Oxidation mechanism of Si3N4-bonded SiC ceramics by CO, CO2 and steam

This paper presents a theoretical and experimental investigation into the oxidation reactions of Si3N4-bonded SiC ceramics. Such ceramics which contain a small amount of silicon offer increased oxidation and wear resistance and are widely used as lining refractories in blast furnaces. The thermodynamics of oxidation reactions were studied using the JANAF tables. The weight gain was measured using a thermogravimetric analysis technique to study the kinetics. The temperature range of oxidation measurements is from 1073 to 1573 K and the oxidation atmosphere is water vapour, pure CO and CO-CO2 gas mixtures with various CO-to-CO2 ratios. Thermodynamic simulations showed that the oxidation mechanism of Si3N4-bonded SiC ceramics is passive oxidation and all components contribute to the formation of a silica film. The activated energies of the reactions follow the sequence Si3N4>SiC>Si. The kinetic study revealed that the oxidation of Si3N4-bonded SiC ceramics occurred in a mixed regime controlled by both interface reaction and diffusion through the silica film. Under the atmosphere conditions prevailing in the blast furnace, this ceramic is predicted to be passively oxidized with the chemical reaction rate becoming more dominant as the CO concentration increases. (C) 1998 Chapman & Hall.

Reply to comments on "Oxidation mechanism of Si3N4-bonded SiC ceramics by CO, CO2 and steam," by Balat et al.

First of all, we would like to clarify that the passive to active transition was determined not by using Solgasmix [1], but by combining thermodynamic equilibrium and mass balance for the oxidation of SiC under pure CO2 and pure CO. The model used in our paper [2]was an extension ofWagner’s model [3], in a similar way as Balat et al. [4] did for the oxidation of SiC in oxygen.

Cutting forces and wear analysis of Si3N4 diamond coated tools in high speed machining

Si3N4 tools were coated with a thin diamond film using a Hot-Filament Chemical Vapour Deposition (HFCVD) reactor, in order to machining a grey cast iron. Wear behaviour of these tools in high speed machining was the main subject of this work. Turning tests were performed with a combination of cutting speeds of 500, 700 and 900 m min−1, and feed rates of 0.1, 0.25 and 0.4 mm rot−1, remaining constant the depth of cut of 1 mm. In order to evaluate the tool behaviour during the turning tests, cutting forces were analyzed being verified a significant increase with feed rate. Diamond film removal occurred for the most severe set of cutting parameters. It was also observed the adhesion of iron and manganese from the workpiece to the tool. Tests were performed on a CNC lathe provided with a 3-axis dynamometer. Results were collected and registered by homemade software. Tool wear analysis was achieved by a Scanning Electron Microscope (SEM) provided with an X-ray Energy Dispersive Spectroscopy (EDS) system. Surface analysis was performed by a profilometer.

Adhesion and wear behaviour of NCD coatings on Si3N4 by micro-abrasion tests

Nanocrystalline diamond (NCD) coatings offer an excellent alternative for tribological applications, preserving most of the intrinsic mechanical properties of polycrystalline CVD diamond and adding to it an extreme surface smoothness. Silicon nitride (Si3N4) ceramics are reported to guarantee high adhesion levels to CVD microcrystalline diamond coatings, but the NCD adhesion to Si3N4 is not yet well established. Micro-abrasion tests are appropriate for evaluating the abrasive wear resistance of a given surface, but they also provide information on thin film/substrate interfacial resistance, i.e., film adhesion. In this study, a comparison is made between the behaviour of NCD films deposited by hot-filament chemical vapour deposition (HFCVD) and microwave plasma assisted chemical vapour deposition (MPCVD) techniques. Silicon nitride (Si3N4) ceramic discs were selected as substrates. The NCD depositions by HFCVD and MPCVD were carried out using H2–CH4 and H2–CH4–N2 gas mixtures, respectively. An adequate set of growth parameters was chosen for each CVD technique, resulting in NCD films having a final thickness of 5 m. A micro-abrasion tribometer was used, with 3 m diamond grit as the abrasive slurry element. Experiments were carried out at a constant rotational speed (80 r.p.m.) and by varying the applied load in the range of 0.25–0.75 N. The wear rate for MPCVD NCD (3.7±0.8 × 10−5 m3N−1m−1) is compatible with those reported for microcrystalline CVD diamond. The HFCVD films displayed poorer adhesion to the Si3N4 ceramic substrates than the MPCVD ones. However, the HFCVD films show better wear resistance as a result of their higher crystallinity according to the UV Raman data, despite evidencing premature adhesion failure.

Titanium oxide adhesion layer for high temperature annealed Si/Si3N4/TiOx/Pt/LiCoO2 battery structures

This work describes the influence of a high annealing temperature of about 700C on the Si(substrate)/Si3N4/TiOx/Pt/LiCoO2 multilayer system for the fabrication of all-solid-state lithium ion thin film microbatteries. Such microbatteries typically utilize lithium cobalt oxide (LiCoO2) as cathode material with a platinum (Pt) current collector. Silicon nitride (Si3N4) is used to act as a barrier against Li diffusion into the substrate. For a good adherence between Si3N4 and Pt, commonly titanium (Ti) is used as intermediate layer. However, to achieve crystalline LiCoO2 the multilayer system has to be annealed at high temperature. This post-treatment initiates Ti diffusion into the Pt-collector and an oxidation to TiOx, leading to volume expansion and adhesion failures. To solve this adhesion problem, we introduce titanium oxide (TiOx) as an adhesion layer, avoiding the diffusion during the annealing process. LiCoO2, Pt and Si3N4 layers were deposited by magnetron sputtering and the TiOx layer by thermal oxidation of Ti layers deposited by e-beam technique. Asdeposited and annealed multilayer systems using various TiOx layer thicknesses were studied by scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The results revealed that an annealing process at temperature of 700C leads to different interactions of Ti atoms between the layers, for various TiOx layer thicknesses (25–45 nm).

Si3N4 single-crystal nanowires grown from silicon micro- and nanoparticles near the threshold of passive oxidation

A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions

Diffraction grating couplers milled in Si3N4 rib waveguides with a focused ion beam

Focused ion beam milling is a processing technology which allows flexible direct writing of nanometer scale features efficiently substituting electron beam lithography. No mask need results in ability for patterns writing even on fragile micromechanical devices. In this work we studied the abilities of the tool for fabrication of diffraction grating couplers in silicon nitride waveguides. The gratings were fabricated on a chip with extra fragile cantilevers of sub micron thickness. Optical characterization of the couplers was done using excitation of the waveguides in visible range by focused Gaussian beams of different waist sizes. Influence of Ga+ implantation on the device performance was studied.

Obtención de Si3N4 mediante SHS

En el presente trabajo se presentan los resultados obtenidos en el estudio de las reacciones de Síntesis Autopropagada a Alta Temperatura (Self-propagating High-temperature Synthesis, SHS) de Nitruro de Silicio. La síntesis autopropagada a alta temperatura consiste básicamente en la generación de reacciones altamente exotérmicas capaces de automantenerse. Se puede considerar como principal ventaja del método el ahorro energético que supone. La síntesis se realiza sobre una mezcla inicial de silicio metálico sobre la cual se realizan adiciones de diluyente y otros aditivos (sales amónicas) que afectan al desarrollo de la reacción. Se ha estudiado la influencia que en este sistema pueden tener las proporciones de las distintas incorporaciones en la mezcla, tanto en el material resultante como en las condiciones de reacción. Igualmente se ha estudiado la posibilidad de utilización de nuevos aditivos que puedan minimizar el impacto medio ambiental. Se presentan los estudios microestructurales del material obtenido, la identificación cristalográfica de las fases presentes así como los comportamientos de los parámetros que definen la propia reacción. Con la información obtenida se propone el mecanismo predominante de la síntesis del Nitruro de Silicio mediante SHS.

Síntesis y sinterización de SiC y Si3N4 a partir de la cascarilla de arroz [por] Brenda Iraís Treviño Cardona

Tesis (Maestría en Ciencias con Especialidad en Ingeniería Cerámica) U.A.N.L.

Si3N4 single-crystal nanowires grown from silicon micro- and nanoparticles near the threshold of passive oxidation

A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

Si3N4 ceramic cutting tool sintered with CeO2 and Al2O3 additives with AlCrN coating

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cutting performance of diamond coated Si3N4 tool during turning

Silicon nitride cutting tools have been used successfully for machining hard materials, like: cast irons, nickel based alloys, etc. However these cutting tools with diamond coating present little information on dry turning operations of gray cast iron. In the present work, Si3N4 square inserts was developed, characterized and subsequently coated with diamond for dry machining operations on gray cast iron. All experiments were conducted with replica. It was used a 1500, 3000, 4500 m cutting length, feed rate of 0.33 mm/rev and keeping the depth of cut constant and equal to 1 mm. The results show that wear in the tool tips of the Si3N4 inserts, in all cutting conditions, was caused by both mechanical and chemical processes. To understand the tool wear mechanisms, a morphological analysis of the inserts, after experiments, has been performed by SEM and optical microscopy. Diamond coated PVD inserts showed to be capable to reach large cutting lengths when machining gray cast iron. © (2010) Trans Tech Publications.

Desenvolvimento de pastilhas cerâmicas à bases de Si3N4 para aplicações tribológicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo da utilização de ferramentas a base de nitreto de silício (Si3N4) e alumina (Al2O3) na usinagem do ferro fundido vermicular

Machining is one of the most commonly manufacturing processes used in the modern world, consuming millions of dollars annually. Because of this, it is crucial for the automotive industry to reduce costs on their heat-resistant alloy machining processes, such as compacted graphite iron (CGI), which has shown an increasing trend of its application in diesel engine blocks, brakes disks, among other applications, due to its superior mechanical properties to gray cast iron. Despite this advantage, its use is still limited due to its difficulty of machining, moreover, cutting tools are displayed as the main factor in increasing the machining cost. Seeking an alternative to a better machinability of CGI, this paper aims to study two types of ceramic tools developed in Brazil, and benchmark their performance by dry turning. For this, were used CGI class 450 and two tools: ceramic of silicon nitride (Si3N4) and alumina-based (Al2O3), with a cutting speed (Vc) of 300, 400 and 500 m / min; feed (f) of 0.2 mm / rev and depth of cut (ap) of 0.5 mm, using three replicates and starting with new cutting edges. The results showed that the Al2O3 tool had the best performance in Vc of 500 m / min, while the Si3N4 tool had the best results in Vc of 300 m / min. This can be explained by the tool of Si3N4 based include soft intergranular phase, called amorphous, while alumina has higher abrasion resistance due to its high refractoriness. The results make it clear that the tools have significant potential for machining of compacted graphite iron, being necessary a strict control of the cutting parameters used