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Premelting of ice adsorbed on a rock surface

Esteso, V; Palacios, SC; MacDowell, LG; Fiedler, J; Parsons, DF; Spallek, F; Miguez, H; Persson, C; Buhmann, SY; Brevik, I; Bostrom, M
Physical Chemistry Chemical Physics, 22 (2020) 11362-11373
Materiales Ópticos Multifuncionales


Considering ice-premelting on a quartz rock surface (i.e. silica) we calculate the Lifshitz excess pressures in a four layer system with rock-ice-water-air. Our calculations give excess pressures across (1) ice layer, (2) water layer, and (3) ice-water interface for different ice and water layer thicknesses. We analyse equilibrium conditions where the different excess pressures take zero value, stabilized in part by repulsive Lifshitz interactions. In contrast to previous investigations which considered varying thickness of only one layer (ice or water), here we present theory allowing for simultaneous variation of both layer thicknesses. For a given total thickness of ice and water, this allows multiple alternative equilibrium solutions. Consequently the final state of a system will depend on initial conditions and may explain variation in experimental measurements of the thicknesses of water and ice layers.

Mayo, 2020 | DOI: 10.1039/c9cp06836h

Thermo-Photocatalytic Methanol Reforming for Hydrogen Production over a CuPd-TiO2 Catalyst

Lopez-Martin, A; Platero, F; Caballero, A; Colon, G
ChemPhotoChem (2020)
Materiales y Procesos Catalíticos de Interés Ambiental y Energético


A bimetallic CuPd/TiO2 system has been prepared by a two-step synthesis and was used for a methanol steam photoreforming reaction. By sequential deposition, palladium is deposited over copper nanoclusters through a galvanic replacement process. Hydrogen production by steam reforming from methanol was achieved by both thermo-photocatalytic and photocatalytic processes. It appears that H-2 production on the bimetallic system is notably higher than the Pd monometallic reference. Moreover this difference in the catalytic performance could be related to the higher CO evolution observed for the monometallic Pd-1.0 TiO2 system which is partially inhibited in the bimetallic catalyst. In addition, an important thermal effect can be envisaged in all cases. Nevertheless, this improved effect in the thermo-photocatalytic process is accompanied by a remarkable CO evolution and SMSI effect (important strong metal-support interactions) that hindered the efficiency as temperature increases. On this basis, optimal operational conditions for H-2 production are obtained for thermo-photocatalytic reforming at 100 degrees C, for which the synergetic effect is higher with lower CO production (H-2/CO=4)

Mayo, 2020 | DOI: 10.1002/cptc.202000010

Time-resolved operando DRIFTS-MS study of the moisture tolerance of small-pore SAPO-34 molecular sieves during CH4/CO2 separation

Romero, M; Navarro, JC; Bobadilla, LF; Dominguez, MI; Ivanova, S; Romero-Sarria, F; Centeno, MA; Odriozola, JA
Microporous and Mesoporous Materials, 298 (2020) 110071
Química de Superficies y Catálisis


This study pretends to evaluate and understand the effect of moisture presence during CO2/CH4 separation on small-pore SAPO-34 molecular sieves. Two SAPO-34 samples with different physicochemical properties (composition, crystal size and texture) were prepared by hydrothermal synthesis using either one or a mixture of two templates. Transient operando DRIFTS-MS measurements revealed that the sample's hydrophobic character is associated to the presence of Si islands, which enhanced sample's moisture tolerance during repetitive adsorption/desorption cycles. This knowledge is fundamental to achieve the rational design of efficient SAPO-34 membranes under realistic conditions.

Mayo, 2020 | DOI: 10.1016/j.micromeso.2020.110071

Structural and surface considerations on Mo/ZSM-5 systems for methane dehydroaromatization reaction

Lopez-Martin, A; Caballero, A; Colon, G
Molecular Catalysis, 486 (2020) 110787
Materiales y Procesos Catalíticos de Interés Ambiental y Energético


We have prepared a series of Mo/ZSM-5 systems by impregnation method with different metal loading. The optimum performance has been attained for 4% metal loading, yielding to ca. 2 mmol(benzene)/g(ca)(t) at the end of the reaction. The obtained catalysts were widely structural and surface characterized. As Mo content increases, the surface feature of the support is affected specially its mesoporosity. It has been stated the enormous complexity of Mo species present in the studied system. In situ characterization by XPS reveals different reduction and carburization behaviour depending on the Mo content.

Mayo, 2020 | DOI: 10.1016/j.mcat.2020.110787

Microwave-assisted sol-gel synthesis of TiO2 in the presence of halogenhydric acids. Characterization and photocatalytic activity

Journal of Photochemistry and Photobiology A: Chemistry, 394 (2020) 112457
Fotocatálisis Heterogénea: Aplicaciones


The synthesis of mesoporous TiO2 nanosheets is reported using Ti(IV) Isopropoxide as Ti(IV) precursor. A sol-gel process combined with microwave activation is used. Three different halogenhydric acids (HX), were used to peptise the sol: HF(ac), HCl (ac) and HBr (ac). The three obtained TiO2-I(HX) samples were characterized by XRD, XRF, N2-adsorption, SEM, TEM, DRS and XPS. The three synthesized samples have high values of specific surfaces (between 100 m2/g and 200 m2/g) and similar band gap values (3.2–3.3 eV). The analysis of the surface composition by XPS confirms the presence of the halogenated species (F, Cl or Br) on the surface of each ones of the samples. The nanometric size (ca 5 nm) of the particles for each of the three samples was confirmed by XRD and by TEM. On the other hand, the nature of the halogenated acid used plays a role in the composition of the phases. While the TiO2-I (HF) sample was 100 % anatase, the other samples turned out to be biphasic, showing anatase/rutile in the TiO2-I(HCl) sample and anatase/brookite in the TiO2-I(HBr) sample. The samples were tested under two illumination conditions (UV and visible light) using rhodamine B and caffeine. The indirect role of the halide agent on the photocatalytic activities thereof is discussed.

Mayo, 2020 | DOI: 10.1016/j.jphotochem.2020.112457

Development of a high-pressure thermobalance working under constant rate thermal analysis

Perejon, A; Sanchez-Jimenez, PE; Criado, JM; Perez-Maqueda, LA
Journal of Thermal Analysis ande Calorimetry, 142 (2020) 1329-1334
Reactividad de Sólidos


A thermogravimetric instrument that works at high pressure of different gases has been designed and assembled. The instrument has been devised to work in a temperature range from room temperature to 1000 degrees C in various controlled pressures of selected gas up to 15 bar, and under conventional rising temperature and constant rate thermal analysis (CRTA) modes. CRTA method allows an intelligent control of the reaction temperature using a feedback system that monitors the mass gain or mass loss of the sample in such a way that the reaction rate is maintained constant all over the process at a preselected value. CRTA method provides a significant advantage for studying processes under high pressure as it reduces heat and mass transfer phenomena that are very relevant under these high-pressure experimental conditions. The thermal oxidation of Ni at 8 bar of pure oxygen has been used for testing the performance of the instrument under both linear heating rate and CRTA conditions.

Abril, 2020 | DOI: 10.1007/s10973-020-09644-5

In Vitro and In Vivo Study of Titanium Grade IV and Titanium Grade V Implants with Different Surface Treatments

Diaz-Sanchez, RM; de-Paz-Carrion, A; Serrera-Figallo, MA; Torres-Lagares, D; Barranco, A; Leon-Ramos, JR; Gutierrez-Perez, JL
Metals, 10 (2020) 449
Nanotecnología en Superficies y Plasma


The aim of our study is to evaluate different implant surface treatments using TiIV and TiV in in vitro and in vivo studies. An in vitro study was established comprising four study groups with treated and untreated TiIV titanium discs (TiIVT and TiIVNT) and treated and untreated TiV titanium discs (TiVT and TiVNT). The surface treatment consisted in a grit blasting treatment with alumina and double acid passivation to modify surface roughness. The surface chemical composition and the surface microstructure of the samples were analyzed. The titanium discs were subjected to cell cultures to determine cell adhesion and proliferation of osteoblasts on them. The in vivo study was carried out on the tibia of three New Zealand rabbits in which 18 implants divided into three experimental groups were placed (TiIVT, TiIVNT, and TiVT). Micro-computed tomography (micro-CT) was performed to determine bone density around the implants. The results showed that cell culture had minor adhesion and cell proliferation in TiIVT and TiVT within the first 6 and 24 h. However, no differences were found after 48 h. No statistically significant differences were found in the in vivo micro-CT and histological study; however, there was a positive trend in bone formation in the groups with a treated surface. Conclusions: All groups showed a similar response to in vitro cell proliferation cultures after 48 h. No statistically significant differences were found in the in vivo micro-CT and histological study

Abril, 2020 | DOI: 10.3390/met10040449

A 4-view imaging to reveal microstructural differences in obliquely sputter-deposited tungsten films

El Beainou, R; Garcia-Valenzuela, A; Raschetti, M; Cote, JM; Alvarez, R; Palmero, A; Potin, V; Martin, N
Materials Letters, 264 (2020) 127381
Nanotecnología en Superficies y Plasma


We report on the morphological disparity of the columnar growth in W thin films sputter-deposited by oblique angle deposition. Oriented tungsten thin films (400 +/- 50 nm thick) are prepared using a tilt angle alpha of 80 degrees and a sputtering pressure of 0.25 Pa. Inclined columns (beta = 38 +/- 2 degrees) are produced and the microstructure is observed by scanning electron microscopy. A 4-view imaging is performed in order to show inhomogeneous growing evolutions in the columns. Morphological features vs. viewing direction are also investigated from a growth simulation of these tilted W columns. Experimental and theoretical approaches are successfully compared and allow understanding how the direction of the W particle flux leads to dense or fibrous morphologies, as the column apexes are in front of the flux or in the shadowing zone. 

Abril, 2020 | DOI: 10.1016/j.matlet.2020.127381

Monitoring, Modeling, and Optimization of Lead Halide Perovskite Nanocrystal Growth within Porous Matrices

Tiede, DO; Rubino, A; Calvo, ME; Galisteo-Lopez, JF; Miguez, H
Journal of Physical Chemistry C, 124 (2020) 8041-8046
Materiales Ópticos Multifuncionales


The growth of lead halide perovskites within metal-oxide nanoporous films has been recently considered as a means to obtain chemically and photostable ligand-free high-quality nanocrystals (NCs). The growth process, governed by the reactions taking place in nanoreactors dictated by the matrix pore size, has not been explored so far. In this work, we use photoluminescence as a tool to monitor the growth of perovskite NCs within the void network of an optically transparent matrix. We consider the effect of different external factors, such as temperature, light illumination, or precursor concentration, on the growth dynamics, and discuss a possible formation mechanism of the confined perovskite NCs. Based on this analysis, guidelines that could serve to improve the fabrication and optoelectronic quality of this type of NCs are also proposed.

Abril, 2020 | DOI: 10.1021/acs.jpcc.0c01750

Advanced Strategies in Thin Films Engineering by Magnetron Sputtering

Palmero, A; Martin, N
Coatings, 10 (2020) 419
Nanotecnología en Superficies y Plasma


This Special Issue contains a series of reviews and papers representing some recent results and some exciting perspectives focused on advanced strategies in thin films growth, thin films engineering by magnetron sputtering and related techniques. Innovative fundamental and applied research studies are then reported, emphasizing correlations between structuration process parameters, new ideas and approaches for thin films engineering and resulting properties of as-deposited coatings.

Abril, 2020 | DOI: 10.3390/coatings10040419

Bio-Based Coatings for Food Metal Packaging Inspired in Biopolyester Plant Cutin

Benitez, JJ; Osbild, S; Guzman-Puyol, S; Heredia, A; Heredia-Guerrero, JA
Polymers, 12 (2020) 942
Materiales de Diseño para la Energía y Medioambiente


Metals used for food canning such as aluminum (Al), chromium-coated tin-free steel (TFS) and electrochemically tin-plated steel (ETP) were coated with a 2-3-mu m-thick layer of polyaleuritate, the polyester resulting from the self-esterification of naturally-occurring 9,10,16-trihydroxyhexadecanoic (aleuritic) acid. The kinetic of the esterification was studied by FTIR spectroscopy; additionally, the catalytic activity of the surface layer of chromium oxide on TFS and, in particular, of tin oxide on ETP, was established. The texture, gloss and wettability of coatings were characterized by AFM, UV-Vis total reflectance and static water contact angle (WCA) measurements. The resistance of the coatings to solvents was also determined and related to the fraction of unreacted polyhydroxyacid. The occurrence of an oxidative diol cleavage reaction upon preparation in air induced a structural modification of the polyaleuritate layer and conferred upon it thermal stability and resistance to solvents. The promoting effect of the tin oxide layer in such an oxidative cleavage process fosters the potential of this methodology for the design of effective long-chain polyhydroxyester coatings on ETP.

Abril, 2020 | DOI: 10.3390/polym12040942

Study of the influence of the precursors on the sensing properties of ZnO:Cu system

Ramos, A; Urbieta, A; Escalante, G; Hidalgo, P; Espinos, JP; Fernandez, P
Ceramics International, 46 (2020) 8358-8367
Nanotecnología en Superficies y Plasma


The properties of ZnO based materials for ethanol detection have been studied. Cu doped samples obtained from different precursors have been investigated. ZnO and ZnS have been used as host and Cu and CuO as dopant sources.

The sensing measurements have been mostly performed at room temperature. To monitor the effect of the presence of gas, resistivity and photoluminescence experiments with and without sensing gas have been carried out. The sensing behaviour is affected by the nature of the precursors used. For ZnO:Cu and ZnO:CuO series, a higher sensitivity is obtained at the lower gas concentrations, the better response is obtained for the sample ZnO:Cu with wt.1% of metallic copper. Strong segregation effects observed in these samples could be deleterious for the sensing properties. In the series ZnS:CuO, no segregation is observed, however the sensing behaviour is erratic and attributed to the reduction of Cu ions to the metallic state.

Abril, 2020 | DOI: 10.1016/j.ceramint.2019.12.068

Vegetable hierarchical structures as template for bone regeneration: New bio‐ceramization process for the development of a bone scaffold applied to an experimental sheep model

Filardo, G; Roffi, A; Fey, T; Fini, M; Giavaresi, G; Marcacci, M; Martinez-Fernandez, J; Martini, L; Ramirez-Rico, J; Salamanna, F; Sandri, M; Sprio, S; Tampieri, A; Kon, E
Journal of Biomedical Materials Research Part B-Applied Materials, 108 (2020) 600-611
Materiales de Diseño para la Energía y Medioambiente


Long bone defects still represent a major clinical challenge in orthopedics, with the inherent loss of function considerably impairing the quality of life of the affected patients. Thus, the purpose of this study was to assess the safety and potential of bone regeneration offered by a load‐bearing scaffold characterized by unique hierarchical architecture and high strength, with active surface facilitating new bone penetration and osseointegration in critical size bone defects. The results of this study showed the potential of bio‐ceramization processes applied to vegetable hierarchical structures for the production of new wood‐derived bone scaffolds, further improved by surface functionalization, with good biological and mechanical properties leading to successful treatment of critical size bone defects in the sheep model. Future studies are needed to evaluate if these scaffolds prototypes, as either biomaterial alone or in combination with augmentation strategies, may represent an optimal solution to enhance bone regeneration in humans.

Abril, 2020 | DOI: 10.1002/jbm.b.34414

A Microstructure Insight of MTA Repair HP of Rapid Setting Capacity and Bioactive Response

Jimenez-Sanchez, MC; Segura-Egea, JJ; Diaz-Cuenca, A
Materials, 13 (2020) 1641
Materiales para Bioingeniería y Regeneración Tisular


Mineral trioxide aggregate (MTA) is considered a bioactive endodontic material, which promotes natural mineralization at the material-tooth tissue interface. MTA Repair HP stands out because of the short setting time and the quick and effective bioactive response in vitro. The bioactivity, depens on material composition and microstructure. This work is devoted to analyze MTA Repair HP microstructural features, of both the powder precursor and set material, to get insights into the material physicochemical parameters-functionality performance relationships. Transmission electron microscopy (TEM), and field emission gun scanning electron microscopy (FEG-SEM) coupled with energy-dispersive X-ray (EDX) analyses were performed. X-ray diffraction (XRD) measurements were carried out at different times to investigate setting process. Bioactivity evaluation in vitro was carried out by soaking the processed cement disk in simulated body fluid (SBF). The presented results point out those MTA Repair HP precursor material characteristics of tricalcium silicate particles of nanometric size and high aspect ratio, which provide an elevated surface area and maximized components dispersion of calcium silicate and very reactive calcium aluminate. The MTA Repair HP precursor powder nanostructure and formulation, allows a hydration process comprising silicate hydrate structures, which are very effective to achieve both fast setting and efficient bioactive response.

Abril, 2020 | DOI: 10.3390/ma13071641

Positron annihilation analysis of nanopores and growth mechanism of oblique angle evaporated TiO2 and SiO2 thin films and multilayers

Garcia-Valenzuela, A; Butterling, M; Liedke, MO; Hirschmann, E; Trinh, TT; Attallah, AG; Wagner, A; Alvarez, R; Gil-Rostra, J; Rico, V; Palmero, A; Gonzalez-Elipe, AR
Microporous and Mesoporous Materials, 295 (2020) 109968
Nanotecnología en Superficies y Plasma


The nano-porosity embedded into the tilted and separated nanocolumns characteristic of the microstructure of evaporated thin films at oblique angles has been critically assessed by various variants of the positron annihilation spectroscopy. This technique represents a powerful tool for the analysis of porosity, defects and internal interfaces of materials, and has been applied to different as-deposited SiO2 and TiO2 thin films as well as SiO2/TiO2 multilayers prepared by electron beam evaporation at 70 and 85 zenithal angles. It is shown that, under same deposition conditions, the concentration of internal nano-pores in SiO2 is higher than in TiO2 nanocolumns, while the situation is closer to this latter in TiO2/SiO2 multilayers. These features have been compared with the predictions of a Monte Carlo simulation of the film growth and explained by considering the influence of the chemical composition on the growth mechanism and, ultimately, on the structure of the films.

Marzo, 2020 | DOI: 10.1016/j.micromeso.2019.109968

Optical Responses of Localized and Extended Modes in a Mesoporous Layer on Plasmonic Array to Isopropanol Vapor

Murai, S; Cabello-Olmo, E; Kamakura, R; Calvo, ME; Lozano, G; Atsumi, T; Miguez, H; Tanaka, K
Journal of Physical Chemistry C, 124 (2020) 5772-5779
Materiales Ópticos Multifuncionales


Mesoporous silica features open and accessible pores that can intake substances from the outside. The combination of mesoporous silica with plasmonic nanostructures represents an interesting platform for an optical sensor based on the dependence of plasmonic modes on the refractive index of the medium in which metallic nanoparticles are embedded. However, so far only a limited number of plasmonic nanostructures are combined with mesoporous silica, including random dispersion of metallic nanoparticles and flat metallic thin films. In this study, we make a mesoporous silica layer on an aluminum nanocylinder array. Such plasmonic arrangements support both localized surface plasmon resonances (LSPRs) and extended modes which are the result of the hybridization of LSPRs and photonic modes extending into the mesoporous layer. We investigate in situ optical reflectance of this system under controlled pressure of isopropanol vapor. Upon exposure, the capillary condensation in the mesopores results in a gradual spectral shift of the reflectance. Our analysis demonstrates that such shifts depend largely on the nature of the modes; that is, the extended modes show larger shifts compared to localized ones. Our materials represent a useful platform for the field of environmental sensing.

Marzo, 2020 | DOI: 10.1021/acs.jpcc.9b10999

Binder-free supercapacitor electrodes: Optimization of monolithic graphitized carbons by reflux acid treatment

Gomez-Martin, A; Gutierrez-Pardo, A; Martinez-Fernandez, J; Ramirez-Rico, J
Fuel Processing Technology, 199 (2020) 106279
Materiales de Diseño para la Energía y Medioambiente


The rational design of electrodes mimicking the cellular structure of natural bio-resources has been a matter of increasing interest for applications in energy storage. Due to their anisotropic and hierarchical porosity, monolithic carbon materials from natural wood precursors are appealing as electrodes for supercapacitor applications due to their interconnected channels, relatively low cost and environmentally friendly synthesis process. In this work, a liquid-phase oxidative treatment with refluxing nitric acid at 100 degrees C for 8 h was performed to enhance the surface properties of beech-derived graphitized carbons treated with an iron catalyst. Microstructural, textural and surface investigations revealed that this strategy was successful in removing amorphous carbon and in functionalizing their surfaces. The crystallinity, accessible surface area, micropore volume and surface functionality of beech-derived carbons were increased upon the reflux treatment. The resulting porous carbon materials were evaluated as binderless monolithic electrodes for supercapacitors applications in aqueous KOH electrolyte. A maximum specific capacitance of 179 F.g(-1) and a volumetric capacitance of 89 Fcm(-3) in galvanostatic charge/discharge experiments were reached. Monolithic electrodes exhibited good cycling stability, with a capacitance retention over 95% after 10,000 cycles.

Marzo, 2020 | DOI: 10.1016/j.fuproc.2019.106279

Optical interference effects on the Casimir-Lifshitz force in multilayer structures

Esteso, V; Carretero-Palacios, S; Miguez, H
Physical Review A, 101 (2020) 033815
Materiales Ópticos Multifuncionales


The Casimir-Lifshitz force F(C-L) between planar objects when one of them is stratified at the nanoscale is herein investigated. Layering results in optical interference effects that give rise to a modification of the optical losses, which, as stated by the fluctuation-dissipation theorem, should affect the Casimir-Lifshitz interaction. On these grounds, we demonstrate that, by nanostructuring the same volume of dielectric materials in diverse multilayer configurations, it is possible to access F(C-L) of attractive or repulsive nature, even getting canceled, at specific separation distances.

Marzo, 2020 | DOI: 10.1103/PhysRevA.101.033815

Potentialization of bentonite properties as support in acid catalysts

Amaya, J; Bobadilla, L; Azancot, L; Centeno, M; Moreno, S; Molina, R
Materials Research Bulletin, 123 (2020) 110728
Química de Superficies y Catálisis


Enhancement of the main physicochemical properties of a natural bentonite was carried out by means of modifications using surfactant, reflux, microwave treatment and, subsequently, the incorporation of AlZr and AlCe species. The evolution of the main changes in each modification stage was evaluated by means of X-ray diffraction, N-2 sortometry, scanning microscopy (SEM), NH3-TPD, NH3-DRIFTS and CO adsorption at low temperature. For the evaluation of the catalytic behavior, the dehydration-dehydrogenation reactions of 2-propanol and hydro-conversion of decane were used; both of which generate, in addition, information regarding the acidic properties of the materials. The correlation of the number, type and acid strength with the catalytic behavior, allowed establishing the effect produced by both the delamination method and the nature of the incorporated cation. This generated tools that allow controlling the physicochemical properties, and more specifically, the enhancement of the acidity of new supports based on this type of natural clay mineral.

Marzo, 2020 | DOI: 10.1016/j.materresbull.2019.110728

Influence of the Test Configuration and Temperature on the Mechanical Behaviour of WC-Co

Gonzalez, LM; Chicardi, E; Gotor, FJ; Bermejo, R; Llanes, L; Torres, Y
Metals, 10 (2020) 322
Reactividad de Sólidos


In this work, the effect of the test configuration and temperature on the mechanical behaviour of cemented carbides (WC-Co) with different carbide grain sizes (d(WC)) and cobalt volume fractions (V-Co), implying different binder mean free paths (lambda (Co)), was studied. The mechanical strength was measured at 600 degrees C with bar-shaped specimens subjected to uniaxial four-point bending (4PB) tests and with disc specimens subjected to biaxial ball-on-three-balls (B3B) tests. The results were analysed within the frame of the Weibull theory and compared with strength measurements performed at room temperature under the same loading conditions. A mechanical degradation greater than 30% was observed when the samples were tested at 600 degrees C due to oxidation phenomena, but higher Weibull moduli were obtained as a result of narrower defect size distributions. A fractographic analysis was conducted with broken specimens from each test configuration. The number of fragments (N-f) and the macroscopic fracture surface were related to the flexural strength and fracture toughness of WC-Co. For a given number of fragments, higher mechanical strength values were always obtained for WC-Co grades with higher K-Ic. The observed differences were discussed based on a linear elastic fracture mechanics (LEFM) model, taking into account the effect of the temperature and microstructure of the cemented carbides on the mechanical strength.

Marzo, 2020 | DOI: 10.3390/met10030322