchical porosity were produced by a one-pot processing method. Periodic mesoporous organosilica (PMO) particles were embedded into a foamed siloxane preceramic polymer. After pyrolysis at 1000°C in inert atmosphere, open celled, permeable SiOC ceramic monoliths with a high amount of pores, ranging in size from hundred of micrometers to a few nanometers, were obtained. The components possessed a specific surface area of 137 m2/g, indicating the retention of most of the mesopores after the pyrolytic conversion of the PMO precursor particles. These fillers converted to truncated rhombic dodecahedral SiOC mesoporous micron-sized grains, homogeneously distributed throughout the SiOC cellular matrix. The produced porous ceramics possessed compression strength of about 1.7 MPa, which is adequate for their use in several engineering applications.

SiOC Ceramic Monoliths with Hierarchical Porosity

Periodic Mesoporous Organosilicas (PMOs) have been used as precursors to produce porous Silicon Oxycarbide glasses after pyrolysis at 1000°C in inert atmosphere. Up to now only PMOs with cubic ordering could be successfully converted into an ordered mesoporous SiCO glass. In our work we prepared, under strong acidic media and using an inorganic salt, a PMO with cubic Fm3m phase starting from 1,2-bis(triethoxysilyl)ethane as organosilane and Pluronic® F127 as templating agent. The as-prepared PMO has been characterized by XRD (Synchrotron beamline), N2 adsorption/desorption and multinuclear solid state NMR (29Si, 13C). After pyrolysis under argon flow the Fm3m phase is retained and the sample still displays a high surface area of 260 m2/g. Further characterizations were performed by 29Si MAS NMR and at 1000°C the product can be described as a true SiCO glass with mixed SiCxO4-x units (0≤x≤4).

A new example of periodic mesoporous SiCO glasses with cubic symmetry stable at 1000°C

Aerosol-generated mesoporous organosilica submicronic spheres have been con- verted into porous silicon oxycarbide (SiCO) glasses by pyrolysis at 1000 °C in an inert at- mosphere. Spherical mesoporous particles obtained from acidic solutions of 1,2-bis(tri- ethoxysilyl)ethane and Pluronic ® F127 structuring agent were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N 2 adsorption/desorption, and multi nuclear solid-state magic-angle spinning (MAS) NMR. These particles were then py- rolyzed at 1000 °C and transformed into a SiCO phase as evidenced by 29 Si MAS NMR, while TEM shows preserved mesoporosity, unfortunately difficult to access owing to the presence of an outer layer of dense silica.

Alberto Pauletti

Papers

Luminescence of heat-treated silicon-based polymers: promising materials for LED applications

SiOC Ceramic Monoliths with Hierarchical Porosity

A new example of periodic mesoporous SiCO glasses with cubic symmetry stable at 1000°C

Aerosol-generated mesoporous silicon oxycarbide particles