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At least 127 records · Page 7

Failure Mechanisms During Isothermal Fatigue of SiC/Ti-24Al-11Nb Composites

Failure mechanisms during isothermal fatigue of unidirectional SiC/Ti-24Al-11Nb (at.%) composites have been determined by microstructural analysis of samples from tests interrupted prior to the end of life and from tests conducted to failure. Specimens from three regions of life were examined based on the maximum strain from a fatigue life diagram: Region 1 (high strain), Region 2 (mid-strain) and Region 3 (low strain). Crack lengths were also measured from interrupted samples and compared based on temperature (23-815 C), region of life and numbers of cycles. Region 1 was controlled by fiber-dominated failure. A transition zone was observed between Regions 1 and 2 due to competition between failure mechanisms. Failure in Region 2 was generally described as surface-initiated cracking with varying amounts of fiber bridging. However, the specific descriptions of crack propagation through the fibers and matrix varied with strain and temperature over this broad region. Region 3 exhibited endurance behaviour at 23 C with no cracking after lO(exp 6) cycles. However at 425 C, surface-initiated cracking was observed after 10(exp 6) cycles with fractured fibers in the crack wake. If endurance behaviour exists for conditions of isothermal fatigue in air at temperatures of greater than or equal to 425 C, it may only be found at very low strains and at greater than 10(exp 6) cycles.

Brindley, P. K.↗

Non-Isothermal Calorimetric Studies of the Crystallization of Lithium Disilicate Glass

The influence of preannealing treatments on the polymorphic crystallization of lithium disilicate glasses is examined. As expected, glasses heated at different rates through the temperature range where there is significant nucleation develop widely different numbers of nuclei. This can dramatically influence the stability and transformation characteristics of the annealed glass. Non-isothermal differential scanning calorimetry (DSC) and differential thermal analysis (DTA) measurements are demonstrated to be useful to probe the nucleation behavior. The first systematic investigations of particle size effects on the non-isothermal transformation behavior are presented and discussed. Based on DTA and microscopy experiments, we show that small particles of lithium disilicate glasses crystallize primarily by surface crystallization. The relative importance of surface versus volume crystallization is examined by varying particle size, by introducing nucleating agents and by exposing glasses to atmospheres of different water content. These data are analyzed quantitatively using a numerical model developed in a second paper following in this volume.

Ray, C. S.↗

Computer Modeling of Non-Isothermal Crystallization

A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.

Kelton, K. F.↗

Chip Scale Package Integrity Assessment by Isothermal Aging

Many aspects of chip scale package (CSP) technology, with focus on assembly reliability characteristics, are being investigated by the JPL-led consortia. Three types of test vehicles were considered for evaluation and currently two configurations have been built to optimize attachment processes. These test vehicles use numerous package types. To understand potential failure mechanisms of the packages, particularly solder ball attachment, the grid CSPs were subjected to environmental exposure. Package I/Os ranged from 40 to nearly 300. This paper presents both as assembled, up to 1, 000 hours of isothermal aging shear test results and photo micrographs, and tensile test results before and after 1,500 cycles in the range of -30/100 C for CSPs. Results will be compared to BGAs with the same the same isothermal aging environmental exposures.

Ghaffarian, Reza↗

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al: Oxidation Kinetics - Part 1

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Raj, S. V.↗

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al: Oxidation Kinetics - Part 1

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 +/- 9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Raj. Sai V.↗

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al: Oxidation Kinetics - Part 1

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Raj. Sai V.↗

Carbon Fiber Composite Processing Using Isothermal Resins

To meet future demand for single-aisle composite aircraft production, manufacturing rates are expected to increase by up to six times current production rates. Resin infusion is a manufacturing method that has potential to enable fabrication of structures at the desired rates. However, production cycle times with currently available commercial infusion resins cannot support the rates needed for an estimated 80 aircraft per month. Recently, rapid-curing isothermal resins were developed that can reduce the overall processing time. These resins can be infused, cured, and demolded at a single temperature below 100 °C, thereby eliminating the need for time consuming temperature ramps and shortening the overall cure time. In addition, the low temperatures enable use of low-cost tooling during production. This presentation will discuss the use of resin transfer molding to produce composites with rapid-curing isothermal resins, manufacturing considerations, and performance characteristics of the composites.

John M Gardner↗

Isothermal oxidation of zirconium using steam

Oxidation of zirconium and its alloys under any atmosphere is generally characterised by a protective and non-protective stage. During the protective stage, the kinetics of oxidation are quasi-parabolic, while the oxide scale formed on the surface of the metal is black, compact, and protective in nature. For the non-protective stage, the oxidation rate becomes linear, while the protective oxide film turns into a deteriorated white scale. Breakaway is known as the transition point from protective to non-protective stage. The actual mechanism leading to breakaway of zirconium is still a matter of controversy, however some of the most common factors affecting breakaway are the following: - Impurities on the metal (Carbon, Oxygen, Nitrogen); - Oxidizing atmosphere (Presence of H{sub 2}O (g) or N{sub 2} (g)); - Sample preparation (Chemically etched or polished); - Temperature (LWR, LOCA). This research investigates the effect of temperature on 'breakaway' when zirconium is oxidized isothermally in steam for 60 min at 800 and 900 deg. C using thermogravimetric and optical microscopic imaging techniques. 1. Steam isothermal oxidations were performed on zirconium at 800 and 900 deg. C using a Thermogravimetric Analyzer (TGA). 2. Log-log plots of mass gain vs time were obtained from thermogravimetric results to calculate the reaction orders (n) and reaction rate constants (K) during oxidation. 3. Results of the kinetics of reaction were correlated with optical microscopic images form Light Microscope (LM) and Scanning Electron Microscope (SEM). Breakaway depends very strongly on temperature. At 800 deg. C, the weight gain followed a cubic-parabolic behaviour with evidence of a protective oxide film. On the other hand, oxidation at 900 deg. C showed signs of breakaway since the oxide film was cracked and oxidation rate was almost linear throughout the reaction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

SaltStone Wastewater Cement Study Using Isothermal Calorimetry, Standard Concrete Characterization Techniques, and CemGEMS - 25169

Cementitious reagents are used to solidify/stabilize aqueous radioactive, hazardous, and mixed salt solutions, and sludges to meet low-level radioactive waste (LLW) and Resource Conservation and Recovery Act (RCRA) requirements for disposal at Department of Energy (DOE). It is flexible enough to solidify radioactive wastewater saturated in complex species that include but are not limited to radioactive isotopes from the bombardment of neutrons in reactor operation, corrosion products from metallic components, and a variety of soluble organic compounds. [1,2]. Waste form testing typically includes processing or fresh properties, cured properties, compressive strength and hydraulic properties, porosity, density, saturated and unsaturated moisture transport, and leachability of contaminants in the waste form pore solution. Properties are collected over a relatively limited time, typically 28 to 365 days [3]. In addition, changes in the waste form as the result of time and changing conditions are important for concrete engineers to predict overall performance of the forms and potential release of contaminants in the disposal process via unintended filtration into the environment [4]. These predictions are determined/calculated characterizing young waste forms (relative to the standard age of concrete) and are based on transport through soluble ions in pore solutions. Characterization methods include X-ray, SEM, and isothermal calorimetry among other methods used to define the composition, amorphous vs. crystalline nature of the components, and the energetic formation mechanisms for multi-phase mineral systems. [5–7] Isothermal calorimetry is a well standardized technique for cements and concretes and can be used to predict the timing and nature of the hydration reactions.[8] The technique can measure long term energetic

Bustamante, Michael E. [Savannah River National La↗

Influence of pH on chloride binding isotherms for cement paste and its components

In this paper, chloride (Cl{sup −}) binding isotherms are developed for cement hydration compounds, specifically, calcium-silicate-hydrates (CSH) and AFm phases including mono-sulfate aluminate, hydroxy-AFm, monocarbonate-AFm, and hemicarbonate-AFm, in simulated concrete pore solutions to account for the effect of pH and the presence of other ions. pH and the presence of other ions have a strong influence on the Cl{sup −} binding capacity of cement compounds, which have not been taken into consideration in previous research. A novel experimental technique is developed to characterize the binding capacity from very low (1 mM) to very high concentrations (5 M). To overcome the existing challenges of measuring both low and high Cl{sup −} concentrations without significant dilution and in the presence of SO{sub 4}{sup 2−} and OH{sup −} ions, a potentiometric method was used. The amorphous CSH in the hydrated cement paste; thus, the heterogeneity of the hydrated components of the cement paste was also quantified and accounted for in this study.

36 MATERIALS SCIENCE↗

Near isothermal compressed air energy storage system in residential and commercial buildings: Techno-economic analysis

Electrical energy storage systems offer a wide range of options to efficiently manage our power supply infrastructure. Energy and environmental security via renewable resources and energy storage devices will also play a critical role in addressing the supply-demand challenges. A novel energy efficient storage system based on near isothermal compressed air energy storage concept, named as Ground-Level Integrated Diverse Energy Storage (GLIDES) is analyzed for integration with residential and commercial buildings. Additionally, the influence of different configurational aspects on key performance and cost attributes is presented in this study. GLIDES modules in the range of 0.5 kWh–15 kWh configurations were considered for residential buildings whereas 25 kW h–500 kW h modules were considered for commercial buildings. Detailed cost and performance analysis of the GLIDES module proved them to be an effective resource in lowering the peak energy demand and corresponding utility bills.

25 ENERGY STORAGE↗

Measured CO 2 sorption isotherms with 25 Bakken Petroleum System rock samples from the Lower and Upper Shales, Middle Bakken, and Three Forks formations

Isotherms were measured with 25 Bakken Petroleum System (BPS) rock samples using a magnetic suspension balance at reservoir conditions of 110 °C and pressures up to 345 bar. Samples from four wells represented the Middle Bakken (MB) and Three Forks (TF) production zones, and the Upper Bakken Shale (UBS) and Lower Bakken Shale (LBS) source shales. UBS and LBS CO 2 sorption capacities at 345 bar averaged 12–14 g/kg rock compared to 1.3 to 2.5 g/kg rock for MB and TF. Increasing pressure from 150 to 345 bar resulted in only small increases in CO 2 sorption for all lithofacies. For the UBS and LBS source shales, the higher average total organic carbon (TOC) values (14.7 and 11.4 wt.%) and clay values (25 and 28 wt.%) corresponded to their higher CO 2 sorption values while for the MB and TF samples, lower TOCs (0.3 and 0.5 wt.%) and clay values (8.2 and 18.2 wt.%) corresponded to lower CO 2 sorption values. Here, when all 25 samples (from all lithofacies) were evaluated as a group, sorption capacities were highly correlated with TOC (Spearman's rho values +0.84 to +0.85), with rock density (rho values -0.75 to -0.76), and clay content (rho values +0.66). However, correlations with porosity and thermal maturity (Tmax) were weak. Measured sorption capacities and rock porosities showed that sorption accounted for about 10-times as much CO 2 storage as the available pore space for the UBS and LBS lithofacies. In contrast, the pore space dominated the storage resource of the TF and MB lithofacies.

54 ENVIRONMENTAL SCIENCES↗

A direct numerical simulation study for confined non-isothermal jet impingement at moderate nozzle-to-plate distances: Capturing jet-to-ambient density effects

A direct numerical simulation (DNS) campaign is deployed for a series of confined downward oriented, non-isothermal turbulent impinging jet configurations. A baseline Reynolds number of 9960 is obtained through a precursor DNS pipe flow simulation (Re τ = 505). Three jet temperature configurations (confinement height to nozzle diameter of three) enter a cylindrical domain that share ambient and impingement plate temperatures (298.15 K). The range of jet temperatures are crafted such that the ratio of inlet to ambient density varies from unity to 0.52, showcasing the effect of density disparity on flow characteristics such as core collapse, radial mixing of momentum and energy, near-wall stagnation behavior, wall-jet profiles, and large-scale vortical structures. Surface quantities provided include mean radial heat flux and wall-shear stress profiles, and heat flux histograms at select radial stations. Results showcase increased radial normal stresses for higher temperature jets that support increased mixing, resulting in large-scale recirculation structures that are smaller, while retaining similar normalized radial wall profiles for shear stress, heat flux and pressure. Furthermore, radial plots for wall shear stress and Nusselt number showcase strong radial decay as compared to previous configurations that share similar jet and ambient temperatures. For the 373.15 K case, a Gaussian-like histogram for heat fluxes at the impingement plate transitions to a log-normal profile as radial distances increase. In contrast, the 573.15 K configuration displays a bi-modal heat flux characteristic at the impingement plate, and in similar manner to the moderate temperature counterpart, transitions to a log-normal profile at larger radial distances.

33 ADVANCED PROPULSION SYSTEMS↗

The overlooked role of adsorption isotherms in electrocatalysis

Electrocatalysts enable the efficient interconversion of electrical and chemical energy for the sustainable production of fuels and chemicals. Here, in this Comment, we highlight the importance of developing electrochemical adsorption isotherms to demystify complex reaction mechanisms and rationalize catalytic activity.

electrocatalysis↗

Influence of side-chain isomerization on the isothermal crystallization kinetics of poly(3-alkylthiophenes)

Flexible alkyl side chain in conjugate polymers (CPs) improves the solubility and promotes solution processability, in addition, it affects interchain packing and charge mobilities. Despite the well-known charge mobility and morphology correlation for these semi-crystalline polymers, there is a lack of fundamental understanding of the impact of side chain on their crystallization kinetics. In the present work, isothermal crystallization of five poly(3-alkylthiophene-2,5-diyl) (P3ATs) with different side-chain structures were systematically investigated. To suppress the extremely fast crystallization and trap the sample into amorphous glass, an advanced fast scanning chip calorimetry technique, which is able to quench the sample with few to tens thousands of K/s, was applied. Results show that the crystallization of P3ATs was greatly inhibited after incorporation of branched side chains, as indicated by a dramatic up to six orders of magnitude decrease in the crystallization rate. The suppressed crystallization of P3ATs were correlated with an increased π–π stacking distance due to unfavorable side-chain steric interaction. This research provides a pathway to use side-chain engineering to control the crystallization behavior for CPs, thus to control device performance.

36 MATERIALS SCIENCE↗

The Isothermal Oxidation of High-Purity Aluminum at High Temperature

The isothermal oxidation in air of high purity aluminum sheet was studied as a function of temperature using Thermogravimetric Analysis simultaneously with Differential Scanning Calorimetry (TGA/DSC). The rates and extents of oxidation were found to be non-linear functions of the temperature, in agreement with the literature. Between 650 °C and 750 °C very little oxidation took place; at 850 °C oxidation occurred after an induction period, while at 950 °C oxidation occurred without an induction period. At oxidation temperatures between 1050 °C and 1150 °C rapid passivation of the surface of the aluminum occurred, while at 1250 °C and above, an initial rapid mass increase was observed, followed by a more gradual increase in mass. The initial rapid increase in mass was accompanied by a significant exotherm, which was quantified by DSC. At temperatures of 1050 °C and above the specimen coalesced into a spheroidal particle, whereas at lower temperatures the original morphology was retained due to the cohesive strength of the native oxide layer. Cross-sections of oxidized specimens were characterized by scanning electron microscopy (SEM); the observed alumina skin thicknesses correlated qualitatively with the observed mass increases. Interrogation of the surface of an oxidized spheroidal particle by SEM showed a fractured alumina shell around a partially hollow core of aluminum which appeared to have grain boundaries.

36 MATERIALS SCIENCE↗