Thermal cross‐linking and pyrolytic conversion of poly(ureamethylvinyl)silazanes to silicon‐based ceramics

Li, Yali; Kroke, Edwin; Riedel, Ralf; Fasel, Claudia; Gervais, Christel; Babonneau, Florence

doi:10.1002/aoc.236

Cited by 153 publications

(171 citation statements)

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“…The SiCN ceramic is composed of 56.1 wt.-% Si, 19.8 wt.-% C, 21.6 wt.-% N and 2.5 wt.-% O and correspond to a molecular formula of Si 1 C 0.82 N 0.77 O 0.08 which is in accordance with our previous study [29] and the EELS analysis. A quantitative examination of the EDS spectra reveals a com-position of Si 1 O 1.36 C 0.31 for the investigated nanowire (see Figure 19).…”

Section: Ceramic 1d Nanotubes and Wires Derived From Anodisc 13 (Whatsupporting

confidence: 88%

“…The appearance of the spectra of the KiON Ceraset polyureasilazane polymer precursor ( Figure 8) cured within the PAOX template at 700°C shows significant similarities with the appearance of the spectrum of bulk ceramic samples obtained from the precursor under no confinement conditions in the characteristic fingerprint region (temperature range 450-600°C). [29] The broad but intense absorption at 3700-3100 cm -1 with the maximal absorption at 3450-3440 cm -1 can be attributed to an O-H (3650-3200 cm -1 ) stretch. However, ν δ of the hydroxy absorption at 1450-1250 cm -1 and 750-650 cm -1 is either absent or too weak to be considered as significant.…”

Section: Ceramic Nanowires Derived From 40 V Paox Templatesmentioning

confidence: 97%

“…Low volatile oligomers can be distilled off at temperatures below the cross-linking temperature of the KiON VL20 polyvinylsilazane (260°C). [29] In the case of cross-linking of the infiltrated polymer in the cylindrical pores of Anodisc 13 PAOX templates the oligomers are able to displace the liquid precursor from the pore surface. Thus, under these conditions ceramic nanotubes are formed.…”

Section: Ceramic 1d Nanotubes and Wires Derived From Anodisc 13 (Whatmentioning

confidence: 99%

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Polymer‐Derived SiOC Nanotubes and Nanorods via a Template Approach

et al. 2009

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The synthesis of silicon‐based ceramic nanowires and nanotubes produced by liquid infiltration of commercially available silicon‐based polymers, namely polysilazane (CerasetTM, polyureasilazane), polysilazane VL20 (Kion Coop.) and polycarbosilane (Starfire Systems SP‐MatrixTM) in alumina templates with defined pore channels is reported. After polymer infiltration, pyrolysis of the preceramic polymer at 1000–1100 °C in Ar atmosphere followed by dissolution of the alumina templates, ceramic nanowires and nanotubes were obtained. In the case of the polymeric ceramic precursor polysilazane, nanorods were formed only if an oligomeric fraction was distilled off from the polymer precursor prior to infiltration of the template. In contrast, the formation of nanotubes was found after infiltration of the untreated (crude) preceramic polymer. Despite the fact that the preceramic polymers contain silicon, carbon and nitrogen and no oxygen as constituting elements, the final ceramic nanostructures obtained were analysed consistantly by various techniques to contain oxygen and only limited amounts of carbon and nitrogen after pyrolysis consistent with a composition as silicon oxycarbide (SiOC). This behaviour strongly indicates that the porous alumina template may significantly influence the pyrolysis process of the precursors thus affecting the chemical composition of the final ceramic products. It is a central result of our study that the alumina templates are not inert under the reaction conditions employed instead acting as a reaction partner at the high temperatures employed during pyrolysis. Taking this into account, reaction of otherwise inert amorphous alumina with inorganic polymers at elevated temperatures could lead to a directed synthesis of new ceramic compositions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Ceramic 1d Nanotubes and Wires Derived From Anodisc 13 (Whatsupporting

confidence: 88%

Section: Ceramic Nanowires Derived From 40 V Paox Templatesmentioning

confidence: 97%

Section: Ceramic 1d Nanotubes and Wires Derived From Anodisc 13 (Whatmentioning

confidence: 99%

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Polymer‐Derived SiOC Nanotubes and Nanorods via a Template Approach

et al. 2009

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“…These can be assigned to Si-CH 3 (0.09 ppm), N-H (0.70 ppm), Si-H (4.24-4.80 ppm), and SiCH --CH 2 (5.54-6.14 ppm). [6] The ratios of the CH 2 --CHSi, H-Si, and CH 3 -Si units were determined from the respective peak intensities to be 1:1.3:4.3, which is in reasonable agreement with the molecular structure provided by the KiON Corporation, which has a corresponding ratio of 1:1.3:5. The PUMVS 13 C NMR spectrum in Figure 2(b) shows two groups of peaks, which were assigned to Si-CH 3 groups (À2.5-4.7 ppm) and CH 2 --CH (137.2-141.8 and 130.3-133.1 ppm).…”

Section: Studies Of Hybrid Compositionsupporting

confidence: 71%

“…[5] Beyond producing mesostructured oxides, it is an interesting challenge to generalize the block copolymer approach towards high temperature polymer-derived ceramics because of their excellent thermal and mechanical properties. [6,7] As the name suggests, these materials start out as polymers, which can be easily shaped into complex structures. Heat treatment transforms the polymeric precursors into ceramic materials, while retaining the original (complex) shape.…”

Section: Full Papermentioning

confidence: 99%

Composition and Morphology Control in Ordered Mesostructured High‐Temperature Ceramics from Block Copolymer Mesophases

Kamperman

Scarlat

et al. 2007

Macro Chemistry & Physics

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The co‐assembly between a polyisoprene‐block‐poly(dimethylaminoethyl methacrylate) block copolymer and poly(ureamethylvinyl)silazane is investigated. The hybrid morphology can be controlled by systematically increasing the inorganic‐to‐organic ratio or by changing the molecular weight of the block copolymer. Temperature treatment up to 1 500 °C of the hybrids resulted in mesoporous, ordered non‐oxide‐type ceramics. The results suggest that careful control of co‐assembly processes enables access to nanostructured high‐temperature ceramics that may have novel mechanical, thermal, and chemical properties.magnified image

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Silicon‐Containing Preceramic Polymers

Mera

Ionescu

2013

Encyclopedia of Polymer Science and Technology

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Polymer‐to‐ceramic transformation is a suitable technology to produce a broad spectrum of ceramic‐based composite materials with adjusted chemical, mechanical, and physical properties. Their properties depend on the chemical structure of preceramic polymers, the carbon content of the ceramic, the conditions used for pyrolysis (eg, temperature, atmosphere) as well as the use of additional active or passive fillers. The intimate relationship between the molecular architecture of the precursor and the nano/microstructure as well as the functional and structural properties of the resulting ceramics is one of the most important features of this class of ceramics. Chemical design of precursors, such as polysilanes, polycarbosilanes, polysiloxanes, polysilazanes, and polysilylcarbodiimides, enables the production of nanostructured SiC, SiOC, and SiCN ceramics via thermal conversion in an inert or active atmosphere. A key aspect of a polymer‐derived ceramics (PDCs) route is the possibility to “dissolve” carbon in phases such as Si 3 N 4 and SiO 2 and to create ternary phase ceramics such as SiOC and SiCN, which is only realizable by using single‐source‐precursors techniques. Synthetic routes for silicon‐based polymers as well as their transformation steps to ceramics (namely cross‐linking and pyrolysis) will be presented in this review. A short overview on PDCs as a unique class of ceramics is provided as well. Preceramic polymers, which are used for the synthesis of multinary PDCs such as SiBCN and SiMOCN (M = metal), are also described.

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Thermal cross‐linking and pyrolytic conversion of poly(ureamethylvinyl)silazanes to silicon‐based ceramics

Abstract: The aim of this work was to study the pyrolytic conversion of a novel commercial polysilazane, poly(ureamethylvinyl)silazane (PUMVS; Ceraset

Cited by 153 publications

References 28 publications

Polymer‐Derived SiOC Nanotubes and Nanorods via a Template Approach

Polymer‐Derived SiOC Nanotubes and Nanorods via a Template Approach

Composition and Morphology Control in Ordered Mesostructured High‐Temperature Ceramics from Block Copolymer Mesophases

Silicon‐Containing Preceramic Polymers

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