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Factors which influence directional coarsening of gamma-prime during creep in nickel-base superalloy single crystals

Changes in the morphology of the gamma prime precipitate were examined as a function of the time during creep at 982 C in 001 oriented single crystals of a Ni-Al-Mo-Ta superalloy. In this alloy, which has a large negative misfit of -0.80 pct., the gamma prime particles link together during creep to form platelets, or rafts, which are aligned with their broad faces perpendicular to the applied tensile axis. The effects of initial microstructure and alloy composition of raft development and creep properties were investigated. Directional coarsening of gamma prime begins during primary creep and continues well after the onset of second state creep. The thickness of the rafts remains constant up through the onset of tertiary creep, a clear indication of the stability of the finely-spaced gamma/gamma prime lamellar structure. The thickness of the rafts which formed was equal to the initial gamma prime size which was present prior to testing. The single crystals with the finest gamma prime size exhibited the longest creep lives, because the resultant rafted structure had a larger number of gamma/gamma prime interfaces per unit volume of material. Reducing the Mo content by only 0.73 wt. pct. increased the creep life by a factor of three, because the precipitation of a third phase was eliminated.

Mackay, R. A.↗

Raman Strain Sensing and Interfacial Stress Transfer of Hierarchical CNT-Coated Carbon Fibers

Hierarchical reinforcements of carbon fibers (CFs) coated with carbon nanotubes (CNTs) were produced via two different methodologies, namely chemical vapor deposition (CVD) and wet chemical treatment. These advanced smart structural materials are possible candidates for inherent strain sensing and improved interfacial properties when incorporated in the volume of structural fiber-reinforced polymer composites. The morphology and wetting properties of the hierarchical CFs were evaluated via SEM and contact angle measurements. Enhanced values in the strain-induced Raman sensing ability of the hierarchical reinforcement produced via CVD in comparison with the uncoated fibers were measured at single fiber level. The residual stress transfer profiles of both the hierarchical and the uncoated carbon fibers were also evaluated using the Raman spectroscopy in order to evaluate the phase interaction in the hierarchical structure. Compressive residual stresses in the order of 1.5 GPa were found to act on the CF surfaces, while tensile residual stresses were measured for both the CNT-coated systems. The effects of the preparation process of the CNT coatings on the residual stress profiles were also prominent, with the CVD-grown coatings resulting in higher tensile residual stresses, 1.76 GPa instead of 1.22 GPa for the coatings produced via wet chemical treatment. The change in the residual stress profiles established the interaction between the CFs and the CNTs via an anchoring mechanism which significantly altered the stress field at the vicinity of the interface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Strength-ductility synergy through microstructural and compositional heterogeneity in directed energy deposition additive manufacturing of face-centered cubic materials

Directed energy deposition (DED) is an additive manufacturing (AM) process based on welding technology and offers the advantages of large build volume, high deposition rate, and ability to fabricate multi-material parts. Epitaxial continuous columnar grain growth is a characteristic microstructural feature of DED processed alloys. In this study, a bamboo-like microstructure (periodic alternation of equiaxed and columnar structure) was produced by adopting an intermittent deposition strategy in 316L stainless steel and Inconel 625. The formation of a bamboo-like alternating microstructure was confirmed through electron backscattered diffraction (EBSD) analysis. Hardness mapping showed that the columnar to equiaxed transition (CET) occurred at the region right below the fusion line. A finite element (FE) model was used to investigate the relationship between the temperature gradient (G) and the solidification rate (R). The FE model showed a low G/R ratio at the region right below the interface promoting the CET. The grain size and material-dependent deformation behaviors are analyzed using digital image correlation (DIC). The lower deformation on the fine-grain regions observed in DIC analysis is attributed to a higher strain hardening rate, which is confirmed through dislocation density analysis on a tensile-interrupted specimen. The periodically alternating grain size coupled with the microstructural changes caused by intermittent deposition strategy result in a better strength-ductility synergy in both single-material and bimetallic specimens.

36 MATERIALS SCIENCE↗

A formational model for the polygonal terrains of Mars: Taking a crack at the genesis of the Martian polygons

The mechanism for the genesis of the polygonal terrains in Acidalia and Utopia Planitia has long been sought: however, no completely satisfying model was put forth that characterizes the evolution of these complexly patterned terrains. The polygons are roughly hexagonal but some are not entirely enclosed by fractures. These polygonal features range in widths from approximately 5 to 20 km. Several origins were proposed that describe the polygon borders as desiccation cracks, columnar jointing in a cooled lava, or frost-wedge features. These tension-induced cracking hypotheses were addressed by Pechmann, who convincingly disputes these mechanisms of formation based on scale magnitude difficulties and morphology. Pechmann suggests instead that the cracks delineating the 5-20-km-wide polygons on the northern plains of Mars are graben resulting from deep-seated, uniform, horizontal tension. The difficulty with this hypothesis is that no analogous polygonal forms are known to have originated by tectonism on Earth. McGill and Hills propose that the polygonal terrains on Mars resulted from either rapid desiccation of sediments or cooling of volcanics coupled with differential compaction of the material over a buried irregular topographic surface. They suggest that fracturing was enhanced over the areas of positive relief and was suppressed above the topographic lows. McGill and Hills suggest that the spacing of the topographic highs primarily controls the size of the Martian polygons and the physics of the shrinkage process is a secondary concern. Ray et. al. conducted a terrestrial study of patterned ground in periglacial areas of the U.S. to determine the process responsible for polygonal ground formation. They developed a model for polygon formation in which convection of seasonal melt water above a permafrost layer, driven by an unstable density stratification, differentially melts the permafrost interface, causing it to become undulatory.

Wenrich, M. L.↗

Effects of build orientation and heat treatment on the evolution of microstructure and mechanical properties of alloy Mar-M-509 fabricated via laser powder bed fusion

We present the main results from an experimental investigation into the consequences of various microstructural features, created by laser powder bed fusion (LPBF) and subsequent heat treatments (HTs), in alloy Mar-M-509 on several aspects of plastic deformation including mechanical anisotropy and elongation-to-fracture (ETF). To ensure successful manufacturing of the alloy, porosity fraction and distribution are first characterized using micro X-ray computed tomography. Next, grain structure, crystallographic texture, and regions of recrystallization in the studied microstructures are measured using electron backscattered diffraction (EBSD). Lastly, chemistry, distribution, and morphological features of carbide phases are extracted using electron microscopy and X-ray diffraction. Strength in tension and compression are measured at room temperature for different initial microstructures created by variations in manufacturing conditions and sample orientations with respect to sample processing frame. While the strength of the alloy varies with sample orientation by approximately 30% in the as-built condition, the alloy is softer, more ductile, and approximately isotropic after HT. These results are discussed and critically compared with the data reported for the as-cast material. The alloy manufactured via LPBF is found to be significantly stronger and more ductile than the same alloy produced by casting. The interesting deformation behavior characteristics of the samples in different conditions are explained in terms of their microstructures. EBSD measurements reveal evolution from columnar grains along the build direction favoring a moderately strong <001> fiber texture in the as-built material to equiaxed grains favoring the {110}<001> Goss texture component after subsequent HTs. The major change in grain structure and texture is a result of recrystallization. While carbide phases precipitate primarily at dendrite and cellular interfaces in the as-built material, these phases are both intra-and inter-granular within the HT materials and coarsen with HT duration. These microstructural observations formed bases to rationalize the observed mechanical behavior of the alloy. With this being said, tailoring the alloy performance characteristics with HTs is reported on.

36 MATERIALS SCIENCE↗

New large-strain FFT-based formulation and its application to model strain localization in nano-metallic laminates and other strongly anisotropic crystalline materials

This paper presents a new robust large-strain (LS) elasto-viscoplastic (EVP) formulation based on Fast Fourier Transforms (FFTs) for the prediction of the micro-mechanical response and microstructure evolution of polycrystalline and multiphase materials, with emphasis on the effect of strong crystallographic and/or morphologic anisotropy on localization of plastic deformation. In this work, the novel LS-EVPFFT formulation allows treatment of complex initial geometries and large deformations considering three grids of material points: a regular grid in the reference configuration, where FFTs can be performed; an irregular grid in the initial configuration, created by applying a stress-free displacement field to the reference regular grid; and an irregular grid in the current configuration, undergoing large strains and rotations as the material is loaded. Further numerical stability of the new formulation also required the use of a novel expression for the discrete modified Green’s operator, which reduces spurious field oscillations. After presenting and validating the new formulation by comparison with preexisting implementations and analytical solutions, LS-EVPFFT is applied to the prediction of slip and kink bands formation in polycrystalline columnar ice, and kink bands in single crystal zinc wires, showing good agreement with classic experiments. Finally, the model is used to study kink band formation during compression of Cu–Nb nano-metallic laminates (NMLs), in which accurate treatment of the complex geometry associated with the tortuosity of interfaces and large deformations become critical, showing consistency with corresponding micropillar experiments.

36 MATERIALS SCIENCE↗

Design of CO 2 Selective Type 3 Porous Liquids Through Porous Host Morphology

Direct air capture (DAC) of CO 2 is a negative emission technology under development to limit the impacts of climate change. The dilute concentration of CO 2 in the atmosphere (~400 ppm) requires new materials for carbon capture with increased CO 2 selectivity that is not met with current carbon capture materials. Porous liquids (PLs) are an emerging candidate for carbon capture and consists of a combination of solvents and porous hosts that creates a liquid with permanent porosity. The fundamental mechanisms of carbon capture in a PL are relatively unknown. To uncover these mechanisms, PLs were synthesized consisting of three different zeolitic-imidazolate framework (ZIF-8, ZIF-67, or ZIF-69) porous host in a water/glycol/2-methylimidazole solvent. The most stable composition was based on ZIF-8 and exhibited carbon capture following exposure to CO 2 . Density functional theory identified a three-step carbon capture mechanism based on (i) reaction of OH- with ethylene glycol in the solution followed by (ii) formation of 2-hydroxyethyl carbonate, which (iii) further react with OH- to form a carbonate species. This mechanism was validated with experimental nuclear magnetic resonance spectroscopy (NMR) to identify the dissolved carbonate phases and the decrease in the pH during CO 2 exposure. Deuterated samples of the ZIF-8 PLs were synthesized and analyzed via neutron diffraction at the Spallation Neutron Sources at Oak Ridge National Laboratory. Results identified differences in diffraction for PLs pre- and post-CO 2 exposure that will be combined with ab initio molecular dynamics data of the same PL composition to identify how the presence of a solvent-porous host interfaces results in carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Building Durable Multimetallic Electrocatalysts from Intermetallic Seeds

When combined with earth-abundant metals, Pt-based alloy nanoparticles (NPs) can be cost-effective electrocatalysts. However, these NPs can experience leaching of non-noble-metal components under harsh electrocatalytic conditions. In this work, the Skrabalak group has demonstrated a novel NP construct in which Pt-based random alloy surfaces are stabilized against non-noble-metal leaching by their deposition onto intermetallic seeds. These core@shell NPs are highly durable electrocatalysts, with the ability to tune catalytic performance by the core@shell architecture, surface alloy composition, and NP shape. This versatility was demonstrated in a model system in which random alloy (ra-) PtM surfaces were deposited onto ordered intermetallic (i-) PdCu seeds using seed-mediated co-reduction (SMCR). In the initial demonstration, ra-PtCu shells were deposited on i-PdCu seeds, with these core@shell NPs exhibiting higher specific and mass activities for the oxygen reduction reaction (ORR) when compared to similarly sized ra-PtCu NPs. These NPs also showed outstanding durability, maintaining ~85% in specific activity after 5000 cycles. Characterization of the NPs after use revealed minimal loss of Cu. The activity enhancement was attributed to the strained surface that arises from the lattice mismatch between the intermetallic core and random alloy surface. The outstanding durability was attributed to the ordered structure of the intermetallic core. The origin of this durability enhancement was investigated by classical molecular dynamics simulations, where Pt atoms were found to have a lower potential energy when deposited on an intermetallic core than when deposited on a random alloy core. Also, ordering of Cu atoms at the core@shell interface appears to enhance the overall binding between the core and the shell materials. Inspired by this initial demonstration, SMCR has been used to achieve shells of different random alloy compositions, PtM (M = Ni, Co, Cu, or Fe). This advance is significant because ligand effects vary as a function of PtM identity and Pt/M ratio. These features also influence the degree of surface strain imparted from the lattice mismatch between the core and shell materials. Like the initial demonstration, standout features of these core@shell NPs were high durability and resistance to non-noble metal leaching. Moving forward, efforts have been directed toward integrating shape-control to this core@shell NP construct. This integration is motivated by the shape-dependent catalytic performance of NPs derived from the selective expression of specific facets. Considering the initial i-PdCu@ra-PtCu system, NPs with a cubic shape have been achieved by judicious selection of capping ligands during SMCR. Evaluation of these NPs as catalysts for the electrooxidation of formic acid found that the nanocubic shape enhances catalytic performance compared to similar core@shell NPs with a spherical morphology. We envision that SMCR can be applied to other NP systems to achieve highly durable catalysts as the syntheses of monodisperse and shape-controlled intermetallic seeds are advanced. This Account highlights the role of intermetallic cores in providing more durable electrocatalysts. More broadly, the versatility of SMCR is highlighted as a route to integrate architecture, alloy surfaces, and shape within one NP system, and how this achievement is inspiring new high-performance and robust catalysts is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accelerating phase field simulations through a hybrid adaptive Fourier neural operator with U-net backbone

Prolonged contact between a corrosive liquid and metal alloys can cause progressive dealloying. For one such process as liquid-metal dealloying (LMD), phase field models have been developed to understand the mechanisms leading to complex morphologies. However, the LMD governing equations in these models often involve coupled non-linear partial differential equations (PDE), which are challenging to solve numerically. In particular, numerical stiffness in the PDEs requires an extremely refined time step size (on the order of 10 -12 s or smaller). This computational bottleneck is especially problematic when running LMD simulation until a late time horizon is required. This motivates the development of surrogate models capable of leaping forward in time, by skipping several consecutive time steps at-once. In this paper, we propose a U-shaped adaptive Fourier neural operator (U-AFNO), a machine learning (ML) based model inspired by recent advances in neural operator learning. U-AFNO employs U-Nets for extracting and reconstructing local features within the physical fields, and passes the latent space through a vision transformer (ViT) implemented in the Fourier space (AFNO). We use U-AFNOs to learn the dynamics of mapping the field at a current time step into a later time step. We also identify global quantities of interest (QoI) describing the corrosion process (e.g., the deformation of the liquid-metal interface, lost metal, etc.) and show that our proposed U-AFNO model is able to accurately predict the field dynamics, in spite of the chaotic nature of LMD. Most notably, our model reproduces the key microstructure statistics and QoIs with a level of accuracy on par with the high-fidelity numerical solver, while achieving a significant 11, 200 × speed-up on a high-resolution grid when comparing the computational expense per time step. Finally, we also investigate the opportunity of using hybrid simulations, in which we alternate forward leaps in time using the U-AFNO with high-fidelity time stepping. We demonstrate that while advantageous for some surrogate model design choices, our proposed U-AFNO model in fully auto-regressive settings consistently outperforms hybrid schemes.

36 MATERIALS SCIENCE↗

Cost-effective Manufacturing and Morphological Stabilization of Nanostructured Cathodes for Commercial SOFCs

The overall goals of the program were to develop methods for preparing and stabilizing SOFC electrodes by infiltration that can be manufactured on a practical scale, then transfer those methods to cells in stacks. Cathodes prepared by infiltration of nanoparticles into a porous scaffold of the electrolyte have demonstrated outstanding electrochemical performance and mechanical strength but are difficult to manufacture due to the large number of infiltration steps required to produce a conductive composite and show poor stability due to sintering of the nanoparticles. At Penn, the main goal was to develop a fabrication method that uses only a small number of infiltration steps. Infiltration with molten salts and electrodeposition were pursued but deemed impractical. A method in which an electronically conductive scaffold consisted of a composite of a mixed conductor, LSF (La 0.9 Sr 0.1 FeO 3 ), with yttria-stabilized zirconia (YSZ) was found to be promising. While some cation mixing between LSF and YSZ was observed during calcination, there was no evidence for new phases in XRD and incorporation of Zr into the perovskite could be minimized by reducing the Sr content of the LSF. To stabilize nanoparticles infiltrated into the LSF-YSZ composite scaffold, the USC team examined the effects of Atomic Layer Deposition with ZrO 2 and infiltrated nanoparticles. Significantly enhanced stability was observed with the infiltrated nanoparticles. The FuelCell Energy team prepared 4”x4” cells in which an LSF-YSZ composite scaffold was cofired with the YSZ electrolyte and infiltrated with LSCF nanoparticles. Apparently because the LSF-YSZ scaffold layer was very thin in this case, the cation mixing that occurred during calcination resulted in a poor scaffold-electrolyte interface which caused reduced performance.

36 MATERIALS SCIENCE↗

Shining light on nanoscale ‘vine-on-stick’ eutectic structures in the Al-Ce-Ni system

Multiphase eutectics often comprise entangled solid phases with nanoscale periodicity, making it difficult to unravel their 3D connectivity using conventional 2D techniques. Among such systems, the three-phase eutectic Al-Al 11 Ce 3 -Al 3 Ni stands out for its ultrafine (∼100 nm) interphase spacing and promising creep resistance, yet its microstructure remains relatively unexplored despite its potential for high-temperature applications. Here, we use scanning hard X-ray microscopy with an unprecedented ∼10 nm pixel size to resolve its 3D morphology. Reconstructions reveal a novel “vine-on-stick” motif, wherein Al 11 Ce 3 wraps around Al 3 Ni pillars. Analysis of phase tortuosities confirms that Al 11 Ce 3 exhibits more convoluted morphologies than Al 3 Ni. No orientation relationship was observed between the two intermetallics, suggesting that growth is controlled by local solute gradients rather than epitaxy. Fragmentation of intermetallics along their longitudinal axis suggests a Rayleigh-type breakup mechanism in solid state. The “vine-on-stick” pattern may generalize to other alloy systems with variable interfacial anisotropies and low mutual solubilities.

36 MATERIALS SCIENCE↗

Designing Ta C Virtual Substrates for Vertical Al x Ga 1 − x N Power Electronics Devices

Power electronics are critical for a sustainable energy future, playing a key role in electrification and integration of renewable energy sources into the grid. Advances in ultrawide band gap materials are needed to handle higher powers in smaller form factors while reducing electrical and thermal losses. High Al content Al x Ga 1 − x N is theoretically capable of meeting these demands, but its impact in power electronics has been severely restricted by a lack of substrates that can satisfy conductivity, lattice matching, and/or thermal expansion requirements. We demonstrate that electrically conductive Ta C can be used as a virtual substrate for Al x Ga 1 − x N heteroepitaxy. Scaleably sputtered Ta C grown on Al 2 O 3 , followed by high-temperature face-to-face annealing, produces a thin film Ta C template with an effective hexagonal lattice constant matched to Al 0.70 Ga 0.30 N . Annealing of the Ta C promotes recrystallization, significantly improving crystallinity and reducing crystalline defects from as-deposited columnar grains to a step-and-terrace surface morphology, enabling the subsequent growth of high-quality Al 0.70 Ga 0.30 N by molecular beam epitaxy. X-ray diffraction and scanning transmission electron microscopy confirm that the Al x Ga 1 − x N layer is heteroepitaxially aligned, strain-free, and lattice-matched, transitioning abruptly from Ta C to Al x Ga 1 − x N without intermediate phases. These results demonstrate Ta C virtual substrates as electrically conductive, lattice-matched, and thermally compatible templates for vertical Al x Ga 1 − x N devices that can meet the growing power needs of a sustainable energy future. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Cost-effective Manufacturing and Morphological Stabilization of Nanostructured Cathodes for Commercial Solid Oxide Fuel Cells (SOFCs) [Slides]

The overall goals of the program were to develop methods for preparing and stabilizing SOFC electrodes by infiltration that can be manufactured on a practical scale, then transfer those methods to cells in stacks. Cathodes prepared by infiltration of nanoparticles into a porous scaffold of the electrolyte have demonstrated outstanding electrochemical performance and mechanical strength but are difficult to manufacture due to the large number of infiltration steps required to produce a conductive composite and show poor stability due to sintering of the nanoparticles. At Penn, the main goal was to develop a fabrication method that uses only a small number of infiltration steps. Infiltration with molten salts and electrodeposition were pursued but deemed impractical. A method in which an electronically conductive scaffold consisted of a composite of a mixed conductor, LSF (La 0.9 Sr 0.1 FeO 3 ), with yttria-stabilized zirconia (YSZ) was found to be promising. While some cation mixing between LSF and YSZ was observed during calcination, there was no evidence for new phases in XRD and incorporation of Zr into the perovskite could be minimized by reducing the Sr content of the LSF. To stabilize nanoparticles infiltrated into the LSF-YSZ composite scaffold, the USC team examined the effects of Atomic Layer Deposition with ZrO 2 and infiltrated nanoparticles. Significantly enhanced stability was observed with the infiltrated nanoparticles. The FuelCell Energy team prepared 4”x4” cells in which an LSF-YSZ composite scaffold was cofired with the YSZ electrolyte and infiltrated with LSCF nanoparticles. Apparently because the LSF-YSZ scaffold layer was very thin in this case, the cation mixing that occurred during calcination resulted in a poor scaffold-electrolyte interface which caused reduced performance.

30 DIRECT ENERGY CONVERSION↗

Influence of the molecular weight and size distribution of PSS on mixed ionic-electronic transport in PEDOT:PSS

The commercially available polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is ubiquitous in organic and hybrid electronics. As such, it has often been used as a benchmark material for fundamental studies and the development of new electronic devices. Yet, most studies on PEDOT:PSS have focused on its electronic conductivity in dry environments, with less consideration given to its ion transport, coupled ionic-electronic transport, and charge storage properties in aqueous environments. These properties are essential for applications in bioelectronics (sensors, actuators), charge storage devices, and electrochromic displays. Importantly, past studies on mixed ionic-electronic transport in PEDOT:PSS neglected to consider how the molecular structure of PSS affects mixed ionic-electronic transport. Herein, we therefore investigated the effect of the molecular weight and size distribution of PSS on the electronic properties and morphology of PEDOT:PSS both in dry and aqueous environments, and overall performance in organic electrochemical transistors (OECTs). Using reversible addition–fragmentation chain transfer (RAFT) polymerization with two different chain transfer agents, six PSS samples with monomodal, narrow (D = 1.1) and broad (D = 1.7) size distributions and varying molecular weights were synthesized and used as matrices for PEDOT. We found that using higher molecular weight of PSS (Mn = 145 kg mol –1 ) and broad dispersity led to OECTs with the highest transconductance (up to 16 mS) and [μC*] values (~140 F cm –1 V –1 s –1 ) in PEDOT:PSS, despite having a lower volumetric capacitance (C* = 35 ± 4 F cm –3 ). The differences were best explained by studying the microstructure of the films by atomic force microscopy (AFM). We found that heterogeneities in the PEDOT:PSS films (interconnected and large PEDOT- and PSS-rich domains) obtained from high molecular weight and high dispersity PSS led to higher charge mobility (μOECT ~4 cm 2 V –1 s –1 ) and hence transconductance. Furthermore, these studies highlight the importance of considering molecular weight and size distribution in organic mixed ionic-electronic conductor, and could pave the way to designing high performance organic electronics for biological interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Internal strain analysis of ceramics using scanning laser acoustic microscopy

Quantitative studies of material behavior characteristics are essential for predicting the functionality of a material under its operating conditions. A nonintrusive methodology for measuring the in situ strain of small dimeter (to 11 microns) ceramic fibers under uniaxial tensile loading and the local internal strains of ceramics and ceramic composites under flexural loading is introduced. The strain measurements and experimentally observed mechanical behavior are analyzed in terms of the microstructural development and fracture behavior of each test specimen evaluated. Measurement and analysis of Nicalon silicon carbide (SiC) fiber (15 microns diameter) indicate that the mean elastic modulus of the individual fiber is 185.3 GPa. Deviations observed in the experimentally determined elastic modulus values between specimens were attributed to microstructural variations which occur during processing. Corresponding variations in the fracture surface morphology were also observed. The observed local mechanical behavior of a lithium alumino-silicate (LAS) glass ceramic, a LAS/SiC monofilament composite, and a calcium alumino-silicate (CAS)/SiC fully reinforced composite exhibits nonlinearities and apparent hysteresis due to the subcritical mechanical loading. Local hysteresis in the LAS matrices coincided with the occurrence of multiple fracture initiation sites, localized microcracking, and secondary cracking. The observed microcracking phenomenon was attributed to stress relaxation of residual stresses developed during processing, and local interaction of the crack front with the microstructure. The relaxation strain and stress predicted on apparent mechanical hysteresis effects were defined and correlated with the magnitude of the measured fracture stress for each specimen studied. This quantitative correlation indicated a repeatable measure of the stress at which matrix microcracking occurred for stress relief of each material system. Stress relaxation occurred prior to the onset of steady state cracking conditions. The relaxation stress occurred at 18.5 percent of the fracture stress in LAS and 11.0 percent of the yield stress in CAS/SiC. The relaxation stress ratio was dependent upon the dominant fracture mode of the LAS/SiC specimens. Relaxation stress ratios greater than 0.30 were observed for specimens which fractured due to shear at the fiber matrix interface; specimens which fracture due to tensile cracking had relaxation stress ratios less than 0.30. The stress relaxation ratio appeared to be a specific characteristic of the glass ceramic material. The measured stress relaxation for LAS indicated a measure of the inherent residual stresses in the material due to processing and suggested localized toughening mechanisms for brittle material structures.

Kent, Renee M.↗

Development of a New Membrane Casting Apparatus for Studying Macrovoid Defects in Low-G

A new membrane-casting apparatus is developed for studying macrovoid defects in polymeric membranes made by the wet- and dry-casting process in low-gravity. Macrovoids are large (10-50 micron), open cavities interspersed among the smaller pores in the substructure under the gelled skin surface layer of the cast membrane. Although their occurrence is considered endemic to the wet- and dry-casting process since they can lead to compaction or skin rupture in the membrane process, recent studies suggest several useful applications such as transdermal and osmotic drug delivery systems, miniature bioreactors, etc. However, lack of knowledge about the macrovoid formation mechanism is an obstacle to further development of applications using them. An on-going debate is the role of the surface-tension-driven solutocapillary convection during macrovoid formation. The rapid growth of macrovoids within 1-5 seconds and the high polymer concentration in and near macrovoids make it difficult to explain the mechanism of macrovoid growth by diffusion alone, which is the widely accepted hypothesis proposed by Reuvers et al. The hypothesis advanced by our research group can explain this rapid growth via a mechanism that involves diffusion from the casting solution in the meta-stable region to the macrovoid enhanced by solutocapillary convection induced by the steep nonsolvent concentration gradient in the vicinity of the macrovoid. Since macrovoid growth is hypothesized to be the interplay of a solutocapillary-induced driving force counteracted by viscous drag and buoyancy, eliminate the latter provides a means for testing this hypothesis. Moreover, free convection mass transfer in the nonsolvent immersion bath used to cause phase-separation in membrane casting complicates developing a model for both the wet-casting process and macrovoid growth. The low-g environment minimizes gravitationally induced free convection thereby permitting a tractable solution to the ternary diffusion equations that characterize membrane formation. NASA's Parabolic Flight Research Aircraft provides a small window of low-g (approximately 25 s) that can be used to study macrovoid development in both wet- and dry-cast membranes if an appropriate casting apparatus is used. This casting apparatus should be able to cast the membrane in both low- and high-g in a manner so that essential one-dimensional mass transfer conditions are achieved to insure lateral uniformity in the membrane. The apparatus used in previous research on membrane casting in low-gravity was operated with the plunger driven mechanism. The spring-loaded plunger pushes the bottom block containing the polymer casting solution well directly under the absorbent chamber located in the upper stationary block. However, membranes made via this casting apparatus often displayed lateral nonuniformities that precluded obtaining quantitative information on the macrovoid growth process. Thus, it was necessary to determine the reason for these structural irregularities observed in the low-g casting apparatus. Both experimental as well as computer simulation studies of the low-g casting apparatus established that the impulsive action of the plunger caused the undesired structural nonuniformities. The simulation results showed that the width-to-depth aspect ratio of the shallow well that contains the casting solution in this apparatus was not an important factor in minimizing this problem. Even for a 40:1 (width : depth) aspect ratio, any convection induced by the horizontal motion of the interface of the casting solution will be damped out within 6.25x10(exp 4) seconds. However, the experimental studies revealed that the impulsive motion of the plunger caused a 'sloshing' of the casting solution that had to be eliminated. Therefore, the plungerdriven mechanism was changed to a cam-driven mechanism that did not cause any impulsive motion of the casting solution. Other refinements to this new membrane-casting apparatus include provision for removing the membranes from the casting wells in a less destructive manner. This was accomplished by using a slit geometry for the casting well that permitted disassembly for removal of the cast membrane. The materials used in the construction of this casting apparatus were chosen to insure wetting at the side walls and to maintain precise control of the thickness of the polymer solution in the casting well. An additional provision in this new casting apparatus is the ability to carry out both wet- as well as dry-casting. As such, this apparatus permitted the first studies of the wet-casting of polymeric membranes in low-g. Both wet- and dry-casting experiments on NASA's KC-135 research aircraft employing this new membrane-casting apparatus are scheduled in July 2002. The morphology of the resulting membranes will be characterized using an environmental scanning electron microscope (ESEM). The results of these low-g studies will be reported later.

Lee, Hanyong↗

Multiple‐Repeated Plasma Surface Treatments for Significantly Improving Bonding Performance of Metal‐Carbon‐Fiber‐Reinforced Thermoplastic Polymer Dissimilar Adhesive Joints

This work investigates how multiple‐repeated plasma surface treatments can significantly enhance adhesively bonded metal‐carbon‐fiber‐reinforced thermoplastic polymer (CFRTP) dissimilar joints, a topic that has been rarely investigated compared to other parameters during the plasma treatment process. By conducting double cantilever beam tests on adhesively bonded AA6061‐carbon‐fiber‐reinforced polyphthalamide (CFRPPA) dissimilar joints, it is shown that the average Mode I specific fracture energy after 20 repetitions of the same plasma treatment, using processing parameters without noticeably changing surface roughness, can be improved and saturated up to almost 2000% compared to non‐treated joints and almost 240% compared to a single plasma treatment commonly used in the literature. The improvement can be attributed to the enhanced chemical bonding at the CFRPPA‐adhesive interface. This study is important for achieving strong bonding performance of CFRTP‐related structural joints using multiple plasma treatments, a simple and effective method.

36 MATERIALS SCIENCE↗

3D Scanning System to Assess Gravity-Dependent Body Shape Changes

The human body shows unique morphological changes when exposed to different gravity conditions, including muscle atrophy, fluid shift, and spinal elongation. Such changes need to be incorporated for human-system integration in the vehicle habitat, garment, and spacesuit designs, as inaccurate body measurements can result in suboptimal crew protection that can potentially decrease injury tolerance. However, measurement tools have not been available for accurate assessments of body shape changes. This work aimed to develop a prototype 3-D body scanning system with the configuration and performance optimized for in-flight crewmember body scanning. A scan hardware system was developed using Intel RealSense commercial off-the-shelf 3D sensors. The sensor parameters were iteratively optimized and tested to obtain the performance level needed for body scanning. A scan booth structure was fabricated, with the overall size 4 x 4 x 8 feet. The specific number of sensors and mounting positions were determined by iterative simulations, which indicated that 16 cameras can capture 94% and 96% of body surface area from the 1st percentile female and 99th percentile male crew population subject. The mounted sensors were linked through a mix of USB-C and USB-3 cables and operated for data acquisition from a Linux laptop computer. A software prototype was developed using Python and Tkinter graphical user interface toolkit. A calibration procedure was also built using a panel of QR codes. A computer vision tool detected and decoded the unique ID and pattern locations of the QR codes. The calibration information determined the position and orientation of the 3D sensors with respect to each other. The scanner performance was assessed using a set of 3D printed custom manikins. The manikin size and shape were derived from the previous ISS study, which measured the crewmembers’ anthropometry changes across the different flight phases. The average anthropometric measurements at the pre-flight and flight day 15 were sampled and projected onto the 1st percentile female and 99th percentile male body shapes. Another pair of manikins were also 3D printed to simulate the neutral body posture, estimated from ISS microgravity environments. A preliminary analysis assessed the performance of the newly developed scanner against the reference scanner, which has been used at the NASA JSC for crew and test subject anthropometry. Although the new scanner data showed several artifacts and missing geometries in the occluded body areas such as armpits and crotch, overall shape matched with the reference scan. When the manikin surface coordinates were compared, a root mean square error of 1.3 cm was observed from the manikin torso segment. Linear measurements including the stature, knee height and circumference measurements at the chest and calf showed differences from the reference scan measurements, ranging between 0.3 and 0.9 cm. Overall, this work demonstrated a development framework for an in-flight scanner with design and operation optimized for crewmember body scanning. Further improvement can potentially provide previously unavailable anthropometric data from different gravitational environments, including 0-g, 1/6-g, and 1-g. Such data can improve suit fit, habitat design, exercise efficacy quantification and sizing of orthostatic intolerance garments.

K H Kim↗