Exploring pressure effects on metallic nanoparticles and surrounding media through plasmonic sensing

The sensing capabilities of gold nanorods under high-pressure conditions were investigated in methanol-ethanol mixtures (up to 13 GPa) and in water (up to 9 GPa) through their optical extinction. The longitudinal SPR band of AuNR exhibits a redshift with pressure which is the result of two main competing effects: compression of the conduction electrons which increases the bulk plasma frequency (blueshift) and increase in the solvent density (redshift). The variation in de SPR peak wavelength allows us to estimate the bulk modulus of the gold nanoparticles with a precision of 10 % and to obtain analytical functions providing the pressure dependence of the refractive index of water in three phases: liquid, ice VI and ice VII. Furthermore, the SPR band shows abrupt jumps at the liquid to ice phase VI and ice phase VII transitions, which are in accordance with the first-order character of these transitions.Financial support from Project PGC2018-101464-B-I00 (FEDER) and MALTA-Consolider Team (RED2018-102612-T) of the Ministerio de Ciencia, Innovación y Universidades is acknowledged

Performance of NiCrAlY Coatings Deposited by Oxyfuel Thermal Spraying in High Temperature Chlorine Environment

A microcrystalline Ni-22Cr-10Al-1Y (wt.%) coating was deposited on AISI 304 stainless steel by the oxyfuel thermal spray technique. The deposited coating was subjected to heat treatment to improve the microstructure characteristics and its corresponding high-temperature properties. The isothermal high-temperature corrosion behavior at 650 and 700 °C in synthetic air and in the presence of 1% Cl2 was investigated using thermogravimetric analysis, x-ray diffraction, and scanning electron microscopy with energy-dispersive x-ray spectroscopy. The results indicated that the deposited NiCrAlY coating possessed acceptable oxidation-corrosion resistance at 650 °C owing to the formation of extensive amounts of the protective oxide of Cr2O3; NiO and a lesser amount of a Cr1.12 Ni2,88 metallic phase are also formed. At 700 °C, the coating lost its protective characteristic because of the excessive consumption of thermodynamically stable phases by oxidation-chlorination process. In this case, the steel base and the coating were attacked by chlorine during the exposure time; the mass gain of the NiCrAlY coating was slightly higher and provided only a limited protection up to 11 h; thereafter, breakdown of the layer of oxides occurred and this is attributed to the formation of non-protective oxides mainly β-Fe2O3 and Fe21.33O32 and the depletion of chromium

Pressure-Induced Phase-Transition Sequence In Cof 2 : An Experimental And First-Principles Study On The Crystal, Vibrational, And Electronic Properties

We report a complete structural study of CoF2 under pressure. Its crystal structure and vibrational and electronic properties have been studied both theoretically and experimentally using first-principles density functional theory (DFT) methods, x-ray diffraction, x-ray absorption at Co K-edge experiments, Raman spectroscopy, and optical absorption in the 0–80 GPa range. We have determined the structural phase-transition sequence in CoF2 and corresponding transition pressures. The results are similar to other transition-metal difluorides such as FeF2 but different to ZnF2 and MgF2, despite that the Co2+ size (ionic radius) is similar to Zn2+ and Mg2+. We found that the complete phase-transition sequence is tetragonal rutile (P42/mnm) → CaCl2 type (orthorhombic Pnnm) → distorted PdF2 (orthorhombic Pbca)+PdF2 (cubic Pa3¯) in coexistence → fluorite (cubic Fm3¯m) → cotunnite (orthorhombic Pnma). It was observed that the structural phase transition to the fluorite at 15 GPa involves a drastic change of coordination from sixfold octahedral to eightfold cubic with important modifications in the vibrational and electronic properties. We show that the stabilization of this high-pressure cubic phase is possible under nonhydrostatic conditions since ideal hydrostaticity would stabilize the distorted-fluorite structure (tetragonal I4/mmm) instead. Although the first rutile → CaCl2-type second-order phase transition is subtle by Raman spectroscopy, it was possible to define it through the broadening of the Eg Raman mode which is split in the CaCl2-type phase. First-principles DFT calculations are in fair agreement with the experimental Raman mode frequencies, thus providing an accurate description for all vibrational modes and elastic properties of CoF2 as a function of pressure

Soil Moisture and Black Truffle Production Variability in the Iberian Peninsula

The relationship between modelled root zone soil moisture (SM) and black truffle production in the Iberian Peninsula was studied. Previous works have investigated the influence that precipitation exerts on truffle yield highlighting the importance of water for the growth of black truffle. However, SM had not been used until now due to the lack of suitable databases. The SM series from the LISFLOOD hydrological rainfall–runoff model was used in this study. Annual black truffle yield series from 175 locations in Spain was correlated with SM for the period 1991–2012. For this, different approaches were applied considering daily, weekly and monthly temporal scales. The same analysis was carried out using precipitation data to compare the behaviors of both variables related to truffle production variability. The results obtained show critical periods in terms of soil water content in summer (June–September) and during October–November months. Moreover, a clear delay between precipitation and SM influence on black truffle was observed. The results obtained in this study highlight the importance of SM for black truffle production, since this variable truly expresses the available water for this fungus, which completes its entire life cycle living below ground. © 2022 by the authors. Licensee MDPI, Basel, Switzerland

Oxidación a 1123 K de sistemas multicapa AISI 304-Ni/Al-Al2O3/TiO2 depositados mediante proyección por llama

The oxidation behaviour of alumina/titania (97/3, 87/13 and 60/40) ceramic coatings using a Ni-Al coupling layer was studied in a thermobalance. Both layers were deposited on an AISI 304 stainless steel base metal by the flame spray technique. The coated steel was heated from room temperature to 1,123 K at 40 K min–1, oxidized in air for 50 h, and then cooled to room temperature at 40 K min–1. The mass gain was mainly attributed to the oxidation of Ni-Al coupling layer. Kinetic laws, DW·S–1 (mg.mm–2) vs. time (hours) were close to a parabolic plot for each sample. Surface composition of ceramic top layer and the cross section of multilayer system were analysed using a wide range of experimental techniques including Scanning Electron Microscopy (SEM), equipped with a link energy dispersive X-Ray spectroscopy (EDX) and X-Ray diffraction (XRD) before and after the oxidation process. Coatings 97/3 and 87/13 presented a stable structure after flame spray deposition and they did not evolve with the oxidation process, while most of the 60/40 coating changed to a metastable structure after deposition and to a more stable structure after oxidation with high micro-cracks content. SEM and EDX microanalysis of the cross-sections showed that significant oxidation and a weak intergranular precipitation had been produced in the coupling layer and on the stainless steel base metal, respectively.El comportamiento a oxidación de recubrimientos cerámicos alúmina/titania (97/3, 87/13, 60/40) usando una capa de anclaje Ni-Al se ha estudiado mediante una termobalanza. Ambas capas se han depositado sobre un acero inoxidable AISI 304 utilizando la técnica de proyección llama (FS). El acero recubierto se ha calentado desde la temperatura ambiente hasta 1.123 K a 40 K min–1, se ha oxidado al aire durante 50 h, y luego se ha enfriado hasta la temperatura ambiente a 40 K min–1. La ganancia en masa se atribuye a la oxidación de la capa de enganche Ni-Al. La cinética DW·S–1 (mg.mm–2) vs. tiempo (horas) se ha ajustado a una ley parabólica para todas las muestras. La composición super- ficial de la capa cerámica y la sección transversal del sistema multicapa se han analizado mediante las técnicas de Microscopía Electrónica de Barrido (SEM), Espectroscopia de Energías Dispersivas de Rayos X (EDX), Difracción de Rayos X (XRD) antes y después del proceso de oxidación. Los recubrimientos 97/3 y 87/13 han presentado una estruc- tura estable tras el proceso de deposición por proyección por llama y esta estructura tampoco ha evolucionado después de la oxidación, mientras la mayor parte del recubrimiento 60/40 ha cambiado a una estructura metaestable después la deposición y finalmente ha evolucionado a una estructura más estable después de la oxidación con alto contenido de microagrietamiento. El microanálisis mediante SEM y EDX de las secciones transversales han mostrado una oxidación significativa en la capa de enganche y una débil precipitación intergranular en el material base AISI 30

Near-field interference map due to a dipolar emission near the edge of a monocrystalline gold platelet

Point source excitation and point detection in the near-field provides new perspective to study the near-field optical phenomena of plasmonic nanostructures. Using the automated dual-tip scanning near-field optical microscope (SNOM), we have measured the optical near-field response of a dipolar emission near the edge of a monocrystalline gold platelet. The image dipole method was used to analytically calculate the interference pattern due to surface plasmon polaritons excited at the position of aperture tip and those reflected from edges of the gold platelet. The near-field enhancement was observed on the edges of the gold platelet. Our results verify that automated dual-tip SNOM is an intriguing technique for quantum plasmonic studies where deterministic coupling of quantum emitters and the detection of the near-field enhancement are of great interest

Mechanical and tribological properties of alumina/titania coatings deposited by Ooxifuel

En este trabajo se ha estudiado, las fases, las propiedades mecánicas y la resistencia al desgaste abrasivo de recubrimientos cerámicos alumina/titania proyectados por el proceso de oxifuel (spray llama). La proporción de titania tiene una fuerte influencia sobre la porosidad de los recubrimientos, habiéndose observado una disminución casi-lineal de la porosidad con el incremento de titania. Las fases cristalinas que resultan después de la proyección han variado según la naturaleza del polvo y el proceso térmico experimentado. Mientras la dureza obtenida depende sólo del porcentaje en peso de titania, la tenacidad es una función inversa de la dureza, y, la resistencia al desgaste por abrasión es una función creciente con la dureza de los recubrimientosIn this paper the porosity, phases, mechanical properties and abrasive wear resistance of ceramic layers of Al2O3/TiO2 deposited using the flame spray process are evaluated. The proportion of titania has a strong influence on the porosity of the coating, having observed an approximately linear plot decrease with the increasing of titania´s content. Crystalline phases of the deposited layers changed according to the characteristics of the powder and the thermal process employed. It has been observed that hardness depends only on the titania percentage, also toughness decreases with coatings hardness but resistance to abrasive wear traces an increasing lineal plot with this propert

An overview of rice cultivation in Spain and the management of herbicide-resistant weeds

Spain is the second highest rice-producing country in the European Union, with approximately 105, 000 ha used to grow this crop. The major rice-producing regions in Spain are Andalusia, Extremadura, Catalonia, and Valencia, followed by Aragon and Navarre. The main soil texture throughout Spanish rice areas is silty clay loam, with alkaline soils (pH > 7.5)—except in the Extremadura area (pH = 5.5–6)—and a low organic matter content. Water quality in terms of salinity is acceptable, although in some coastal rice areas salinity issues occasionally appear to be a determining factor for high yield achievement. According to a survey carried out on farmers and technicians, the most problematic weeds found in rice crops today in Spain are Echinochloa spp., Leptochloa spp., and Cyperus difformis. Most of the currently authorized herbicides can be classified according to two modes of action: ALS-inhibiting and ACCase-inhibiting. Repeated field applications of herbicides with the same mode of action have resulted in the selection of herbicide-resistant weeds. At present, resistance has been confirmed in different regions of Spain to ALS inhibitors in Echinochloa spp., Leptochloa spp., and Cyperus difformis, and to ACCase inhibitors in Echinochloa spp. and Leptochloa spp. The mechanism of resistance in these species is a mutation in the target site of these herbicides. Several mutations have been found in the ALS gene, both in Echinochloa spp. and Cyperus difformis, distributed in the different rice-growing regions considered in this work. ACCase gene mutations have been mainly found in Leptochloa spp. individuals from Extremadura and Valencia. These different mutations have resulted in different patterns of cross-resistance to ALS- and ACCase-inhibiting herbicides. It is likely that the repeated use of these two modes of action in rice will result in the evolution of more resistant weed populations. The possible availability of new herbicides with alternative modes of action in a short space of time seems very limited, suggesting the need for a more appropriate use of the available alternative strategies (crop rotation, dry sowing, manual weeding, etc.). This work presents a review of the main characteristics of rice cultivation in Spain, emphasizing the current problems in this crop and the management of herbicide-resistant weeds. © 2021 by the authors

Proteínas morfogenéticas óseas (BMPs): Efecto de la proteína osteogénica-1 (OP-l/BMP-7) en la condrogénesis y osteogenesis

En la actualidad, los estudios sobre biología molecular han facilitado el análisis de ciertos factores de transformación del crecimiento tipo ß(TGF-ß)I, entre los que destaca una familia de proteínas morfogenéticas óseas (BMPs). Las técnicas de ingeniería genética han permitido replicar alguno de estos factores y localizar los genes que codifican dichas proteínas. La proteína osteogenics-1 (OP-1) ha sido caracterizada y sintetizada in vitro y muestra un elevado potencial osteogénico y condrogénico tanto in vivo como in vitro. Se presenta una revisión de los últimos avances en la aplicación experimental de las BMPs, y especialmente de la OP-1, en el área de la Cirugía Ortopédica y la TraumatologíaNowadays, molecular biology studies have promoted the bone morphogenetic proteins (BMPs) analysis. These multifunctional proteins are structurally related to transforming growth factor-6 (TGF-6). Genetic engineering techniques have allowed to sequence some of these BMPs. It has been characterized the expression and processing of osteogenic protein-1 (OP-1), a bone morphogenetic protein of the TGF-6 family. The OP-1 shows a high osteogenic and chondrogenic potential. The aim of this paper is to review some updated advances of the BMPs experimental applications, particularly OP-1, in relation to Orthopaedic Surgery and Traumatolog