Dissertations / Theses: 'Polymer Derived Ceramics'

1

Hill, Arnold Hill. "PRODUCTION OF BULK CERAMIC SHAPES FROM POLYMER DERIVED CERAMICS." Master's thesis, University of Central Florida, 2008. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4248.

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A method has been developed to produce bulk ceramic components from a class of ceramics known as polymer derived ceramics. In the past polymer derived ceramics have been limited to thin film applications or in the fabrication of MEMS devices. The reason being that when the polymer is into a ceramic, large quantities of gas are generated which produce internal pressure that fractures the ceramic components. The method developed here solves that issue by casting into the polymer a 3 dimensional network of polymer fibers in the form of a foam which, during pyrolysis, burns out and leaves a network of open channels that allows decomposition gases to escape thus preventing pressure from building up. The inclusion of the polymer foam allows for the formation of strong plastic like green bodies which can be machined into any shape. The green bodies are then pyrolized into ceramic components. This process allows for the simple and inexpensive fabrication of complex ceramic components that have the potential to replace current components that are made with traditional methods.
M.S.M.S.E.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr MSMSE

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2

xu, weixing. "POLYMER-DERIVED CERAMICS: ELECTRONIC PROPERTIES AND APPLICATION." Doctoral diss., University of Central Florida, 2006. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4202.

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In this work, we studied the electronic behavior of polymer-derived ceramics (PDCs) and applied them for the synthesis of carbon nanotube reinforced ceramic nanocomposites and ceramic MEMS (Micro-Electro-Mechanical Systems) structures. Polymer-derived SiCN ceramics were synthesized by pyrolysis of a liquid polyureasilazane with dicumyl peroxide as thermal initiator. The structural evolution during pyrolysis and post-annealing was studied using FTIR, solid state NMR and Raman. The results revealed that the resultant ceramics consisted of SiCxNx-4 as major building units. These units were connected with each other through C-C/C=C bonds or by shearing N/C. The amount of sp2 free carbon strongly depends on composition and processing condition. Electron paramagnetic resonance (EPR) was used to investigate electronic structure of PDCs; the results revealed that the materials contain unpaired electron centers associated with carbons. Electronic behavior of the SiCN ceramics was studied by measuring their I-V curves, temperature dependence of d.c.-conductivities and impendence. The results revealed that the SiCN ceramics exhibited typical amorphous semiconductor behavior, and their conductivity varied in a large range. The results also revealed that the materials contain more than one phase, which have the different electronic behavior. We explored possibility of using polymer-derived ceramics to make ceramic MEMS for harsh environmental applications with a lithography technique. The cure depth of the polymer precursor was measured as a function of UV intensity and exposure time. The experimental data was compared with the available theoretical model. A few typical SiCN parts were fabricated by lithography technique. We also prepared carbon nanotube reinforced ceramic nanocomposites by using PDC processing. The microstructures of the composites were characterized using SEM and TEM; the mechanical properties were studied characterized using nanoindentation. The significant improvement in mechanical properties was observed for the nanocomposites.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science and Engineering

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3

Chen, Yaohan. "Structure and Properties of Polymer-Derived SiBCN Ceramics." Doctoral diss., University of Central Florida, 2012. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/5164.

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Polymer-derived ceramics (PDCs) are a unique class of multifunctional materials synthesized by thermal decomposition of polymeric precursors. Due to their unique and excellent properties and flexible manufacturing capability, PDC is a promising technology to prepare ceramic fibers, coatings, composites and micro-sensors for high-temperature applications. However, the structure-property relationships of PDCs have not been well understood. The lack of such understandings drastically limited the further developments and applications of the materials. In this dissertation, the structure and properties of amorphous polymer-derived silicon carbonitride (SiCN) and silicoboron carbonitride (SiBCN) have been studied. The SiCN was obtained using commercially available polysilazane as pre-ceramic precursor, and the SiBCN ceramics with varied Si-to-B ratio were obtained from polyborosilazanes, which were synthesized by the hydroboration and dehydrocoupling reaction of borane and polysilazane. The structural evolution of polymer-derived SiCN and SiBCN ceramics from polymer to ceramics was investigated by NMR, FTIR, Raman, EPR, TG/DTA, and XRD. The results show a phase-separation of amorphous matrix and a graphitization of "free" carbon phase, and suggest that the boron doping has a great influence on the structural evolution. The electric and dielectric properties of the SiCN and SiBCNs were studied by I-V curves, LCR Meter, and network analyzer. A new electronic conduction mechanism and structure model has been proposed to account for the relationships between the observed properties and microstructure of the materials. Furthermore, the SiBCN ceramics showed the improved dielectric properties at characterization temperature up to 1300 [degrees]C, which allows the fabrication of ultrahigh-temperature wireless microsensors for extreme environments.
ID: 031001462; System requirements: World Wide Web browser and PDF reader.; Mode of access: World Wide Web.; Title from PDF title page (viewed July 8, 2013).; Thesis (Ph.D.)--University of Central Florida, 2012.; Includes bibliographical references (p. 150-170).
Ph.D.
Doctorate
Materials Science Engineering
Engineering and Computer Science
Materials Science and Engineering

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4

wei, yun. "SYNTHESIS AND CHARACTERIZATION OF POLYMER-DERIVED POROUS SICN CERAMICS." Master's thesis, University of Central Florida, 2008. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/3566.

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The synthesis and characterization of porous SiCN ceramics produced by the method of polymer-derived ceramics were studied in this work. The polymer-to-ceramic conversion technique is a novel revolution in the methods for fabricating porous materials with controlled morphologies and tailored properties. The porous SiCN ceramics can be successfully prepared from thermal decomposition of polymeric precursors (polysilazane) and the pore former (polyvinyl alcohol (PVA)). The fabrication procedures involved the mixing of the pre-ceramic precursor with appropriate concentration of the PVA, curing, pyrolysis and subsequent PVA removal, leaving pores in the ceramic matrix. The material obtained revealed a homogeneous amorphous microstructure consisting of Si, C and N elements. The effects of the concentration and the particle size of PVA on the bulk density, open porosity, line shrinkage, microstructure, pore size, permeability, mechanical behavior, oxidation behavior and thermal stability were examined in this thesis. An increase in both concentration and particle size of PVA contribute to a decrease in the bulk density and an increase in the open porosity and line shrinkage. The morphology development, in particular, was investigated by scanning electron microscopy (SEM). The properties in terms of the pore size and permeability were measured by the water expulsion method. The mechanical behavior of the porous SiCN ceramic was characterized by the three- point bending strength test, thermal shock strength test and hertzian indentation strength test. The flexural strength and hertzian indentation strength of these porous ceramics at room temperature decrease with an increase in porosity. However, the flexural strength after thermal shock was significantly improved by increasing the temperature change. The oxidation behavior and thermal stability of porous SiAlCN ceramics were also explored by the mass change versus oxidation time and temperature. The phase evolution at different temperatures was also investigated by XRD analysis.
M.S.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr MSMSE

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5

Santhosh, Balanand. "Thermal properties of polymer derived Si-O-C-N ceramics." Doctoral thesis, Università degli studi di Trento, 2020. http://hdl.handle.net/11572/267913.

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The main objective of the thesis is to study the thermal properties of Si-based polymer derived ceramics (PDCs) at elevated temperatures and to classify the main factors affecting the thermal transport through these ceramics. The polymer derived ceramics with the chemistry Si- O-C-N were prepared starting from commercial polycarbosilane, polysiloxane, and polysilazane precursors. These precursors are cross-linked at room temperature to obtain the preceramic, followed by controlled pyrolysis (at different temperatures ranging from 1200 oC to 1800 oC in argon, nitrogen or carbon-di-oxide atmospheres), to get the final ceramic. The first part of the thesis discusses on development and studies of dense polymer derived thin disks having a basic chemistry, Si-C, Si-O- C, and, Si-C-N-O, developed via a casting technique followed by specific pyrolysis cycles. Having a thickness in the range of 100 μm- 300 μm, these ceramic disks were studied to be nanocrystalline/amorphous at least up to a temperature of 1400 oC and were found to have a significant amount of Cfree phase existing in them along with the intended chemistry. The high-temperature thermal properties were primarily investigated on ceramics prepared at a pyrolysis temperature of 1200 oC (ceramic still in nanocrystalline/amorphous glassy phase). The disks were found to have very low expansion coefficients (CTE) measured up to ~900 oC and the thermal diffusivity (k) and thermal conductivity (l) of these disks were also measured. An attempt to understand the influence of the different phases in a SiOC ceramic (mainly the Cfree phase, studied by enriching the carbon percentages using DVB) in determining the final thermal properties was also conducted. The influence of carbon enrichment on the mechanical properties of these disks is also studied as a sub-part of this work. The second part of the work deals with testing the possibility to use these ceramics for high-temperature insulation applications. ‘Reticulated’ ceramic foams of relatively same chemistries as that of the disks were prepared by a template replica approach, using polyurethane (PU) foams (more open-celled to more closed-celled types of PU foams were used in the study) as the template. Porous structures having densities ranging from as low as 0.02 g.cm-3 to 0.56 g.cm-3 and with a porosity ~ 80 % to ~99% were prepared and tested. The developed foams showed excellent thermal stability up to a temperature of 1400 oC and possessed very low thermal expansion. The thermal conductivity measured on them at RT gave values in the range 0.03 W.m-1.K-1- 0.25 W.m-1.K-1. A Gibson-Ashby modeling approach to explain the thermal conductivity of the porous ceramics was also attempted. The developed foams were also found to be mechanically rigid. In a nutshell, the thesis work studies the thermal properties of Si-O-C- N ceramics in detail and probes into the possibility to develop these class of Si-O-C-N ceramics into promising high-temperature insulation material.

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6

Santhosh, Balanand. "Thermal properties of polymer derived Si-O-C-N ceramics." Doctoral thesis, Università degli studi di Trento, 2020. http://hdl.handle.net/11572/267913.

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The main objective of the thesis is to study the thermal properties of Si-based polymer derived ceramics (PDCs) at elevated temperatures and to classify the main factors affecting the thermal transport through these ceramics. The polymer derived ceramics with the chemistry Si- O-C-N were prepared starting from commercial polycarbosilane, polysiloxane, and polysilazane precursors. These precursors are cross-linked at room temperature to obtain the preceramic, followed by controlled pyrolysis (at different temperatures ranging from 1200 oC to 1800 oC in argon, nitrogen or carbon-di-oxide atmospheres), to get the final ceramic. The first part of the thesis discusses on development and studies of dense polymer derived thin disks having a basic chemistry, Si-C, Si-O- C, and, Si-C-N-O, developed via a casting technique followed by specific pyrolysis cycles. Having a thickness in the range of 100 μm- 300 μm, these ceramic disks were studied to be nanocrystalline/amorphous at least up to a temperature of 1400 oC and were found to have a significant amount of Cfree phase existing in them along with the intended chemistry. The high-temperature thermal properties were primarily investigated on ceramics prepared at a pyrolysis temperature of 1200 oC (ceramic still in nanocrystalline/amorphous glassy phase). The disks were found to have very low expansion coefficients (CTE) measured up to ~900 oC and the thermal diffusivity (k) and thermal conductivity (l) of these disks were also measured. An attempt to understand the influence of the different phases in a SiOC ceramic (mainly the Cfree phase, studied by enriching the carbon percentages using DVB) in determining the final thermal properties was also conducted. The influence of carbon enrichment on the mechanical properties of these disks is also studied as a sub-part of this work. The second part of the work deals with testing the possibility to use these ceramics for high-temperature insulation applications. ‘Reticulated’ ceramic foams of relatively same chemistries as that of the disks were prepared by a template replica approach, using polyurethane (PU) foams (more open-celled to more closed-celled types of PU foams were used in the study) as the template. Porous structures having densities ranging from as low as 0.02 g.cm-3 to 0.56 g.cm-3 and with a porosity ~ 80 % to ~99% were prepared and tested. The developed foams showed excellent thermal stability up to a temperature of 1400 oC and possessed very low thermal expansion. The thermal conductivity measured on them at RT gave values in the range 0.03 W.m-1.K-1- 0.25 W.m-1.K-1. A Gibson-Ashby modeling approach to explain the thermal conductivity of the porous ceramics was also attempted. The developed foams were also found to be mechanically rigid. In a nutshell, the thesis work studies the thermal properties of Si-O-C- N ceramics in detail and probes into the possibility to develop these class of Si-O-C-N ceramics into promising high-temperature insulation material.

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Cox, Sarah. "Processing and Characterization of Continuous Basalt Fiber Reinforced Ceramic Matrix Composites Using Polymer Derived Ceramics." Master's thesis, University of Central Florida, 2014. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/6259.

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The need for high performance vehicles in the aerospace industry requires materials which can withstand high loads and high temperatures. New developments in launch pads and infrastructure must also be made to handle this intense environment with lightweight, reusable, structural materials. By using more functional materials, better performance can be seen in the launch environment, and launch vehicle designs which have not been previously used can be considered. The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Polymer matrix composites can be used for temperatures up to 260°C. Ceramics can take much higher temperatures, but they are difficult to produce and form in bulk volumes. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, allowing a shape to be formed and cured and then to be pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in the composites. In this study, continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material. The oxyacetylene torch testing and three point bend testing have been performed on test panels and the test results are presented.
M.S.M.S.E.
Masters
Materials Science Engineering
Engineering and Computer Science
Materials Science and Engineering

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8

Burghard, Zaklina. "Behaviour of glasses and polymer derived amorphous ceramics under contact stress." [S.l. : s.n.], 2004. http://www.bsz-bw.de/cgi-bin/xvms.cgi?SWB11406707.

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9

JIANG, TAO. "ELECTRONIC PROPERTIES AND MICROSTRUCTURES OF AMORPHOUS SICN CERAMICS DERIVED FROM POLYMER PRECURSORS." Doctoral diss., University of Central Florida, 2009. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/2988.

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Polymer-derived ceramics (PDCs) are a new class of high-temperature materials synthesized by thermal decomposition of polymeric precursors. These materials possess many unique features as compared with conventional ceramics synthesized by powder metallurgy based processing. For example, PDCs are neither amorphous nor crystalline. Instead, they possess nano-domain structures. Due to the direct chemical-to-ceramic processing, PDCs can be used for making components and devices with complex shapes. Thus, understanding the properties and structures of these materials are of both fundamental and practical interest. In this work, the structures and electronic behavior of polymer-derived amorphous silicon carbonitrides (SiCNs) were investigated. The materials were synthesized by pyrolysis of a commercially available liquid precursor. Ceramic materials with varied structures/properties were successfully synthesized by modifying the precursor and using different pyrolysis temperatures. The structures of the obtained materials were studied using XRD, solid state NMR, EPR, FTIR and Raman Spectroscope. The electronic behavior of the materials was investigated by measuring I-V curves, Hall effects, temperature dependent conductivity. The experiments were also performed to measure UV-Visible absorption and dielectric properties of the materials. This work leads to the following significant progresses: (i) developed quantitative technique for measuring free carbon concentration; (ii) achieved better understanding of the electronic conduction mechanisms and measured electronic structures of the materials for the first time; and (iii) demonstrated that these materials possess unusual dielectric behavior and provide qualitative explanations.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering
Engineering and Computer Science
Materials Science & Engr PhD

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10

Scarlete, Mihai. "Spectroscopic methods for the characterization of thin films of polymer-derived ceramics." Thesis, McGill University, 1995. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=39994.

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Poly(methylsilane) (PMS) has been used as a precursor to form a variety of ceramic materials within the Si-C-N system. Special emphasis was placed on the synthesis of SiC, $ rm Si sb3N sb4$ and derived tertiary ceramic materials for use in semiconductor applications, mainly as thin films coated onto various substrates.
Detailed insight into the chemical transformations occurring during pyrolysis under inert (N$ sb2$, Ar) or reactive (NH$ sb3$) atmospheres was achieved by analysis of the layers coated on silicon single-crystal wafers. The oxidation of PMS and its transformation during pyrolysis into SiC were monitored by IR reflectance and transmission spectroscopy. The degree of the oxidation of PMS is not only a critical factor in determining the electronic properties of the final resulting materials, but is also a key factor in determining the pyrolysis mechanism. An important observation was the low-temperature ($ sim$200$ sp circ$C) Kumada rearrangement of the PMS to poly(cabosilane) (PCS). This reaction was evident at 200$ sp circ$C on silicon substrates, when the oxygen concentration in PMS was below 40 parts per million (ppm). Ultrathin layers of amorphous SiC (a-SiC) with thicknesses of $ sim$100 nm were obtained by deposition of the volatile species resulting from the thermal cracking of the precursor. The cracked-polymer vapor deposition (CP-VD) method allowed the synthesis of smooth (mirror-like) ceramic layers. The layers obtained by both CP-VD and spin-coating procedures exhibited resistivities in the range of $10 sp3-10 sp6 Omega$ cm and good adhesion properties onto the silicon substrates.
n-type SiC layers doped with nitrogen having a resistivity range suitable for Si/SiC heterojunctions in solar cells were also synthesized on silicon single-crystal wafers. A homogeneous doping procedure was developed that consists of reacting the Wurtz PMS prepolymer with NH$ sb3$ to form a "doping polymer". Partial pressure of NH$ sb3$ can enhance the rate of deposition of ceramics on cold substrates. In this case, CP-VD appears to combine some advantages of the two currently used procedures for growing thin films--i.e., a high deposition rate characteristic of pyrolysis of spin-coated films of precursors and good texture of the layers, characteristic of the chemical vapor deposition process (CVD).
The inclusion of higher concentrations of nitrogen into the ceramic material was studied during the synthesis of $ rm Si sb3N sb4$ by pyrolysis of PMS under pure NH$ sb3$. The analysis of the intermediate products resulting from the reaction of the precursor with NH$ sb3$ revealed that carbon loss occurred at temperatures below 600$ sp circ$C, and involves poly(carbosilazane) species. The stoichiometric 4:3 atomic ratio of N to Si is achieved below 500$ sp circ$C. A reaction path way is proposed in which only heterodehydrocoupling between Si-H and N-H groups occurs. This pathway is sufficient to explain the incorporation of excess nitrogen (compared to $ rm Si sb3N sb4$) usually observed in the intermediate pyrolysis products. Carbon loss is not directly related to nitrogen incorporation, thus the two processes are, at least partially, independent.
The effect of the thermal decomposition of NH$ sb3$, as an independent variable, on the carbon/nitrogen exchange process was studied. Deviations from thermodynamic equilibrium were related to dynamic conditions characterizing the flow regime.

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11

Wang, Yiguang. "POLYMER-DERIVED SI-AL-C-N CERAMICS:OXIDATION, HOT-CORROSION, AND STRUCTURAL EVOLUTION." Doctoral diss., University of Central Florida, 2006. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4214.

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Polymer-derived ceramics are a new class of materials synthesized by thermal decomposition of polymer precursors. Previous studies have shown that the materials exhibit excellent thermo-mechanical properties and can be stable at temperatures up to 2000oC. Furthermore, the novel polymer-to-ceramics process enables the manipulation of the ceramic structures at the atomic/nano level by designing the chemistry of polymer precursors and controlling the pyrolysis conditions, thereby, the properties of ceramics. In this dissertation, oxidation/hot-corrosion behavior and the structural evolution of Si-Al-C-N ceramics have been studied. The structural evolution and crystallization behavior of the SiCN and SiAlCN ceramics are investigated using FT-IR, XRD, and NMR. The results revealed that aluminum could greatly affect the structural evolution and crystallization behavior of polymer-derived ceramics, resulting to better stability. The oxidation kinetics of the SiCN and SiAlCN ceramics in air is determined by directly measuring the thickness of the oxide scale with SEM as a function of oxidation time. The results revealed that while the oxidation of the SiCN ceramics follows parabolic kinetics in all of the ranges of testing temperatures, oxidation of the SiAlCN ceramics is complicated: their oxidation rates are similar to that of SiCN ceramics at the earlier stage, but they decrease to very low levels after a certain time. The oxidation rate of the SiAlCN ceramics is more than an order of magnitude lower than any other silicon based ceramics previously reported. The transportation behavior of oxygen through the oxide scales is studied by 18O diffusion. The results indicate that oxidation is controlled by molecular oxygen diffusing through the oxides for both SiCN and SiAlCN ceramics; however, the oxygen diffusion rate in the oxides on SiAlCN ceramics is remarkably retarded. The structures of the oxides are characterized by XRD and NMR. A structural model is advanced to account for the aluminum effect on the oxygen diffusion in the oxide. The oxidation and hot-corrosion kinetics of the SiCN and SiAlCN ceramics in water vapor are determined by measuring their weight changes as a function of annealing time. The kinetic constants, kp and kl, are obtained by fitting the weight-change data with a paralinear model. The results reveal that the SiAlCN ceramics have a much better corrosion resistance than the SiCN and CVD SiC/Si3N4. After annealing at 1400oC for 300 hours, the SiAlCN-20 still retains more than 70% of its original strength, while the SiCN only retains about 20% of its original strength. The improvement in oxidation/hot-corrosion resistance of the SiAlCN ceramics is attributed to the low activity of the SiO2 in the Al2O3-containing silica. In summary, I have developed a new class of high-temperature materials, Si-Al-C-N ceramics. It is demonstrated that these new materials have excellent oxidation and corrosion resistance and thermal stability. Together with their easy processability, the materials will find many high temperature applications such as environmental barrier coatings, ceramic matrix composites, and MEMS for harsh environments.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science and Engineering

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Kulkarni, Apoorv Sandeep. "Ceramic Si-C-N-O cellular structures by integrating Fused Filament Fabrication 3-D printing with Polymer Derived Ceramics." Doctoral thesis, Università degli studi di Trento, 2022. http://hdl.handle.net/11572/349905.

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Ceramic additive manufacturing is gaining popularity with methods like selective laser sintering (SLS), binder jetting, direct ink writing and stereolithography, despite their disadvantages. Laser sintering and binder jetting are too expensive, while direct ink writing lacks resolution and stereolithography lacks scalability. The project aims to combine one of the most versatile, affordable, and readily available 3D printing methods: fused filament fabrication (FFF) with polymer derived ceramics to produce cellular ceramics to overcome the disadvantages posed by the other methods. The process uses a two-step approach. The first step is to 3D print the part using a polymer FFF 3D printer with a thermoplastic polyurethane filament and the second step is to impregnate the part in a polysilazane preceramic polymer and then pyrolyze it in an inert environment up to 1200C. The resulting product is a high-resolution cellular ceramic of the composition SiOC(N). This type of cellular ceramic can find an application in several fields such as scaffolds for bone tissue regeneration, liquid metal filtering, chemical and gas filtering, catalytic converters and electric applications. The process can provide an affordable alternative to the products used in these fields currently.

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Prasad, Ravi Mohan. "Polymer-Derived Microporous Ceramics for Membranes and Sensors for High Temperature Hydrogen Purification and Sensing." Phd thesis, tuprints, 2012. http://tuprints.ulb.tu-darmstadt.de/3181/1/PhD_Dissertation_Ravi_Mohan_Prasad_%28TU_Darmstadt%29.pdf.

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The growing interest in the use of hydrogen as main fuel has increased the need for pure hydrogen (H2) production and purification. There are several by-products (CO, H2O, CO2) associated with the production of hydrogen which might damage the production rate. Therefore, separation of hydrogen from other gases is an important step in the hydrogen production process. If H2 can be selectively removed from the product side during hydrogen production in membrane reactors, then it would be possible to achieve complete CO conversion in a single-step under high temperature conditions. The main goal of the present work is the high temperature H2 purification and sensing by applying polymer-derived ceramics. To prove the concept, the microporous SiBCN, Si3N4 and SiCN ceramic membranes have been synthesized by the polymer-pyrolysis route and their performance for the hydrogen separation have been evaluated in tubular membranes as well as in planar chemiresistors. The synthesis of amorphous SiBCN ceramics has been realized through pyrolysis of poly(organoborosilazanes) in argon. Multilayered amorphous SiBCN/γ-Al2O3/α-Al2O3 membranes with gradient porosity have been realized and assessed with respect to the thermal stability, pore-size distribution and H2/CO permeance. N2-adsorption measurement indicates micropores in the range of 0.68-0.73 nm for three-fold SiBCN/γ-Al2O3/α-Al2O3 membrane. SEM characterization of three-fold SiBCN/γ-Al2O3/α-Al2O3 membrane shows the thickness of SiBCN membrane layer is 2.8 μm; gas permeance measurements of the membrane shows H2/CO selectivity of about 10.5 and the H2 permeance of about 1.05x10-8 mol m-2 s-1 Pa-1. The observed gas permeation properties point out that the transportation of gas molecules through the membrane is governed by both activated and Knudsen diffusion. The stability and sensing characteristics of SnO2 sensors coated with amorphous microporous SiBCN layers have been studied in oxygen-free atmospheres. The SiBCN layers coated on SnO2 sensors are amorphous, crack-free and microporous. The diameter of micropores (about 0.70 nm) is larger than the kinetic diameter of H2 (0.289 nm) and CO (0.376 nm) molecules, allowing in this way their diffusion towards the bottom SnO2 sensing layer. Transient response characteristics and sensor signals of uncoated SnO2, three-fold and five-fold SiBCN-coated SnO2 sensors exposed to CO (10, 20 and 120 ppm) and H2 (40, 400 and 900 ppm) in nitrogen at 350 and 530 °C are obtained. Uncoated SnO2 sensor is reduced at 530 °C in H2 to tin while SiBCN-coated SnO2 sensors show reversible resistance changes while exposed to CO and H2. Si3N4-ceramics have been synthesized via a dry ammonia pyrolysis of commercially available polysilazane (KiON HTT 1800). Amorphous microporous-Si3N4 ceramic layers deposited on the top of GaN sensing layer followed by dry ammonia treatment leads to the improved H2 to CO selectivity of Si3N4/GaN sensors in the oxygen-free atmosphere. Transient response of the uncoated-, three-fold Si3N4 coated- and ammonia treated-GaN sensors exposed to CO (10, 20 and 120 ppm) and H2 (40, 400 and 900 ppm) in pure nitrogen at 350 and 530 °C are investigated. The results indicate that uncoated-GaN sensor shows high response towards both CO and H2 whereas for microporous Si3N4 coated- and ammonia treated-GaN gas sensors the sensitivity towards the interfering gas CO is significantly reduced. High-surface area micro- and mesoporous carbon-rich SiCN ceramics have been obtained by controlled thermolysis of a carbon-rich poly(diphenylsilylcarbodiimide) precursor under argon. The formation of porous SiCN ceramics is due to the carbothermal reaction of amorphous silicon nitride phase with excess carbon, which leads to materials with high specific surface area of about 500-600 m2 g−1. High-resolution Transmisson Electron Microscopy indicates that pores are embedded only in the free carbon phase. The transformation from micro- to mesoporous ceramics after heat treatment between 1600 and 1700 °C, due to the organization of graphene-like free carbon phase, is discussed.

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Termoss, Hussein. "Préparation de revêtements de nitrure de bore (BN) par voie polymère précéramique : étude des paramètres d’élaboration : caractérisations physico-chimiques." Thesis, Lyon 1, 2009. http://www.theses.fr/2009LYO10145/document.

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L’objectif de cette thèse est de réaliser des revêtements de nitrure de bore sur différents types de substrats comme le graphite, le quartz, le pyrex, en allant jusqu’aux métaux et en particulier le titane. Le choix de la voie PDCs s’avère intéressant grâce à la maîtrise du précurseur de départ au niveau atomique d’une part et à la facilité du procédé de dépôt, d’autre part. Nos objectifs étaient d’étudier la faisabilité de réaliser des revêtements BN sur différents types de substrat en utilisant un traitement thermique résistif et de mettre en place un dispositif qui nous permette de pyrolyser les films polymériques sur métaux sans dommage pour le substrat, en vue de leur protection contre l’oxydation ou d’autres applications mécaniques. Dans ce sens, nous avons démontré la possibilité d’utiliser un traitement thermique alternatif par lampe halogène émettant dans l’infra-rouge pour densifier les revêtement BN déposer sur substrats métalliques
The aim of this work was to prepare boron nitride coatings onto different substrates using the Polymers Derived Ceramics (PDCs) approach. In that way, BN coatings were obtained onto graphite, pure silica and metal especially titanium. The first part of this thesis was to study parameters (of the solution used and of the dip-coating process), to obtain the best coatings in terms of morphology, cristallinity and chemical composition. The second part was dedicated to BN coatings obtained onto metal substrates using an alternative thermal treatment allowing the polymer-to-ceramic conversion without any damage for the metal. Actually, annealing by infrared irradiation allows heating only the coating, energy being reflected by the metal

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Abass, Monsuru A. "Boron nitride nanotube-modified silicon oxycarbide ceramic composite: synthesis, characterization and applications in electrochemical energy storage." Thesis, Kansas State University, 2017. http://hdl.handle.net/2097/35423.

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Master of Science
Department of Mechanical and Nuclear Engineering
Gurpreet Singh
Polymer-derived ceramics (PDCs) such as silicon oxycarbide (SiOC) have shown promise as an electrode material for rechargeable Li-ion batteries (LIBs) owing to the synergy between its disordered carbon phase and hybrid bonds of silicon with oxygen and carbon. In addition to their unique structure, PDCs are known for their high surface area (~822.7 m² g⁻¹), which makes them potential candidates for supercapacitor applications. However, low electrical conductivity, voltage hysteresis, and first cycle lithium irreversibility have hindered their introduction into commercial devices. One approach to improving charge storage capacity is by interfacing the preceramic polymer with boron or aluminium prior pyrolysis. Recent research has shown that chemical interfacing with elemental boron, bulk boron powders and even exfoliated sheets of boron nitride leads to enhancements in thermal and electronic properties of the ceramic. This thesis reports the synthesis of a new type of PDC composite comprising of SiOC embedded with boron nitride nanotubes (BNNTs). This was achieved through the introduction of BNNT in SiOC pre-ceramic polymer at varying wt.% loading (0.25, 0.5 and 2.0 wt.%) followed by thermolysis at high temperature. Electron microscopy and a range of spectroscopy techniques were employed to confirm the polymer-to-ceramic transformation and presence of disordered carbon phase. Transmission electron microscopy confirmed the tubular morphology of BNNT in the composite. To test the material for electrochemical applications, the powders were then made into free-standing paper-like electrodes with reduced graphene oxide (rGO) acting as support material. The synthesized free-standing electrodes were characterized and tested as electrochemical energy storage materials for LIBs and symmetric supercapacitor applications. Among the SiOC-BNNT composite paper tested as anode materials for LIBs, the 0.25 wt.% BNNT composite paper demonstrated the highest first cycle lithiation capacity corresponding to 812 mAh g⁻¹ (at a current density of 100 mA g⁻¹) with a stable charge capacity of 238 mAh g⁻¹ when asymmetrically cycled after 25 cycles. On the contrary, the 0.5 wt.% BNNT composite paper demonstrated the highest specific capacitance corresponding to 78.93 F g⁻¹ at a current density of 1 A g⁻¹ and a cyclic retention of 86% after 185 cycles. This study shows that the free carbon content of SiOC-BNNT ceramic composite can be rationally modified by varying the wt.% of BNNT. As such, the paper composite can be used as an electrode material for electrochemical energy storage.

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Shao, Gang. "Development of Polymer Derived SiAlCN Ceramic and Its Applications for High-Temperature Sensors." Doctoral diss., University of Central Florida, 2013. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/5868.

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Polymer-derived ceramic (PDC) is the name for a class of materials synthesized by thermal decomposition of polymeric precursors which excellent thermomechanical properties, such as high thermal stability, high oxidation/corrosion resistance and high temperature multifunctionalities. Direct polymer-to-ceramic processing routes of PDCs allow easier fabrication into various components/devices with complex shapes/structures. Due to these unique properties, PDCs are considered as promising candidates for making high-temperature sensors for harsh environment applications, including high temperatures, high stress, corrosive species and/or radiation. The SiAlCN ceramics were synthesized using the liquid precursor of polysilazane (HTT1800) and aluminum-sec-tri-butoxide (ASB) as starting materials and dicumyl peroxide (DP) as thermal initiator. The as-received SiAlCN ceramics have very good thermal-mechanical properties and no detectable weight loss and large scale crystallization. Solid-state NMR indicates that SiAlCN ceramics have the SiN4, SiO4, SiCN3, and AlN5/AlN6 units. Raman spectra reveals that SiAlCN ceramics contain "free carbon" phase with two specific Raman peaks of "D" band and "G" band at 1350 cm-1 and 1600 cm-1, respectively. The “free carbon” becomes more and more ordered with increasing the pyrolysis temperature. EPR results show that the defects in SiAlCN ceramics are carbon-related with a g-factor of 2.0016 [plus or minus] 0.0006. Meanwhile, the defect concentration decreases with increasing sintered temperature, which is consistent with the results obtained from Raman spectra. Electric and dielectric properties of SiAlCN ceramics were characterized. The D.C. conductivity of SiAlCN ceramics increases with increasing sintered temperature and the activation energy is about 5.1 eV which higher than that of SiCN ceramics due to the presence of oxygen. The temperature dependent conductivity indicates that the conducting mechanism is a semiconducting band-gap model and follows the Arrhenius equation with two different sections of activation energy of 0.57 eVand 0.23 eV, respectively. The temperature dependent conductivity makes SiAlCN ceramics suit able for high temperature sensor applications. The dielectric properties were carried out by the Agilent 4298A LRC meter. The results reveal an increase in both dielectric constant and loss with increasing temperature (both pyrolysis and tested). Dielectric loss is dominated by the increasing of conductivity of SiAlCN ceramics at high sintered temperatures. SiAlCN ceramic sensors were fabricated by using the micro-machining method. High temperature wire bonding issues were solved by the integrity embedded method (IEM). It's found that the micro-machining method is a promising and cost-effective way to fabricate PDC high temperature sensors. Moreover IEM is a good method to solve the high temperature wire bonding problems with clear bonding interface between the SiAlCN sensor head and Pt wires. The Wheatstone bridge circuit is well designed by considering the resistance relationship between the matching resistor and the SiAlCN sensor resistor. It was found that the maximum sensitivity can be achieved when the resistance of matching resistor is equal to that of the SiAlCN sensor. The as-received SiAlCN ceramic sensor was tested up to 600 degree C with the relative output voltage changing from -3.932 V to 1.153 V. The results indicate that the relationship between output voltage and test temperature is nonlinear. The tested sensor output voltage agrees well with the simulated results. The durability test was carried out at 510 degree C for more than two hours. It was found that the output voltage remained constant for the first 30 min and then decreased gradually afterward by 0.02, 0.04 and 0.07 V for 1, 1.5 and 2 hours.
Ph.D.
Doctorate
Materials Science Engineering
Engineering and Computer Science
Materials Science and Engineering

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Nonnenmacher, Katharina [Verfasser], Hans-Joachim [Akademischer Betreuer] Kleebe, and Ralf [Akademischer Betreuer] Riedel. "Microstructure Characterization of Hafnium-Modified Polymer-Derived SiOC and SiCN Ceramics / Katharina Nonnenmacher ; Hans-Joachim Kleebe, Ralf Riedel." Darmstadt : Universitäts- und Landesbibliothek Darmstadt, 2016. http://d-nb.info/1122286260/34.

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18

Stackpoole, Margaret Mary. "Reactive processing and mechanical properties of polymer derived silicon nitride matrix composites and their use in coating and joining ceramics and ceramic matrix composites /." Thesis, Connect to this title online; UW restricted, 2002. http://hdl.handle.net/1773/10564.

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Franchin, Giorgia. "Additive Manufacturing of Ceramics. Printing Beyond the Binder." Doctoral thesis, Università degli studi di Padova, 2017. http://hdl.handle.net/11577/3426205.

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This research project focuses on the production of ceramics via Additive Manufacturing (AM) techniques, with particular focus on extrusion-based technologies. The main advantage of AM is the ability to produce cellular structures with high complexity and controlled porosity, allowing to manufacture light but efficient stretch-dominated structures. The inspiration comes from nature: bone architectures are a great example, consisting of thin, solid skins attached to highly porous, cellular cores. Very few commercially available AM systems are suited for ceramic materials, and most of them use ceramic powders as feedstock. Residual pores and cracks are very hard to avoid and result in low strength, poor reliability and loss of unique material properties such as glass optical transparency. AM technologies employing polymers are at a much more advanced stage of development. The goal has been to exploit such advances and to provide alternatives to the ceramic powder-binder approaches. Three different material families were explored: preceramic polymers, geopolymers, and glass. The same preceramic polymer, a commercial polysilsesquioxane, was employed as a non sacrificial, reactive binder to develop inks for stereolithography (SL) and direct ink writing (DIW). The first technology allowed for production of dense, crack-free SiOC micro-components with strut size down to ~200 μm and optimal surface quality. No shape limitations were experienced, but porous structures or small dense parts are the best options in order to avoid residual pores and cracks. The second approach was employed for the fabrication of complex biosilicate scaffolds for tissue engineering with a rod diameter of 350 µm and unsupported struts. The preceramic polymer had the double role of source of silica and rheology modifier. Ceramic matrix composites (CMCs) were also fabricated; the preceramic polymer developed the ceramic matrix (SiOC) upon pyrolysis in inert atmosphere, whereas reinforcement was given by chopped carbon fibers. Geopolymer components with controlled porosity were designed and produced first by negative replica of PLA sacrificial templates and then by DIW. Highly porous ceramic components with features of ~800 μm and unsupported parts with very limited sagging were produced with the latter approach. A novel extrusion-based AM approach was finally developed for the production of objects starting from molten glass. The system processed glass from the molten state to annealed components of complex, digitally designed forms. Objects possessing draft angles and tight radii were fabricated. Within the design space it was possible to print with high precision and accuracy; parts showed a strong adhesion between layers, and high transparency through the layers.
Questo progetto di ricerca riguarda la produzione di ceramici tramite tecniche di manifattura additiva (AM), con particolare focus su tecnologie estrusive. Il principale vantaggio dell’AM è la possibilità di produrre strutture cellulari ad elevata complessità e porosità controllata, consentendo di produrre reticoli stretch-dominated leggeri ma efficienti. L’ispirazione è offerta dalla natura: le strutture ossee sono un ottimo esempio, in quanto si compongono di un involucro esterno, denso e sottile, e di un cuore a struttura cellulare altamente porosa. I sistemi di AM disponibili in commercio per la produzione di componenti ceramici sono molto pochi, e la maggior parte di essi utilizza polveri ceramiche. È molto difficile evitare porosità residua e cricche, e di conseguenza si ottengono oggetti dalla resistenza limitata e privi delle peculiarità di alcuni materiali, come ad esempio la trasparenza del vetro. Le tecnologie di AM che utilizzano polimeri sono ad uno stadio di sviluppo molto più avanzato. L’obiettivo è di sfruttare tale vantaggio e di fornire alternative agli approcci polvere-legante. Sono stati esplorati tre diversi materiali: polimeri preceramici, geopolimeri, e vetro. Un unico polimero preceramico, un polisilsesquiossano commerciale, è stato utilizzato come legante reattivo, non sacrificale per lo sviluppo di inchiostri per stereolitografia (SL) e direct ink writing (DIW). La prima tecnologia ha consentito di produrre micro-componenti in SiOC densi e privi di cricche, con una dimensione dei pilastri fino a ~200 μm e ottima qualità superficiale. Non ci sono state limitazioni di forma, anche se strutture porose o oggetti densi di piccole dimensioni sono da preferire per evitare porosità residua e cricche. Il secondo approccio ha portato alla fabbricazione di scaffold bioceramici per ingegneria tissutale con filamenti di diametro 350 µm e parti non supportate. Il polimero preceramico ha il doppio ruolo di fonte di silice e di modificatore reologico. Sono stati prodotti anche compositi a matrice ceramica (CMCs); il polimero preceramico sviluppa la matrice (SiOC) tramite pirolisi in atmosfera inerte, mentre il rinforzo è dato da fibre di carbonio macinate. Componenti in geopolimero a porosità controllata sono stati progettati e prodotti prima tramite replica negativa di template sacrificali in PLA, e poi via DIW. Il secondo approccio ha portato alla produzione di reticoli ceramici con filamenti di ~800 μm e parti non supportate con deflessione molto limitata. È stato sviluppato infine un innovativo processo estrusivo a partire da vetro fuso. Un unico sistema è in grado di lavorare il vetro dallo stato fuso fino alla ricottura di componenti complessi progettati digitalmente. Sono stati realizzati oggetti comprendenti sporgenze di diversa entità e piccoli raggi di curvatura. All’interno dello spazio di progettazione è stato possibile stampare con elevata precisione e accuratezza; le parti stampate mostrano una forte adesione tra gli strati e un’elevata trasparenza attraverso di essi.

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Yang, Ni. "Fundamental Understanding and Functionality of Silicon Oxycarbide." Diss., Virginia Tech, 2021. http://hdl.handle.net/10919/101789.

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Silicon oxycarbide (SiOC) is a unique polymer-derived ceramic (PDC) containing silicon, oxygen, and carbon atoms in the form of an amorphous network structure. The phase separation of SiOC is determined by polymeric precursors, pyrolysis temperatures, and atmosphere, which results in different compositions and microstructures. Because of its unique properties (high thermal stability, corrosion resistance, among others), SiOC has numerous applications in fields such as additive manufacturing, lithium-ion batteries, and advanced optics. In the SiOC system, SiO2 nanoclusters can be removed through the etching process, to create nanopores for increasing the surface area. By introducing the SiO2-forming filler (perhydropolysilazane) into SiOC, more SiO2 nanodomains with an average size of 1.72 nm were generated for an ultrahigh surface area of ~2100 m2/g material. Meanwhile, the distributions of domain wall thickness and pore distribution can be calculated by our modified model, to further understand the pore formation. The formation of porous SiOC ceramics with ultrahigh surface areas is greatly desired in numerous applications. Transition metal-containing SiOC composites have more functional properties over pure SiOC and receive more attention in different areas. High-temperature resistant TiC/SiOC was successfully synthesized by pyrolysis of polysiloxane (PSO) and titanium isopropoxide at 1200-1400 °C in argon. It had the first reported conductivity of >1000 S/m for TiC/SiOC ceramics. Nickel-containing SiOC magnetoceramics with soft ferromagnetism was fabricated from a base PSO with the addition of nickel 2,4‐pentanedionate. The effect of water vapor on the phase evolution of Ni/SiOC composites was studied at different pyrolysis temperatures, and the formation of nickel silicides was suppressed by the effect of water vapor during the pyrolysis. Our investigation showed the catalysts from transition metals induced the generation of metal silicides, silicon carbide, and turbostratic carbon with the catalytic activity corresponding to Fe > Co > Ni, which agrees with the activation energy calculation. Also, the phase separation of SiOC was proved to be predominant than local carbothermal reduction. In addition to these findings, a novel approach was developed through the Gibbs free energy minimization method to predict the phase content in PDCs with transition metal additives. And this work provides useful guidance to fabricate the transition metal-containing SiOCs with the desired phase content. Last, the state-of-the-art 4D-STEM technique, collaborated with Lawrence Berkeley National Laboratory, was applied to SiOC ceramics containing amorphous phase. The results showed that 4D-STEM is a valid approach to characterize the nanostructure of the amorphous phase as well as the crystallites. It solves the problem of analyzing SiOC materials at nanoscale due to the disordered atomic arrangement and properties.
Doctor of Philosophy
With the development of science and technology, some novel ceramics have begun to attract attention and become alternatives, such as polymer-derived ceramics (PDCs), due to more advantages over traditional ceramics. Silicon oxycarbide (SiOC) is the main part of the PDC family and possessing good combined thermophysical and mechanical properties. Highly porous SiOC ceramic has broad applications in the fields of catalyst, filters, and thermal insulation. A novel preparation to synthesize SiOC with a specific surface area above 2000 m2/g was investigated. Adding transition metals into the SiOC system can enlarge its application potentials to some extent. The bright spot of nickel-containing SiOC (Ni/SiOC) composites is in the magnetic area. Ni/SiOC composites show soft ferromagnetism and can be used as magnetic sensors, transformers, and so on. In this dissertation, the effect of water vapor on the phase evolution of Ni/SiOC was illustrated. The fabrication of high-temperature-resistant Ti/SiOC composite with large than 1000 S/m conductivity was studied. To further uncover the influence of transition metals on SiOC ceramics, the effects of transition metals on the phase and microstructure evolution of polysiloxane-derived SiOC ceramics were deeply demonstrated. A novel method was even developed to predict the phase content in SiOC ceramic with different transition metals. By working with Lawrence Berkeley National Laboratory, the nanoscale structures of SiOC ceramic was studied using state-of-the-art 4D-STEM. The findings of this dissertation shed light on more potential applications for SiOC ceramics in the future.

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Gao, Yan [Verfasser], Ralf [Akademischer Betreuer] Riedel, and Wolfgang [Akademischer Betreuer] Ensinger. "Nanodomain Structure and Energetics of Carbon Rich SiCN and SiBCN Polymer-Derived Ceramics / Yan Gao. Betreuer: Ralf Riedel ; Wolfgang Ensinger." Darmstadt : Universitäts- und Landesbibliothek Darmstadt, 2014. http://d-nb.info/1108094201/34.

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Termoss, Hussein. "Préparation de revêtements de nitrure de bore (BN) par voie polymère précéramique : étude des paramètres d'élaboration : caractérisations physico-chimiques." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00699530.

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L'objectif de cette thèse est de réaliser des revêtements de nitrure de bore sur différents types de substrats comme le graphite, le quartz, le pyrex, en allant jusqu'aux métaux et en particulier le titane. Le choix de la voie PDCs s'avère intéressant grâce à la maîtrise du précurseur de départ au niveau atomique d'une part et à la facilité du procédé de dépôt, d'autre part. Nos objectifs étaient d'étudier la faisabilité de réaliser des revêtements BN sur différents types de substrat en utilisant un traitement thermique résistif et de mettre en place un dispositif qui nous permette de pyrolyser les films polymériques sur métaux sans dommage pour le substrat, en vue de leur protection contre l'oxydation ou d'autres applications mécaniques. Dans ce sens, nous avons démontré la possibilité d'utiliser un traitement thermique alternatif par lampe halogène émettant dans l'infra-rouge pour densifier les revêtement BN déposer sur substrats métalliques.

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Cross, Tsali Jacob. "Mechanical properties of polymer-derived ceramics constituted from silicon-carbon-oxygen-nitrogen and their tribological behavior in dry and humid environments." Diss., Connect to online resource, 2006. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:3207728.

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Pahwa, Saksham. "Titanium dioxide/ silicon oxycarbide hybrid polymer derived ceramic as high energy & power lithium ion battery anode material." Thesis, Kansas State University, 2015. http://hdl.handle.net/2097/20593.

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Master of Science
Mechanical and Nuclear Engineering
Kevin B. Lease
Gurpreet Singh
Energy has always been one of the most important factors in any type of human or industrial endeavor. Clean energy and alternative energy sources are slowly but steadily replacing fossil fuels, the over-dependence on which have led to many environmental and economic troubles over the past century. The main challenge that needs to be addressed in switching to clean energy is storing it for use in the electrical grid and transportation systems. Lithium ion batteries are currently one of the most promising energy storage devices and tremendous amount of research is being done in high capacity anode and cathode materials, and better electrolytes and battery packs as well, leading to overall high efficiency and capacity energy storage systems. Polymer derived ceramics (PDCs) are a special class of ceramics, usually used in high temperature applications, but some silicon based PDCs have demonstrated good electrochemical properties in lithium ion batteries. The goal of this research is to explore a special hybrid ceramic of titanium dioxide (TiO₂) and silicon oxy carbide (SiOC) ceramic derived from 1,3,5,7 -- tetravinyl -- 1,3,5,7 -- tetramethylcyclotetrasiloxane (TTCS) polymer for use in lithium ion batteries and investigate the source of its properties which might make the ceramic particularly useful in some highly specialized energy storage applications.

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Bhandavat, Romil. "Molecular precursor derived SiBCN/CNT and SiOC/CNT composite nanowires for energy based applications." Diss., Kansas State University, 2013. http://hdl.handle.net/2097/15347.

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Doctor of Philosophy
Department of Mechanical and Nuclear Engineering
Gurpreet Singh
Molecular precursor derived ceramics (also known as polymer-derived ceramics or PDCs) are high temperature glasses that have been studied for applications involving operation at elevated temperatures. Prepared from controlled thermal degradation of liquid-phase organosilicon precursors, these ceramics offer remarkable engineering properties such as resistance to crystallization up to 1400 °C, semiconductor behavior at high temperatures and intense photoluminescence. These properties are a direct result of their covalent bonded amorphous network and free (-sp2) carbon along with mixed Si/B/C/N/O bonds, which otherwise can not be obtained through conventional ceramic processing techniques. This thesis demonstrates synthesis of a unique core/shell type nanowire structure involving either siliconboroncarbonitride (SiBCN) or siliconoxycarbide (SiOC) as the shell with carbon nanotube (CNT) acting as the core. This was made possible by liquid phase functionalization of CNT surfaces with respective polymeric precursor (e.g., home-made boron-modified polyureamethylvinylsilazane for SiBCN/CNT and commercially obtained polysiloxane for SiOC/CNT), followed by controlled pyrolysis in inert conditions. This unique architecture has several benefits such as high temperature oxidation resistance (provided by the ceramic shell), improved electrical conductivity and mechanical toughness (attributed to the CNT core) that allowed us to explore its use in energy conversion and storage devices. The first application involved use of SiBCN/CNT composite as a high temperature radiation absorbant material for laser thermal calorimeter. SiBCN/CNT spray coatings on copper substrate were exposed to high energy laser beams (continuous wave at 10.6 μm, 2.5 kW CO2 laser, 10 seconds) and resulting change in its microstructure was studied ex-situ. With the aid of multiple techniques we ascertained the thermal damage resistance to be 15 kW/cm2 with optical absorbance exceeding 97 %. This represents one order of magnitude improvement over bare CNTs (1.4 kW/cm2) coatings and two orders of magnitude over the conventional carbon paint (0.1 kW/cm2) currently in use. The second application involved use of SiBCN/CNT and SiOC/CNT composite coatings as energy storage (anode) material in a Li-ion rechargeable battery. Anode coatings (~1mg/cm2) prepared using SiBCN/CNT synthesized at 1100 °C exhibited high reversible (useable) capacity of 412 mAh/g even after 30 cycles. Further improvement in reversible capacity was obtained for SiOC/CNT coatings with 686 mAh/g at 40 cycles and approximately 99.6 % cyclic efficiency. Further, post cycling imaging of dissembled cells indicated good mechanical stability of these anodes and formation of a stable passivating layer necessary for long term cycling of the cell. This improved performance was collectively attributed to the amorphous ceramic shell that offered Li storage sites and the CNT core that provided the required mechanical strength against volume changes associated with repeated Li-cycling. This novel approach for synthesis of PDC nanocomposites and its application based testing offers a starting point to carry out further research with a variety of PDC chemistries at both fundamental and applied levels.

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Burghard, Zaklina [Verfasser]. "Behaviour of glasses and polymer-derived amorphous ceramics under contact stress / Institut für Nichtmetallische Anorganische Materialien der Universität Stuttgart ... Vorgelegt von Zaklina Burghard." Stuttgart : Max-Planck-Inst. für Metallforschung, 2004. http://d-nb.info/97251760X/34.

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Wang, Xifan [Verfasser], Aleksander [Akademischer Betreuer] Gurlo, Aleksander [Gutachter] Gurlo, and Paolo [Gutachter] Colombo. "Photoinduced thiol-ene click chemistry assisted additive manufacturing and freeze casting of polymer-derived ceramics / Xifan Wang ; Gutachter: Aleksander Gurlo, Paolo Colombo ; Betreuer: Aleksander Gurlo." Berlin : Universitätsverlag der TU Berlin, 2019. http://d-nb.info/1196200122/34.

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Vry, Sébastien. "Elaboration de céramiques hautes performances par voie polymère précéramique - Mise en forme par fabrication additive de type Digital Light Processing." Thesis, Université Grenoble Alpes, 2021. http://www.theses.fr/2021GRALI024.

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Les technologies de fabrication additive offrent actuellement l’opportunité d’atteindre des géométries complexes pour une offre de matériau relativement large, allant des polymères aux métaux, ainsi que pour certaines céramiques. L’offre commerciale de matériaux de structure est encore limitée par des verrous technologiques généralement associés à la compatibilité entre le procédé de mise en forme et le matériau visé. Dans cette thèse, une nouvelle voie, encore peu explorée dans la littérature, porte sur la fabrication additive de type Digital Light Processing (DLP) de la céramique de type carbure de silicium (SiC), à partir de polymères pré-céramiques. En effet l’utilisation d’une poudre de SiC dans une formulation photosensible, présente des limites en termes de taux de charge, liées à la compatibilité optique entre cette poudre et la longueur d’onde UV utilisée lors de la mise en forme couche par couche. L’utilisation de polymères se convertissant en céramique, avec des traitements thermiques adaptés, apporte la possibilité d’améliorer la compatibilité des constituants à la longueur d’onde de travail et permet l’obtention d’une céramique de type SiC. Trois polymères pré-céramiques commerciaux (deux polysiloxane et un polycarbosilane) ont été sélectionnés et des traitements thermiques de réticulation à 200 °C, suivis d’un traitement de pyrolyse compris entre 1000 et 1700 °C, sous argon, ont été réalisés pour étudier les évolutions microstructurales, les compositions chimiques, ainsi que les propriétés mécaniques. Il en ressort que ces matériaux polymères peuvent être convertis en céramique SiC polycristalline, avec une phase secondaire résiduelle riche en carbone. Des formulations photopolymérisables sous exposition UV, contenant un fort taux de charge en polymère pré-céramique (de 25 à 75 %pds), ont été développées et étudiées afin de pouvoir mettre en forme un objet cru par DLP, qui sera ensuite converti en céramique par traitement thermique. Avant la mise en forme par ce procédé, la réactivité de ces formulations a été caractérisée, en faisant varier les proportions des constituants, en particulier le système amorceur et l’incorporation d’un photoabsorbeur UV. La caractérisation de ces formulations a été principalement réalisée en mesurant l’épaisseur d’une monocouche polymérisée sous exposition UV, ainsi qu’en caractérisant la cinétique de photopolymérisation par spectroscopie infrarouge en temps réel. Pour finir, les objets fabriqués par DLP ont été convertis en céramique et leurs propriétés mécaniques et leur intégrité géométrique ont été caractérisées
Additive manufacturing technologies currently offer the opportunity to achieve complex geometries for a relatively wide material range, from polymers to metals, as well as for certain ceramics. The commercial offer of structural materials is still limited by technological obstacles generally associated with the compatibility between the forming process and the targetted material. In this thesis, a new way of study, still little explored in the literature, concerns the additive manufacturing by Digital Light Processing (DLP) of silicon carbide (SiC) ceramic, from preceramic polymers. In fact, the use of a SiC powder into a photosensitive formulation has limits in terms of charge rate, linked to the optical compatibility between this powder and the UV wavelength used during the layer-by-layer shaping. The use of polymers converting into ceramic, with suitable heat treatments, brings the possibility of improving the compatibility of the constituents at the working wavelength and allows the production of a ceramic of the SiC type. Two commercial preceramic polymers (a polysiloxane and a polycarbosilane) were selected and cross-linked at 200 ° C, followed by a pyrolysis treatment between 1000 and 1700 ° C, under argon. The microstructural changes, chemical compositions, as well as mechanical properties were studied. It appears that these polymer materials can be converted into polycrystalline SiC ceramic, with a residual carbon-rich secondary phase. Photopolymerizable formulations under UV exposure, containing a high load of preceramic polymer (from 25 to 75 wt.%), have been developed and studied in order to be able to shape a green object by DLP, which will then be converted into ceramic by heat treatment. Before additively manufacture parts, the reactivity of these formulations was characterized by varying the proportions of the constituents, including the initiator system and the incorporation of a UV photoabsorbent. The characterization of these formulations was mainly carried out by measuring the thickness of a monolayer polymerized under UV exposure, as well as by characterizing the photopolymerization kinetics by real time infrared spectroscopy. Finally, green parts were produced by DLP and were converted into ceramics and their mechanical properties and geometric integrity were characterized

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Asok, Deepu. "Study of Si(Al)CN functionalized carbon nanotube composite as a high temperature thermal absorber coating material." Kansas State University, 2013. http://hdl.handle.net/2097/16876.

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Master of Science
Department of Mechanical & Nuclear Engineering
Gurpreet Singh
Carbon nanotubes (CNT) and polymer-derived ceramics (PDC) have gained considerable research attention due to their unique structure and physical properties. Carbon nanotubes are known for their exceptional mechanical (Young’s modulus= 1 TPa) and thermal properties (thermal conductivity = 4000 W/m.K). However, CNTs tend to lose their unique -sp2 carbon structure and cylindrical geometry at temperatures close 400°C in air. PDC, which are obtained by the controlled degradation of certain organosilicon polymers however exhibit high temperature stability (upto approx. 1400 °C). To this end, a hybrid composite material consisting of PDC functionalized CNT is of interest as it can combine the unique physical properties of the two materials for applications requiring operation under harsh conditions. Here, we report synthesis and chemical characterization of an Al-modified polysilazane polymer, which was later utilized to functionalize the outer surfaces of four commercially available CNTs. This polymer-CNT composite upon heating in nitrogen environment resulted in Si(Al)CN-CNT ceramic composite. The composite was characterized using a variety of spectroscopic methods such Raman, FTIR and electron microscopy. The thermal stability of the ceramic composite was studied by use of Thermogravimetric analysis (TGA) that showed an improvement in the thermal stability compared to bare nanotubes. Further, we also demonstrate that a stable dispersion of the composite in organic solvents such as toluene can be spray coated on a variety of substrates such as copper disks and foils. Such coatings have application in high energy laser power meters. This research opens new avenues for future applications of this novel material as coatings on surfaces that require both good thermal properties and protection against degradation in high temperature environments. We also suggest the future use of this material as an electrode material in high electrochemical capacity rechargeable batteries.

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Prasad, Ravi Mohan [Verfasser], Ralf [Akademischer Betreuer] Riedel, Christina [Akademischer Betreuer] Roth, Wolfgang [Akademischer Betreuer] Ensinger, and Jörg [Akademischer Betreuer] Schneider. "Polymer-Derived Microporous Ceramics for Membranes and Sensors for High Temperature Hydrogen Purification and Sensing / Ravi Mohan Prasad. Betreuer: Ralf Riedel ; Christina Roth ; Wolfgang Ensinger ; Jörg Schneider." Darmstadt : Universitäts- und Landesbibliothek Darmstadt, 2012. http://d-nb.info/110625709X/34.

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Zhong, Wenli. "Préparation de matériaux à base de nitrure de bore pour des applications 'énergie'." Thesis, Montpellier 2, 2012. http://www.theses.fr/2012MON20186.

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Bien que proposant des avantages importants par rapport à d'autres matériaux, les céramiques présentent un défaut récurrent, qui est leur plus ou moins grande fragilité due à des défauts de structure ou à des impuretés dans les réseaux structuraux. On s’affranchit de ces contraintes en améliorant la pureté des matériaux de base, en maîtrisant mieux les processus de fabrication, en les renforçant et en nanostructurant le matériau. C’est ce qui a donné naissance aux méthodes chimiques d’élaboration dites de « Bottom-up » qui reprennent le schéma de principe de la conception de la céramique naturelle en s’adaptant à la démarche des chimistes : des briques élémentaires représentant une architecture moléculaire sont assemblées pour former un composé macromoléculaire dont la composition est contrôlée à l’échelle atomique. Ce composé est mis en forme, durcit pour être transformé par cuisson en une céramique dont la composition est directement liée à la structure moléculaire des briques. Cette démarche est à l’origine de la voie dite des « polymères précéramiques ». Cette voie chimique s’adapte aux exigences des domaines de l’énergie. Notamment et afin d’exploiter et de saisir les opportunités que constituent l’apparition de nouveaux besoins en matériaux et/ou l’établissement de cahiers des charges stricts au regard des propriétés des matériaux dans ce domaine, la présente étude a pour objet d’élaborer des matériaux à base de BN comme les composites à renforts fibreux, les nanocomposites et les mousses.Après une introduction générale, le chapitre 1 décrit l’état de l’art de BN. Il s’intéresse à la littérature sur les propriétés des différentes formes du BN. La voie PDCs est détaillée et son application à l’élaboration du h-BN. Les différents types de précurseurs et de polymères sont décrits et l’accent est mis sur le borazine et le polyborazylène. La dernière partie concerne l’élaboration des composites à renforts fibreux, les nanocomposites et les mousses à base de BN qui sont considérés.Le chapitre 2 s’intéresse à l’élaboration de C/BN composites à partir de polyborazylènes qui est un projet de recherche sur ITER. Après un rappel sur le contexte de CEA, les différentes étapes liées au procédé d’élaboration des composites sont décrites et étudiées à l’aide d’outils de caractérisation comme la RMN solide,TGA, XRD et SEM. Le chapitre 3 s’intéresse à des nanocomposites qui se caractérisent par des phases nanocristallines de nitrure métallique parmi le nitrure de titane, de zirconium et d’hafnium dispersés dans une matrice de BN faiblement cristallisée. L’accent est mis sur la chimie moléculaire et sur la synthèse de polymétalloborazines qui permettent de conduire par pyrolyse à la formation directe de ces nanocomposites par croissance in-situ de la phase nanocristalline dans la matrice BN. Une étude préliminaire sur la possibilité de mettre en forme les polyméres en vue d’élaborer des structures massives nanocomposites est abordée.Le chapitre 4 se consacre à deux procédés de préparation de mousses. Le premier procédé qui combine la voie PDCs à la chimie intégrative vise à élaborer des mousses BN à porosité hiérarchisée. Le second procédé consiste à mélanger PMMA avec polyborazylènes pour subir des étapes de compactage et de pyrolyse générant des mousses. Pour ces deux types de matériaux, des mesures texturales comme BET et la porosimétrie mercure sont entreprises.Une conclusion générale termine le manuscrit. Elle fait un rappel des travaux entrepris dans chacun des trois chapitres et donne des perspectives liées aux trois types de matériau étudiés pendant la thèse
Energy developments have brought hexagonal boron nitride-based materials increasing interest for future materials and technologies. The objective of this thesis concerns the preparation of BN shapes for energy applications including fiber-reinforced BN composites, BN-based nanocomposites and BN foams. Fiber-reinforced BN composite and BN nanocomposites display potential as tiles for protection limiters for the Ion Cyclotron Range Frequency antennas in fusion nuclear reactors. Porous BN materials have interests as host material for hydrogen storage and as catalyst supports. The Polymer-Derived Ceramics route which offers new preparation opportunities in chemistry and ceramic sciences is applied to manufacture shaped BN-based materials.Firstly, in the context of C/BN composite, polyborazylene vacuum-assisted infiltration and pyrolysis process was successfully introduced. We focused on the design, elaboration and properties of the C/BN composite through the study of the (1) synthesis and polymerization of borazine, (2) the polyborazylene-to-boron nitride conversion, (3) the morphological texture and mechanical properties of derived C/BN composites. We firstly demonstrated that it is possible to obtain dense-derived C/BN composites (density: 1.773 g cm-3, open porosity: 5.09%) by tuning the viscosity of polyborazylene in the infiltration process. SEM observation presented a very strong bonding between fibers and matrix. TGA under air analysis confirmed the improved oxidation resistance property of C/BN composite compared with C fiber.Secondly, we investigated the design, processing, and properties of transition metal-containing boron nitride nanocomposites from polymetalloborazine. With proper choice of boron nitride precursor, and by controlling the B/M ratio (M = Ti, Zr, Hf), a set of representative polymetalloborazines has been prepared as precursors of nanocomposites. In the reaction of BN source with metal precursor leading to polymetalloborazines, two main mechanisms are mainly concerned: N-H and B-H units of BN percursor react with N-alkyl groups presented in metal precursors. After its pyrolysis under ammonia up to 1000 oC then nitrogen from 1000 to 1500oC, the derived nanocomposites reveal the presence of metal nitride nanocrystales with an average diameter of 6.5 nm homogeneously embedded in a poorly crystallized boron nitride matrix. A preliminary study is presented on the preparation of monolith-type nanocomposites from selected polytitanoborazines. Finally, we applied two PDCs route-based strategies to prepare hierarchically porous and micro cellular BN foams. In the first strategy, monolith-type BN foams with a hierarchical porosity were synthesized from polyborazylene using an integrative chemistry combined-based sequence set-up that consists of the impregnation of silica and carbonaceous templates followed by pyrolysis process and elimination of the template. These novel porous BN architectures display hierarchical and high porosity (76 %) with an open-cell interconnected macroporosity and a surface area up to 300 m2g-1. In the second strategy, a sacrificial processing route has been proposed to fabricate micro cellular BN foams with a porosity of 79 % from a mixture of polyborazylene and poly(methylmethacrylate) (PMMA) microbeads by warm-pressing followed by pyrolysis consisting of the burn-out of PMMA while polyborazylene is converted into BN. These novel BN foams display potential as catalyst supports and host material for hydrogen storage

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Nardin, Thibaud. "Elaboration de carbure de silicium poreux et mésoporeux par voie moléculaire." Thesis, Montpellier, 2015. http://www.theses.fr/2015MONTS120/document.

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Grâce à ses excellentes propriétés de résistance et de conductivité thermique ainsi qu'à sa stabilité mécanique et chimique à température ambiante et à haute température, le carbure de silicium (SiC) est un matériau de choix pour le gainage du combustible nucléaire ou les supports de catalyseurs. Cependant, une grande surface spécifique est souvent requise pour ce type d'applications. Cette étude propose deux approches de synthèse :(1) L'approche « Soft Templating ». La porosité et la structure des matériaux finaux sont définies par l'auto-assemblage supramoléculaire d'un agent de structure (SDA) dans un précurseur moléculaire de SiC. Des organogélateurs à faible masse moléculaire et un copolymère tri-bloc commercial sont considérés pour la synthèse de SiC méso-poreux.(2) L'approche « Hard Templating ». Des céramiques SiC sont synthétisées par nanomoulage de silices méso-poreuses par des polymères précéramiques. Ce procédé conserve la nanostructure du template solide et conduit à des SiC méso-poreux à forte surface spécifique.L'approche hard templating permet une bonne réplication du template solide mais la difficulté de cette méthode provient de l'étape d'élimination de ce même template. L'approche soft templating ne présente pas ce désavantage et peut, suivant le SDA utilisé, mener à des céramiques poreuses possédant des structures beaucoup plus variées. La complexité de cette approche réside dans l'étape de réplication du template
Due to its excellent thermal resistance, mechanical and chemical stability both at room and elevated temperature, silicon carbide (SiC) is an attractive material for nuclear fuel cladding or catalyst substrates. Pore size control and high porosity are the key factors for such applications. Two approaches are studied during this PhD thesis:(1) The Soft Templating Approach. The porosity and the structure of the final materials are defined by the supramolecular self-assembly of a structure directing agent (SDA) into a molecular SiC precursor. Low molecular-mass organic gelators and a commercial tri-block copolymer are considered as SDA for the synthesis of mesoporous SiC materials.(2) The Hard Templating Approach. SiC materials are synthesized by preceramic polymer nanocasting into mesoporous silica. This process preserves the nanoscale structure of the solid template and leads to mesostructured SiC materials with a high specific surface area.The hard templating approach allows a good replication of the solid template but the difficulty of this method lies in the elimination step of this template. Meanwhile, soft templating approach does not have this drawback and may lead to porous ceramics with more varied structures depending on the SDA used. The complexity of this approach is the template replication step

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Ben, Miled Marwan. "Synthèse in situ de nanoparticules métalliques dans une matrice céramique dérivées de polymères précéramiques pour l'électrolyse de l'eau en milieu alcalin." Electronic Thesis or Diss., Limoges, 2024. http://www.theses.fr/2024LIMO0083.

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Face au réchauffement climatique dû aux activités humaines et à l’utilisation de ressources fossiles, le besoin de trouver de nouvelles sources d’énergies décarbonées devient urgent. Le dihydrogène (H2) communément appelé « hydrogène » s’impose comme un vecteur énergétique d’intérêt de par sa capacité à produire une énergie de combustion supérieure à celle des énergies fossiles et à ne produire que de l’eau comme déchet lors de son utilisation dans une pile à combustible. De plus, son utilisation ne génère aucune nuisance sonore à la différence des moteurs thermiques couramment employés. Néanmoins, elle requiert un très haut degré de pureté afin d’éviter la pollution des matériaux catalytiques contenus dans ces piles à combustible. De nos jours, près de 95% de l’hydrogène produit se fait par reformage catalytique du méthane et nécessite donc des procédés de purification souvent complexes et couteux. Une façon de s’affranchir de ces procédés serait de produire l’hydrogène directement par électrolyse de l’eau. Cette méthode consiste à séparer une molécule d’eau sous l’action d’un courant électrique (produit de façon renouvelable) pour produire de l’hydrogène et du dioxygène (O2) aux bornes d’électrodes d’un électrolyseur. Malheureusement, cette réaction se heurte à des limitations cinétiques en raison d’un mécanisme de réaction de dégagement de dioxygène (RDO) très complexe, incluant plusieurs électrons et plusieurs intermédiaires réactionnel. L’émergence de nouvelles technologies de membranes échangeuses d’anion a ouvert la voie à l’utilisation de l’électrolyse en milieu alcalin, permettant donc l’utilisation de métaux de transition non nobles comme catalyseurs, moins couteux que les métaux traditionnellement employés (Ir et Ru). Ce manuscrit de thèse a donc exploré la synthèse de matériaux à visée catalytique pour réduire les barrières énergétiques et cinétiques de la RDO. Afin de proposer des matériaux performants, stables dans le temps et résistant aux milieux agressifs imposés par l’électrolyse de l’eau en milieu alcalin, la voie des céramiques dérivées de polymères précéramiques (PDC pour Polymer-Derived Ceramics) s’est avéré être une méthode d’élaboration de choix pour y parvenir. L’intérêt de cette méthode est de mettre en œuvre des polymères organosiliciés (ici un polysilazane) servant de plateforme moléculaire pour la croissance de métaux non nobles via l’utilisation de complexes métalliques tels que des chlorures et des acétylacétonates de nickel (Ni), de fer (Fe) ou encore de cobalt (Co). Ce polymère modifié par ces métaux sert de précurseur à la formation in situ de nanoparticules métalliques dans une matrice poreuse à base des éléments silicium (Si), carbone (C), oxygène (O) et azote (N) et garantissant leur accessibilité et stabilité après traitement thermique à 500°C sous argon. Ce manuscrit illustré à travers cinq chapitres décrit des travaux sur la synthèse et la caractérisation de nanoparticules de Ni (chapitre 3), Ni-Fe (chapitre 4) et d’alliages à moyenne et haute entropie (chapitre 5) qui complètent un état de l’art (chapitre 1) et une description des matériaux et méthodes mises en œuvre au cours de cette thèse (chapitre 2). Les matériaux formés ont été étudiés à chaque étape de leur synthèse à travers la mise en œuvre d’outils de caractérisation complémentaires avant d’en évaluer les performances électrochimiques ; notamment par mesure de la surtension anodique lors de la RDO afin d’identifier la meilleure combinaison métallique. Des tests post mortem ont été réalisés pour évaluer le potentiel des matériaux préparés. Compte tenu de la simplicité de la voie de synthèse et du faible coût des réactifs utilisés, ces travaux conduisent à une nouvelle famille de matériaux et à plusieurs perspectives prometteuses, non seulement pour le développement de catalyseurs efficaces et stables pour l'OER mais plus généralement pour de nombreuses applications en électrochimie. Ces opportunités sont désormais exploitées
Global warming caused by human activity and the use of fossil fuels, urges the need to find new sources of carbon free energy. Dihydrogen (H2) more known as “hydrogen” is rapidly emerging as a technically viable and benign energy vector according to its ability to produce a higher density of combustion than fossil fuels and to produce only water as a waste product when used in a fuel cell. Moreover, its use generates no noise pollution, unlike the combustion engines currently in use. Nevertheless, it requires a very high degree of purity in order to avoid pollution of the catalytic materials contained in the cells. Nowadays, nearly 95% of the hydrogen produced is obtained by catalytic reforming of methane, and therefore requires purification processes that are often complex and costly. One way of avoiding these purification steps would be to produce hydrogen directly by electrolysis of water more known as water splitting. This process consists of separating a molecule of water under the action of an electric current (produced in a renewable way) to produce hydrogen and dioxygen (O2) at the electrodes of an electrolyser. Unfortunately, this reaction has kinetic limitations due to a very complex Oxygen Evolution Reaction (OER) mechanism, including several electrons and several reaction intermediates. The emergence of new anion exchange membrane technologies has paved the way for the use of electrolysis in alkaline media, thus allowing the use of non-noble transition metals as catalysts, which are less expensive than the metals traditionally used (Ir and Ru). Within this context, this PhD thesis has explored the synthesis of catalytic materials to reduce the energy and kinetic barriers of OER. In order to propose materials that are performant, stable over time and resistant to the aggressive environments imposed by the electrolysis of water in an alkaline medium, the polymer-derived ceramics (PDC) route has been selected as a synthesis method of choice. The interest of this method is to implement organosilicon polymers (here a polysilazane) serving as a molecular platform for the growth of non-noble metals via the use of metal complexes such as chlorides and acetylacetonates of nickel (Ni), iron (Fe) or cobalt (Co). This polymer modified by these metals serves as a precursor for the in situ formation of metal nanoparticles in a porous matrix based on the elements silicon (Si), carbon (C), oxygen (O) and nitrogen (N) allowing their accessibility and stability after heat treatment at 500 ° C under argon. This manuscript illustrated through five chapters describes works dedicated to the synthesis and characterization of Ni (chapter 3), Ni-Fe (chapter 4) and medium and high entropy alloys (chapter 5) nanoparticles which complete a state of the art (chapter 1) and a description of the materials and methods implemented during this thesis (chapter 2). The materials which have been prepared were studied at each stage of their synthesis through the implementation of complementary characterization tools before assessing their electrochemical performances; in particular by measuring the anodic overpotential during OER, in order to determine the best metal combinations. Post mortem tests were carried out to evaluate the potential of the prepared materials. Considering the simplicity of the synthesis route, and the low cost of reactants used, this work leads to a new family of materials and to several promising perspectives, not only for the development of efficient and stable catalysts for the OER but more generally for numerous applications in electrochemistry. These opportunities are now being addressed

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Balestrat, Maxime. "Elaboration et caractérisation d'objets massifs nanocomposites base carbure de silicium comme absorbeurs solaires." Thesis, Limoges, 2019. http://www.theses.fr/2019LIMO0102.

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Pour améliorer l'efficacité de la conversion solaire en électricité, les Centrales solaires thermodynamiques (CSP) doivent relever le défi industriel de fonctionner à des températures élevées (jusqu’à 1000 °C). Les recherches et développements au cours des dernières années ont donc mis l'accent sur les matériaux qui composent l'absorbeur solaire, ou récepteur, dont le rôle est clé dans la performance globale du système CSP. Le carbure de silicium (SiC) présente une inertie chimique, une résistance à l'oxydation à haute température et une robustesse compatibles qui font de cette céramique la référence des matériaux récepteurs dans les CSP. Dans le cadre de cette thèse, il est développé différentes compositions de matériaux composites à matrice en SiC, issues de toute la chimie des polymères précéramiques. L’incorporation chimique, dans ces polymères, d’éléments précurseurs d’une seconde phase carbonitrure de titane permet d’améliorer la sélectivité optique du matériau final. Les précurseurs des systèmes TiCxN(1-x)/Si(B)C et TiCxN(1-x)/SiC(N) (avec 0<1) ont principalement été étudiés par RMN solide et spectroscopie infrarouge. La céramisation de ces polymères a été suivie par ATG/MS. Et enfin, les phases céramiques obtenues ont été principalement caractérisées par DRX, Raman, MEB-EDX et TEM. L’élaboration en pièces denses de matériaux dans ces mêmes systèmes a également été développée dans ce travail de thèse par un procède de compactage à chaud des polymères ou par des techniques de frittage flash sous charge des poudres amorphes. Des mesures de réflectance et de propriétés mécaniques ont ainsi pu être effectuées
A common industrial challenge to improve the efficiency of the solar-to-electricity conversion for concentrating solar power (CSP) is to operate at high temperatures (around 1000°C). Research and development efforts on over recent years have therefore focused on the materials that compose the solar absorber which plays the key role in the overall CSP system performance. Silicon carbide (SiC) exhibits a chemical inertness, a high temperature oxidation resistance and a robustness compatible with the operating conditions of further CSP systems. In this work, Polymer derived nanocomposites ceramics TiCxN(1-x)/Si(B)C et TiCxN(1-x)/SiC(N) (with 0<1) have been developed to be use as solar absorber. A complete characterization from the polymer to the final material is done using techniques as Solid-state NMR, FTIR, TGA, XRD, Raman SEM and TEM. The bulk shaping process was also investigated. Hot pressing at the polymeric state and Flash Sintering on amorphous PDCs powders has been done

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Torrey, Jessica D. "Polymer derived ceramic composites as environmental barrier coatings on steel /." Thesis, Connect to this title online; UW restricted, 2006. http://hdl.handle.net/1773/10562.

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Martins, Nilda. "Development of plasma assisted pyrolysis of polymer derived ceramic coatings on sintered steel." reponame:Repositório Institucional da UFSC, 2017. https://repositorio.ufsc.br/xmlui/handle/123456789/179647.

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Tese (doutorado) - Universidade Federal de Santa Catarina, Centro Tecnológico. Programa de Pós-graduação em Ciência e Engenharia de Materiais, Florianópolis, 2017
Made available in DSpace on 2017-09-19T04:10:10Z (GMT). No. of bitstreams: 1 347970.pdf: 5112577 bytes, checksum: 26ca02d8d2f3634b3516965d62c2b87f (MD5) Previous issue date: 2017
Abstract: The use of precursors loaded with fillers to process ceramic coatings rises the possibility to tailor the microstructure and coating properties for a wide range application, like thermal barrier coatings, environmental barrier coating or for wear applications. Thus, the present research aims to develop and to employ the novel process of plasma assisted pyrolysis (PAP) for developing ceramic composites coating on sintered steel substrate. The coatings are based on polymer derived ceramic, being the precursor a polyorganosilazane. During the development of the PDC based coating different fillers were used. The active fillers TiSi2 and TiB2 were used in order to compensate the shrinkage of the precursor and to generate in situ formation of phases as nitrides and carbides. Initially it was necessary to investigate the influence of PAP both on the pyrolysis behavior of the pure precursor and on the polymer precursor loaded with filler particles, in comparison to conventional pyrolysis. For such investigations, cylindrical bulk specimens were used (diameter of 13 mm and thickness between of 2-4 mm). It was demonstrated that the ceramic yield as well as the elemental composition of the polyorganosilazane are not adversely influenced by PAP process. The bulk samples based on precursor and TiSi2 under conventional pyrolysis, under N2 atmosphere, showed no significant conversion of the fillers into nitrides. In contrast, the use of PAP led not only to an enhances filler conversion but also to a densification of the composite. The resulting microstructure is dominated by Ti(C,N) as well as a mixture of a- and ß- Si3N4 phases embedded in an amorphous SiCN matrix. In the same way the coatings, on sintered substrates, based on polyorganosilazane and TiB2, processed under conventional pyrolysis showed almost no filler conversion up to temperature of 1150 °C. The final coating was based mainly on TiB2 and the formed SiCN network. While in the specimens after PAP process mainly Ti (C, N) and C0.858 (BN)0.571 were formed, and no residual TiB2 was detect. The diffusion phenomenon between coating and sintered substrate was also drastically affected under plasma conditions. Considerable amount of iron could be detected in the coating, after the plasma assisted pyrolysis. Such difference between conventional and plasma assisted pyrolysis process is attributed to the high reactivity of the plasma environment, in which reactive species, as atomic nitrogen, are available to react with the sample. It could be demonstrated that plasma assisted pyrolysis is a very suitable way to process polymer derived ceramic composite materials with a tailored microstructure.
O uso de precursores carregados com fillers possibilita projetar a microestrutura e as propriedades de revestimentos cerâmicos para diferentes aplicações, como revestimentos de barreira térmica, revestimento de barreira ambiental ou para aplicações tribológicas. O objetivo deste trabalho foi desenvolver e empregar o novo processo de pirólise assistida por plasma (PAP) para o desenvolvimento de revestimentos compósitos cerâmicos sobre substratos de aço sinterizado. Os revestimentos são baseados em cerâmica derivada de polímero, sendo o precursor um poliorganossilazano. Durante o desenvolvimento do revestimento utilizaram-se diferentes fillers. As cargas ativas, como TiSi2 e TiB2, foram utilizadas para compensar a retração do precursor e para gerar a formação in situ de fases como nitretos e carbonetos. Inicialmente foi necessário investigar a influência da PAP sobre o comportamento do precursor puro e no comportamento do precursor carregado com partículas de fillers, em comparação com a pirólise convencional. Para tais investigações, foram utilizados amostras cilíndricas (diâmetro de 13 mm e espessura entre 2 e 4 mm). Foi demonstrado que o rendimento cerâmico, assim como a composição elementar do poliorganossilazano, não são influenciados negativamente pelo processo PAP. As amostras baseada no precursor e TiSi2 sob pirólise convencional, atmosfera de N2, não mostrou nenhuma conversão significativa dos fillers em nitretos. No entanto, a utilização da PAP promoveu tanto ao aumento na conversão do filler, assim como uma maior densificação do compósito. A microestrutura resultante é dominada por Ti (C, N), e uma mistura de fases a- e ß-Si3N4 incorporadas numa matriz amorfa de SiCN. Do mesmo modo, os revestimentos sobre os substratos sinterizados, compostos por poliorganossilazano e TiB2, processados em pirólises convencionais, mostraram quase nenhuma conversão do filler até na temperatura de 1150 ° C. O revestimento final baseou-se principalmente em TiB2 e na fase SiCN. Enquanto, as amostras após o processo de PAP formaram principalmente fases como Ti (C, N) e C0.858 (BN) 0.571, e não foi detectado TiB2 residual. O fenômeno de difusão entre o revestimento e o substrato sinterizado também foi drasticamente afetado no ambiente de plasma. Uma quantidade considerada de ferro pode ser detectada no revestimento, após a pirólise assistida por plasma. Essas diferenças entre o processo de pirólise convencional e assistido por plasma é atribuída à alta reatividade do ambiente de plasma, no qual as espécies reativas, como o nitrogênio atômico, estão disponíveis para reagir com a amostra. Pode ser demonstrado que a pirólise assistida por plasma é uma maneira muito adequada para processar materiais compósitos cerâmicos derivados de polímeros com uma microestrutura projetada.

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Glaser, Raymond Hans. "Structure-property behavior of sol-gel derived hybrid materials." Diss., Virginia Polytechnic Institute and State University, 1988. http://hdl.handle.net/10919/54327.

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Structure-property studies were carried out on a number of different hybrid sol·gel materials. Multifunctional silicon ethoxides were prepared and studied by solid state ²⁹Si NMR and Raman spectroscopy to determine the type of silicate structures formed and the degree of conversion attained by the sol-gel process under previously established reaction conditions. New procedures were developed to incorporate titaniumisopropoxide as well as Al, Zr and Zn acetylacetonates into functlonalized polyltetramethylene oxide) modified sol-gel systems. The physical properties of titanium containing poIy(tetramethyIene oxide) modified sol-gel materials were studied in detail and correlated to morphological and structural information gained from dynamic mechanical analysis, small angle x-ray scattering and scanning electron microscopy. The incorporation of titanium was found to increase the measured Young’s modulus and stress at break relative to comparable materials based solely on TEOS.
Ph. D.

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David, Lamuel Abraham. "Van der Waals sheets for rechargeable metal-ion batteries." Diss., Kansas State University, 2015. http://hdl.handle.net/2097/32796.

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Doctor of Philosophy
Department of Mechanical and Nuclear Engineering
Gurpreet Singh
The inevitable depletion of fossil fuels and related environmental issues has led to exploration of alternative energy sources and storage technologies. Among various energy storage technologies, rechargeable metal-ion batteries (MIB) are at the forefront. One dominant factor affecting the performance of MIB is the choice of electrode material. This thesis reports synthesis of paper like electrodes composed for three representative layered materials (van der Waals sheets) namely reduced graphene oxide (rGO), molybdenum disulfide (MoS₂) and hexagonal boron nitride (BN) and their use as a flexible negative electrode for Li and Na-ion batteries. Additionally, layered or sandwiched structures of vdW sheets with precursor-derived ceramics (PDCs) were explored as high C-rate electrode materials. Electrochemical performance of rGO paper electrodes depended upon its reduction temperature, with maximum Li charge capacity of 325 mAh.g⁻¹ observed for specimen annealed at 900°C. However, a sharp decline in Na charge capacity was noted for rGO annealed above 500 °C. More importantly, annealing of GO in NH₃ at 500 °C showed negligible cyclability for Na-ions while there was improvement in electrode's Li-ion cycling performance. This is due to increased level of ordering in graphene sheets and decreased interlayer spacing with increasing annealing temperatures in Ar or reduction at moderate temperatures in NH₃. Further enhancement in rGO electrodes was achieved by interfacing exfoliated MoS₂ with rGO in 8:2 wt. ratios. Such papers showed good Na cycling ability with charge capacity of approx. 225.mAh.g⁻¹ and coulombic efficiency reaching 99%. Composite paper electrode of rGO and silicon oxycarbide SiOC (a type of PDC) was tested as high power-high energy anode material. Owing to this unique structure, the SiOC/rGO composite electrode exhibited stable Li-ion charge capacity of 543.mAh.g⁻¹ at 2400 mA.g⁻¹ with nearly 100% average cycling efficiency. Further, mechanical characterization of composite papers revealed difference in fracture mechanism between rGO and 60SiOC composite freestanding paper. This work demonstrates the first high power density silicon based PDC/rGO composite with high cyclic stability. Composite paper electrodes of exfoliated MoS₂ sheets and silicon carbonitride (another type of PDC material) were prepared by chemical interfacing of MoS₂ with polysilazane followed by pyrolysis . Microscopic and spectroscopic techniques confirmed ceramization of polymer to ceramic phase on surfaces on MoS₂. The electrode showed classical three-phase behavior characteristics of a conversion reaction. Excellent C-rate performance and Li capacity of 530 mAh.g⁻¹ which is approximately 3 times higher than bulk MoS₂ was observed. Composite papers of BN sheets with SiCN (SiCN/BN) showed improved electrical conductivity, high-temperature oxidation resistance (at 1000 °C), and high electrochemical activity (~517 mAh g⁻¹ at 100 mA g⁻¹) toward Li-ions generally not observed in SiCN or B-doped SiCN. Chemical characterization of the composite suggests increased free-carbon content in the SiCN phase, which may have exceeded the percolation limit, leading to the improved conductivity and Li-reversible capacity. The novel approach to synthesis of van der Waals sheets and its PDC composites along with battery cyclic performance testing offers a starting point to further explore the cyclic performance of other van der Waals sheets functionalized with various other PDC chemistries.

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Nagaiah, Narasimha. "NOVEL CONCEPTUAL DESIGN AND ANLYSIS OF POLYMER DERIVED CERAMIC MEMS SENSORS FOR GAS TURBINE ENVIRONMENT." Master's thesis, University of Central Florida, 2006. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4086.

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Technical challenges for developing micro sensors for Ultra High Temperature and turbine applications lie in that the sensors have to survive extremely harsh working conditions that exist when converting fuel to energy. These conditions include high temperatures (500-1500°C), elevated pressures (200-400 psi), pressure oscillations, corrosive environments (oxidizing conditions, gaseous alkali, and water vapors), surface coating or fouling, and high particulate loading. Several technologies are currently underdeveloped for measuring these parameters in turbine engines. One of them is an optical-based non-contact technology. However, these nondirective measuring technologies lack the necessary accuracy, at least at present state. An alternative way to measure these parameters without disturbing the working environments is using MEMS type sensors. Currently, the techniques under development for such harsh environment applications are silicon carbide (SiC) and silicon nitrite (Si3N4) –based ceramic MEMS sensors. But those technologies present some limitation such as narrow processing method, high cost (materials and processing cost), and limited using temperatures (typically < 800 C). In this research we propose to develop two sensors based on recently developed polymer-derived ceramics (PDCs): Constant Temperature Hot wire Anemometer, temperature/heat-flux sensor for turbine applications. PDC is a new class of high temperature ceramics. As we shall describe below, many unique features of PDCs make them particularly suitable for the proposed sensors, including: excellent thermo-mechanical properties at high temperatures, enable high temperature operation of the devices; various well-developed processing technologies, such as injection molding,photolithography, embossing, DRIE etching and precise machining, can be used for the fabrication of the devices; and tunable electric conductivity, enable the proposed sensors fabricated from similar materials, thus reliability considerations associated with thermal mismatch, which is a big concern when using MEMS-based sensors at elevated temperatures, will be minimized.
M.S.M.E.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Mechanical Engineering

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Yang, Hongjiang. "Synthesis, Processing and Characterization of Polymer Derived Ceramic Nanocomposite Coating Reinforced with Carbon Nanotube Preforms." Master's thesis, University of Central Florida, 2014. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/6387.

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Ceramics have a number of applications as coating material due to their high hardness, wear and corrosion resistance, and the ability to withstand high temperatures. Critical to the success of these materials is the effective heat transfer through a material to allow for heat diffusion or effective cooling, which is often limited by the low thermal conductivity of many ceramic materials. To meet the challenge of improving the thermal conductivity of ceramics without lowering their performance envelope, carbon nanotubes were selected to improve the mechanical properties and thermal dispersion ability due to its excellent mechanical properties and high thermal conductivity in axial direction. However, the enhancements are far lower than expectation resulting from limited carbon nanotube content in ceramic matrix composites and the lack of alignment. These problems can be overcome if ceramic coatings are reinforced by carbon nanotubes with good dispersion and alignment. In this study, the well-dispersed and aligned carbon nanotubes preforms were achieved in the form of vertically aligned carbon nanotubes (VACNTs) and Buckypaper. Polymer derived ceramic (PDC) was selected as the matrix to fabricate carbon nanotube reinforced ceramic nanocomposites through resin curing and pyrolysis. The SEM images indicates the alignment of carbon nanotubes in the PDC nanocomposites. The mechanical and thermal properties of the PDC nanocomposites were characterized through Vickers hardness measurement and Thermogravimetric Analysis. The ideal anisotropic properties of nanocomposites were confirmed by estimating the electrical conductivity in two orthogonal directions.
M.S.M.E.
Masters
Mechanical and Aerospace Engineering
Engineering and Computer Science
Mechanical Engineering; Mechanical Systems Track

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Gasch, Matthew J. "Processing and mechanical properties of silicon nitride/silicon carbide ceramic nanocomposites derived from polymer precursors /." For electronic version search Digital dissertations database. Restricted to UC campuses. Access is free to UC campus dissertations, 2003. http://uclibs.org/PID/11984.

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Hicks, David Cyprian. "Aligned Continuous Cylindrical Pores Derived from Electrospun Polymer Fibers in Titanium Diboride." Thesis, Virginia Tech, 2019. http://hdl.handle.net/10919/99423.

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The use of electrospun polystyrene (PS) fibers to create continuous long range ordered multi-scale porous structures in titanium diboride (TiB2) is investigated in this work. The introduction of electrospun PS fibers as a sacrificial filler into a colloidal suspension of TiB2 allows for easy control over the pore size, porosity, and long range ordering of the porous structures of the sintered ceramic. Green bodies were formed by vacuum infiltrating an electrospun-fiber-filled mold with the colloidal TiB2 suspension. The size, volume, distribution, and dispersion of the pores were optimized by carefully selecting the sacrificial polymer, the fiber diameter, the solvent, and the solid content of TiB2. The green bodies were partially sintered at 2000 C in argon to form a multiscale porous structure via the removal of the PS fibers. Aligned continuous cylindrical pores were derived from the PS fibers in a range of ~5 - 20 μm and random porosity was revealed between the ceramic particles with the size of ~0.3 - 1 μm. TiB2 near-net-shaped parts with the multi-scale porosities (~50 to 70%) were successfully cast and sintered. The multi-scale porous structure produced from electrospun fibers was characterized both thermally and mechanically, at room temperature. The conductivity ranged from 12-31 W m^(-1) K^(-1) at room temperature and the compressive strength ranged from 2-30 MPa at room temperature. Analytical thermal and mechanical models were employed to understand and verify he processing-structure-properties relationship. Finally, a method was devised for estimating the effective thermal conductivity of candidate materials for UHTC applications at relevant temperatures using a finite difference model and a controlled sample environment. This low-cost processing technique facilitates the production of thermally and mechanically anisotropic structures into near-net shape parts, for extreme environment applications, such as ultra high temperature insulation and active cooling components.
MS

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Sarkar, Sourangsu. "The fabrication of polymer-derived SiCN/SiBCN ceramic nanostructures and investigation of their structure-property relationship." Doctoral diss., University of Central Florida, 2010. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4666.

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Polymer-derived Ceramics (PDCs) represent a unique class of high-temperature stable materials synthesized directly by the thermal decomposition of polymers. This research first focuses on the fabrication of high temperature stable siliconcarbonitride (SiCN) fibers by electrospinning for ceramic matrix composite (CMC) applications. Ceraset™ VL20, a commercially available liquid cyclosilazane, was functionalized with aluminum sec-butoxide in order to be electrospinnable. The surface morphology of the electrospun fibers was investigated using the fibers produced from solvents. The electrospun fibers produced from the chloroform/N,N-dimethylformamide solutions had hierarchical structures that led to superhydrophobic surfaces. A “dry skin” model was proposed to explain the formation of micro/- and nanostructures. The second objective of the research is to align the multiwalled carbon nanotubes (MWCNTs) in PDC fibers. For this purpose, a non-invasive approach to disperse carbon nanotubes in polyaluminasilazane chloroform solutions was developed using a conjugated block copolymer synthesized by ATRP. The effect of the polymer and CNT concentration on the fiber structure and morphology was also examined. Detailed characterization using SEM and TEM was performed to demonstrate the orientation of CNTs inside the ceramic fibers. Additionally, the electrical properties of the ceramic fibers were investigated. Finally, the structural evolution of polymer-derived amorphous siliconborocarbonitride (SiBCN) ceramics with pyrolysis temperatures was studied by solid-state NMR, Raman and EPR spectroscopy. Results suggested the presence of three major components: (i) hexagonal boron nitride (h-BN), (ii) turbostratic boron nitride (t-BN), and (iii) BN2C groups in the final ceramic. The pyrolysis at higher temperature generated boron nitride (BN3) with a simultaneous decomposition of BN2C groups. A thermodynamic model was proposed to quantitatively explain the conversion of BN2C groups into BN3 and “free” carbon. Such structure evolution is believed to be the reason that the crystallization of Si4.0B1.0 ceramics starts at 1500 °C, whereas Si2.0B1.0 ceramics is stable upto 1600 °C.
ID: 029050506; System requirements: World Wide Web browser and PDF reader.; Mode of access: World Wide Web.; Thesis (Ph.D.)--University of Central Florida, 2010.; Includes bibliographical references.
Ph.D.
Doctorate
Department of Chemistry
Sciences

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Hao, Wenjun. "Atomic layer deposition of boron nitride." Thesis, Lyon, 2017. http://www.theses.fr/2017LYSE1311/document.

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Cette thèse conclut 3 années d'études doctorales sur le "dépôt de couches atomiques (ALD) de nitrure de bore (BN)". Le but de ce travail a été d'adapter la voie des céramiques dérivées de polymères (PDC) Ã la technique ALD pour la croissance de films minces de h-BN et l'élaboration de nanostructures fonctionnelles. Tout d'abord, un nouveau procédé d'ALD sans ammoniac en deux étapes, comprenant une croissance par ALD à basse température (80 Â°C) de polyborazine (PBN) à partir de 2,4,6-trichloroborazine et d'hexaméthyldisilazane suivi un traitement thermique à haute température sous atmosphère contrôlée a été développé. Ainsi, des films minces uniformes et homogènes de BN ont pu être déposés sur divers substrats. Le caractère autolimité des réactions mises en jeu ainsi que l'homogénéité des films sur des supports très structurés ont été vérifiés. De ce fait des nanostructures fonctionnelles BN ont été réalisées à partir de substrats ou de templates de dimensionnalité variée. Leurs applications en tant que revêtements protecteurs et comme filtres et éponges absorbantes pour purifier les eaux polluées par des hydrocarbures ont en particulier été étudiées. Enfin, un deuxième procédé ALD basse température (85-150°C) utilisant le tri(isopropylamino)borane et la méthylamine comme précurseurs a été préalablement étudié afin de confirmer l'adaptabilité de la voie PDC et la technique ALD. Des films minces de BN ont été obtenus sur des substrats plans et il a été prouvé que les vapeurs de tri(isopropylamino)borane peuvent infiltrer des fibres de polyacrylonitrile électrofilées.Ce travail a été entièrement réalisé à l'Université de Lyon et a reçu le soutien financier du China Scholarship Council (CSC) pour la bourse de doctorat ainsi que de l'Agence Nationale de la Recherche (projet n° ANR-16-CE08-0021-01)
This thesis achieves 3 years of PhD studies on “Atomic layer deposition (ALD) of boron nitride (BN)”. The aim of this PhD work is to adapt the polymer derived ceramics (PDCs) route to the ALD technique for h-BN thin film growth and elaboration of functional nanostructures. A novel two-step ammonia-free ALD process, which includes ALD deposition of polyborazine at low temperature (80 °C) from 2,4,6-trichloroborazine and hexamethyldisilazane followed by post heat treatment under controlled atmosphere, has been established. Conformal and homogeneous BN thin films have been deposited onto various substrates. The self-limitation of the reactions on flat substrates and the conformality of the films on structured substrates have been verified. Functional BN nanostructures have thus been fabricated using substrates or templates with different dimensionalities. In particular, their applications as protective coatings as well as filter and absorber to purify polluted water from organic/oil hav e been investigated. Finally, a second low temperature (85-150 °C) ALD process using tri(isopropylamine)borane and methylamine as precursors has preliminary been studied in order to confirm the adaptability of PDCs route to ALD technique. BN thin films have been grown onto flat substrate and it has been proven that tri(isopropylamino)borane vapor can infiltrate into electrospun polyacrylonitrile fibers.This work was carried out at University of Lyon and financially supported by the National Research Agency (project n° ANR-16-CE08-0021-01)

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Viard, Antoine. "Structure, élaboration, propriétés et modification de surface de fibres creuses non-oxydes à partir de polymères pré-céramiques pour des applications membranaires." Thesis, Montpellier, 2016. http://www.theses.fr/2016MONTT243.

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Les matériaux céramiques se sont énormément développés durant le dernier siècle et ne cessent d'attirer l'attention pour diverses applications. Cela tient aux propriétés nombreuses et variées qu'elles peuvent présentées. Un avantage certain de ce type de matériaux réside dans leurs stabilités mécanique, thermique et chimique, ce qui en fait des candidats de choix pour des applications dans des environnements sévères. Ceci est notamment observable dans le domaine des membranes. En effet, malgré leurs coût réduit, les membranes polymères, constituant l'essentiel des membranes utilisées à ce jour, sont très sensibles à l'environnement dans lequel elles sont utilisées et nécessitent d'être renouvelées régulièrement. Cela justifie la recherche d'alternatives, comme par exemple les céramiques plus résistantes. Différentes mises en forme sont possibles pour la formation de membranes, mais parmi celles-ci, les formes en tubes ont suscité un engouement certain en raison des avantages en termes de rapport surface/volume et de la résistance au transport de masse moindre. La majorité des céramiques utilisées et commercialisées reposent sur des compositions chimiques à base d'oxydes. Il apparaît cependant que ces matériaux trouvent leurs limites en termes de vieillissement et de stabilité à très haute température. Un autre type de céramiques, les céramiques non-oxydes à base de silicium, présentent des propriétés très intéressantes, pouvant potentiellement répondre à ces problématiques. De tels matériaux sont produits par la voie PDC (Polymer Derived Ceramic), notamment en raison de l'impossibilité de procéder autrement pour la majorité d'entre eux. Cette méthode consiste à synthétiser des polymères pré-céramiques pouvant être convertis en céramiques par un traitement thermique adéquat. Cela permet notamment un très bon contrôle de la structure chimique de la céramique finale, et donc une grande versatilité. Parmi ces matériaux, le système quaternaire Si-B-C-N a particulièrement attiré l'attention en raison de ses propriétés thermostructurales couplées à sa stabilité chimique singulière. Les travaux de thèses présents se sont donc focalisés sur l'utilisation de cette céramique. Un autre avantage de la voie des polymères pré-céramiques réside dans les mises en forme rendues possibles par l'utilisation de polymères. Cette méthode a déjà été utilisée abondamment pour produire des fibres céramiques avec des diamètres de l'ordre de la dizaine de microns, notamment par le recours à la technique de filage en fondu (melt-spinning en anglais). L'objectif principal de cette thèse est la production de fibres creuses et de capillaires céramiques SiBCN en se basant sur cette méthode de mise en forme. Le but est la formation de supports membranaires très stables à un coût relativement faible comparé aux procédés généralement utilisés pour la mise en forme de céramiques, impliquant souvent un traitement de frittage à très haute température. Ces supports offriront à terme des applications en séparation de gaz ou en traitement de l'eau. Plus exactement, le chapitre 1 concerne l'état de l'art et permet de présenter le contexte de ces travaux, ainsi que leur intérêt. Le chapitre 2 présente les techniques de synthèses mises en œuvre et les matériaux utilisés. Le chapitre 3 est consacré à la production de fibres creuses céramiques SiBCN en présentant notamment une étude complète de la structure chimique du polymère utilisé, ainsi que l'évolution de la microstructure de la céramique résultante à haute température. Le chapitre 4 a pour objet la formation de capillaires céramiques SiBCN. Ici aussi, le précurseur utilisé est caractérisé en détail, de même que la céramique issue de sa pyrolyse. Le dernier chapitre consiste en une ouverture et propose différentes méthodes de modification de surface des fibres creuses et des capillaires élaborés dans les chapitres 3 et 4
New ceramic materials have progressively emerged during the last century and continuously drew attention for diverse applications. This comes from the numerous and various properties they can exhibit. A great advantage of this type of materials is their mechanical, thermal and chemical stabilities, that makes ceramics of great interest for applications in harsh environments. This trend is especially perceptible in the field of membranes. In fact, despite their moderate cost, polymer membranes, which are mostly used, are very sensitive to the environment in which they are used and require to be replaced regularly. This justifies the search for alternatives and for more resistant materials like ceramics. Various shaping are possible to build a membrane, but among these, shapings in form of tubes have aroused particular enthusiasm because of their advantages in terms of surface/volume ratio and of lower mass transport resistance. Most of used and commercialized ceramics are based on oxide chemical compositions. This constitutes a drawback concerning the aging of the membranes and their stability at very high temperatures. Another type of ceramics, non oxide silicon based ceramics, exhibits very interesting properties which could eventually palliate these problems. In general, such materials are produced through the PDC route (Polymer Derived Ceramic route), especially because of the impossibility to proceed by more conventional methods for many of them. The principle of this bottom-up method is to synthesize preceramic polymers which can be converted into ceramics through an appropriate heat treatment. This enables a very good control of the chemical structure of the final ceramics and so a great versatility. Among these materials, the quaternary system Si-B-C-N has aroused big interest because of its extraordinary thermostructural properties coupled to chemical inertness. Thus, the present work has been focused on the preparation and application of this ceramic. Another advantage of the PDC route can be found in the possible shaping arising from the polymeric nature of the precursors. This method has been widely used for the production of thin ceramic fibers by using the melt-spinning process. The main objective of this thesis is the design of SiBCN ceramic hollow fibers and capillaries based on this shaping method. The aim is the preparation of very stable membrane supports at relatively low costs compared to conventional processes used to shape ceramic materials, often involving a sintering treatment at a very high temperature. These supports could be used in gas separation and water treatment applications. More precisely, chapter 1 presents a state of the art and allows to give the context and the motivations of this work. Chapter 2 discusses on the synthesis techniques and on the used methods. Chapter 3 is dedicated to the production of SiBCN ceramic hollow fibers by studying in details the precursors chemical structure used for this purpose before investigating its ceramic conversion and the evolution of the microstructure of the resulting ceramic. Chapter 4 is dealing with the production of SiBCN ceramic capillaries. The precursor used is characterized as well as the resulting ceramic. The last chapter gives some perspectives by proposing different methods of surface modifications of the hollow fibers and the capillaries presented in chapters 3 and 4

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Zhang, Huixing Verfasser], Kurosch [Akademischer Betreuer] Rezwan, Kurosch [Gutachter] Rezwan, and Michael [Gutachter] [Scheffler. "Macroporous Polymer-Derived Ceramic Monoliths for Cryogenic Applications Manufactured by Water-Based Freeze Casting / Huixing Zhang ; Gutachter: Kurosch Rezwan, Michael Scheffler ; Betreuer: Kurosch Rezwan." Bremen : Staats- und Universitätsbibliothek Bremen, 2018. http://d-nb.info/1162620633/34.

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47

Faulmann, Christophe. "Conducteurs derives de metaux de transition : complexes moleculaires, polymeres, oxydes de cuivre." Toulouse 3, 1988. http://www.theses.fr/1988TOU30160.

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Zunjarrao, Suraj C. "Polymer derived ceramics processing-structure-property relationships /." 2008. http://digital.library.okstate.edu/etd/umi-okstate-2726.pdf.

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Sudhakar, Bhukya. "Fabrication of polymer derived silica bonded alumina ceramics." Thesis, 2014. http://ethesis.nitrkl.ac.in/6449/1/110CR0581-13.pdf.

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Present work focuses on the polymer derived silica bonded alumina ceramics. Sintering has been done at 1500oC and 1600 oC. The alpha-alumina phase of (305 nm from ALMATIS&449 nm of TRL alumina) micron particle size has been used as starting material. Along with Polymethylsiloxane or puresilica is added with isopropylalcohol. The study of the densification of pellet at varying soaking time of 1, 2, 4, and 6 hours has also been carried. For better densification mixing is done under magnetic stirring. The microstructure of the sintered body is analyzed and densification due to a grain growth has been observed. We are successful to minimize the porosity up to 0.7% and preparing a dense product. The Vickers hardness test has been carried out for testing of mechanical property and was found to have good hardness value.

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Rath, Durga Prasad. "Phase Evolution in Doped Polymer Derived Silicon Oxycarbide Ceramics." Thesis, 2015. http://ethesis.nitrkl.ac.in/6834/1/PHASE_Rath_2015.pdf.

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Polymer derived ceramics (PDC) is an important class of ceramics that are fabricated from the inert atmosphere pyrolysis of Si- containing precursors. Various Si- based ceramics including silicon oxycarbide (SiCO), silicon carbonitride (SiCN), silicon carbide (SiC), silicon borocarbonitride (SiBCN) etc. can be prepared from various Si- containing precursors. These ceramics are characterized by their high specific strength, oxidation resistance, enhanced creep resistance and other functional properties. One of the most important developments in the ceramic system is the possibility of using these materials as coatings for high temperature structural ceramics. Although oxidation resistance of PDCs are good, they need to be fabricated in the multilayer structures that includes phase stability with various other metal oxides and carbides. The present work focuses on transition metal modified Polymer derived ceramics (PDC). Poly (methyl) silsesquioxane was used as the preceramic polymer in the process. Various transition metal elements having similar atomic size and different valence such as Al and Ti were introduced in the SiCO structure to form modified PDC. The doping amount in the structure is varied to study effect of amount of transition metal doping at the molecular level on phase evolution at different temperatures Phase evolution and thermal behavior of the modified PDCs at different high temperatures are studied.

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Dissertations / Theses on the topic 'Polymer Derived Ceramics'

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