Zhou, Cong (2017)
Ternary Si-Metal-N Ceramics: Single-Source-Precursor Synthesis, Nanostructure and Properties Characterization.
Technische Universität Darmstadt
Ph.D. Thesis, Primary publication
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ZHOU Cong‘s Ph.D. thesis final.pdf Copyright Information: In Copyright. Download (8MB) | Preview |
Item Type: | Ph.D. Thesis | ||||
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Type of entry: | Primary publication | ||||
Title: | Ternary Si-Metal-N Ceramics: Single-Source-Precursor Synthesis, Nanostructure and Properties Characterization | ||||
Language: | English | ||||
Referees: | Riedel, Prof. Dr. Ralf ; Yu, Prof. Dr. Zhaoju | ||||
Date: | 11 April 2017 | ||||
Place of Publication: | Darmstadt | ||||
Date of oral examination: | 23 February 2017 | ||||
Abstract: | Si-M-N (M=metal) ceramic nanocomposites are novel materials that combine the advantages of both ceramics and metals. Additionally, a variety of intriguing functional properties are observed in the metal-modified ceramics due to the formation of a second phase, which reveals promising applications in the fields of optics (e.g., light-emitting diodes), semiconductors, catalysis and energy technology. Until now, most of the metal-modified nanocomposites are fabricated by using traditional powder techniques, but the grain sizes of the composites are limited to the micrometer range, and the dispersion of metal particles is not homogeneous. Polymer-derived ceramics route is widely considered as a promising approach in the synthesis of novel nanocomposites, where the nanocomposites are derived from the corresponding single-source precursors and exhibit improved structural and functional properties due to the unique nanostructures. This Ph.D. thesis is focused on the synthesis of ternary Si-M-N ceramics derived from single-source precursors with tailored compositions and structures, which were synthesized via the chemical modification of polysilazane with metallic compounds. The main objective of this research is to study the chemical modification of the precursors and nanostructures of Si-M-N ceramics and to gain a better understanding of the effect caused by the modification with different metallic compounds on the structures and properties of resultant ceramic nanocomposites. In the present research, single-source precursors with varied compositions and structures were synthesized by chemical modification of perhydropolysilazane (PHPS) with transition-metal compounds. Si-Hf-N, Si-V-N(O) and Si-Fe-N(O) single-source precursors were synthesized by using TDMAH, VO(acac)2 and Fe(acac)2, respectively. Amorphous single-phase Si-M-N ceramics were prepared via the subsequent cross-linking and pyrolysis under an ammonia atmosphere. The syntheses of these preceramic polymers were investigated by means of spectroscopic techniques including FT-IR, Raman and solid MAS NMR spectroscopy, and the results indicated the formation of expected transition-metal-modified precursors. Then, the structural evolution during the polymer-to-ceramic conversion of the precursors was monitored with FT-IR measurements. The prepared materials were investigated with respect to their crystallization behaviors and phase compositions using spectroscopic techniques together with X-ray diffraction (XRD), elemental analysis (EA) and scanning/transmission electron microscopy (SEM/TEM). Annealing experiments on the Si-M-N ceramics were performed in a nitrogen atmosphere at temperatures ranging from 1100 to 1800 °C, leading to the conversion of the amorphous materials into crystalline nanocomposites. It was found that α- and β-Si3N4 were obtained in the Si-M-N composites during the high-temperature treatment and built a matrix, while the transition-metals formed different crystallites such as metal nitrides (HfN, VN and Fe2N), pure metal (α-Fe) and metal silicide (Fe3Si) depending on the intrinsic characteristics of transition-metals and sintering temperatures, and these metal-containing crystallites homogeneously dispersed in the silicon nitride matrix. The high-temperature phase separation and crystallization behaviors of the Si-M-N ceramics were intensively investigated. The focus was firstly placed on the synthesis of novel polymer-derived SiHfN ceramics. They were prepared via the pyrolysis of a single-source precursor which was synthesized by the chemical reaction between perhydropolysilazane (PHPS) and tetrakis(dimethylamido) hafnium(IV) (TDMAH). The hafnium-modified PHPS precursor convert upon heat treatment in an ammonia atmosphere at 1000 °C into an XRD amorphous single-phase Si1Hf0.056N1.32 ceramic and remained amorphous even after annealing at 1400 °C in a nitrogen atmosphere. The PHPS-derived ceramic without modification showed a composition of Si1N0.71 at 1000 °C and started to crystallize at 1300 °C. The electron microscopy investigation exhibited that the annealing of the highly homogeneous single-phase SiHfN ceramic induced a local enrichment (clustering) of hafnium, leading to amorphous HfN/SiNx nanocomposites. The modification with TDMAH not only increases the nitrogen content of the ceramic materials but also efficiently improves the high-temperature stability of the Si3N4 against crystallization greatly. Annealing in nitrogen at 1600 °C resulted in a phase separation, and crystallized HfN/Si3N4 nanocomposite was obtained. The α- to β-Si3N4 phase transformation was greatly inhibited in the SiHfN ceramics at 1800 °C. Extensive STEM characterizations of the polycrystalline nanocomposites indicated further substitutional and interstitial doping of hafnium in Si3N4. An amorphous single-phase SiVN(O) ceramic was prepared via the ammonolysis of the corresponding single-source precursor, which was synthesized by the chemical modification of PHPS with vanadyl acetylacetonate (VO(acac)2). The as-obtained SiVN(O) ceramic exhibited high-temperature resistance against crystallization up to 1400 °C. Annealing at 1600 °C caused a phase separation and intensive crystallization. As a result, the nanocomposite composed of VN, α- and β-Si3N4 was obtained. Further investigation suggested that the introduction of VO(acac)2 promoted the α- to β-Si3N4 phase transformation at 1600 °C, and a VN/β-Si3N4 nanocomposite was obtained when the sample was annealed at 1600 °C. Furthermore, mesoporous SiVN(O) ceramics with high specific surface area (SSA) were successfully prepared by using polystyrene (PS) as self-sacrificial templates via a one-pot synthesis. After cross-linking and pyrolysis in an ammonia atmosphere at 1000 °C, a mesoporous SiVN(O) ceramic with a SSA of 506 m2/g was produced. Both the specific surface area and pore size distribution of the mesoporous ceramics can be adjusted by changing the amount of PS templates in the feed. Moreover, the mesoporous SiVN(O) ceramics exhibited good structural stability up to 1400 °C (SSA maintained ca. 200 m2/g), but a total collapse of the mesoporous structures was observed at 1600 °C. A SiFeN(O) precursor was synthesized by the reaction of PHPS with iron(II) acetylacetonate (Fe(acac)2) via the formation of Si-O-Fe bonds. The pyrolysis of SiFeN(O) precursor in ammonia induced a phase separation with the formation of Fe2N at 600 °C, and then the Fe2N decomposed into α-Fe by increasing the temperature to 1000 °C. Crystalline Fe3Si was obtained when the temperature was over 1200 °C. The observations demonstrated that the modification with Fe(acac)2 had a considerable influence on the phase separation and crystallization behaviors of the ceramics. Subsequently, a SiFeN(O)-based ceramic paper with in-situ generated hierarchical micro/nano-morphology was prepared by pyrolyzing a filter paper template that was modified with a SiFeN(O) precursor. After ammonolysis at 1000 °C, the obtained SiFeN(O)-based ceramic paper decorated with crystalline α-Fe had the same morphology as that of the used paper template. Ultra-long silicon nitride nanowires with great aspect ratios (~200 nm in diameter and several millimeters in length) were in-situ formed in a large quantity both on the surface and in the pores of the ceramic paper, when the ceramic paper was further annealed in nitrogen at temperatures from 1200 to 1400 °C. The nanowires exhibited a round Fe3Si tip at the end, indicating that the growth of one-dimensional nanostructures occurred via an iron-catalyzed VLS (vapor-liquid-solid) mechanism, and the length and yield of nanowires can be controlled by adjusting the experimental conditions, including temperatures and the addition of Fe(acac)2. Therefore, the combination of the single-source precursor, catalyst-assisted pyrolysis and template method provides a convenient one-pot route for the fabrication of ceramic paper and one-dimensional structures with high yields. In summary, the present Ph.D work proved that Si-M-N single-source precursors can be synthesized via the PDC route by modifying PHPS with different metallic compounds, and amorphous Si-M-N single-phase ceramics can be obtained via pyrolysis of the corresponding precursors. Polymer-derived ceramic nanocomposites composed of X/Si3N4 (X = metal, metal nitride or metal silicide) with a homogenous microstructure can be prepared by further annealing at higher temperatures. This thesis provides some new insights into the design and synthesis of metal-modified precursors and enables the production of Si-M-N ceramic nanocomposites via the PDC approach. |
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URN: | urn:nbn:de:tuda-tuprints-61456 | ||||
Classification DDC: | 500 Science and mathematics > 500 Science 500 Science and mathematics > 540 Chemistry 600 Technology, medicine, applied sciences > 620 Engineering and machine engineering |
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Divisions: | 11 Department of Materials and Earth Sciences > Material Science > Dispersive Solids | ||||
Date Deposited: | 13 Apr 2017 09:49 | ||||
Last Modified: | 09 Jul 2020 01:36 | ||||
URI: | https://tuprints.ulb.tu-darmstadt.de/id/eprint/6145 | ||||
PPN: | 402360648 | ||||
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