Planar,Polysilazane‐Derived Porous Ceramic Supports for Membrane and Catalysis Applications

Porous, silicon carbonitride‐based ceramic support structures for potential membrane and catalysis applications were generated from a preceramic polysilazane precursor in combination with spherical, ultrahigh‐molecular weight polyethylene microparticles through a sacrificial filler approach. A screening evaluation was used for the determination of the impact of both porogen content and porogen size on pore structure, strength, and permeability characteristics of planar specimens. By optimizing both the composition as well as cross‐linking parameters, maximum characteristic biaxial flexural strengths of 65 MPa and porosities of 42% were achieved. The evolution of an interconnected, open‐pore network during thermal porogen removal and conversion of the preceramic polymer led to air permeabilities in the order of 10^?14 m². The materials were further exposed to long‐term heat treatments to demonstrate the stability of properties after 100 h at 800°C in oxidizing, inert, and reducing environments. The determined performance, in combination with the versatile preparation method, illustrates the feasibility of this processing approach for the generation of porous ceramic support structures for applications at elevated temperatures in a variety of fields, including membrane and catalysis science.     

Laser pyrolyzed organosilazane-based Al/ZrO2 composite coating on stainless steel: Resulting microstructure and mechanical properties

Protective ceramic-based coatings are frequently the most suitable solutions for problems like corrosion and wear. It has been shown that the precursor technology is suitable for the preparation of ceramic coatings by pyrolysis in a furnace. However, the required high temperature for the preparation of the ceramic coatings limits this approach to high temperature-resistant substrates. A very innovative approach to overcome this restriction is the use of laser radiation as a thermal source for the pyrolysis of the preceramic polymer. In this paper, we report on a coating system, for steel substrates, consisting of a polysilazane (Durazane 2250) bond coat and a hard and dense top-coat composed of an organosilazane (Durazane 1800) with tetragonal ZrO₂ particles and aluminum flakes as fillers pyrolyzed using Nd:YVO₄ laser. The aluminum fillers led to a significant increase in absorption of the laser energy leading to the formation of a dense coating with a thickness up to 20 μm and a mainly cellular/columnar-dendritic microstructure. The microstructure, mechanical, and tribological behaviors of these composite coatings are reported and compared to those of laser pyrolyzed glass/ZrO₂-filled polysilazane-based coatings reported in the literature.     

Processing of Polymer-Derived Ceramic Composite Coatings on Steel

Polymer-derived ceramic composites are being investigated as environmental barrier coatings to protect stainless steel from oxidation and carburization. Coatings have been produced using poly(hydridomethylsiloxane) as a preceramic polymer and titanium disilicide as an expansion agent. Processing parameters have been optimized and a relationship has been derived to predict the final coating thickness based on slurry viscosity and dip coating withdrawal speed. Microstructural analysis reveals a composite coating of oxidized filler particles in a silica matrix. A diffusion layer is visible at the coating–steel interface, indicating good bonding. The optimized coatings are ∼18 μm thick, and have some residual porosity and a density of 2.56 g/cm³.     

Analysis of Sintering of a Composite with a Glass or Ceramic Matrix

A recently developed theory for sintering of bimodal powders is applied to a composite where the matrix is either a glass or a ceramic. The filler phase is assumed to be rigid and nonsintering. It is shown that glass-matrix composites should have predictable sintering behavior which follows the rule of mixtures, but ceramic-matrix composites are expected to be more difficult to sinter, and their sintering behavior may deviate considerably from the rule of mixtures, even at low concentrations of the filler phase.     

Isotropic Constitutive Model for Sintering Particle Packings

This paper presents an isotropic model for the effective viscosities of sintering particle packings. The relationship between the macroscopic stress and deformation rate is based on the behavior of individual interparticle contacts, represented by contact viscosities, and the statistics of the packing. The contact viscosities depend on the contact area, which is the primary variable used to describe the state of the packing. A direct consequence of this choice of state variable is that the effective viscosities are identically zero for an undeformed and unsintered packing. Specific results are presented for the case of Newtonian viscous materials. The model is compared with existing models for porous Newtonian viscous materials. Experiments conducted with spherical glass powder packings show good agreement with the model. Finite-element simulations using the model have been used to study forging of a pellet.     

When employees strike back: Investigating mediating mechanisms between psychological contract breach and workplace deviance.

In this article, psychological contract breach, revenge, and workplace deviance are brought together to identify the cognitive, affective, and motivational underpinnings of workplace deviance. On the basis of S. L. Robinson and R. J. Bennett's (1997) model of workplace deviance, the authors proposed that breach (a cognitive appraisal) and violation (an affective response) initiate revenge seeking. Motivated by revenge, employees then engage in workplace deviance. Three studies tested these ideas. All of the studies supported the hypothesized relationships. In addition, self-control was found to be a moderator of the relationship between revenge cognitions and deviant acts; the relationship was weaker for people high in self-control. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The effect of gelation on statically and dynamically freeze-cast structures

Freeze-casting is a technique used to produce structures with anisotropic porosity in the form of well-defined microchannels throughout a sample. Here, this technique is used on the magnetocaloric ceramic La_0.66Ca_0.26Sr_0.07 Mn_1.05O₃. We show that a dynamic freezing profile, where the temperature is decreased continuously at −10 K/min, results in homogeneous, lamellar channels with widths of ∼15 µm, while static freezing, where the temperature is kept constant at 177 K, results in channels of increasing size away from the initial ice crystal nucleation site. The effect of gelation before freeze-casting is also investigated. Gelation inhibits ice crystal growth, which significantly changes the morphology by making channel cross sections less elongated, while additionally introducing more dendrites and ceramic bridges in the structure. The latter significantly dominates the flow path through the gelated structures, affecting the calculated tortuosity, which increases to τ ≈ 4 when compared to non-gelated samples where calculated tortuosities are in the range of ∼1.3 to ∼3. Finally, we present a systematic and automatic approach for evaluating channel and wall sizes and calculating tortuosities. This is based on analysis of images obtained by scanning electron microscopy using a continuous particle size distribution method and the TauFactor application in MATLAB^®.     

Low/intermediate temperature pyrolyzed polysiloxane derived ceramics with increased carbon for electrical applications

This study focuses on the chemistry, thermal stability, and electrical conductivity of low/intermediate pyrolysis temperature (700?900 °C) polysiloxane derived ceramics. These ceramics were modified with additional carbon derived from divinylbenzene (DVB) added to the precursor. Their electrical properties were investigated for potential uses in micro-electrical mechanical systems (MEMS) and anodes for lithium batteries. The microstructure and chemical composition was investigated by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), Raman spectroscopy, and x-ray photoelectron spectroscopy (XPS); thermogravimetric analysis (TGA) provided insight into the thermal stability; and electrochemical impedance spectroscopy (EIS) into the electrical properties of the material. The increase of pyrolysis temperature and carbon content lead to an enhancement of the electrical conductivity, higher than previously reported values for intermediate pyrolysis temperature SiOC polymer derived ceramics. A limit of the amount of DVB that can be added to PHMS to produce a hybrid precursor has also been obtained.