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159 records · Page 9

Machine learning prediction of glass transition temperature of conjugated polymers from chemical structure

Predicting the glass transition temperature (T g ) is of critical importance as it governs the thermomechanical performance of conjugated polymers (CPs). Here, we report a predictive modeling framework to predict T g of CPs through the integration of machine learning (ML), molecular dynamics (MD) simulations, and experiments. With 154 T g data collected, an ML model is developed by taking simplified “geometry” of six chemical building blocks as molecular features, where side-chain fraction, isolated rings, fused rings, and bridged rings features are identified as the dominant ones for T g . MD simulations further unravel the fundamental roles of those chemical building blocks in dynamical heterogeneity and local mobility of CPs at a molecular level. The developed ML model is demonstrated for its capability of predicting T g of several new high-performance solar cell materials to a good approximation. The established predictive framework facilitates the design and prediction of T g of complex CPs, paving the way for addressing device stability issues that have hampered the field from developing stable organic electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sintering and Creep Behavior of Plasma-Sprayed Zirconia and Hafnia Based Thermal Barrier Coatings

The sintering and creep of plasma-sprayed ceramic thermal barrier coatings under high temperature conditions are complex phenomena. Changes in thermomechanical and thermophysical properties and in the stress response of these coating systems as a result of the sintering and creep processes are detrimental to coating thermal fatigue resistance and performance. In this paper, the sintering characteristics of ZrO2-8wt%y2O3, ZrO2-25wt%CeO2-2.5wt%Y2O3, ZrO2-6w%NiO- 9wt%Y2O3, ZrO2-6wt%Sc2O3-2wt%y2O3 and HfO2-27wt%y2O3 coating materials were investigated using dilatometry. It was found that the HfO2-Y2O3 and baseline ZrO2-Y2O3 exhibited the best sintering resistance, while the NiO-doped ZrO2-Y2O3 showed the highest shrinkage strain rates during the tests. Higher shrinkage strain rates of the coating materials were also observed when the specimens were tested in Ar+5%H2 as compared to in air. This phenomenon was attributed to an enhanced metal cation interstitial diffusion mechanism under the reducing conditions. It is proposed that increased chemical stability of coating materials will improve the material sintering resistance.

Zhu, Dongming↗

The 371 deg C mechanical properties of graphite/polyimide composites

A series of condensation polyimides based on pyromellitic dianhydride is synthesized and evaluated for potential application at 371 C. Several three-and four-ring benzenoid diamine systems containing oxygen bridging groups are investigated. Thermomechanical analysis of neat resin specimens indicate that the polyimide prepared from the dimethyl ester of pyrometallitic acid (PMDE) and 2,2-bis4-(4'-aminophenoxy) phenyl]-1,1,1,3,3,3- hexafluoropropane (BDAF) is the only resin system which has a glass transition temperature (Tg) above 371 C. The Tg of the PMDE/BDAF polyimide is found to be 390 C after a postcure air at 371 C for 24 hr. Unidirectional composites are fabricated from the PMDE/BDAF system and unsized Celion 6000 graphite fibers. Final cure temperatures in the range of 371 to 427 C with an applied pressure of 10.34 to 13.78 MPa are investigated. The void content of the composites ranges from 4.6 to 8.6 percent. Composites cured at 399 C under a pressure of 10.34 MPa and postcured in air at 371 C for 24 hr exhibit the highest 371 C interlaminar shear strength (ILSS, 40.7 MPa) and flexural strength (758 MPa). The thermo-oxidative stability of the composites is determined by subjecting specimens to isothermal exposure at 371 C in air at atmospheric pressure, as well as a pressure of 0.52 MPa. Specimens exposed at atmospheric pressure exhibit a weight loss of 12 percent after 200 hr of exposure and 88 percent retention of its original 371 C ILSS. In contrast, the specimens exposed at 0.52 MPa pressure exhibit a comparable weight loss after only 72 hr, and a 71 percent retention of its original 371 C ILSS.

Delvigs, P.↗

Structure-to-glass transition temperature relationships in high temperature stable condensation polyimides

The presence of a hexafluoroisopropylidene (6F) connecting group in aryl dianhydrides used to prepare aromatic condensation polyimides provides high glass transition temperature (T sub g) polyimides with excellent thermo-oxidative stability. The purpose of this study was to determine if a trifluorophenyl-ethylidene (3F) connecting group would have a similar effect on the T sub g of aromatic condensation polyimides. A new dianhydride containing the 3F connecting group was synthesized. This dianhydride and an aromatic diamine also containing the 3F connecting group were used together and in various combinations with known diamines or known dianhydrides, respectively, to prepare new 3F containing condensation polyimides. Known polyimides, including some with the 6F connecting linkage, were also prepared for comparison purposes. The new 3F containing polymers and the comparison polymers were prepared by condensation polymerization via the traditional amic-acid polymerization method in N,N-dimethylacetamide solvent. The solutions were characterized by determining their inherent viscosities and then were thermally converted into polyimide films under nitrogen atmosphere at 300 to 500 C, usually 350 C. The T sub g's of the films and resin discs were then determined by thermomechanical analysis and were correlated as a function of the final processing temperatures of the films and resin discs. The results showed that similarities existed in the T sub g's depending on the nature of the connecting linkage in the monomers used to prepare the condensation polyimides.

Alston, W. B.↗

Effects of thermomechanical processing on the microstructure and mechanical properties of Nb-1Zr-C alloys

A systematic study to evaluate the effects of thermomechanical processing on the microstructure and mechanical properties of Nb-1Zr alloy sheet containing 0.06 and 0.1 wt.%C (PWC-11) was conducted and compared to the results of Nb-1Zr. Coarse orthorhombic Nb2C precipitates were present in all the cast, extruded and cold rolled Nb-Zr samples containing C. After high temperature (greater than 0.5 T(sub m)) exposure (with or without applied stress), the Nb2C transforms to very fine and extremely stable FCC (Zr, Nb)C dispersoid, resulting in a highly creep resistant material. Only ZrO2 precipitates were found in Nb-1Zr. The creep strength of the 0.06C and the 0.1C carbide strengthened alloys were much superior to Nb-1Zr. At 1350 K the strength of the 0.06C alloy was about three times that of Nb-1Zr, while the 0.1C alloy had about five times the creep stress capability of Nb-1Zr. The tensile strength, long term creep strength, and stability of the microstructure of the PWC-11 sheet appear to be independent of the number of 1900 K extrusions performed prior to cold rolling. The microhardness of these single, double and triple extnided PWC-11 sheets also were comparable. The tensile strength of PWC-11 and Nb-1Zr at room temperature and 1350 K were comparable.

Titran, Robert H.↗

Life-Extending Control for Aircraft Engines Studied

Current aircraft engine controllers are designed and operated to provide both performance and stability margins. However, the standard method of operation results in significant wear and tear on the engine and negatively affects the on-wing life--the time between cycles when the engine must be physically removed from the aircraft for maintenance. The NASA Glenn Research Center and its industrial and academic partners have been working together toward a new control concept that will include engine life usage as part of the control function. The resulting controller will be able to significantly extend the engine's on-wing life with little or no impact on engine performance and operability. The new controller design will utilize damage models to estimate and mitigate the rate and overall accumulation of damage to critical engine parts. The control methods will also provide a means to assess tradeoffs between performance and structural durability on the basis of mission requirements and remaining engine life. Two life-extending control methodologies were studied to reduce the overall life-cycle cost of aircraft engines. The first methodology is to modify the baseline control logic to reduce the thermomechanical fatigue (TMF) damage of cooled stators during acceleration. To accomplish this, an innovative algorithm limits the low-speed rotor acceleration command when the engine has reached a threshold close to the requested thrust. This algorithm allows a significant reduction in TMF damage with only a very small increase in the rise time to reach the commanded rotor speed. The second methodology is to reduce stress rupture/creep damage to turbine blades and uncooled stators by incorporating an engine damage model into the flight mission. Overall operation cost is reduced by an optimization among the flight time, fuel consumption, and component damages. Recent efforts have focused on applying life-extending control technology to an existing commercial turbine engine, and doing so without modifying the hardware or adding sensors. This approach makes it possible to retrofit existing engines with life-extending control technology by changing only the control software in the full-authority digital engine controller (FADEC). The significant results include demonstrating a 20- to 30-percent reduction in TMF damage to the hot section by developing and implementing smart acceleration logic during takeoff. The tradeoff is an increase, from 5.0 to 5.2 sec, in the time required to reach maximum power from ground idle. On a typical flight profile of a cruise at Mach 0.8 at an altitude of 41,000 ft, and cruise time of 104 min, the optimized system showed that a reduction in cruise speed from Mach 0.8 to 0.79 can achieve an estimated 25-to 35-percent creep/rupture damage reduction in the engine's hot section and a fuel savings of 2.1 percent. The tradeoff is an increase in flight time of 1.3 percent (1.4 min).

Guo, Te-Huei↗

Multiscale investigation of the microstructural mechanisms driving ratchet growth in PBX 9502

The high explosive PBX 9502 undergoes irreversible expansion during thermal cycling (“ratchet growth”). Recent innovations in thermomechanical modeling via homogenization strategies are beginning to incorporate mesoscale information such as grain size, total porosity, and spatial distribution of voids and cracks. To generate a complete experimental data set to challenge and inform these models, PBX 9502 pellets were thermally cycled, cross-sectioned using ion polishing, and imaged in high resolution with scanning electron microscopy. Ratchet growth was found to drive expansion through microcracking. Microcracks were affected by agglomeration of crystals within the PBX. Virgin material showed greater ratchet growth than recycled material.

36 MATERIALS SCIENCE↗

Extensive 3D mapping of dislocation structures in bulk aluminum

Abstract Thermomechanical processing such as annealing is one of the main methods to tailor the mechanical properties of materials, however, much is unknown about the reorganization of dislocation structures deep inside macroscopic crystals that give rise to those changes. Here, we demonstrate the self-organization of dislocation structures upon high-temperature annealing in a mm-sized single crystal of aluminum. We map a large embedded 3D volume ( $$100\times 300\times 300$$ 100 × 300 × 300 $$\upmu$$ μ m $$^3$$ 3 ) of dislocation structures using dark field X-ray microscopy (DFXM), a diffraction-based imaging technique. Over the wide field of view, DFXM’s high angular resolution allows us to identify subgrains, separated by dislocation boundaries, which we identify and characterize down to the single-dislocation level using computer-vision methods. We demonstrate how even after long annealing times at high temperatures, the remaining low density of dislocations still pack into well-defined, straight dislocation boundaries (DBs) that lie on specific crystallographic planes. In contrast to conventional grain growth models, our results show that the dihedral angles at the triple junctions are not the predicted 120 $$^{\circ }$$ ∘ , suggesting additional complexities in the boundary stabilization mechanisms. Mapping the local misorientation and lattice strain around these boundaries shows that the observed strain is shear, imparting an average misorientation around the DB of $$\approx$$ ≈ 0.003 to 0.006 $$^{\circ }$$ ∘ .

36 MATERIALS SCIENCE↗

High-Temperature Extensometry and PdCr Temperature-Compensated Wire Resistance Strain Gages Compared

A detailed experimental evaluation is underway at the NASA Lewis Research Center to compare and contrast the performance of the PdCr/Pt dual-element temperature-compensated wire resistance strain gage with that of conventional high-temperature extensometry. The advanced PdCr gage, developed by researchers at Lewis, exhibits desirable properties and a relatively small and repeatable apparent strain to 800 C. This gage represents a significant advance in technology because existing commercial resistance strain gages are not reliable for quasi-static strain measurements above approx. 400 C. Various thermal and mechanical loading spectra are being applied by a high-temperature thermomechanical uniaxial testing system to evaluate the two strain-measurement systems. This is being done not only to compare and contrast the two strain sensors, but also to investigate the applicability of the PdCr strain gage to the coupon-level specimen testing environment typically employed when the high-temperature mechanical behavior of structural materials is characterized. Strain measurement capabilities to 800 C are being investigated with a nickel-base superalloy, Inconel 100 (IN 100), substrate material and application to TMC's is being examined with the model system, SCS-6/Ti-15-3. Furthermore, two gage application techniques are being investigated in the comparison study: namely, flame-sprayed and spot welding. The apparent strain responses of both the weldable and flame-sprayed PdCr wire strain gages were found to be cyclically repeatable on both IN 100 and SCS-6/Ti-15-3 [0]_8. In general, each gage exhibited some uniqueness with respect to apparent strain behavior. Gages mounted on the IN 100 specimens tended to show a repeatable apparent strain within the first few cycles, because the thermal response of IN 100 was stable. This was not the case, however, for the TMC specimens, which typically required several thermal cycles to stabilize the thermal strain response. Thus, progressive changes in the apparent strain behavior were corroborated by the extensometer, which unlike the mounted gage can distinguish quantitative changes in the material's thermal strain response. One specimen was instrumented with both a fixed and floating gage. From the difference in output of these two gages, the thermal expansion strains were calculated. These data, which are given in the figure, show excellent agreement with the values measured by the high-temperature extensometry.

Source record↗

Factors Influencing Lava-Substrate Heat Transfer and Implications for Thermomechanical Erosion

We develop numerical simulations of basaltic lava flowing laminarly over a basalt substrate in order to examine the details of the lava dynamics and thermal boundary layers and to understand the implications for substrate heating. As the initial stage of a larger study of thermomechanical erosion in different planetary environments, we aim to understand why erosion occurs on Earth, why erosion features are not ubiquitous given the high temperatures involved, and whether it is a plausible mechanism for the formation of planetary channels such as lunar sinuous rilles and Venusian canali. Here we confine our attention to terrestrial lavas with well-known properties and eruption parameters. With relatively simple computational fluid dynamic simulations, most closely representing tube-fed hawaiian basalts (for which erosion has been documented), we demonstrate the importance of incorporating several key factors in models of lava flow/ substrate heat transfer, which have commonly been neglected in previous treatments. By addressing the interaction of the flow dynamics and heat transfer in the lava, our work suggests that the development of a temperature gradient in the base of the lava, even for undeveloped flow, has a significant influence on substrate temperature. The sensitivity of the lava-substrate interface temperature to the thermophysical properties of the lava and substrate suggests that a delicate balance is required for partial melting to occur. Thus, it might take weeks of continuous flow to initiate partial melting of the substrate at distances of several kilometers from the vent. These durations exceed the periods of stability typical of lava flowing in tubes; pauses, blockages, surges, and break-outs frequently disrupt the flow. However, natural irregularities in the flow dynamics or substrate topography might help to initiate and maintain substrate melting on shorter timescales by disturbing the intimately coupled dynamic and thermal boundary layers. Although a purely thermal mechanism cannot be ruled out, our findings support the premise that mechanical erosion may play a key role in reports of erosion based on field evidence.

Fagents, S. A.↗

Fabrication of yttrium hydride for high-temperature moderator application

We report given the superior thermal stability and highly attainable hydrogen density, yttrium hydride is an excellent high-temperature moderator material in advanced thermal neutron spectrum reactors that require small core volumes. Large-scale, crack-free, bulk yttrium hydride is in high demand; however, fabrication of yttrium hydride is challenging and has not been demonstrated for nearly half century. The associated challenges are discussed herein. In response to these challenges, a hydriding system was designed and constructed at Oak Ridge National Laboratory and was used to successfully fabricate crack-free yttrium hydride in complex geometries at large scales. This was accomplished by precisely controlling the hydrogen’s partial pressure and the retort temperature, which was informed by the well-established thermodynamic properties of the binary H–Y system. Hydrogen content in as-fabricated hydride was determined by weight change, an approach which was considered reliable based on the use of ultra–high-purity yttrium, the absence of oxide phases up to levels detectable using x-ray diffraction (XRD), and the significant weight gain. Hydrogen distribution along one yttrium hydride rod was evaluated with XRD analysis on materials extracted from different locations on the rod. The results indicated a relatively homogeneous hydrogen distribution along the hydride rod, with <3% uncertainty in the fraction of the δ-phase hydride. In addition, significant efforts are being dedicated to establish a complete database summarizing the thermomechanical and physical properties of as-fabricated yttrium hydride and the irradiation response to facilitate its deployment as a high-temperature moderator in advanced nuclear reactors.

36 MATERIALS SCIENCE↗

Thermo-mechanical behavior of hypoeutectic Ni-Y-Zr alloys

Microstructure refinement and optimized alloying can improve metallic alloy performance: stable nanocrystalline (NC) alloys with immiscible second phases, e.g., Cu-Ta, are stronger than unstable NC alloys and their coarse-grained (CG) counterparts, but higher melting point matrices are needed. Hypoeutectic, CG Ni-Y-Zr alloys were produced via arc-melting to explore their potential as high-performance materials. Microstructures were studied to determine phases present, local composition and length scales, while heat treatments allowed investigating microstructural stability. Alloys had a stable, hierarchical microstructure with ~250 nm ultrafine eutectic, ~10 µm dendritic arm spacing and ~1 mm grain size. Hardness and uniaxial compression tests revealed that mechanical properties of Ni-0.5Y-1.8Zr (in wt%) were comparable to Inconel 617 despite the small alloying additions, due to its hierarchical microstructure. Here, uniaxial compression at 600 °C showed that ternary alloys outperformed Ni-Zr and Ni-Y binary alloys in flow stress and hardening rates, which indicates that the Ni 17 Y 2 phase was an effective reinforcement for the eutectic, which supplemented the matrix hardening due to increased solubility of Zr. Results suggest that ternary Ni-Y-Zr alloys hold significant promise for high temperature applications.

36 MATERIALS SCIENCE↗

Analytical modeling and simulation of electrical contact resistance for elastic rough electrode surface contact including frictional temperature rise

An improved electrical contact resistance (ECR) model for elastic rough electrode contact is proposed, incorporating the effects of asperity interactions and temperature rise by frictional and joule heating. The analytical simulation results show that the ECR decreases steeply at the beginning of the contact between Al and Cu. However, it becomes stabilized after reaching a specific contact force. It is also found that the longer elapsed sliding contact time, the higher ECR due to the increase in electrical resistivity of electrode materials by the frictional temperature rise at the interface. The effects of surface roughness parameters on ECR are studied through the 3 2 full-factorial design-of-experiment analysis. Based on the two representative roughness parameters, i.e., root-mean-square (rms) roughness and asperity radius, their individual and coupled effects on the saturated ECR are examined. The saturated ECR increases with the rms roughness for a rough machined surface condition, but it is hardly affected by the asperity radius. On the other hand, the saturated ECR increases with both the rms roughness and the asperity radius under a smooth thin film surface condition.

42 ENGINEERING↗

Effect of Molding and Machining on Neoflon CTFE M400H Polychlorotrifluoroethylene Rod Stock and Valve Seat Properties

Since 1997 numerous fires have been reported to the Food and Drug Administration involving cylinder valves installed on medical use oxygen cylinders sold and operated within the United States. All of the cylinder valves in question had polychlorotrifluoroethylene (PCTFE) valve seats. Subsequent failure analysis showed that the main seat was the primary source of ignition. A review of the incidents involving cylinder valve fires indicated three possible ignition mechanisms: contaminant promotion, flow friction, and resonance. However, gas purity analysis showed that uncombusted, residual oxygen was within specification. Infrared and energy dispersive spectroscopy further showed that no contaminants or organic compounds were present in the remaining, uncombusted valve seat material or on seat plug surfaces. Therefore, contaminant-promoted ignition did not appear to be responsible for the failures. Observations of extruded material along the outer edge of the coined or loaded seat area produced by cylinder overuse or poppet overload led to concerns that accelerated gas flow across a deformed seat surface could generate enough localized heating to ignite the polymeric seat. Low molecular weight or highly amorphous quick-quenched PCTFE grades might be expected to be especially prone to this type of deformation. Such a failure mechanism has been described as flow friction; however, the corresponding mechanistic parameters are poorly understood. Subsequent revelation of low-temperature dimensional instability by thermomechanical analysis (TMA) in a variety of PCTFE sheet and rod stock samples led to new concerns that PCTFE valve seats could undergo excessive expansion or contraction during service. During expansion, additional extrusion and accompanying flow friction could occur. During contraction, a gap between the seal and adjacent metal surfaces could form. Gas flowing past the gap could, in turn, lead to resonance heating and subsequent ignition as described in ASTM Guide for Evaluation Nonmetallic Materials for Oxygen Service (G 63). Attempts to uncover the origins of the observed dimensional instability were hindered by uncertainties about resin grade, process history, and post-process heat history introduced by machining, annealing, and sample preparation. An approach was therefore taken to monitor property changes before and after processing and machining using a single, well-characterized lot of Neoflon CTFE.1 M400H resin. A task group consisting of the current PCTFE resin supplier, two molders, and four valve seat manufacturers was formed, and phased testing on raw resin, intermediate rod stock, and finished valve seats initiated. The effect of processing and machining on the properties of PCTFE rod stock and oxygen gas cylinder valve seats was then determined. Testing focused on two types of extruded rod stock and one type of compression-molded rod stock. To accommodate valve seat manufacturer preferences for certain rod stock diameters, two representative diameters were used (4.8 mm (0.1875 in.) and 19.1 mm (0.75 in.)). To encompass a variety of possible sealing configurations, seven different valve seat types with unique geometries or machining histories were tested. The properties investigated were dimensional stability as determined by TMA, specific gravity, differential scanning calorimetry (DSC), compressive strength, zero strength time, and intrinsic viscosity. Findings are discussed in the context of polymer structure-process-property relationships whenever possible.

Waller, Jess M.↗

Thermal loading effects on chalk hydromechanical behavior for nuclear waste disposal

Safe disposal of heat-generating nuclear waste depends on host rock stability under thermal, hydrological, and mechanical stresses. This study investigates the effect of thermal loading on mechanical behavior of the shallowly buried Ghareb formation chalk through triaxial and hydrostatic constant strain rate and creep tests at temperatures up to 100 ˚C and effective pressures up to 20.7 MPa. Experimental results show that thermal loading reduces the elastic moduli of chalk by 50–75%, and a transition occurs above 60 ˚C where creep rates increase rapidly. Water saturation nearly doubles the thermally induced strain compared to dry conditions and strongly decreases material rigidity. Thermal loading also leads to significant pore pressure increases under undrained conditions and leads to reductions in the apparent permeability during drained conditions. Laboratory experimental data were used to parameterize and develop a preliminary constitutive model for predicting future deformation during repository operations in the Ghareb. The strongly coupled effects – mechanical weakening, fluid pressure fluctuations, and permeability modification – demonstrate that elevated repository temperatures will have a pronounced effect on the near field Ghareb behavior during waste disposal operations. The findings indicate that the coupled interactions must be considered in predictive models and repository design to ensure long-term nuclear waste isolation and safety.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗