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Results for “Polyhedral Analysis and Transformation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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A Polyhedral Transformation Framework for Compiler Optimization (Final Project Report)

The project developed the polyhedral compiler transformation module PolyOpt/Fortran in the ROSE compiler framework. PolyOpt/Fortran performs automated transformation of affine loop nests within FORTRAN programs for enhanced data locality and parallel execution. A FORTAN version of the Polybench library was also developed by the project. A third development was a dynamic analysis approach to gauge vectorization potential within loops of programs; software (DDVec) for automated instrumentation and dynamic analysis of programs was developed.

97 MATHEMATICS AND COMPUTING↗

Mechanistic Insights into Superlattice Transformation at a Single Nanocrystal Level Using Nanobeam Electron Diffraction

Understanding the mechanism and ultimately directing nanocrystal (NC) superlattice assembly and attachment have important implications on future advances in this emerging field. Here, we use 4D-STEM to investigate a monolayer of PbS NCs at various stages of the transformation from a hexatic assembly to a nonconnected square-like superlattice over large fields of view. Maps of nanobeam electron diffraction patterns acquired with an electron microscope pixel array detector (EMPAD) offer unprecedented detail into the 3D crystallographic alignment of the polyhedral NCs. Our analysis reveals that superlattice transformation is dominated by translation of prealigned NCs strongly coupled along the <11n>AL direction and occurs stochastically and gradually throughout single grains. We validate the generality of the proposed mechanism by examining the structure of analogous PbSe NC assemblies using conventional transmission electron microscopy and selected area electron diffraction. Here, the experimental results presented here provide new mechanistic insights into NC self-assembly and oriented attachment.

36 MATERIALS SCIENCE↗

Experimental study of UV induced tensile properties deterioration and chemical aging of polyurea–POSS composites

Ultraviolet (UV) radiation present in natural sunlight degrades the chemical and mechanical properties of polymeric matrices in composites. Polyurea possess a unique set of chemical and mechanical properties due to its complex microstructure comprising of hard and soft segments (phases). The primary objective of the work presented here is to characterize the chemical and mechanical degradation of pure polyurea and polyurea - polyhedral oligomeric silsesquioxane (POSS) nanocomposites subjected to UV radiation exposure for 45 days. Control specimen in as-received condition (reference specimen) and UV-aged tensile test specimen are tested in the study. Analysis of Fourier transformed infrared (FTIR) spectra for UV-aged polyurea and polyurea-POSS composites reveals that the addition of POSS nanoparticles accelerate the deterioration of polyurea matrix by breaking the hard phase network and altering the mechanism of degradation for the soft phase present in polyurea microstructure. The deterioration of hard and soft segments cause a significant reduction in tensile properties of polyurea-POSS composites.

Materials Science↗

Analytical Modeling of Cache Behavior for Affine Programs

Modern optimizing compiler design integrates program transformation strategies aimed at reducing data movement to/from main memory by exploiting the data cache hierarchy. But in reality, the effect of these transformations on the actual cache miss count is ignored in compilers due to the lack of precise compile-time models of misses for hierarchical caches. The current state of practice for cache miss analysis is based on accurate simulation. However, simulation requires time proportional to the dataset/problem size as well as the number of distinct cache configurations of interest to be evaluated. This paper takes a fundamentally different approach, made possible by focusing on polyhedral programs with static control flow: instead of relying on costly simulation, this paper develops the first closed-form solution for exact modeling of misses in a set-associative cache hierarchy. It enabling simulation-less selection of program transformations at compile-time to optimize cache misses. A push-button tool implementing the approach is developed and used for extensive validation of the complete framework.

affine programs, cache modeling, set associativity↗

Thermal Stability of Quasi-1D NbS 3 Nanoribbons and Their Transformation to 2D NbS 2 : Insights from in Situ Electron Microscopy and Spectroscopy

Here in situ electron microscopy imaging and spectroscopy enabled us to study the evolution of quasi-1D NbS 3 -IV nanoribbons with respect to morphology and chemical structure at temperatures between room temperature and 1000 °C. Scanning transmission electron microscopy (STEM) experiments included imaging in the secondary electron, (transmitted) bright field, and high-angle annular dark-field modes while operating in the low kV regime. The results showed that NbS 3 -IV samples transform dramatically from smooth nanoribbons into highly textured configurations featuring polyhedral divots and steps. Similar in situ heating experiments conducted with aberration-corrected STEM revealed that bilayers of NbS 3 -IV chains convert topotactically into aligned 2H-NbS 2 sheets upon loss of sulfur. Atomic resolution imaging, fast Fourier transform analysis, and electron energy loss spectroscopy confirmed these chemical changes, from which we propose an atomistic mechanism for the NbS 3 -IV → 2H-NbS 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and theoretical evidence for hydrogen doping in polymer solution-processed indium gallium oxide

The field-effect electron mobility of aqueous solution-processed indium gallium oxide (IGO) thin-film transistors (TFTs) is significantly enhanced by polyvinyl alcohol (PVA) addition to the precursor solution, a >70-fold increase to 7.9 cm 2 /Vs. To understand the origin of this remarkable phenomenon, microstructure, electronic structure, and charge transport of IGO:PVA film are investigated by a battery of experimental and theoretical techniques, including In K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS); resonant soft X-ray scattering (R-SoXS); ultraviolet photoelectron spectroscopy (UPS); Fourier transform-infrared (FT-IR) spectroscopy; time-of-flight secondary-ion mass spectrometry (ToF-SIMS); composition-/processing-dependent TFT properties; high-resolution solid-state 1 H, 71 Ga, and 115 In NMR spectroscopy; and discrete Fourier transform (DFT) analysis with ab initio molecular dynamics (MD) liquid-quench simulations. The 71 Ga{ 1 H} rotational-echo double-resonance (REDOR) NMR and other data indicate that PVA achieves optimal H doping with a Ga···H distance of ~3.4 Å and conversion from six- to four-coordinate Ga, which together suppress deep trap defect localization. This reduces metal-oxide polyhedral distortion, thereby increasing the electron mobility. Finally, hydroxyl polymer doping thus offers a pathway for efficient H doping in green solvent-processed metal oxide films and the promise of high-performance, ultra-stable metal oxide semiconductor electronics with simple binary compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotropic Low Thermal Expansion over a Wide Temperature Range in Ti 1– x Zr x F 3+ x (0.1 ≤ x ≤ 0.5) Solid Solutions

TiF 3 exhibits a rhombohedral to ReO 3 -type cubic phase transformation at ~340 K. Here we report that, by introducing ZrF 4 into TiF 3 , the cubic phase is stabilized at least down to 123 K in the Ti 1–x Zr x F 3+x compounds. All compounds exhibit low thermal expansion (LTE) between 123 and 623 K, and a nearly zero thermal expansion (ZTE) was obtained in Ti 0.7 Zr 0.3 F 3.3 (α L = 0.91 ppm/K). The analysis of pair distribution function reveals that the cation-centered octahedra are partially changed to pentagonal bipyramids in Ti 1–x Zr x F 3+x due to the excess fluorines relative to the case of TiF 3 . Therefore, the cooperative rotation of the polyhedra tends to be restricted, and the cubic phase is thus stabilized. The restrained polyhedral rotations compete against the lattice softening caused by the introduction of Zr 4+ , giving rise to the LTE. Lastly, our present strategy is applicable to other rhombohedral metal trifluorides for the design of new isotropic ZTE materials.

36 MATERIALS SCIENCE↗

Computational Algorithms for Unit Commitment with AC Power Flows (Final Report)

Security-constrained unit commitment (SCUC) is a key component in power system operations. When AC power flow constraints are considered in the SCUC model (AC-SCUC), the problem becomes extremely difficult due to its discrete and non-convex nature, as described in “Grid Optimization Competition Challenge 3 Problem Formulation (GOCC)”. There are four main challenges: (i) Discrete decisions regarding unit online/offline status and start-up/shut-down procedures for every single unit. The number of discrete decision variables increases considerably when a system integrates multiple generators; (ii) Configuration-based combined-cycle formulations, and multi-commodity models that include ramping products, spin/non-spin products, and regulation up/down products. The combined-cycle units introduce additional discrete decision variables and auxiliary service products further complicate the model by connecting multi-commodity products’ continuous and discrete variables; (iii) SCUC models with AC power flow constraints are far more complex due to massive bilinear terms in the large-scale nonlinear power balance equations. The nonlinear power balance equations are further complicated by the discrete step control variables of shunts; (iv) N − 1 contingency analysis. The size of the model increases linearly with the number of contingencies considered, greatly increasing the size of the optimization model. Accordingly, there is an emergent need to develop a robust algorithm capable of deriving a high-quality solution in a short time and passing through contingency tests simultaneously. In this project, we explore innovative techniques to address this challenging problem by integrating advanced polyhedral theory, approximation methods, relaxation strategies, decomposition techniques, and parallel computing. Each technique approaches the problem from a different perspective, leveraging its specific strengths to tackle distinct challenges. Each individual method has demonstrated its effectiveness in the PI’s previous research. Their integration is expected to significantly reduce the computational time required to solve the proposed complex problem. Successful completion of this project has the potential to transform the industry by enhancing optimization solvers capable of handling large-scale day-ahead energy market clearing models within strict time constraints, while incorporating AC power flow constraints. This advancement will lead to reduced overall generation costs and, consequently, increased social welfare.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Final Report for Award #DE-SC3956 Separating Algorithm and Implementation via programming Model Injection (SAIMI)

Programming parallel machines is fraught with difficulties: the obfuscation of algorithms due to implementation details such as communication and synchronization, the need for transparency between language constructs and performance, the difficulty of performing program analysis to enable automatic parallelization techniques, and the existence of important "dusty deck" codes. The SAIMI project developed abstractions that enable the orthogonal specification of algorithms and implementation details within the context of existing DOE applications. The main idea is to enable the injection of small programming models such as expressions involving transcendental functions, polyhedral iteration spaces with sparse constraints, and task graphs into full programs through the use of pragmas. These smaller, more restricted programming models enable orthogonal specification of many implementation details such as how to map the computation on to parallel processors, how to schedule the computation, and how to allocation storage for the computation. At the same time, these small programming models enable the expression of the most computationally intense and communication heavy portions in many scientific simulations. The ability to orthogonally manipulate the implementation for such computations will significantly ease performance programming efforts and expose transformation possibilities and parameter to automated approaches such as autotuning. At Colorado State University, the SAIMI project was supported through DOE grant DE-SC3956 from April 2010 through August 2015. The SAIMI project has contributed a number of important results to programming abstractions that enable the orthogonal specification of implementation details in scientific codes. This final report summarizes the research that was funded by the SAIMI project.

97 MATHEMATICS AND COMPUTING↗

Exploring poly-crystallization in semiconductors through assumption-less growth simulations: CdTe/CdS case study

Crystal growth is a complex process with far-reaching implications for high-performance materials across various fields. Recent advancements in structural analysis methods such as polyhedral template matching, which allows semiconductor-specific analysis, coupled with simulation technology, have enabled the comprehensive study of crystallization dynamics in semiconductors. However, the exploration of polycrystalline semiconductors created with minimal external intervention of the crystallization processes is relatively uncharted in comparison with metals. In this study, we employ molecular dynamics to simulate the growth of polycrystalline CdTe/CdS with the assumptions of classical mechanics, a Stillinger–Weber potential, an amorphous substrate, and common vapor growth conditions to allow the polycrystalline structures to evolve naturally. Post-simulation, we identify and analyze impactful structures and events, comparing them to theory and experiment to gain insight into various modes of crystallization dynamics. Two research questions guided the study: (1) How realistic are assumption-less simulated polycrystalline semiconductor structures? (2) To what extent can the approach provide insight into crystallization? The simulations, performed with minimal external control, yield polycrystalline structures mirroring experimental findings. The analysis reveals key crystallization insights, such as the role of amorphous atoms in the transition from nucleation to grain growth and the transformative impact of single events, such as dislocations, on crystallization dynamics. The method paves the way for reproducing and analyzing realistic polycrystalline semiconductor structures with minimal simulation assumptions across various growth modes.

Abdullah, Sharmin↗

Structural, vibrational, thermal, and magnetic properties of mullite-type NdMnTiO 5 ceramic

Mullite-type $R$Mn 2 O 5 ($R$ = Y, rare-earth element) ceramics are of ongoing research attention because of their interesting crystal-chemical and magnetic properties. We report nuclear and magnetic structures of NdMnTiO 5 together with its spectroscopic, thermogravimetric, and magnetic properties. The polycrystalline sample is prepared by solid-state synthesis and characterized from neutron and X-ray powder diffraction data Rietveld refinements. NdMnTiO 5 crystallizes in the orthorhombic space group $Pbam$ with metric parameter $a$ = 755.20(1) pm, $b$ = 869.91(1) pm, $c$ = 582.42(1) pm, and $V$ = 382.62(1) 10 6 pm 3 . The Mn 3+ and Ti 4+ cations are observed to be located in the octahedral and pyramidal sites, respectively. The vibrational features in these polyhedral sites are characterized by Raman and Fourier transform infrared spectroscopes. The higher decomposition temperature of NdMnTiO 5 , compared to other $R$Mn 2 O 5 phases, is explained in terms of the higher bond strength of Ti-O bonds than those of Mn-O bonds. Temperature-dependent DC magnetic susceptibility suggests a paramagnetic to antiferromagnetic phase transition at 43(1) K. Inverse susceptibility in the paramagnetic region above 120 K follows the Curie-Weiss law, resulting in a magnetic moment of 6.33(1) μ B per formula unit. Neutron diffraction data collected at 7.5 K reveal that the magnetic moments of Nd 3+ and Mn 3+ in NdMnTiO 5 are incommensurately ordered with a propagation vector $k$ = (0, 0.238, 0.117).

36 MATERIALS SCIENCE↗

Zirconium and hafnium polyhedral oligosilsesquioxane complexes – green homogeneous catalysts in the formation of bio-derived ethers via a MPV/etherification reaction cascade

The polyhedral oligosilsesquioxane complexes, {[(isobutyl) 7 Si 7 O 12 ]ZrOPr i ·(HOPr i )}2 (I), {[(cyclohexyl) 7 Si 7 O 12 ]ZrOPr i ·(HOPr i )} 2 (II), {[(isobutyl) 7 Si 7 O 12 ]HfOPr i ·(HOPr i )} 2 (III) and {[(cyclohexyl) 7 Si 7 O 12 ]HfOPr i ·(HOPr i )} 2 (IV), were synthesized in good yields from the reactions of M(OPr i ) 4 (M = Zr, Hf) with R-POSS(OH) 3 (R = isobutyl, cyclohexyl), resp. I–IV were characterized by 1 H, 13 C and 29 Si NMR spectroscopy and their dimeric solid-state structures were confirmed by X-ray analysis. I–IV catalyze the reductive etherification of 2-hydroxy- and 4-hydroxy and 2-methoxy and 4-methoxybenzaldehyde and vanillin to their respective isopropyl ethers in isopropanol as a “green” solvent and reagent. I–IV are durable and robust homogeneous catalysts operating at temperatures of 100–160 °C for days without significant loss of catalytic activity. Likewise, I–IV selectively catalyze the conversion of 5-hydroxymethylfurfural (HMF) into 2,5-bis(isopropoxymethyl)furane (BPMF), a potentially high-performance fuel additive. Similar results were achieved by using a combination of M(OPr i ) 4 and ligand R-POSS(OH) 3 as a catalyst system demonstrating the potential of this “in situ” approach for applications in biomass transformations. A tentative reaction mechanism for the reductive etherification of aldehydes catalysed by I–IV is proposed.

09 BIOMASS FUELS↗