Ab initio tensile experiment on a model of an intergranular glassy film in β-Si3N4 with prismatic surfaces

We report the results of a large-scale ab initio simulation of an intergranular glassy film (IGF) model in β-Si3N4. It is shown that the stress-strain behavior under uniaxial load in the model with prismatic surfaces and few defective bonds is very different from an earlier IGF model with basal planes. The results are explained by the fundamental electronic structure of the model. This work is supported by the U.S. Department of Energy under Grant No. DE-FG02-84DR45170. This research used the resources of NERSC supported by the Office of Science of DOE under Contract No. DE-AC03-76SF00098

Theoretical study of the elasticity, mechanical behavior, electronic structure, interatomic bonding, and dielectric function of an intergranular glassy film model in prismatic β-Si3N4

This is the published version. Copyright © 2010 The American Physical SocietyMicrostructures such as intergranular glassy films (IGFs) are ubiquitous in many structural ceramics. They control many of the important physical properties of polycrystalline ceramics and can be influenced during processing to modify the performance of devices that contain them. In recent years, there has been intense research, both experimentally and computationally, on the structure and properties of IGFs. Unlike grain boundaries or dislocations with well-defined crystalline planes, the atomic scale structure of IGFs, their fundamental electronic interactions, and their bonding characteristics are far more complicated and not well known. In this paper, we present the results of theoretical simulations using ab initio methods on an IGF model in β-Si3N4 with prismatic crystalline planes. The 907-atom model has a dimension of 14.533 Å×15.225 Å×47.420 Å. The IGF layer is perpendicular to the z axis, 16.4 Å wide, and contains 72 Si, 32 N, and 124 O atoms. Based on this model, the mechanical and elastic properties, the electronic structure, the interatomic bonding, the localization of defective states, the distribution of electrostatic potential, and the optical dielectric function are evaluated and compared with crystalline β-Si3N4. We have also performed a theoretical tensile experiment on this model by incrementally extending the structure in the direction perpendicular to the IGF plane until the model fully separated. It is shown that fracture occurs at a strain of 9.42% with a maximum stress of 13.9 GPa. The fractured segments show plastic behavior and the formation of surfacial films on the β-Si3N4. These results are very different from those of a previously studied basal plane model [J. Chen et al., Phys. Rev. Lett. 95, 256103 (2005)] and add insights to the structure and behavior of IGFs in polycrystalline ceramics. The implications of these results and the need for further investigations are discussed

Ab initio tensile experiment on a model of an intergranular glassy film in β-Si3N4 with prismatic surfaces

This is the published version. Copyright 2009 American Institute of PhysicsWe report the results of a large-scale ab initio simulation of an intergranular glassy film (IGF) model in β-Si3N4. It is shown that the stress-strain behavior under uniaxial load in the model with prismatic surfaces and few defective bonds is very different from an earlier IGF model with basal planes. The results are explained by the fundamental electronic structure of the model

Electronic structure and physical properties of the spinel-type phase of BeP2N4 from all-electron density functional calculations

Using density-functional-theory-based ab initio methods, the electronic structure and physical properties of the newly synthesized nitride BeP2N4 with a phenakite-type structure and the predicted high-pressure spinel phase of BeP2N4 are studied in detail. It is shown that both polymorphs are wide band-gap semiconductors with relatively small electron effective masses at the conduction-band minima. The spinel-type phase is more covalently bonded due to the increased number of P-N bonds for P at the octahedral sites. Calculations of mechanical properties indicate that the spinel-type polymorph is a promising superhard material with notably large bulk, shear, and Young’s moduli. Also calculated are the Be K, P K, P L3, and N K edges of the electron energy-loss near-edge structure for both phases. They show marked differences because of the different local environments of the atoms in the two crystalline polymorphs. These differences will be very useful for the experimental identification of the products of high-pressure syntheses targeting the predicted spinel-type phase of BeP2N4

Complex Nonlinear Deformation of Nanometer Intergranular Glassy Films in β−Si3N4

This is the published version. Copyright 2005 American Physical SocietyThe mechanical properties of a model of Y-doped intergranular glassy film in silicon nitride ceramics are studied by large-scale ab initio modeling. By linking directly to its electronic structure, it is shown that this microstructure has a complex nonlinear deformation under stress and Y doping significantly enhances the mechanical properties. The calculation of the electrostatic potential across the film supports the space charge model in ceramic microstructures

Origin of the TTC values for compounds that are genotoxic and/or carcinogenic and an approach for their revaluation

The threshold of toxicological concern (TTC) approach is a resource-effective de minimismethod for the safety assessment of chemicals, based on distributional analysis of the results of a large number of toxicological studies. It is being increasingly used to screen and prioritise substances with low exposure for which there is little or no toxicological information. The first step in the approach is the identification of substances that may be DNA-reactive mutagens, to which the lowest TTC value is applied. This TTC value was based on analysis of the cancer potency database and involved a number of assumptions that no longer reflect the state-of-the-science and some of which were not as transparent as they could have been. Hence, review and updating of the database is proposed, using inclusion and exclusion criteria reflecting current knowledge. A strategy for the selection of appropriate substances for TTC determination, based on consideration of weight of evidence for genotoxicity and carcinogenicity is outlined. Identification of substances that are carcinogenic by a DNA-reactive mutagenicmode of action and those that clearly act by a non-genotoxic mode of action will enable the protectiveness to be determined of both the TTC for DNA-reactive mutagenicityand that applied by default to substances that may be carcinogenic but are unlikely to be DNA-reactive mutagens (i.e. for Cramer class I-III compounds). Critical to the application of the TTC approach to substances that are likely to be DNA-reactive mutagens is the reliability of the software tools used to identify such compounds. Current methods for this task are reviewed and recommendations made for their application

Electronic structure methods for complex materials: the orthogonalized linear combination of atomic orbitals

This title details the application of the OLCAO method for calculating the properties of solids from fundamental principles to a wide array of material systems. The method specialises in large and complex models and is able to compute a variety of useful properties including electronic, optical, and spectroscopic properties

First-Principles Calculations of the Structural, Electronic, Optical, and Mechanical Properties of 21 Pyrophosphate Crystals

Pyrophosphate crystals have a wide array of applications in industrial and biomedical fields. However, fundamental understanding of their electronic structure, optical, and mechanical properties is still scattered and incomplete. In the present research, we report a comprehensive theoretical investigation of 21 pyrophosphates A2M (H2P2O7)2•2H2O with either triclinic or orthorhombic crystal structure. The molecule H2P2O7 is the dominant molecular unit, whereas A = (K, Rb, NH4, Tl), M = (Zn, Cu, Mg, Ni, Co, Mn), and H2O stand for the cation elements, transition metals, and the water molecules, respectively. The electronic structure, interatomic bonding, partial charge distribution, optical properties, and mechanical properties are investigated by first-principles calculations based on density functional theory (DFT). Most of these 21 crystals are theoretically investigated for the first time. The calculated results show a complex interplay between A, M, H2P2O7, and H2O, resulting in either metallic, half-metallic, or semi-conducting characteristics. The novel concept of total bond order density (TBOD) is used as a single quantum mechanical metric to characterize the internal cohesion of these crystals to correlate with the calculated properties, especially the mechanical properties. This work provides a large database for pyrophosphate crystals and a road map for potential applications of a wider variety of phosphates

Structure and properties of the low-density phase ι-Al2O3 from first principles

Of the various phases of transition alumina, iota-alumina (ι-Al2O3) is the least well known. It is considered to be the end member of the mullite series in the limit of zero Si content. The structural details of ι-Al2O3 are not available and its physical properties are totally unknown. Based on an appropriately modified structure of a high alumina content mullite phase close to the 9-1 mullite, we have successfully constructed a structural model for ι-Al2O3. The simulated x-ray diffraction (XRD) pattern of this model agrees well with a measured XRD pattern obtained from samples that claim to belong to ι-Al2O3. ι-Al2O3 is a highly disordered ultralow-density phase of alumina with a theoretical density of 2854 kg/m3. The calculated total energy per Al2O3 is much higher than α-Al2O3 and the other well-known disordered phase, γ-Al2O3. Using this theoretically constructed model, we have calculated the elastic, thermodynamic, electronic, and spectroscopic properties of ι-Al2O3 and compared them with those of α-Al2O3 and γ-Al2O3. It is shown that the mechanical strength of ι-Al2O3 is much weaker with bulk and shear moduli that are only 57 and 42% of α-Al2O3. Phonon dispersion results and the subsequently calculated thermodynamic properties point to the fact that ι-Al2O3 is an alumina phase preceding γ-Al2O3 in the processing of alumina before reaching α-Al2O3. Electronic structure calculations show it to be an insulator with a direct band gap of only 3.0 eV at the Γ point and a higher ionic bonding character than α-Al2O3 and γ-Al2O3. It has a calculated static dielectric constant of 2.73 and a corresponding refractive index of 1.65 that are in agreement with reported data. Also calculated are the Al-K, Al-L3, and O-K edges of the x-ray absorption near edge structure in ι-Al2O3, showing sensitive dependence on its local bonding environment. However, only the weighted average of these spectra can be directly compared with the measured ones which are currently unavailable