Quantum Mechanical Metric for Internal Cohesion in Cement Crystals

This is the published version. Copyright 2014 Nature Publishing Group.Calcium silicate hydrate (CSH) is the main binding phase of Portland cement, the single most important structural material in use worldwide. Due to the complex structure and chemistry of CSH at various length scales, the focus has progressively turned towards its atomic level comprehension. We study electronic structure and bonding of a large subset of the known CSH minerals. Our results reveal a wide range of contributions from each type of bonding, especially hydrogen bonding, which should enable critical analysis of spectroscopic measurements and construction of realistic C-S-H models. We find the total bond order density (TBOD) as the ideal overall metric for assessing crystal cohesion of these complex materials and should replace conventional measures such as Ca:Si ratio. A rarely known orthorhombic phase Suolunite is found to have higher cohesion (TBOD) in comparison to Jennite and Tobermorite, which are considered the backbone of hydrated Portland cement

Next Generation Neutron Detection for Next Generation Nuclear Reactors

Track I: Power GenerationIncludes audio file (31 min.)As the demand for nuclear energy increases worldwide, and MO reactors come online, so does the availability of spent fuel that may be used as a medium of terror. That is, fuel for and waste or byproducts from fissile material refining and nuclear reactors (e.g. plutonium) pose a serious threat with respect to radiological dispersal and nuclear bomb detonation. Radiological dispersal can include fallout by means of water or atmospheric transport (e.g., dumping waste in a river) while fissile trafficking can include the transport of plutonium across a border by seaport entry. In order to safely increase the use of nuclear energy in Missouri, sensitive techniques for nuclear detection must be developed. Presently available commercial detectors are not sensitive enough to detect even large (~3kg) quantities of weapons grade plutonium that are hidden in a barrel of water; our borders are effectively open to critical mass sized plutonium transport. Profs. Caruso, Ching and Kruger (UMKC Physics) are developing detectors capable of a ten times increase in detection sensitivity over existing commercial detectors that will provide a critical component to the future Missouri nuclear safeguarding infrastructure

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

Elastic and electronic properties of Ti2Al(CxN1−x) solid solutions

The elastic coefficients and mechanical properties (bulk modulus, shear modulus, Young\u27s modulus and Poisson\u27s ratio) of Ti2Al(CxN1−x) continuous solid solutions for x from 0 to 1 are calculated using ab initio DFT methods on 4×4×1 supercell models. It is shown that the properties of these solid solutions do not vary linearly with x. Although the lattice constant c is almost constant for x≤0.5, a increases linearly. For x\u3e0.5, c starts to increase with x while the rate of increase in a slows down. For x between 0.5 and 0.85, the elastic coefficients and the mechanical parameters show interesting dependence on x and crossovers, signifying the complex interplay in the structure and properties in Ti2Al(CxN1−x) solid solutions. The nonlinear variations in mechanical properties are explained in terms of subtle difference in the electronic structure and bonding between nitrides and carbides in complex MAX phase compounds

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

Ab initio calculations of thermomechanical properties and electronic structure of vitreloy Z r41.2 T i13.8 C u12.5 N i10 B e22.5

The thermomechanical properties and electronic structure of vitreloy (Zr41.2Ti13.8Cu12.5Ni10Be22.5) are investigated using accurate ab initio molecular dynamic (AIMD) simulations and ab initio calculations. The structure of the model with 512 atoms is validated by comparison to the experimental data with calculated thermomechanical properties in good agreement with the existing measurements. Detailed calculation of the electronic structure and bonding at the density functional level is obtained. It is revealed that the traditional definition of bond length in metallic glasses has a limited interpretation, and any theory based on geometrical consideration of their values for discussion on the structural units in metallic glasses has similarly limited applications. On the other hand, we advocate the use of a quantum mechanical based metric, the total bond order density (TBOD), and their partial components or PBOD as valuable parameters to characterize the interatomic bonding in multicomponent glasses such as vitreloy

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

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

High-Resolution Spectroscopy of Bonding in a Novel BeP2N4 Compound

The recently discovered compound BeP2N4 that crystallizes in the phenakite-type structure has potential application as a high strength optoelectronic material. Therefore, it is important to analyze experimentally the electronic structure, which was done in the present work by monochromated electron energy-loss spectroscopy. The detection of Be is challenging due to its low atomic number and easy removal under electron bombardment. We were able to determine the bonding behavior and coordination of the individual atomic species including Be. This is evident from a good agreement between experimental electron energy-loss near-edge structures of the Be-K-, P-L2,3-, and N-K-edges and density functional theory calculations