Procedimiento para la síntesis de materiales nanoestructurados con propiedades funcionales y estructurales mediante métodos de aerosol (Spray pirólisis)

La universidad española Carlos III de Madrid ha desarrollado un método para la síntesis de partículas nanoestructuradas (cerámicas, metálicas y compuestas) con propiedades funcionales y estructurales. Las partículas nanoestructuradas se obtienen por el método de Spray pirólisis. La optimización de las variables del proceso de síntesis, como son la concentración y naturaleza de la disolución precursora, el pH, la viscosidad, la densidad, el gas portador, la temperatura del reactor, etc. permiten obtener nanopartículas con propiedades mejoradas. El grupo de investigación busca proyectos de cooperación técnica con empresas

Procedure for Synthesis of nanostructured materials with improved functional and/or structural properties via aerosol methods (Spray pyrolysis)

The Spanish University Carlos III de Madrid has developed a new method in order to obtain nanostructured particles (ceramic, metallic and composite) with improved functional and structural properties. Spray pyrolysis is a way in order to obtain nanostructured particles. Optimization of synthesis process, evaluating the experimental parameter as pH, concentration and chemical nature of precursor solution, density, viscosity, carrier gas, temperature of reactor, etc. allow us to synthesize materials with improved properties. The group is looking for technical cooperation with companies

Efecto de la Molienda Mecánica en la Síntesis y en las Propiedades Magnéticas de Ferritas MFe2O4 (M=Mg y Ni)

En esta Tesis Doctoral se estudia la influencia del proceso de molienda mecánica en la síntesis y en las propiedades magnéticas de materiales ferrimagnéticos blandos con estequiometría MFe2O4, siendo M = Mg y Ni, ambas con estructura espinela inversa. Esta tesis consta de dos partes muy diferenciadas, una primera, en que se ha analizado la influencia de las condiciones experimentales de molienda para la obtención de ferritas vía reacciones mecanoquímicas, y una segunda, en la que a partir de polvo policristalino, preparado mediante reacciones de estado sólido a altas temperaturas, se ha estudiado la influencia de la molienda mecánica, analizando la influencia de la relación de masa bolas-masa de polvo, material de los útiles de molienda y tipo de molino. Se ha realizado una minuciosa caracterización estructural para explicar los cambios observados en las propiedades magnéticas debidas a modificaciones de la distribución catiónica o a la disminución del grado de cristalinidad. Se ha evaluado el efecto de la contaminación, principal desventaja, inherente a los procesos de molienda, y se ha cuantificado en función de las condiciones de molienda: tipo de molino, diámetro de bolas, relación masa-bolas: masas-polvo, etc

Synthesis of Cerium-Activated Yttrium Aluminate Based Fine Phosphors by an Aerosol Route

Polycrystalline fine powders of yttrium aluminate doped with Ce³⁺ were synthesised by spray pyrolysis of a polymeric pre-cursor, which was obtained by dissolving the corresponding nitrates in a solution of ethylenediaminetetraacetic acid (EDTA) in ethylene glycol (EG). Aerosol decomposition was performed at 550 °C followed by an additional thermal treat-ment (900–1100 °C). The yield of either a single yttrium alu-minium perovskite (YAP) phase or a single yttrium alumin-ium garnet (YAG) phase was investigated as a function of the predefined yttrium/aluminium ratio, the cerium doping concentration, the processing temperature, and the thermal-treatment regime, which included the variation of the heat-ing and cooling rates (dT/dt), the residence time (τ), and the atmosphere. Changes in the composition and structure of the precursor during thermal decomposition were investigated by thermogravimetric and differential thermal analysis (TGA/DTA) and FTIR spectroscopy. The particle morphology and structure were analysed by a combination of scanning electron microscopy and energy-dispersive X-ray spec-troscopy (SEM/EDS) and by highresolution transmission electron microscopy (HR-TEM). The structural refinement was based on the phase identification performed by X-ray powder diffraction (XRPD). The emission spectra were re-corded within the range 325–800 nm by applying excitation wavelengths of 297 (YAP) and 450 nm (YAG). The employed synthesis conditions assured the formation of spherical, non-agglomerated particles with well-developed surfaces and diameters between 200 and 800 nm. For a predefined Y/Al ratio of 1:1, lower processing temperatures combined with longer heat treatments under stationary conditions resulted in a multiphase system, composed of YAP, YAG, and mono-clinic yttrium aluminate (YAM) phases. However, a short heat treatment with a high heating rate (200 °C/min) at higher temperatures results in the formation of a kinetically favoured pure YAP hexagonal phase. On the other hand, for a predefined Y/Al ratio of 3:5, the generation of a thermody-namically favoured pure YAG phase has been confirmed, re-gardless of the applied heat-treatment conditions. Although incomplete, Ce³⁺ introduction into the host matrix has been detected by XRPD and luminescence measurements.The authors gratefully acknowledge the Ministry of Science and Education of the Republic of Serbia (Project No 172035), the University Carlos III (Madrid, Spain), and the Santander Bank (Chairs of Excellence Program for the academic year 2010–2011) for financial suppor

In-situ electrochemical synthesis of inorganic compounds for materials conservation: Assessment of their effects on the porous structure

This study refers to the application of in-situ electrochemical synthesis as an alternative method to improve the properties of porous materials against harmful external agents that deteriorate them. It is oriented to an understanding of the effects of crystallisation on the pore structure of different compounds commonly used in the restoration and conservation of porous materials (historical ceramics, building walls, sculptures, or biomedical applications). It analyses the microstructural, chemical details, and stability of the neo-formed phases that modify the pore network. The electrochemical synthesis was carried out at ambient temperature (20 °C), over high porous sandstone for crystallising Ca carbonate, Mg carbonate, Ca phosphate, and Ca oxalate compounds. Based on the neo-formed minerals, a comparison was made depending on their specific properties defining how they affected the pore structure. The characterisation included polarised light optical microscopy, environmental and field-emission scanning electron microscopy, digital image analysis, cathodoluminescence (CL-ESEM),energy-dispersive X-ray spectroscopy, and X-ray microdiffraction. Aragonite, hydromagnesite, hydroxyapatite, and whewellite were identified as the majority phases depending on the treatment. Phase transformation, dehydration, and dissolution-re-precipitation processes suggested different degrees of stability, including aragonite/calcite (CaCO3 treatment) and hydromagnesite/magnesite (MgCO3 treatment) transformations and simultaneous crystallisation of brushite/hydroxyapatite ((Ca3(PO4)2 treatment). Electrocrystallisation induced changes in inter-granular porosity, the development of secondary porosity inherent to the minerals, and differences in pore cementation depending on its mineralogy. Among the treatments, Mg carbonate reduced porosity most effectively, followed in descending order by calcium carbonate and calcium phosphate, being the calcium oxalate the less effective.This work was funded by the following projects: TOP-HERITAGE- (Technologies in Heritage Sciences (S2018/NMT_4372, Community of Madrid); MULTIMAT CHALLENGE: Multifunctional Materials for Society Challenges (S2013/MIT-2862, Community of Madrid); Additive Manufacturing: from material to application, ADITIMAT-CM (S2018/ NMT-4411, Community of Madrid); MAT2016-80875-C3-3-R, (Spanish Ministry of Science, Innovation and Universities); Author J.F.‘s participation was supported by a Spanish Ministry of Sciences, Innovation and Universities Juan de la Cierva grant

Evaluation of synthesis time in the growth of vertical-aligned MWCNTs by spray pyrolysis

Multi-Wall Carbon Nanotubes (MWCNTs) were analyzed on crystalline silicon substrates (type P) under optimal temperature conditions, using different synthesis times (2, 3, 4, 5, 10, 20, 30, 60, 120, and 180 min) in order to examine the effect on the structural quality and length of the CNTs produced by ultrasonic spray pyrolysis, using pure toluene and ferrocene as precursor solutions under argon flow. Structural, optical, and morphological differences of the MWCNTs grown were analyzed. Raman spectroscopy evidenced the MWCNTs' high quality, noted by the ID/IG (from 0.41 to 0.68) and I2D/IG intensity ratios around 0.75. Morphological differences of the MWCNTs grow evaluated by Field Emission Scanning Electron Microscopy (FE-SEM); the micrographs examined the thickness of CNTs' layers. High-Resolution Transmission Electron Microscopy (HRTEM) technique was used to determine the diameters of CNTs, which were found from 15 to 140 nm. X-Ray Diffraction (XRD) showed two characteristic peaks around 26° and 44°, which corroborated that the MWCNTs were well-graphitized. The influence of the time in these CNTs demonstrated that the final length of these nanotubes could easily reach micrometers. The alienation was better as time increased, and the graphitization extent is good in most cases compared to other more expensive synthesis methods.We thank Technician Adrian Gómez Herrero, Technician Cristina Moral Gil and Hugo Solera for the TEM, SEM and Raman characterization, respectively. This work has been supported by the thematic network "Nanostructure advanced materials and applications in Mexico" between Spain and Mexico sponsoring this international collaboration. This work has been financially supported by Comunidad de Madrid, Spain (S2018/NMT-4411) and Ministry of Economia, Industría y Competividad (PID2019-106631GB-C43)

TEM-STEM study of europium doped gadolinium oxide nanoparticles synthesized by spray pyrolysis

Proocedings of: Fourth Conference on the Characterization and Control of Interfaces for High Quality Advanced Materials. Kurashiki, Japan, 02-05 September 2012.Scanning-Transmission and Transmission Electron Microscopy techniques (STEM and TEM) have been applied to the characterization of nanostructured gadolinium oxides doped with europium synthesized by spray pyrolysis. The High Angle Annular Dark Field (HAADF) &- Scanning Transmission Electron Micros-copy (STEM) tools have been used to perform a tomographic study to identify morphological character-istics of nanostructured particles, and to differentiate them according to the heat treatments to which these have been subjected. With these techniques it has been possible to confirm the hollowness and por-ous nature of samples subjected to low temperature annealing (900 ºC). Moreover, the beginning of the densification and sintering processes in samples subjected to thermal treatment at higher temperature (1100 ºC) have been evaluated. Chemical analysis by electron energy loss spectroscopy (EELS) and X ray energy dispersive spectroscopy (EDS) carried out in STEM mode have allowed to confirm the high uni-formity and the expected chemical composition. The high resolution tools either allowed to confirm the presence of a cubic (Ia3 symmetry) and the monoclinic (c2/m symmetry) phases in the nanostructured particles.This work has been supported by the Advanced Structural Materials Program- ESTRUMAT (S2009/MAT-1585) and MAT2010-19837-C06-05. Thanks are extended to NanoPort (FEI)- Eindhoven, especially to Eng. L. Fernando Mendoza and to the Ministry of Science and Technology of Serbia (Project #142010).Publicad

Influence of nanoscale defects on the improvement of photocatalytic activity of Ag/ZnO

This study presents the advances in the field of ZnO/Ag catalysts from the synthesis of hierarchical ZnO nanowires (NWs) decorated with Ag nanoparticles, prepared by a facile solvothermal method at 120°C. It evaluates the photocatalytic efficiency from studying the time reaction of Ag/Zn concentration ratio and the presence of cetyltrimethylammonium bromide (CTAB) as an organic dispersant. X-ray diffraction, scanning electron microscopy, and analytical/high-resolution transmission electron microscopy results confirmed the presence of homogeneous cylindrical ZnO nanowires and quasi-spherical Ag crystals. ZnO NWs exhibited hexagonal wurtzite structure and cubic FCC symmetry in Ag nanoparticles (NPS). Two types of nanostructures, including homogeneous cylindrical ZnO NWs in the absence of Ag and simultaneous presence of ZnO NWs and Ag NPs, formed depending on experimental conditions. The photocatalytic activity was evaluated by studying methylene blue (MB) degradation time under UV light excitation. Diffuse reflectance UV–Vis spectrophotometry (UV–Vis DRS) allowed identifying the ZnO absorption band at ~393 nm. Crystal size varied depending on the reaction time and the addition of CTAB. Synthesis time increased bandgap values, getting better photocatalytic performance in samples synthesized in intermediate times (6 h), higher Ag+/Zn2+ molar ratio (0.2/1.0), and CTAB. According to HRTEM observations, the presence of silver nanocrystals with high content of defects (twinning, stacking faults) could play an essential role in the photocatalytic response. In this context, the specific synthesis conditions of Ag/ZnO might be more appropriate for their use in organic dyes degradation in water and the potential use in protective treatments against materials biodeterioration processes.This work has been supported by the Innovation and Education Ministry (ref. MAT2013-47460-C5-5-P and MAT2016-80875-C3-3-R), the Autonomous Region Program of Madrid (ref. S2018/NMT-4411 and S2013/MIT-2862), the Geomateriales 2 program (S2013/MIT_2914), the TOP Heritage (P2018/NMT-4372) of the Community of Madrid, the Innovation and Education Ministry (MAT201347460-C5-5-P) and the Ministry of Education, Science and Technological Development of Serbia (projects No. 172035 and 45020). Besides, we would like to thank the Master of “Materials Science” of Carlos III University (Spain) for providing financial and laboratory equipment support

Application of magnesium hydroxide nanocoatings on cellulose fibers with different refining degrees

Paper aging and protection are of crucial interest for improving the preservations of library collections and archives. Highly aging-resistant cellulose fiber sheets were obtained by treatment with magnesium hydroxide nanoparticles (Mg(OH)(2)). The procedure was tested on the sheets made of bleached (B) and refined unbleached (UB) pine cellulose fibers as well as their 50%/50% mixture (M). The mor and structural properties of the obtained sheets were studied by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) methods. Stress-strain, smoothness and pH measurements were employed to determine the changes in physical-chemical characteristics of the sheets after mixing two types of the fibers and subsequent treatment with Mg(OH)(2). It has been shown that the sheets made of the fiber mixture show a higher tensile index and smoothness. The modification with Mg(OH)(2) nanoparticles induces an increase in the pH of the sheets to slightly basic values (around pH 8), facilitates the inter-fiber bonding and additionally enhances the smoothness of the sheets. Finally, by exposing the sheets to thermo-hygrometric accelerated artificial ageing, it was found that the physical properties of the treated sheets were not significantly dependent on the environmental factors.This study was supported by the Geomaterials 2 Programme (S2013/MIT_2914),the Innovation and Education Ministry (ref. MAT2013-47460-C5-5-P) and the Autonomous Region Program of Madrid, MULTIMAT CHALLENGE (ref.S2013/MIT-2862

Synthesis and morpho-structural characterization of nanostructured magnesium hydroxide obtained by a hydrothermal method

Controlled magnesium hydroxide particles were successfully synthesized via a simple hydrothermal method. The influence of temperature and reaction time on the hydrothermal synthesis of Mg(OH)(2) was studied. The results provide new parameters to control the morphologies, particle sizes, agglomeration level and crystallographic structures of the brucite nanosized. The physic chemical properties of synthesized Mg(OH)(2) nanoparticles have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), high resolution transmission electron microscopy (HR-TEM) and thermogravimetry/differential scanning calorimetry (TG/DSC). It has been shown that the prolongation of reaction time improves the crystalline degree of magnesium hydroxide particles. It was also possible to detect a relevant increase in the degree of crystallinity and a faster crystal growth with defined hexagonal morphologies in the samples obtained at higher temperature. Our results show that this simple hydrothermal route is highly interesting for the large scale production of these nanomaterials. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.This study has been supported by the Geomaterials Programme (S2009/MAT-1629) and the ESTRUMAT Programme (S2009/MAT-1585) and it has been carried out in the Department of Materials Science and Engineering and Chemical Engineering of the University Carlos III of Madrid, Spain. The authors are grateful to the National Center for Electron Microscopy (CNME) for its support with TEM