Evaluation of Forging Process Induced Residual Stress in Aluminum Die Forgings

Aircraft structural components are being produced from forgings with increasingly complex geometries in a wide range of aerospace alloys. The forging process involves a number of steps required to attain favorable material properties (e.g., heat treatment, rapid quench, cold work stress relieving, and artificial aging). These processing steps, however, also result in the introduction of bulk residual stress. Excessive bulk residual stresses can have negative consequences including: part distortion during machining and/or during service, reduced crack initiation life, increased crack growth rates, and an overall reduction in part life. This presentation will summarize recent work related to quantifying and accounting for residual stress in aluminum die forgings. Key residual stress engineering concepts will be described. Since the artifacts studied are associated with an aircraft supply chain (multiple parts and multiple lots), the results are relevant to the aerospace community. Overall, the results show that forging residual stress is a repeatable phenomenon with approximate repeatability less than 5% of A-basis yield strength.

Dissecting the low catalytic capability of flavin-dependent halogenases

Although flavin-dependent halogenases (FDHs) are attractive biocatalysts, their practical applications are limited because of their low catalytic efficiency. Here, we investigated the reaction mechanisms and structures of tryptophan 6-halogenase (Thal) from Streptomyces albogriseolususing stopped-flow, rapid-quench flow, QM/MM calculations, crystallography and detection of intermediate (hypohalous acid (HOX)) liberation. We found that the key flavin intermediate, C4a-hydroperoxyflavin (C4aOOH-FAD), formed by Thal and other FDHs(tryptophan 7-halogenase (PrnA) and tryptophan 5-halogenase (PyrH)), can react with I-, Br-, and Cl-but not F-, to form C4a-hydroxyflavin and HOX. Our experiments revealed that I-reacts with C4aOOH-FAD the fastest with the lowest energy barrier, and have shown for the first time that a significant amount of the HOX formed leaks out as free HOX. This leakage is probably a major cause of low product coupling ratios in all FDHs. Site-saturation mutagenesis of Lys79 showed that changing Lys79 to any other amino acid resulted in an inactive enzyme. However, the levels of liberated HOX of these variants are all similar, implying that Lys79 probably does not form a chloramine or bromamine intermediateas previously proposed. Computational calculations revealed that Lys79 has an abnormally lower pKa compared to other Lys residues, implying that the catalytic Lys may act as a proton donor in catalysis. Analysis of new X-ray structures of Thal also explains why pre-mixing of FDHs with FADH- generally results in abolishment of C4aOOH-FAD formation. These findings reveal the hidden factors restricting FDHs capability which should be useful for future development of FDHs applications.

Constraints on non-isothermal diffusion modeling: An experimental analysis and error assessment using halogen diffusion in melts

Diffusion chronometry on zoned crystals allows constraining duration of magmatic evolution and storage of crystals once temperatures are precisely known. However, non-isothermal diffusion is common in natural samples, and thus timescales may not be determined with confidence while assuming isothermal conditions. The “non-isothermal diffusion incremental step (NIDIS) model” (Petrone et al. 2016) is proposed for such cases for a non-isothermal diffusive analysis. We conducted diffusion experiments with stepwise temperature changes to analyze and test the model, evaluated the associated errors and improved the accuracy by suggesting an alternative algorithm to model diffusion times. We used Cl and F (≤0.4 wt%) as the diffusing elements in nominally anhydrous (H2O ≤ 0.3 wt%) phonolitic melt with composition of Montana Blanca (Tenerife, Spain) in an experimental setup that successively generates multiple diffusive interfaces for different temperatures by adding glass blocks of different Cl and F concentrations. This compound set of two diffusion interfaces represents distinct compositional zones that diffusively interact at different temperatures, which can be taken as an equivalent to non-isothermal diffusion in zoned magmatic crystals. The starting temperature ranged from 975 to 1150 °C, and each set of experiments included a temperature change of 85–150 °C and a total duration of 8–12 h. The experiments were carried out in an internally heated pressure vessel equipped with a rapid quench device at 1 kbar pressure. Cl and F concentration profiles were obtained from the quenched samples by electron microprobe analysis. Although the estimated diffusion times from the NIDIS-model matched well with true experimental values, the errors on estimated timescales, due to errors in curve-fitting and uncertainty in temperature, were ±10–62% (1σ). The errors are much larger at 61–288% (1σ) when the uncertainty in diffusivity parameters is included. We discuss the efficiency and limitations of the model, assess the contribution from different sources of error, and their extent of propagation. A simpler alternative algorithm is proposed that reduces errors on the estimates of diffusion time to 10–32% (1σ) and 60–75% (1σ), with and without including uncertainty in diffusivity parameters, respectively. Using this new algorithm, we recalculated the individual diffusion times for the clinopyroxene crystals analyzed by Petrone et al. (2016) and obtained a significantly reduced error of 26–40% compared to the original error of 61–100%. We also analyzed a sanidine megacryst from Taapaca volcano (N. Chile) as a test case for non-isothermal modeling and obtained diffusion times of 1.5–9.4 ky, which is significantly different from isothermal analyses including a previous study on similar sample. In this analysis, the error estimated by our new method is reduced by 63–70%.

Kinetically-arrested single-polymer nanostructures from amphiphilic mikto-grafted bottlebrushes in solution: a simulation study

Molecular bottlebrushes under a rapid quench into a selective solvent can self-assemble into kinetically-arrested nanostructures.

Vortex Fluidic Ethenolysis, Integrating a Rapid Quench of Ruthenium Olefin Metathesis Catalysts

Ruthenium-catalysed ethenolysis occurs in a vortex fluidic device (VFD) – a scalable, thin-film microfluidic continuous flow process. This process takes advantage of the efficient mass transfer of gaseous reagents into the dynamic thin film of liquid. Also reported is the rapid quenching of the ruthenium-based olefin metathesis catalyst by the addition of a saturated solution of N-acetyl-l-cysteine in MeCN, as a convenient alternative to previously reported quenching methods.

Nitrogen Solubility in Liquid Ni-V, Ni-Ta, Ni-Cr-V, and Ni-Cr-Ta Alloys

An investigation has been made concerning the solubility of nitrogen in liquid binary alloys (Ni-V and Ni-Ta) and ternary alloys (Ni-Cr-V and Ni-Cr-Ta) by sampling method. The experiments were carried out in the temperature range from 1773 K to 1873 K and under the nitrogen partial pressure up to 1.0 bar. A technique involving induction melting and a rapid quench device has been used in this study. It has been found that Sieverts’ law successfully describes the nitrogen dissolution in all these liquid alloys up to 1.0 bar of nitrogen gas partial pressure. The additions of vanadium, tantalum and chromium significantly increase the nitrogen solubility, especially vanadium-alloying addition. Furthermore, we have determined the interaction parameters, enthalpies and entropies of nitrogen dissolution in these liquid alloys.