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Hierarchical microstructures are created when additional γ particles form in γ’ precipitates and they are linked to improved strength and creep properties in high-temperature alloys. Here, we follow the formation and evolution of a hierarchical microstructure in Ni86.1Al8.5Ti5.4 by in situ synchrotron X-ray diffraction at 1023 K up to 48 h to derive the lattice parameters of the γ matrix, γ’ precipitates and γ particles and misfits between phases. Finite element method-based computer simulations of hierarchical microstructures allow obtaining each phase's lattice parameter, thereby aiding peak identification in the in situ X-ray diffraction data. The simulations further give insight into the heterogeneous strain distribution between γ’ precipitates and γ particles, which gives rise to an anisotropic diffusion potential that drives the directional growth of γ particles. We rationalize a schematic model for the growth of γ particles, based on the Gibbs-Thomson effect of capillary and strain-induced anisotropic diffusion potentials. Our results highlight the importance of elastic properties, elastic anisotropy, lattice parameters, and diffusion potentials in controlling the behavior and stability of hierarchical microstructures.
KEY COMPARISON
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.c, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2012. Twenty National Measurement Institutes or Designated Institutes and the BIPM participated. Participants were required to assign the mass fraction of valine present as the main component in the comparison sample for CCQM-K55.c. The comparison samples were prepared from analytical grade L-valine purchased from a commercial supplier and used as provided without further treatment or purification.
Valine was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of low structural complexity [molecular weight range 100300] and high polarity (pKOW > –2).
The KCRV for the valine content of the material was 992.0 mg/g with a combined standard uncertainty of 0.3 mg/g. The key comparison reference value (KCRV) was assigned by combination of KCRVs assigned from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 1 mg/g to 6 mg/g when using mass balance based approaches alone, 2 mg/g to 7 mg/g using quantitative 1H NMR (qNMR) based approaches and from 1 mg/g to 2.5 mg/g when a result obtained by a mass balance method was combined with a separate qNMR result.
The material provided several analytical challenges. In addition to the need to identify and quantify various related amino acid impurities including leucine, isoleucine, alanine and a-amino butyrate, care was required to select appropriate conditions for performing Karl Fischer titration assay for water content to avoid bias due to in situ formation of water by self-condensation under the assay conditions. It also proved to be a challenging compound for purity assignment by qNMR techniques.
There was overall excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content, residual solvent and total non-volatile content of the sample. Appropriate technical justifications were developed to rationalise observed discrepancies in the limited cases where methodology differences led to inconsistent results.
The comparison demonstrated that to perform a qNMR purity assignment the selection of appropriate parameters and an understanding of their potential influence on the assigned value is critical for reliable implementation of the method, particularly when one or more of the peaks to be quantified consist of complex multiplet signals.
The demonstration of competency and equivalence for the assessment of levels of contaminants and nutrients in primary foodstuffs is a priority within the 10-year strategy for the OAWG Track A core comparisons. The measurements are core challenges for reference material producers and providers of calibration Services. This key comparison related to low polarity analytes in a high fat, low protein, low carbohydrate food matrix and Benzo[a]pyrene in edible oil was the model System selected to align with this class within the OAWG strategy. Evidence of successful participation in formal, relevant international comparisons is needed to document measurement capability claims (CMCs) made by national metrology institutes (NMIs) and designated institutes (Dis). 16 National Metrology Institutions participated in the Track A Key Comparison CCQM-K146 Low-Polarity Analyte in high fat food: Benzo[a]pyrene in Olive Oil. Participants were requested to evaluate the mass fractions, expressed in µg/kg, of Benzo[a]pyrene in the olive oil material. The KCRV was determined from the results of all NMIs/DIs participating in the key comparison that used appropriately validated methods with demonstrated metrological traceability. Different methods such as liquid-liquid extraction, GPC and SPE were applied in the sample pretreatment and HPLC-FLD, HPLC-MS/MS, and GC-MS or GC-MS/MS were applied for detection by the participants. The mass fractions for BaP were in the range of (1.78 to 3.09) µg/kg with Standard uncertainties of (0.026 to 0.54) µg/kg, with corresponding relative Standard uncertainties from 0.9% to 21%. Five labs withdrew their result from the Statistical evaluation of the KCRV for technical reasons. One lab was excluded from the KCRV evaluation, as they did not meet the CIPM metrological traceability requirements. A Hierarchical Bayes option was selected for the KCRV value, which was determined as 2.74 µg/kg with a Standard uncertainty of 0.03 µg/kg. The 10 institutes those were included in the calculation of the consensus KCRV all agreed within their Standard uncertainties. Successful participation in CCQM-K146 demonstrates the measurement capabilities in determining mass fraction of organic compounds, with molecular mass of 100 g/mol to 500 g/mol, having low polarity pKow < -2, in mass fraction range from 0.1 µg/kg to 1000 µg/kg in a high fat, low protein, low carbohydrate food matrix.
Phase transitions are a common phenomenon in condensed matter and act as a critical degree of freedom that can be employed to tailor the mechanical or electronic properties of materials. Understanding the fundamental mechanisms of the thermodynamics and kinetics of phase transitions is, thus, at the core of modern materials design. Conventionally, studies of phase transitions have, to a large extent, focused on pristine bulk phases. However, realistic materials exist in a complex form; their microstructures consist of different point and extended defects. The presence of defects impacts the thermodynamics and kinetics of phase transitions, but has been commonly ignored or treated separately. In recent years, with the significant advances in theoretical and experimental techniques, there has been an increasing research interest in modeling and characterizing how defects impact or even dictate phase transitions. The present review systematically discusses the recent progress in understanding the kinetics of defect-characterized phase transitions, derives the key mechanisms underlying these phase transitions, and envisions the remaining challenges and fruitful research directions. We hope that these discussions and insights will help to inspire future research and development in the field.
Full penetration laser welding was carried out on a 10 mm steel plate using a 16 kW maximum power continuous wave thin disk laser. Upper surface and lower surface of molten pool were observed synchronously with two high speed CCD cameras during the welding process. The lower surface was much longer and more unstable than the upper one. A three dimensional laser deep penetration welding model in which volume of fluid (VOF) method was combined with a ray-tracing algorithm was used to simulate the dynamic coupling between keyhole and molten pool in laser full penetration welding. The calculated weld cross-section morphology and molten pool length on both upper side and lower side agree well with experimental results. Evolution of molten pool in lower side during full penetration laser welding was analyzed, periodical features of energy coupling, molten pool behavior and keyhole dynamics in laser full penetration welding were identified and discussed.
Sixteen laboratories have performed electrochemical noise (EN) measurements based on two systems. The first uses a series of dummy cells consisting of a 'star' arrangement of resistors in order to validate the EN measurement equipment and determine its baseline noise performance, while the second system, based on a previous round-robin in the literature, examines the corrosion of aluminium in three environments. All participants used the same measurement protocol and the data reporting and analysis were performed with automatic procedures to avoid errors. The measurement instruments used in the various laboratories include commercial general-purpose potentiostats and custom-built EN systems. The measurements on dummy cells have demonstrated that few systems are capable of achieving instrument noise levels comparable to the thermal noise of the resistors, because of its low level. However, it is of greater concern that some of the instruments exhibited significant artefacts in the measured data, mostly because of the absence of anti-aliasing filters in the equipment or because the way it is used. The measurements on the aluminium samples involve a much higher source noise level during pitting corrosion, and most (though not all) instruments were able to make reliable measurements. However, during passivation, the low level of noise could be measured by very few systems. The round-robin testing has clearly shown that improvements are necessary in the choice of EN measurement equipment and settings and in the way to validate EN data measured. The results emphasise the need to validate measurement systems by using dummy cells and the need to check systematically that the noise of the electrochemical cell to be measured is significantly higher than the instrument noise measured with dummy cells of similar impedance.
Exceptional ion mobility spectrometry mass spectrometry (IMS-MS) developments by von Helden, Jarrold, and Clemmer provided technology that gives a view of chemical/biological compositions previously not achievable. The ionization method of choice used with IMS-MS has been electrospray ionization (ESI). In this Special issue contribution, we focus on fundamentals of heretofore unprecedented means for transferring volatile and nonvolatile compounds into gas-phase ions singly and multiply charged. These newer ionization processes frequently lead to different selectivity relative to ESI and, together with IMS-MS, may provide a more comprehensive view of chemical compositions directly from their original Environment such as surfaces, e.g., tissue. Similarities of results using solvent- and matrix-assisted ionization are highlighted, as are differences between ESI and the inlet ionization methods, especially with mixtures such as bacterial extracts. Selectivity using different matrices is discussed, as are results which add to our fundamental knowledge of inlet ionization as well as pose additional avenues for inquiry. IMS-MS provides an opportunity for comparison studies relative to ESI and will prove valuable using the new ionization technologies for direct analyses. Our hypothesis is that some ESI-IMS-MS applications will be replaced by the new ionization processes and by understanding mechanistic aspects to aid enhanced source and method developments this will be hastened.
An assessment of the elastic-plastic buckling limit state for multi-strake wind turbine support towers poses a particular challenge for the modern finite element analyst, who must competently navigate numerous modelling choices related to the tug-of-war between meshing and computational cost, the use of solvers that are robust to highly nonlinear behaviour, the potential for multiple near-simultaneously critical failure locations, the complex issue of imperfection sensitivity and finally the interpretation of the data into a safe and economic design.
This paper reports on an international ‘round-robin’ exercise conducted in 2022 aiming to take stock of the computational shell buckling expertise around the world which attracted 29 submissions. Participants were asked to perform analyses of increasing complexity on a standardised benchmark of an 8-MW multi-strake steel wind turbine support tower segment, from a linear elastic stress analysis to a linear bifurcation analysis to a geometrically and materially nonlinear buckling analysis with imperfections. The results are a showcase of the significant shell buckling expertise now available in both industry and academia.
This paper is the first of a pair. The second paper presents a detailed reference solution to the benchmark, including an illustration of the Eurocode-compliant calibration of two important imperfection forms.
An international interlaboratory comparison of the measurement capabilities of four National Metrology Institutes (NMIs) and one Designated Institute (DI) in the determination of the chemical composition of thin Fe-Ni alloy films was conducted via a key comparison (K-67) of the Surface Analysis Working Group of the Consultative Committee for Amount of Substance. This comparison was made using XPS (four laboratories) and AES (one laboratory) measurements. The uncertainty budget of the measured chemical composition of a thin alloy film was dominated by the uncertainty of the certified composition of a reference specimen which had been determined by inductively coupled plasma mass spectrometry using the isotope dilution method. Pilot study P-98 showed that the quantification using relative sensitivity factors (RSFs) of Fe and Ni derived from an alloy reference sample results in much more accurate result in comparison to an approach using RSFs derived from pure Fe and Ni films. The individual expanded uncertainties of the participants in the K-67 comparison were found to be between 2.88 and 3.40 atomic %. The uncertainty of the key comparison reference value (KCRV) calculated from individual standard deviations and a coverage factor (k) of 2 was 1.23 atomic %.
The Key Comparison K67 and the parallel Pilot Study P108 on quantitative analysis of thin alloy films have been completed in the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The aim of these inter-laboratory comparisons is to determine the degree of equivalence in the measurement capability of national metrology institutes (NMIs) and designated institutes (DIs) for the determination of the composition of thin alloy films. The measurand is expressed in atomic percent. A Fe-Ni alloy film with a certified composition was available for the participants of the inter-laboratory comparison. It has been used as a reference specimen to determine the relative sensitivity factors (RSF) of Fe and Ni for the different analytical methods used by the participants to determine the composition of the test sample. As was shown in the preceding Pilot Study P98, the degrees of equivalence in the measurement capabilities of the participants can be improved in that way. The composition of the reference specimen was certified by inductively coupled plasma mass spectrometry (ICP-MS) using the isotope dilution method. The in-depth and lateral homogeneity, determined in terms of elemental composition, of the certified reference sample and the unknown test sample were confirmed by secondary ion mass spectrometry (SIMS) using C60 primary ions by the leading laboratory. Five laboratories participated in the key comparison. Four of them used x-ray photoelectron spectroscopy (XPS) and one Auger electron spectroscopy (AES). One laboratory participated in the parallel P108 pilot study using electron probe micro analysis with an energy-dispersive spectrometer (ED EPMA) and XPS.
Sialic acid (SA) is a monosaccharide usually linked to the terminus of glycan chains on the cell surface. It plays a crucial role in many biological processes, and hypersialylation is a common feature in cancer. Lectins are widely used to analyze the cell surface expression of SA.
However, these protein molecules are usually expensive and easily denatured, which calls for the development of alternative glycan-specific receptors and cell imaging technologies. In this study, SA-imprinted fluorescent core-shell molecularly imprinted polymer particles (SA-MIPs) were employed to recognize SA on the cell surface of cancer cell lines. The SA-MIPs improved suspensibility and scattering properties compared with previously used core-shell SA-MIPs. Although SA-imprinting was performed using SA without preference for the alpha-2,3- and alpha-2,6-SA forms, we screened the cancer cell lines analyzed using the lectins Maackia Amurensis Lectin I (MAL I, alpha-2,3-SA) and Sambucus Nigra Lectin (SNA, alpha-2,6-SA). Our results show that the selected cancer cell lines in this study presented a varied binding behavior with the SA-MIPs. The binding pattern of the lectins was also demonstrated. Moreover, two different pentavalent SA conjugates were used to inhibit the binding of the SA-MIPs to breast, skin, and lung cancer cell lines, demonstrating the specificity of the SA-MIPs in both flow cytometry and confocal fluorescence microscopy. We concluded that the synthesized SA-MIPs might be a powerful future tool in the diagnostic analysis of various cancer cells.
Welding is one of the most common methods in industrial practice for joining components. Its main advantages are high speed in manufacturing combined with low costs and, usually, a high degree of flexibility, integrity and reliability. Nevertheless, welding is a highly complex metallurgical process and, therefore, weldments are susceptible to material discontinuities, flaws and residual stresses which may lead to structural failure and life time reduction. As a consequence weldments are an important field of fracture mechanics methods although its application is more complex than for homogeneous or non-welded structures. The aim of the paper is to provide an overview on the current state of fracture mechanics application to weldments. It starts by discussing the specific features which any fracture mechanics analysis of weldments has to take into account. Then, the experimental determination of fracture toughness, fatigue crack propagation and tensile properties of weldments is addressed. Finally, the analytical determination of the crack driving force in components and structural integrity assessment approaches for weldments are presented.
Lanthanide-doped upconversion nanoparticles (UCNPs) are of great interest for biomedical applications. Currently, the applicability of UCNP bionanotechnology is hampered by the generally low luminescence intensity of UCNPs and inefficient energy Transfer from UCNPs to surface-bound chromophores used e.g. for photodynamic therapy or analyte sensing. In this work, we address the low-Efficiency issue by developing versatile core-Shell nanostructures, where high-concentration sensitizers and activators are confined in the core and Shell Region of representative hexagonal NaYF2:Yb,Er UCNPs. After Doping concentration optimization, the sensitizer-rich core is able to harvest/accumulate more excitation energy and generate almost one order of Magnitude higher luminescence intesity than conventional homogeneously doped nanostructures. At the same time, the activator Ions located in the Shell enable a ~6 times more efficient resonant energy Transfer from UCNPs to surface-bound acceptor dye molecules due to the short distance between donor-acceptor pairs. Our work provides new insights into the rational design of UCNPs and will greatly encrease the General applicability of upconversion nanotechnologies.
Light-induced NO release based on exogenous NO donors has attracted substantial attention in clinical applications; the induction light source usually converts near-infrared light to blue or ultraviolet light.
However, the low efficiency of near-infrared light-assisted chemical light energy conversion remains a challenge, especially for NaYF4:Yb3+/Tm3+ photoconverting near-infrared light to ultraviolet (UV) and blue light. In this paper, a luminescence-enhanced strategy is reported by doping Ca2+ into NaYF4:Yb3+/Tm3+ and coating it with NaGdF4 through a two-step solvothermal method. Then, UCNPs modified with methyl-b-cyclodextrin (M-b-CD) are loaded on a ruthenium nitrosyl complex [(3)Ru(NO)(Cl)] as nitric oxide release-molecules (NORMs). X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS) data demonstrated that Ca2+ was successfully doped into NaYF4:Yb3+/Tm3+ nanoparticles as the core, and a pure hexagonal phase, NaYF4, was obtained from the doping of Ca2+. TEM revealed that the crystallinity was significantly improved after Ca2+ doping, and the core–shell structure was successfully synthesized, with NaGdF4 directionally grown on the NaYF4:Ca/Yb/Tm core. Fluorescence tests showed that, especially in the ultraviolet and blue light excitation wavelength regions, the UC emission intensity of the Ca-doped NaYF4:Yb3+/Tm3+@NaGdF4 core–shell UCNPs increased by 302.95 times vs. NaYF4:Yb3+/Tm3+ UCNPs. Finally, the release of NO was tested by the Griess method. Under 980 nm irradiation, the cell viability distinctly decreased with increasing UCNPs@M-b-CD-NORMs concentration. This study Shows that NORM release of NO is triggered by enhanced up-converted UV and blue light, which can be used for the development of UV photo-sensitive drugs.
Real-time monitoring of newly acidified organelles during autophagy in living cells is highly desirable for a better understanding of intracellular degradative processes. Herein, we describe a reaction-based boron dipyrromethene (BODIPY) dye containing strongly electron-withdrawing diethyl 2-cyanoacrylate groups at the α-positions. The probe exhibits intense red fluorescence in acidic organelles or the acidified cytosol while negligible fluorescence in other regions of the cell. The underlying mechanism is a nucleophilic reaction at the central meso-carbon of the indacene core, resulting in the loss of π-conjugation entailed by dramatic spectroscopic changes of more than 200 nm between its colorless, non-fluorescent leuco-BODIPY form and its red and brightly emitting form. The reversible transformation between red fluorescent BODIPY and leuco-BODIPY along with negligible cytotoxicity qualifies such dyes for rapid and direct intracellular lysosome imaging and cytosolic acidosis detection simultaneously without any washing step, enabling the real-time monitoring of newly acidified organelles during autophagy.
Dehydration is a common process occurring in natural environments, rocks, and building materials. Suitable methods for monitoring the changing moisture content should be identified.
We have investigated the impact of dehydration of sandstones on complex conductivity spectra. Spectral induced polarization measurements were performed on five sandstone samples during evaporative drying. The complex conductivity spectra indicate considerable changes with decreasing saturation. The relationship between conductivity and saturation can be described by a power law known as the second empirical Archie equation. Separate saturation exponents have been determined for the real and imaginary parts of conductivity. The imaginary part of conductivity indicates higher saturation exponents for the investigated sandstones compared to the real part. Obviously, the saturation exponents depend on the method used for changing water saturation. Evaporative drying, which is used in our experiments, causes an increase of pore-water salinity and results in lower saturation exponents for the real part of conductivity but higher exponents for the imaginary part in comparison with the classical imbibition/Drainage technique. We evaluate a theoretical approach that considers the influence of pore water salinity on the saturation exponents of the real and imaginary parts of conductivity. The complex conductivity spectra are processed by a Debye decomposition procedure.
The resulting integrating parameters such as direct current resistivity, total chargeability, normalized chargeability, and mean relaxation time indicate a power law dependence on saturation. Our experiments indicate that the imaginary part of conductivity and normalized chargeability have a high sensitivity related to the drying process of rocks and might be suitable indicators to Monitor the changes of moisture content in sandstones.
Optimizing the properties of next-generation high-temperature and corrosion-resistant alloys is rooted in balancing structure-property relationships and phase chemistry. Here, we implement a complementary approach based on transmission electron microscopy (TEM) and atom probe tomography (APT) to ascertain aspects of hierarchical phase separation behavior, by understanding the microstructural evolution and the three-dimensional (3D) nanochemistry of a single crystal Fe79.5Si15.5V5.0 (at%) alloy. A maze-like hierarchical microstructure forms, in which a complex network of metastable disordered α plates (A2 phase) emerges within ordered α1 precipitates (D03 phase). The supersaturation in α1 (D03) precipitates with Fe and V drives the formation of α (A2) plates. The morphology of α (A2) plates is discussed concerning crystal structure, lattice misfit, and elastic strain. Phase compositions and a ternary phase diagram aid the thermodynamic assessment of the hierarchical phase separation mechanism via the Gibbs energy of mixing. A perspective on the stabilization of hierarchical microstructures beyond Fe79.5Si15.5V5.0 is elaborated by comparing hierarchical alloys. We find that the ratio of elastic anisotropy (Zener ratio) serves as a predictor of the hierarchical particles’ morphology. We suggest that the strengthening effect of hierarchical microstructures can be harnessed by improving the temporal and thermal stability of hierarchical particles. This can be achieved through phase-targeted alloying aiming at the hierarchical particles phase by considering the constituents partitioning behavior. Beyond Fe79.5Si15.5V5.0, our results demonstrate a potential pathway for improving the properties of high-temperature structural materials.
Oxidative aging induces significant stiffening of asphalt binders that leads to a pronounced reduction in the overall durability of asphalt pavements. The strategic implementation of antioxidant additives provides a potential solution to alleviate this issue. This work presents results from the second phase of the global consortium for antioxidants research aimed at investigating the effectiveness of potential antioxidants in increasing the durability of asphalt binders. Sixteen laboratories around the world participated in this effort and a total of 28 binders from diverse geographical regions were tested. Two promising antioxidants, namely zinc diethyldithiocarbamate (ZDC) and kraft lignin were evaluated in this phase and blended with the binders at specific proportions. Subsequently, a comprehensive investigation was conducted to assess rheological characteristics and chemical properties of the various blends, utilising Dynamic Shear Rheometer (DSR) measurements and Fourier Transform Infrared (FTIR) Spectroscopy. The findings indicate that additives such as ZDC hold considerable promise as an effective antioxidant, particularly when considering a wide diversity of binders. In general, its incorporation does not compromise the rutting performance of the binders and significantly improves fatigue performance. Therefore, research efforts should be focused on exploring additional facets to assess its practical applicability in field.