Phase-Sensitive Vibrational Sum and Difference Frequency-Generation Spectroscopy Enabling Nanometer-Depth Profiling at Interfaces

The unique physical and chemical properties of interfaces are governed by a finite depth that describes the transition from the topmost atomic layer to the properties of the bulk material. Thus, understanding the physical nature of interfaces requires detailed insight into the different structures, chemical compositions, and physical processes that form this interfacial region. Such insight has traditionally been difficult to obtain from experiments, as it requires a combination of structural and chemical sensitivity with spatial depth resolution on the nanometer scale. In this contribution, we present a vibrational spectroscopic approach that can overcome these limitations. By combining phase-sensitive sum and difference frequency-generation (SFG and DFG, respectively) spectroscopy and by selectively determining different nonlinear interaction pathways, we can extract precise depth information and correlate these to specific vibrationally resonant modes of interfacial species. We detail the mathematical framework behind this approach and demonstrate the performance of this technique in two sets of experiments on selected model samples. An analysis of the results shows an almost perfect match between experiment and theory, confirming the practicability of the proposed concept under realistic experimental conditions. Furthermore, in measurements with self-assembled monolayers of different chain lengths, we analyze the spatial accuracy of the technique and find that the precision can even reach the sub-nanometer regime. We also discuss the implications and the information content of such depth-sensitive measurements and show that the concept is very general and goes beyond the analysis of the depth profiles. The presented SFG/DFG technique offers new perspectives for spectroscopic investigations of interfaces in various material systems by providing access to fundamental observables that have so far been inaccessible by experiments. Here, we set the theoretical and experimental basis for such future investigations

Powder Bed Fusion Additive Manufacturing Using Critical Raw Materials: A Review.

The term "critical raw materials" (CRMs) refers to various metals and nonmetals that are crucial to Europe's economic progress. Modern technologies enabling effective use and recyclability of CRMs are in critical demand for the EU industries. The use of CRMs, especially in the fields of biomedicine, aerospace, electric vehicles, and energy applications, is almost irreplaceable. Additive manufacturing (also referred to as 3D printing) is one of the key enabling technologies in the field of manufacturing which underpins the Fourth Industrial Revolution. 3D printing not only suppresses waste but also provides an efficient buy-to-fly ratio and possesses the potential to entirely change supply and distribution chains, significantly reducing costs and revolutionizing all logistics. This review provides comprehensive new insights into CRM-containing materials processed by modern additive manufacturing techniques and outlines the potential for increasing the efficiency of CRMs utilization and reducing the dependence on CRMs through wider industrial incorporation of AM and specifics of powder bed AM methods making them prime candidates for such developments

Suppressing the Use of Critical Raw Materials in Joining of AISI 304 Stainless Steel Using Activated Tungsten Inert Gas Welding

The aim of this study was to study the influence of TiO2 coating for its efficacy during the activated-tungsten inert gas (TIG) welding and to suppress the use of consumables that are rich in critical raw materials. Post-welding penetration depth, particle size distribution, microstructure, and microhardness of welded samples were assessed. Based on these results, it was found that there is no direct correlation between the weld metal surface area and the coating. The particle size in the coating, although, seemed to have played an important role, e.g., nanoparticles resulted in an increased penetration depth and depth/width (D/W) ratio as opposed to the submicron-sized particles. The most optimal welding condition resulted when a mixture of submicron-sized and nanometric-sized particles were used. It was demonstrated by the Zeta analyser results that the micron particles rub the nanoparticles due to mechanical friction resulting in smaller oxide particle formation in the coating. Finally, the presence of Marangoni convection in TIG and reversed Marangoni convection in the activated TIG (A-TIG) process were proven by means of the microstructure analysis and measurement, which were found to be positively correlate

THz and IR spectroscopy of endofullerene H₂O@C₆₀

Terahertz time-domain and infrared Fourier-transform spectroscopy techniques are used to investigate the properties of H2O@C60 endofullerene in 6 K – 300 K temperature interval. A number of absorption lines associated with rotational transitions of water molecule entrapped inside C60 cages are observed and assigned. Fitting the resonances with Lorenzian lineshapes allowed us to obtain temperature dependencies of absorption lines parameters – frequency, strength and damping

Rotational coherence of encapsulated ortho and para water in fullerene-C₆₀ revealed by time-domain terahertz spectroscopy

We resolve the real-time coherent rotational motion of isolated water molecules encapsulated in fullerene-C60 cages by time-domain terahertz (THz) spectroscopy. We employ single-cycle THz pulses to excite the low-frequency rotational motion of water and measure the subsequent coherent emission of electromagnetic waves by water molecules. At temperatures below ~ 100 K, C60 lattice vibrational damping is mitigated and the quantum dynamics of confined water are resolved with a markedly long rotational coherence, extended beyond 10 ps. The observed rotational transitions agree well with low-frequency rotational dynamics of single water molecules in the gas phase. However, some additional spectral features with their major contribution at ~2.26 THz are also observed which may indicate interaction between water rotation and the C60 lattice phonons. We also resolve the real-time change of the emission pattern of water after a sudden cooling to 4 K, signifying the conversion of ortho-water to para-water over the course of 10s hours. The observed long coherent rotational dynamics of isolated water molecules confined in C60 makes this system an attractive candidate for future quantum technology

Of the importance of a leaf: the ethnobotany of sarma in Turkey and the Balkans

BACKGROUND: Sarma - cooked leaves rolled around a filling made from rice and/or minced meat, possibly vegetables and seasoning plants - represents one of the most widespread feasting dishes of the Middle Eastern and South-Eastern European cuisines. Although cabbage and grape vine sarma is well-known worldwide, the use of alternative plant leaves remains largely unexplored. The aim of this research was to document all of the botanical taxa whose leaves are used for preparing sarma in the folk cuisines of Turkey and the Balkans. Methods: Field studies were conducted during broader ethnobotanical surveys, as well as during ad-hoc investigations between the years 2011 and 2014 that included diverse rural communities in Croatia, Bosnia and Herzegovina, Serbia, Kosovo, Albania, Macedonia, Bulgaria, Romania, and Turkey. Primary ethnobotanical and folkloric literatures in each country were also considered. Results: Eighty-seven botanical taxa, mainly wild, belonging to 50 genera and 27 families, were found to represent the bio-cultural heritage of sarma in Turkey and the Balkans. The greatest plant biodiversity in sarma was found in Turkey and, to less extent, in Bulgaria and Romania. The most commonly used leaves for preparing sarma were those of cabbage (both fresh and lacto-fermented), grape vine, beet, dock, sorrel, horseradish, lime tree, bean, and spinach. In a few cases, the leaves of endemic species (Centaurea haradjianii, Rumex gracilescens, and R. olympicus in Turkey) were recorded. Other uncommon sarma preparations were based on lightly toxic taxa, such as potato leaves in NE Albania, leaves of Arum, Convolvulus, and Smilax species in Turkey, of Phytolacca americana in Macedonia, and of Tussilago farfara in diverse countries. Moreover, the use of leaves of the introduced species Reynoutria japonica in Romania, Colocasia esculenta in Turkey, and Phytolacca americana in Macedonia shows the dynamic nature of folk cuisines. Conclusion: The rich ethnobotanical diversity of sarma confirms the urgent need to record folk culinary plant knowledge. The results presented here can be implemented into initiatives aimed at re-evaluating folk cuisines and niche food markets based on local neglected ingredients, and possibly also to foster trajectories of the avant-garde cuisines inspired by ethnobotanical knowledge

Can rights stop the wrongs? Exploring the connections between framings of sex workers’ rights and sexual and reproductive health

<p>Abstract</p> <p>Background</p> <p>There is growing interest in the ways in which legal and human rights issues related to sex work affect sex workers’ vulnerability to HIV and abuses including human trafficking and sexual exploitation. International agencies, such as UNAIDS, have called for decriminalisation of sex work because the delivery of sexual and reproductive health services is affected by criminalisation and social exclusion as experienced by sex workers. The paper reflects on the connections in various actors’ framings between sex workers sexual and reproductive health and rights (SRHR) and the ways that international law is interpreted in policing and regulatory practices.</p> <p>Methods</p> <p>The literature review that informs this paper was carried out by the authors in the course of their work within the Paulo Longo Research Initiative. The review covered academic and grey literature such as resources generated by sex worker rights activists, UN policy positions and print and online media. The argument in this paper has been developed reflectively through long term involvement with key actors in the field of sex workers’ rights.</p> <p>Results</p> <p>International legislation characterises sex work in various ways which do not always accord with moves toward decriminalisation. Law, policy and regulation at national level and law enforcement vary between settings. The demands of sex worker rights activists do relate to sexual and reproductive health but they place greater emphasis on efforts to remove the structural barriers that limit sex workers’ ability to participate in society on an equal footing with other citizens.</p> <p>Discussion and conclusion</p> <p>There is a tension between those who wish to uphold the rights of sex workers in order to reduce vulnerability to ill-health and those who insist that sex work is itself a violation of rights. This is reflected in contemporary narratives about sex workers’ rights and the ways in which different actors interpret human rights law. The creation of regulatory frameworks around sex work that support health, safety and freedom from abuse requires a better understanding of the broad scope of laws, policies and enforcement practices in different cultural contexts and economic settings, alongside reviews of UN policies and human rights conventions.</p