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Polymer‐Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics
Abstract
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.
  • References (432)
  • Cited By (697)
Dietmar Seyferth53
Estimated H-index: 53
(Massachusetts Institute of Technology),
Gary H. Wiseman9
Estimated H-index: 9
(Massachusetts Institute of Technology),
Christian Prud’homme1
Estimated H-index: 1
(Massachusetts Institute of Technology)
Silicon nitride, Si3N4, is of great current interest as a material of high thermal and oxidative stability and high hardness for ceramics, electronic and other applications. 1 Silicon nitride may be prepared by the reaction of elemental silicon with gaseous nitrogen or ammonia at elevated temperatures. Ceramic bodies may be produced directly (reaction sintering) or, alternatively, Si3N4 powder may be obtained first and converted to solid bodies by subsequent processing. 1 Chemical vapor synthesi...
Ref 9Cited 9 Source Cite this paper
L.A. Harrah1
Estimated H-index: 1
,
J.M. Zeigler1
Estimated H-index: 1
We have examined the emission spectra of a variety of polysilanes as thin films and solutions. The solution fluorescence thermochromism provides evidence to support the rotational isomeric state model used to interpret the absorption spectrum. The structured character and low yield of phosphorescence in the alkyl polysilanes suggest that the triplet is the immediate precursor to photochemical scission. The change in character of both fluorescence and phosphorescence on going from phenyl to napht...
Cited 2
Shohei Inoue41
Estimated H-index: 41
(University of Tokyo),
Takuzo Aida79
Estimated H-index: 79
(University of Tokyo)
Heterocyclic compounds which can undergo ring-opening polymerization by anionic (nucleophilic) mechanisms are more limited than those polymerized by cationic (electrophilic) mechanisms.(1) Table 2.1 displays the representative types of monomers for anionic ring-opening polymerization. Some of the monomers can be polymerized by both anionic and cationic mechanisms.
Ref 2Cited 16
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2000 in Journal of Materials Science [IF: 2.60]
O. Dernovsek3
Estimated H-index: 3
(University of Erlangen-Nuremberg),
José Carlos Bressiani20
Estimated H-index: 20
,
Ana Helena A. Bressiani17
Estimated H-index: 17
... more
Manufacturing of novel reaction bonded Niobium Carbide (NbC) containing ceramic composites derived from polymer/filler mixtures was investigated. Poly(methylsiloxane) filled with 40 vol.% of a mixture of metallic Niobium (Nb) (reactive filler) and alumina powder (inert filler) was pyrolysed in inert atmosphere up to 1450°C. During pyrolysis metallic niobium reacted with carbon from the decomposition products of the preceramic polymer binder to form microcrystalline composites of NbC, Al2O3 and a...
Ref 3Cited 23 Source Cite this paper
C.-J. Chu1
Estimated H-index: 1
(University of California),
G. D. Soraru1
Estimated H-index: 1
(University of California),
F. Babonneau1
Estimated H-index: 1
(University of California)
... more
Advanced ceramics like carbides and nitrides can be obtained by the pyrolysis of metal-organic polymers. An intermediate amorphous phase is obtained after the removal of the organics and before crystallization. They can be considered as a new family of disordered materials called Amorphous Covalent Ceramics (ACC). By this polymer process, amorphous SiC films have been deposited on different substrates using metal-organic solutions with certain firing schedules. Some of the properties have been s...
Ref 6Cited 7
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Barry C. Arkles1
Estimated H-index: 1
Linear polysilane-siloxane copolymers having remarkable sensitivity to radiation have the general formula [(SiMe.sub.2).sub.m ].sub.a [(OSiMeR).sub.n ].sub.b wherein Me is a methyl group, R is lower alkyl or phenyl, m=4 to about 30 inclusive, n=1 to about 100 inclusive, a and b may each be 1 to about 10 inclusive, and a units alternate with b units. The copolymers of the invention may be in the form of oligomers, random copolymers where n=1 to 9, block copolymers where n=10 to 100, and mixed (ra...
Ref 3Cited 14
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Hussein Termoss4
Estimated H-index: 4
(University of Lyon),
Mikhael Bechelany3
Estimated H-index: 3
(University of Lyon),
Bérangère Toury8
Estimated H-index: 8
(University of Lyon)
... more
Abstract The present paper is focused on the synthesis of a series of poly[ N -(alkylimino)alanes] of the type [HAlNR] n as preceramic polymers for the preparation of aluminum nitride (AlN). Polymers were characterized by means of Fourier transform infrared spectra (FT-IR), liquid-state 1 H and 13 C NMR spectrometry and elemental analyses. The polymers were prepared in different physical states going from viscous liquid to solid (soluble and/or fusible) compounds with the decrease of the carbon ...
Ref 24Cited 12
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Tanguy Rouxel26
Estimated H-index: 26
(University of Rennes),
Georges Massouras1
Estimated H-index: 1
(Centre national de la recherche scientifique),
G. D. Soraru6
Estimated H-index: 6
(University of Trento)
The high temperature behavior of a sol-gel derived silicon oxycarbide glass containing 12 at.% carbon has been characterized by means of creep and in-situ ultrasonic echography measurements. Temperature induced changes include structural relaxation and densification from 1000 to 1200°C, and crystallization to form a fine and homogeneous β-SiC/glass-matrix nanocomposite with 2.5 nm large crystals above 1200°C. Young's modulus measurements clearly reveal a consolidation of the material upon anneal...
Cited 87 Source Cite this paper
1998 in Journal of Materials Science [IF: 2.60]
Toshikazu Nishimura1
Estimated H-index: 1
,
Rainer Haug4
Estimated H-index: 4
,
Joachim Bill35
Estimated H-index: 35
... more
Cited 4
Norman Grassie1
Estimated H-index: 1
,
Elizabeth Morrison1
Estimated H-index: 1
Abstract : A report is given of work involving the thermal degradation of a series of styrene/methyl methacrylate copolymers of various compositions but having molecular weights of the same order. Consideration is given to the nature of the changes in molecular weight during degradation, the nature of the products of degradation and the measurement of rates.
Cited 70 Source
  • References (432)
  • Cited By (697)
Elena P. Ivanova22
Estimated H-index: 22
,
Kateryna Bazaka21
Estimated H-index: 21
,
Russell J. Crawford3
Estimated H-index: 3
: Polymeric biomaterials derived from inorganic and organo-metallic precursors promise to overcome the drawbacks associated with organic polymers. Their versatile chemistry, excellent physico-chemical and biological properties, and ability to undergo controlled biodegradation render them highly suited for a host of medical applications, from transient implants to drug and biomolecular delivery vehicles. In this chapter, inorganic, organic–inorganic hybrid and organo-metallic polymers are reviewe...
Ref 80
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Gabriela Mera17
Estimated H-index: 17
(Technische Universität Darmstadt),
Ilaria Menapace3
Estimated H-index: 3
(Technische Universität Darmstadt),
Scarlett Widgeon8
Estimated H-index: 8
(University of California, Davis)
... more
For the first time, photoluminescence properties of four polysilylcarbodiimides, comprised of a phenyl pendant group attached at the silicon atom and a second substituent being either phenyl (S1), methyl (S2), hydrogen (S3) or vinyl (S4), are reported. Distinctive fluorescence emissions are detected in the polymers with one phenyl group at the silicon atom (S2, S3 and S4), due to a phenyl excimer emission. The polymer with two phenyl groups attached at the same silicon atom (S1) shows, besides t...
Ref 41Cited 8
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2015 in Journal of Materials Science [IF: 2.60]
Anran Guo4
Estimated H-index: 4
(University of Padua),
Martina Roso11
Estimated H-index: 11
(University of Padua),
Paolo Colombo42
Estimated H-index: 42
(Pennsylvania State University)
... more
Various electrospun metal/SiOC (Ag/SiOC, Co/SiOC, and Cu/SiOC) composite fibers were synthesized via a carbon thermal reduction of four kinds of metal source (silver oxide nanoparticles, silver acetate, cobalt acetate, and copper trifluoro acetylacetonate). XRD results indicate that both common metal–organic metal precursors and seldom used metal oxide particles were successfully carbon thermally reduced to the corresponding metallic particles embedded in SiOC fibers, indicating that the range o...
Ref 28Cited 9
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Emanuel Ionescu20
Estimated H-index: 20
(Technische Universität Darmstadt),
Gabriela Mera17
Estimated H-index: 17
(Technische Universität Darmstadt),
Ralf Riedel52
Estimated H-index: 52
(Technische Universität Darmstadt)
Polymer-derived ceramics (PDCs) represent a rather novel class of ceramics which can be synthesized via cross-linking and pyrolysis of suitable polymeric precursors. In the last decades, PDCs have been attaining increased attention due to their outstanding ultrahigh-temperature properties, such as stability with respect to decomposition and crystallization processes as well as resistance in oxidative and corrosive environments. Moreover, their creep resistance is excellent at temperatures far be...
Ref 139
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Thomas Konegger6
Estimated H-index: 6
(Clemson University),
Jessica D. Torrey9
Estimated H-index: 9
(United States Bureau of Reclamation),
Octavio Flores5
Estimated H-index: 5
(University of Bayreuth)
... more
Due to their high hardness, high temperature stability, and high chemical stability, ceramic materials have significant uses and potential in existing and emerging sustainable technologies . In this paper, we provide a thorough overview of ceramics in a variety of sustainable applications. This is followed by a detailed discussion of an emerging process to make ceramics called polymer (or precursor)-derived ceramics . It is shown that due to the versatility of this process in making a wide range...
Ref 74Cited 3
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D. E. Holcomb1
Estimated H-index: 1
(Oak Ridge National Laboratory),
S. M. Cetiner1
Estimated H-index: 1
(Oak Ridge National Laboratory)
Ref 61Cited 4
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Weiqi He2
Estimated H-index: 2
(Northwestern Polytechnical University),
Lixin Chen4
Estimated H-index: 4
(Northwestern Polytechnical University),
Tingting Xu3
Estimated H-index: 3
(Northwestern Polytechnical University)
... more
Abstract Two UV-curable single source precursors of borazine derivatives [B{CH 2 (SiR 3 )}NH] 3 (a-TSMB) and [B{CH(CH 3 )(SiR 3 )}NH] 3 (a-TSEB) (R=acrylate group) were synthesised from chloromethyltrichlorosilane and trichlorovinylsilane as starting materials, respectively. a-TSMB and a-TSEB were characterised via Fourier transform infrared, 1 H NMR, 11 B NMR and 29 Si NMR spectroscopy. B and N existed in the form of a six-membered borazine ring, and the UV-curable acrylate groups were successf...
Ref 26Cited 5
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Andrea Zocca9
Estimated H-index: 9
(University of Padua),
Hamada Elsayed9
Estimated H-index: 9
(University of Padua),
Enrico Bernardo28
Estimated H-index: 28
(University of Padua)
... more
Silicate bioceramics possess an excellent bioactivity; however, shaping them into complex geometries is still challenging. Therefore, this paper aims to present a new strategy for the shaping of a bioglass-ceramic with controlled geometry and properties starting from a glass powder combined with a preceramic polymer, i.e. a silicon resin, and reactive fillers. The powder-based three-dimensional (3D)-printing of wollastonite (CaSiO3)-based silicate bioceramic parts was demonstrated in this work. ...
Ref 32Cited 24
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Shiwei Mou4
Estimated H-index: 4
(Donghua University),
Yong Liu3
Estimated H-index: 3
(Donghua University),
Keqing Han5
Estimated H-index: 5
(Donghua University)
... more
Abstract A novel precursor for preparing SiBNC ceramic fibers was successfully prepared via co-polymerization of trichlorosilane (SiHCl 3 ), boron trichloride (BCl 3 ) and methyl amine (MeNH 2 ). The polymeric precursor exhibited good melt spinnability due to its relatively linear-chain chemical structure, which could be easily melt spun into green fibers with a diameter of 28 μm. The green fibers were subsequently pyrolyzed to SiBNC ceramic fibers with ca. 24 μm in diameter and 750 MPa in tensi...
Ref 13Cited 9
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