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Engineered Ceramics for Extreme Environments

Research Group:

  • Designed Materials for the Energy and Environment


Castro Arroyo, Miguel Angel

954 48 95 46

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Jiménez Melendo, Manuel

954 55 97 36

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Malet Maenner, María del Pilar

954 48 95 27

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Martínez Fernández, Julián

954 55 28 94

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Ramírez de Arellano-López, Antonio

954 55 97 32

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Científicos Titulares

Alba Carranza, María Dolores

954 48 95 46

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Benítez Jiménez, José Jesús

954 48 95 51

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Profesores Titulares

Bravo León, Alfonso

954 55 09 37

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Clauss Klamp, Caroline Maria

954 55 09 41

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Investigadores/Doctores Contratados

Ramírez Rico, Joaquín

954 55 97 58

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Becarios Predoctorales

Cabezas Rodríguez, Rafael

954 55 09 54

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Orihuela Espina, María del Pilar

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Osuna Barroso, Francisco Javier

954 48 95 00 + ext. 90 92 14

Grupo de Investigación:
Materiales de Diseño para la Energía y Medioambiente

Bioceramic Materials for New Biomass Domestic Bolier Concept based on Porous Combustion for a Wide Biomass/Residues Feedstock

Research head: Joaquín Ramírez Rico
Period: 30-12-2016 / 29-12-2019
Financial source: Ministerio de Economía y Competitividad
Code: MAT2016-76526-R
Research group: Julián Martínez Fernández, Manuel Jiménez Melendo

Abstract [+]

EU generates more than five tons of waste per person every year and about 60 % is organic waste. Current biomass domestic boiler technology does not allow the use of these residues with high efficiency, ultra-low emissions and high reliability operation. The main objective of this proposal is the development of a new concept of biomass domestic boiler technology able to combine these characteristics for operation with multiple biomass/residues blends. It is based on the integration of novel bioceramic porous materials matrices in combustion chamber and gases pathflow with functions as microporous combustors, particles filters and heat accumulators. These functions are simultaneous depending on the region of the boiler. Matrices of bioceramic materials are developed from wood precursors to obtain SiC elements through a process patented by the University of Seville. It uses local raw material, and produces parts with tailor made microstructure/properties, adequate for high temperature and reactive operation. Products with complex geometries can be obtained at relatively low cost compared with other materials of similar chemical and mechanical properties. The integration of components based on these materials allows new designs of biomass boilers with high control of combustion, temperature and particle emission. It avoids ash sintering and melting, acting on the formation and evolution mechanisms of ash and dioxins and activating the complete oxidation of CO and soots. The new concept allows the operation to a wider biomass/residues feedstock with low emissions and low maintenance even with fuels with high ash content, produced from many residues, solving main challenges for their extended use and increasing the European fuel resources for domestic heating. Domestic heating in Europe consumes 30% of the total energy. The proposal includes prototypes development, fuel supply characteristics and preparation (geometry, compactness, composition, etc.) and combustion products management. Biomass/residues blends from agriculture, forestry, olive oil industry among others will be tested both in laboratory . 

Genetic basis of the composition and biophysical properties of tomato fruit cuticle: exploiting natural variability

Research head: Fafael Fernández Muñoz (IHSM)
Period: 01-01-2016 / 31-12-2018
Financial source: Ministerio de Economía y Competitividad
Code: AGL2015-65246-R
Research group: José Jesús Benítez, Fernando Gallardo Alba (UMA), Antonio Heredia Bayona (IHSM)

Abstract [+]

Production of fruits with high quality and added value is currently an important challenge in agriculture. The cuticle that covers the outer epidermal cell walls plays a significant role in tomato fruit quality mainly in its external appearance (color, glossiness, texture, uniformity), in the occurrence of disorders of great economical importance such as fruit cracking, and also in the maintanance of fruit water status during postharvest. In previous projects (AGL2006-12494, AGL2009-12134 and AGL2012-32613) of which this can be considered a continuation, the important role of cuticle on fruit cracking and how changes in cuticle biomechanical properties affect cracking were highlighted. Moreover, it was shown that cuticle flavonoids, which are involved in the color of ripen fruits, play an important role in the regulation of cuticle synthesis and water permeability. Both a recombinant inbred (RIL) and an introgression line (IL) S. lycopersicum x S. pimpinellifolium populations will be used for validation and identification of QTLs and candidate genes involved in the deposition of different cuticle components (waxes, cutin, flavonoids, polysaccharides) and also for identification of QTL/genomic regions associated to unstudied cuticle traits such as thickness and density. This multidisciplinary approach, that includes cuticle biophysical analyses, will allow designing tomato cultivars with adequate biomechanical and hydrodinamical properties to reduce cracking, maintaining fruit water status during postharvest and avoiding skin traits undesirable for consumers. A collection of wild tomato species accessions will be studied and will provide insights in cuticle evolution within the Lycopersicon taxon. This evolutionary study could reveal different combinations of components and structures that will be useful to increase the current cuticle variability for future breeding programs.

Susteinable industrial waste treatment: designed adsorbent materials and bionanocomposites for inmobilizing heavy metals and fision products

Research head: Maria Dolores Alba Carranza
Period: 01-01-2016 / 31-12-2018
Financial source: Ministerio de Economía y Competitividad
Code: MAT2015-63929-R
Research group: Miguel Angel Castro Arroyo, Ana Carmen Perdigón Aller, María del Mar Orta Cuevas

Abstract [+]

The focus of the project addresses the requirement of advanced environmental technology methodologies for removing pollutants. Recently, the interest and efforts to develop new technologies for more efficient treatments for the immobilization and the revaluation of hazardous waste are increasing in  R & D plans. The overall object of the project is based on the design of a strategy of functionalization of highly charged swelling phyllosilicates and their later transformation on bionanocomposite for the effective retention and immobilization of hazardous waste, both cationic and anionic. This object represents a qualitative change in the work that is being nowdays developed in the field of model adsorbents systems with environmental applications that will improve the quality life of the population and the environmental conservation, because the designed functionalization of the synthetic silicates will allow the adsorption of a wide range of adsorbents in different oxidation states, cationic or anionic. The objectives are conformed to the Focus Area WASTE of the H2020 program and it is developed on the 2nd and 5th challenge of the H2020 program and on the 5th and 3rd challenge of the national research program.

The project has attracted interest from various observers companies, EPOs, (ENRESA and the Water and Local Energy Agency and Sustainability of the City of Seville), the public-private collaboration being promoted. Therefore, the research combines the basic principles of the National Strategy of Science and Technology: Putting the R&D&I at the service of citizens, social welfare and sustainable development, making the R&D&I a factor of improving business competitiveness (transfer of results to the private sector, see interest of EPOs) and recognize and promote R&D&I as an essential element for the generation of new excellence knowledge.

The viability of the proposal is ensured, first, because the research team, RT, has accomplished the synthesis of hydratable high charged phyllosilicates, with a novel and original method that allows setting the material desired charge, and, later, has successfully achieved their organofunctionalization (patent ES 2 362 597 B1). Second, the RT has developed the required methodology for the development of this project in closed scientific collaboration with other well recognized international groups (i.e. CNRS-University of Lille, University of Cambridge...). The RT enhances the clustering of their capabilities and scientific-technical skills which are essential to address this proposal with a remarkable transverse character.

Adsorption mechanisms study of harmful anionic pollutants by tailor-made aluminosilicates

Research head: Esperanza Pavón González
Period: 01-02-2015 / 28-02-2017
Financial source: Junta de Andalucía
Code: TAHUB-082. Programa Talent HUB
Research group:

Abstract [+]

The scientific, technological and industrial development carried out in the second half of last century has caused an increasing pollution in the natural environment. Consequently, a widespread recognition of the need to develop technologies and strategies for pollution control has arisen in the recent times. The main objective of this Project is to design swelling layered silicates of high charge and their surface modification for an effective activity with respect to the retention and immobilization of toxic and dangerous anionic wastes.
The proposed methodology consists on the synthesis of high charge swelling mica with isomorphic substitution of Si4+ by Al3+ with a charge density in the range of brittle mica but with a cation exchange and swelling capacities unusual in these silicates. In order to enhance the anionic adsorption capacity, the mica will be functionalized in the surface with magnetite and with the inclusion of alkylammonium cations in their interlayer space.
An immobilization protocol of harmful anionic products like AsO42-, SO42- will be established, using the best adsorbent in function of both the structure and the funcionalization of the highly charged swelling mica. Afterwards, the applicability of these adsorption reactions will be tested in actual contaminated soils from Chili and Spain.

Development of processes for the catalytic combustion of hydrogen and study of the integration in devices for portable applications

Research head: Asunción Fernández Camacho
Period: 16-05-2014 / 15-05-2016
Financial source: Junta de Andalucía
Code: P12-TEp-862
Research group: Julián Martínez, Gisela Arzac, Dirk Hufschmidt, Joaquín Ramírez, M.Carmen Vera, Vanda Godinho, Lionel Cervera, T.Cristina Rojas, Olga Montes, Mariana Paladini, Jaime Caballero-Hernández

Abstract [+]

Hydrogen is an attractive candidate as a vector for storage and transport of energy in the context of an increased use of renewable and clean energies. The production and use of energy based on hydrogen technology is particularly important for small-scale portable (and potentially scalable for stationary) applications. In this project the process of catalytic (controlled) combustion of hydrogen will be investigated in the various aspects that could lead to a final integrated configuration with a H2 generation system for portable applications. For that the project will take advantage of the synergy of integrating two researcher groups from the PAI: i) The TEP217 group, specialists in storage and generation of hydrogen based on metal hydrides, complex hydrides and hydride composites reactive systems; and in the use of catalysts and additives to control and improve the kinetics of these processes. ii) The FQM342, specialist group for the fabrication of porous ceramics of high interest as catalyst supports for harsh combustion environments. Further collaboration is completed with the participation of the company Abengoa Hidrógeno SA that will be involved as sub-contractor as specialist in systems for the production and storage of hydrogen.
In particular we will work on this project in the following lines:
1.- Development of catalysts and supports for catalytic combustion. Typically porous biomorphic silicon carbide ceramics and classic noble metal catalysts, as well as new low cost catalysts to be developed in the project.
2.- Development of reactors needed for the study of the catalytic combustion. Typically hydrogen flows from a few ml/min to the scale of a H2 generator already available in the range 0.5 to 1.5 L/min.
3.- Coupling the catalytic combustion system with a portable hydrogen generation systems that we have developed in previous projects.
4.- Application of the sputtering technology in an exploratory manner in this project to deposit the catalyst materials for the H2 catalytic combustion on porous substrates.
5.- Microstructural and chemical characterization of the supports and catalysts in the nanoscale to follow the procedures of synthesis and evolution in operation.


Inmobilization of heavy metals by synthetic high-charged organomicas: Test at laboratory scale

Research head: María Dolores Alba Carranza
Period: 16-05-2014 / 16-02-2019
Financial source: Junta de Andalucía
Code: P12-FQM-567
Research group:

Abstract [+]

The focus of the project addresses the environmental technological requirement to develop advanced methods for removing pollutants. The interest and efforts to develop new technologies aimed at more efficient treatment in detention and revaluation of hazardous waste is increasing in R & D plans. It is in this scenario where this project should be framed and in particular in the framework of the management of heavy metal cations, issue of high public interest in this decade.

Since the second half of the twentieth century, humanity has faced a huge scientific and technological development that is responsible for increased environmental pollution. As an example, we can mention two problems that are currently of concern and action of the Andalusian: Andalusian coastal pollution and urban wastewater. Therefore, this is a complex problem that pollutants sources are varied of origin and routes followed by various pollutants are diverse and, frequently, it is beyond the control necessary to avoid urban undesirable effects on the natural environment and. Therefore, a basic level research is demaned to implement the necessary mechanisms for the immobilization of such harmful cations.

The objectives and scope of this project are based on advances made by other research groups in the management of these types of contaminants and the latest research conducted by the research team that allowed design expandable high-charged layered silicates with special properties as precursors for the retention of harmful residues. Therefore, it is proposed in this project the organofunzionalization of such synthetic micas with thiol groups or alkylammonium cations of varying chain length and evaluation of its adsorption capacity and irreversible retention of heavy metals.

Bio-ceramics for diesel engine particulate filters

Research head: Julián Martínez Fernández / Ricado Chacartegui
Period: 01-01-2014 / 31-12-2016
Financial source: Ministerio de Economía y Competitividad
Code: MAT2013-41233-R (Programa Retos)
Research group: José Antonio Becerra Villanueva, Alfonso Bravo León, Manuel Jiménez Melendo, Antonio Ramírez de Arellano López, Joaquín Ramirez Rico, Francisco Varela Feria

Abstract [+]

The importance of controlling particulate emissions from diesel engines is essential given its volume and the associated environmental and economic impact. Control systems based on modifications of the combustion process in the engine are not sufficient to meet the requirements of current regulations, less future ones, and therefore it must necessarily be employed post treatment systems such as filters. There is considerable scope for improving them both in reliability, degradation of control performance, durability, multifuel operation and cost reduction.

This project will assess the development and manufacturing of regenerative particulate filter for diesel engines to improve the current system specifications, based on a new generation of ceramic bio-derivated materials, with integrated systems for particle combustion. This objectives will be achieved integrating researchers synergies from: i ) Thermal Engines and Machines Group, GMTS , specialists in internal combustion engines ii ) Multifunctional Biomimetic Materials Group, MBM, specialists in obtaining bio-derivated porous ceramic as well as physical, chemical and microstructural characterization. In addition, the project is completed with the collaboration of companies in assessing technology and its industrial applicability.

The following research lines will be addressed:

- Determination of processing routes that enable the development of filter elements with suitable physical, and chemical properties, based on prior knowledge in bio-derivated materials and new technologies regarding the use of SiO2 gels.
- Identification of suitable catalysts and systems for its deposition.
- Manufacture of the filter elements consisting of porous support and catalyst.
- Thorough characterization of the physical, chemical and microstructural properties of interest for the application.
- Development of activation systems for the filter regeneration.
- Design and manufacturing of the filters with suitable geometry and prototype dimensions.
- Pilot unit design and study of the integration and operation of engine.
- Final design of the filter for industrial facility.

Previous studies developed by MBM in these bio-derivated materials have demonstrated their potential as gas filter elements at high temperatures in coal gasification plants, which supports the likelihood of success of this project, which will address the improvements needed to develop the technology in the combustion conditions of diesel engines, under dynamic conditions in vehicles and regenerative filters.

A reduction of pollutant emissions from diesel engines would have a great environmental impact, health and economic development, with about 100 million diesel vehicles circulating in Europe and a related industry with over 2 million direct jobs and growing trend in market. This project addresses the Social Challenge 3 Horizon 2020, Secure, clean and efficient energy. In addition, using bioceramics allows replacement of metal components used today, which also aligns with the Social Challenge 5 of the Horizon 2020 in search of alternatives to essential raw materials in existing applications by reducing dependence on imports and sustainability of applications.

The obtention of fatty polyhydroxyalcanoate (PHA) bioplastics from peels residues of commercial fruits

Research head: José Jesús Benítez Jiménez
Period: 16-05-2013 / 15-05-2016
Financial source: Junta de Andalucía
Code: P11-TEP-7418 (Proyecto de Excelencia)
Research group: Antonio Heredia Bayona, Miguel Angel San Miguel Barrera, Jaime Oviedo López, J. Alejandro Heredia Guerrero, Santiago Domínguez Meister, Daniel Aguilera Puerto, Francisco Javier Navas Martos, José Manuel de la Torre Ramírez

Abstract [+]

The main objective of this project is to evaluate the feasibility of scaling up a procedure to obtain fatty polyhydroxyalcanoate (PHA) bioplastics from a low-cost and abundant source like peels residues of commercial fruits. The strength of the proposal relies on the introduction of a new non-toxic and fully biodegradable polymeric material as a substitute for environmental-hostile petroleum-based plastics. The overall sustainability is extended to the use of a low-impact synthetic route and to the processing of a plant residue rather than crops intended for human or cattle feeding. The project is considered of additional interest in regions with an agricultural based economy like Andalusia and with an important environmental impact arising from the greenhouse activity. The proposal also covers the study of new and more specific applications of such bio-based fatty polyhydroxyalcanoates.

Fatty hydroxyacids molecular interactions as model for biomimetic polyester design

Research head: José Jesús Benítez Jiménez
Period: 01-01-2012 / 31-12-2014
Financial source: Ministerio de Ciencia e Innovación
Code: CTQ2011-24299
Research group: Alejandro Heredia Guerrero, Miguel Angel San Mibuel Barrera, Jaime Oviedo López, Miguel Salmerón Batalle

Abstract [+]

The objective of this Project is to study and characterize the specific interactions between fatty carboxylic acids molecules arising from selective  hydroxylation of the alkyl chain. To address this issue, molecular self-assembled systems showing a low interaction with an atomically flat support are proposed as models. The use of low binding energy supports is to ensure the packing structure to be mainly driven by the molecule to molecule interactions rather than the molecule to substrate adsorption. These self-assembled systems will be characterized by scanning probe microscopies  such as AFM and STM and infrared spectroscopy. Results will be complemented with molecular dynamics atomistic simulations. Basic information  obtained from self-assembled models will be used to design the in-vitro chemical synthesis of cutin mimetic polyesters. Cutin is a non toxic, fully  biodegradable barrier biopolymer present at the skin of fruits, leaves and non lignified stems of higher plants. Physical (mechanical, water  permeability, ionic transport, etc…) and chemical (ester yield, controlled chemical degradation rate, etc…) properties of synthetic polyesters will be determined. Material features will be related with both, the main structure arising from the ester bonds formation and the secondary network resulting from hydrogen bonding between spare non reacted hydroxyl groups. Structure-function patterns will be used to redesign the synthesis route to obtain polymeric esters with tailored properties. To achieve this goal, both the primary and secondary structural networks will be manipulated. In the first  case non hydroxylated molecules will be used to prevent ester bonding propagation. To modify hydrogen bonding crosslinking, additives with selected  hydroxylation (primary or secondary) will be employed. The final motivation of this research is to explore the applicability of such mimetic polyester as substitutes for the highly contaminant hydrocarbon based plastics.

Immobilization of cations in high-density charge confined spaces: management of harmful cations wastes

Research head: María Dolores Alba Carranza
Period: 01-01-2011 / 31-12-2013
Financial source: Ministerio de Ciencia e Innovación
Code: CTQ2010-14874/BQU
Research group: Miguel Angel Castro Arroyo, Maria del Mar Orta Cuevas, Mery Carolina Pazos Zarama, Said ElMrabet, Esperanza Pavón González, Maria Villa Alfageme, Santiago Medina Carrasco, Ana Isabel Becerro Nieto, Alberto José Fernández Carrión

Abstract [+]

The central subject of this Project deals with the environmental technological exigency for development of advanced technologies for the elimination of polluting agents. The interest and the effort dedicated to the development of new technologies that allow more effective treatments of retention and new procedures of valorisation is increasing in numerous R&D plans in the last years. It is in this scene where the present proposal must be fitted and circumscribed into two experimental basic findings: designing expansible high layer charge silicates with a controlled distribution of active centres, which can be effective materials for the retention of hazardous and radioactive wastes, and obtaining insoluble disilicate phases in smooth conditions, appropriate for the immobilization of such species. This objective represents a qualitative change in the work that has been developed up to now in relation to the elimination of radioactive and toxic wastes as well as in the application of the methodology to silicate systems. The objectives are adapted, in general, to the high-priority lines of Basic Investigation of Chemistry, in the area of Inorganic Chemistry (Solid State Chemistry) and Environmental Chemistry in particular but, in spite of its basic character, the Project is adapted to diverse lines of investigation of Oriented Chemistry and it is supported by different EPOs (ENRESA, BEFESA and ALQUIMIA). These objectives, of eminent basic character, require the development of techniques of sophisticated analysis like advanced Solid State NMR, X-ray diffraction, under conditions of controlled pressure and temperature or gamma spectroscopy of low counts. This fact fits to the particular objective of the Chemistry Area of “using the instrumental and experimental technology for the study of materials” and with objective O2.5 (Enhance the availability of interdisciplinary infrastructures and sharing use of them) of the R+D+I National Plan 2008-2011. A guarantee of this proposal is that, in a first place, the Research Group (RG) has recently published the synthesis of expansible mica using a method that allows obtaining the desired layer charge in the material; secondly, the RG has a wide experience in the design of synthesis mechanisms of silicates as demonstrated by the number of papers published on this area during the last decade, and, finally, the RG has developed useful methodologies for the present Project in collaboration with other Groups with which it maintains a narrow scientific relationship.

Bioener: Aplicación de tecnologías biomiméticas a sistemas energéticos

Research head: Julián Martínez Fernández
Period: 01-01-2010 / 31-12-2012
Financial source: Junta de Andalucía
Code: P09-TEP-5152 (Proyecto de Excelencia)
Research group: Manuel Jiménez Melendo, Antonio De Arellano-López, Alfonso Bravo León, F.M. Varela Feria

Abstract [+]

Technological advances have made possible to diversify and optimize energy produc-tion, which in turn has motivated the development of new ways to store energy. In particular, as production methods diversify, it is necessary to develop new materials for energy storage, both large scale and in consumer devices and transportation. This is especially important in the context of higher penetration of renewable energies, which often depend on climatological conditions and require ways to store excess energy at production peaks, so it can be used when production decreases. In parallel to this strategy and to reduce the share of fossil fuels in the overall energy production, it is necessary to increase the efficiency of conventional power generation sys-tems, for example by increasing material’s life and operating temperatures, for example in gas turbine systems, among others. The development of materials for high temperature applications, especially ceramics, has been traditionally linked to the search for increased efficiency of power generation systems. Ceramic materials, due to their high melting point, good creep resistance and resistance to corrosion, are seen as candidates for application in chemically aggressive environments at temperatures over 1000 ºC. Carbides and nitrides in particular are being studied extensively for this kind of applications. Porous ceramics are also of great interest in energy applications, such as heat exchangers or syngas filtration systems, among others. Among active research lines in the development of new materials for energy storage, electrochemical storage is expected to have the largest impact in the end consumer, as the design of high capacity batteries and electrochemical capacitors is key for the viability of tech-nologies such as plug-in electric cars. For this reason, research into new materials for electro-chemical storage has become a strong focal point among the scientific community and consti-tutes one to the great technological challenges of today. Biomorphic silicon carbide (bioSiC) is a ceramic material obtained by reactive infiltra-tion of carbon performs derived by pyrolysis of natural precursors. The precursor, usually wood, is rough-machined and then converted to carbon by pyrolysis in a controlled atmos-phere at high temperatures. The result is a macroporous carbon material (bioC) with a micro-structure that closely resembles that of the original precursor. This carbon template is then machined to near net shape and is melt reacted with silicon either in liquid or vapor phase to obtain a SiC composite with some residual Si that shows excellent thermomechanical proper-ties and a microstructure that closely mimics that of the original wood precursor. Tailoring the material’s properties is possible by adequate selection of the precursor, which determines the microstructure and thus the properties of the bioSiC. It is also possible to remove the remaining silicon through chemical etching to obtain a macroporous SiC material which can then be reinfiltrated to create novel composites and cermets, such as bioSiC/Al or bioSiC/Cu. The prospect of producing macroporous carbon materials with controlled nanoporosi-ty is interesting for electrochemical applications, as it would be possible to infiltrate or coat macropores with a second phase the provides additional function, for instance in three dimensional lithium batteries [3, 20] or carbon/oxide supercapacitors [4, 5]. In this way, the development of new carbon materials with controlled structure and porosity could open the door to novel architectures and designs for devices able to store larger amounts of energy. Most nanoporous carbon materials used nowadays are obtained through activation of carbons made from pyrolysis of synthetic precursors [21], although in the last years carbide-derived carbons have been the subject of great interest [22, 23, 24]. It is possible to obtain high-purity nanoporous carbon through high temperature chlorination of metallic carbides, which rank among the best carbon materials for electrochemical applications. In this direction, is has already been shown that carbides obtained from natural precursors, such as bioSiC are viable precursors to carbide-derived carbons [25]. This proposal’s aim is two-fold: on one side, the bioC processing will be studied in de-tail, paying special attention to precursor selection and to the possibility of introducing differ-ent atmospheres during the pyrolysis process, such as CO2 or water vapor, that promote nanoporosity in the material. The effect of processing parameter in the degree of crystallinity, nanoporosity, crystallite size and structure of the resulting carbon material will be assessed. The possibility of promoting carbon graphitization through the use of different catalysis in the pyrolysis process will be studied. The resulting carbon’s microstructure and physical properties will be studied and correlated to the processing parameters. On the other side, the effect of the aforementioned treatments on the bioSiC material will be studied, and the possibility of obtaining novel cermets in-situ, such as bioSiC/Al, bioSiC/Ti, through melt infiltration, will be assessed. In a last step, the possibility of obtained carbon materials with enhanced structure from the ceramic carbides will be explored.

Microestructura y deformación plástica a alta temperatura de óxidos eutécticos basados en Al2O3. Superplasticidad

Research head: Manuel Jiménez Melendo
Period: 01-01-2010 / 31-12-2012
Financial source: Ministerio de Ciencia y Tecnología
Code: MAT2009-13979-C03-01
Research group: Julián Martínez Fernández, Antonio Ramírez De Arellano-López, Alfonso Bravo León, Caroline Clauss Klamp, F.M. Varela Feria, C. Vaquero Aguilar

Abstract [+]

This research addresses to produce binary and ternary oxide eutectics –specifically, Al2O3/ZrO2, Al2O3/Y3Al5O12(YAG), Al2O3/ZrO2/YAG and Al2O3/SiO2/ZrO2, zirconia being stabilized with different amounts of Y2O3– with well-controlled microstructures in the micro- to nanometric range for structural and thermal applications in efficient-enhanced power generation and conversion systems: fuel cells, chemical and high-temperature gas cooled reactors, thermal barriers of steels and super alloys in gas turbines and diesel engine components, etc. These materials are very attractive because of their excellent properties: high melting point, low density, thermal conductivity and chemical reactivity, and superior mechanical performance at both low and high temperature: mechanical strength close to 5 GPa at room temperature, and high creep, wear and erosion resistance. Very recently, superplasticity has been discovered in nanosized materials by the applicant team. Oxide eutectics will be produced by laser-assisted processing techniques in three configurations: bulk, plates (on ceramic and metallic substrates) and multilaminates. For the later configuration, microarquitectures with optimized residual stresses will be designed for enhanced mechanical and thermal performance. The residual stresses will be investigated by using piezo- and Raman spectroscopy, and the data compared to numerical predictions. Laser techniques will be also used to modify the microstructure of conventional ceramic coatings deposited on metallic engine components by Air Plasma Spray, and for machining of ceramic components to obtain a given functional geometry or to modify the external surfaces for improved wear behavior. One of the main goals of this Project is to produce materials with nanosized phases in order to achieve superplasticity (which contrasts with the superior creep resistance of mi-crosized materials). This capability opens the possibility of using superplastic joining and forming as processing methods for complex pieces with near net shape, recovering back its characteristic resistance after thermal treatments. The mechanical properties (flexural and compression resistance, elastic modulus, hardness, toughness and wear) will be evaluated from room temperature up to 1950 K in air as well as under other different environmental atmospheres in order to investigate their effect in the mechanical behavior or material degradation. A significant part of the Project is the structural and microstructural characterization of the as-received materials, and their evolution during mechanical tests. Such an investigation is critical to establish relationships between the experimental mechanical behavior (necessary for engineering designs) and the microstructural and processing parameters. To this end, techniques of optical (particularly confocal), electron (image, microanalysis and diffraction) and atomic force microscopy, and X-ray diffraction with texture facilities will be used. Mechanical and microstructural data will feedback the fabrication process in order to obtain materials with tailored properties for specific applications.

Structure, packing and tribology of Fatty Self-assembled monolayers of Alkylamines

Research head: José Jesús Benítez Jiménez
Period: 01-01-2009 / 31-12-2011
Financial source: Ministerio de Ciencia y Tecnología
Code: CTQ2008-00188
Research group: Miguel Salmerón, Eduardo Garzón Garzón, Pedro J. Sánchez Soto, J. Alejandro Heredia Guerrero

Abstract [+]

The aim of this research project is to study the contribution of molecular scale events to the tribological properties of self-assembled monolayers of alkyl molecules. The amount of topographic and frictional AFM data available on typical self-assembled systems such as thiols on gold and silanes on mica is very extensive. Here, we propose alkylamines on mica as a new self-assembled system. The reason is that the weaker interaction between the amino end group and mica, if compared with S-gold and silane-mica, leads to a less effective molecular packing. The ability to control the quality of molecular packing by tunning the preparation conditions is a good model to test the contribution of defects to friction. Molecular resolution using contact AFM is not possible on alkylamine self-assembled monolayers, so there is a lack of structural information on this system. The new methodology described in this project proposes the use of Scanning Polarization Force Microscopy (SPFM) to address this issue based on the high polarization signal contrast between mica and self-assembled layers. Furthermore, the high sensitivity of SPFM to the presence of water molecules filling vacancies, can be used to evaluate the quality of the molecular packing by monitoring the screening effect exerted by the self-assembled layer. Consequently, the study of both, the frictional and the SPFM properties of self-assembled monolayers of alquilamines, are complementary to describe the contribution of defects to friction.

Ceramic composites and low-dimensional phases to waste management

Research head: Miguel Angel Castro Arroyo
Period: 01-10-2007 / 30-09-2010
Financial source: Ministerio de Educación y Ciencia
Code: CTQ2007-63297
Research group: Alba, M.D., Alvero, R., Becerro, A.I., Chain, P., Escudero, A., Naranjo, M., Trillo, J.M.

Abstract [+]

The main objective of this Project is obtaining composite materials from especially designed expansible and high layer charge laminar silicates containing low dimensional phases with effective activity for the retention and immobilization of toxic and dangerous wastes. The main innovating aspect of the Project arises, on one hand, from the confluence of the studies that the research team has performed with researchers from University of Cambridge (United Kingdom) within the development of the current national project. On the other hand, it arises from the action of reunification of the researchers who participate in a unique multidisciplinary project in the border of the basic chemistry of silicates in connection with the waste management. The proposed hypothesis, elaborated from the results obtained by the research team during the last decade, states that the effectiveness of the elimination of polluting agents by layered aluminosilicates is controlled by the structural disposition and the composition of the low dimensional phases originated during the treatments. Methodology is not limited to synthesis of the composite materials and its characterization, and it incorporates a measurement of the potential which they would represent in the treatment of wastes, essentially based on some organic polluting agents and heavy, toxic and radioactive cations. The development of the Project will affect the relations of the research team with Research Groups of the University of Bayreuth (Germany) and Cambridge (United Kingdom) and the multidisciplinary character of the Project and the noticeable academic and educational character of the team can be considered a guarantee of its high formative capacity.

Inmobilization of toxic and radioactive wastes by silicates

Research head: Miguel Angel Castro Arroyo
Period: 28-2-2007 / 1-3- 2010
Financial source: Junta de Andalucía
Code: P06-FQM-02179
Research group: Alba, M.D., Alvero, R., Becerro, A.I., Chain, P., Escudero, A., Naranjo, M., Pavón, E., Trillo, J.

Abstract [+]

In The present Project tries to use high-charged silicates, which are designed under procedures that allow controling the quantity and distribution of the tetrahedral active centers. They will be submitted to a set of chemical soft treatments in order to inmobilize toxic elements. This project will be carried out in collaboration with BEFESA and ENRESA companies. Firstly, the effect that the experimental variables involved in the procedure of synthesis exert on the distribution of the active centers of the materials will be analyzed. In the second stage, the synthetic silicates will be treated under soft hydrothermal conditions with solutions containing carefully selected toxic and radioactive elements. Finally, the degree of retention of these elements in the new obtained phases will be estimated. The Research Team (R.T.) will incorporate an experimental methodology developed by itself that includes the combined employment of Nuclear Magnetic Resonance of Solids, X-ray Diffraction, X-rays Fluorescence and Microfluorescence, which will give information of the long range order and the local environment of the active centers of the residues, responsible of it dangerousness. It will have to give direct and not yet available information of the final mechanism of fixation, which is the main objective of this Project. The expected Results will bring basic useful information about the mechanisms of interaction of metallic ions with the framework of expansible aluminosilicates and its relation with the local arrangement of their atoms. Moreover, it will bring a useful knowledge allowing to develop new suitable procedures for immobilization of industrial waste, in collaboration with the companies of the sector, which marks the innovative character of the Project.

New Bio-ceramization processes applied to vegetable hierarchical structures

Research head: Julián Martínez Fernández
Period: 01-10-2006 / 30-09-2010
Financial source: Unión Europea
Code: STRP 033277 TEM-PLANT
Research group: Ramírez de Arellano-López, A., Jiménez, M., Marrero, M., Clauss, M., Bravo, A., Quispe, J.J.

Abstract [+]

TEM-PLANT project focuses on the development and application of breakthrough processes to transform plant-derived hierarchical structures into templates for the exploitation of innovative biomedical devices with smart anisotropic performances and advanced biomechanical characteristics, designed for bone and ligament substitution.  The TEM-PLANT project primary addresses the nano-biotechnologies area and will push the current boundaries of the state-of-the-art in production of hierarchical structured biomaterials. By combining biology, chemistry, materials science, nanotechnology and production technologies, new and complex plant transformation processes will be investigated to copy smart hierarchical structures existing in nature and to develop breakthrough biomaterials that could open the door to a whole new generation of biomedical applications for which no effective solution exists to date.

Starting from suitably selected vegetal raw material, ceramization processes based on pyrolysis will be applied to produce carbon templates, which will be either infiltrated by silicon to produce inert SiC ceramic structures or exchanged by electrophoresis deposition to produce bioresorbable ceramics. For ligament yielding two processes will be developed: pH-controlled and electrophoresis-controlled fibration to generate fibrous collagenous cords with high tensile strength and wear-resistance.

Crust to core: The fate of subducted material

Research head: Ana Isabel Becerro Nieto
Period: 01-7-2006 / 31-01-2011
Financial source: Unión Europea
Code: MRTN-CT-2006-035957
Research group: Universidad de Bayreuth (Alemania), Universidad de Milán (Italia), University College London (Reino Unido), Geological Survey of Norway (Noruega), Universidad Pierre et Marie Curie, París (Francia), Friedrich Schiller Universitat Jena (Alemania), UniverzitaKarlova V Praga (República Checa)

Abstract [+]

At convergent plate boundaries material is transported from the Earth's surface to its interior; this is one of the central processes in the solid Earth, determining its dynamic, chemical, and thermal evolution. It is linked to a wide range of surface features, ranging from plate tectonics to earthquakes and volcanoes to the chemical evolution of the Earth's atmosphere.Despite this importance many aspects of the subduction process and associated material fluxes are poorly understood to date, and advances in understanding require the integrated efforts of many sub-disciplines in the Earth sciences as well as integration of neighbouring fields. To overcome the fragmentation and advance the basic understanding of the subduction process we form a European network which combines unique facilities and expertise in petrology, experimental and computational mineralogy, analysis, synthesis, and dynamic studies of the Earth's interior.


Experimental measurement of the filtration efficiency and pressure drop of wall-flow diesel particulate filters (DPF) made of biomorphic Silicon Carbide using laboratory generated particles

Orihuela, MP; Gomez-Martin, A; Miceli, P; Becerra, JA; Chacartegui, R; Fino, D
Applied Thermal Engineering, 131 (2018) 41-53


Biomorphic Silicon Carbide (bioSiC) has been recently introduced in the scope of porous ceramic substrates for hot gas filtration applications, where it has demonstrated to have good thermal and mechanical properties, and a high potential to meet the requirements for current Diesel Particulate Filters (DPF). In this experimental study, a small wall-flow bioSiC diesel filter was characterized using a soot generator, the particle size distribution of which being similar to the one generated by a diesel engine. The bioSiC samples were manufactured from Medium Density Fiberboard (MDF) following a general manufacturing procedure for bioSiC ceramics, but paying special attention in the mechanizing stage to the geometry and optimal design of the honeycomb structure required for diesel engine applications. The samples had a cell density of 57.59 cell/cm(2) (371.6 cpsi), a square cross section of 9.2 x 9.2 mm, and a length of 31 mm. To generate the particle laden stream and perform the filtration tests, a synthetic Soot Generator (SG) was used. Tests were performed under controlled and reproducible conditions, with a fixed gas flow rate of 5 LPM and a soot mass flow rate of 4 mg/h. The filtration efficiency was determined with the aid of a Scanning Mobility Particle Sizer (SMPS) from the measurements of the particle concentration upstream and downstream the filter samples. During the soot loading process, the pressure drop was also monitored. The results show that, in the initial stage (clean filter), bioSiC wall-flow DPFs may have a filtration efficiency between 0.7 and 0.85 and a pressure drop of around 2 kPa for a normalized wall velocity of 0.01 m/s at ambient temperature. The filtration performance of wall-flow bioSiC particle filters showed in this work can help us to better understand their real potential for automotive applications. 

February, 2018 | DOI: 10.1016/j.applthermaleng.2017.11.149

Packing Defects in Fatty Amine Self-Assembled Monolayers on Mica as Revealed from AFM Techniques

Benitez, JJ; Heredia-Guerrero, JA; San-Miguel, MA; Galloway, HC
Journal of Physical Chemistry B, 122 (2018) 493-499


Self-assembled monolayers of n-octadecylamine (ODA-SAMs) on mica have been prepared and studied by contact and jumping mode atomic force microscopy (AFM). Adhesion and friction data show that the compactness of the monolayers spontaneously increases as they are allowed to ripen. Molecular packing can also be induced by the controlled mechanical perturbation exerted by the probe when getting into and out of contact intermittently. Under these conditions, defects and vacancies aggregate giving rise to detectable pinholes uniformly distributed in AFM images. Created pinhole density was found to decrease with ripening time, thus confirming the proposed spontaneous self-healing mechanism. Pinhole density is also suggested as a parameter characterizing the packing degree of ODA-SAMs, and it has been related to their tribological properties. Additionally, molecular dynamics simulations were used to corroborate the compatibility between the packing degree and the observed topography of ODA-SAMs on mica.

January, 2018 | DOI: 10.1021/acs.jpcb.7b03603


Performance of biomorphic Silicon Carbide as particulate filter in diesel boilers

Orihuela, M Pilar; Gomez-Martin, Aurora; Becerra, Jose A; Chacartegui, Ricardo; Ramirez-Rico, Joaquin
Journal of Environmental Management, 203 (2017) 907-919


Biomorphic Silicon Carbide (bioSiC) is a novel porous ceramic material with excellent mechanical and thermal properties. Previous studies have demonstrated that it may be a good candidate for its use as particle filter media of exhaust gases at medium or high temperature. In order to determine the filtration efficiency of biomorphic Silicon Carbide, and its adequacy as substrate for diesel particulate filters, different bioSiC-samples have been tested in the flue gases of a diesel boiler. For this purpose, an experimental facility to extract a fraction of the boiler exhaust flow and filter it under controlled conditions has been designed and built. Several filter samples with different microstructures, obtained from different precursors, have been tested in this bench. The experimental campaign was focused on the measurement of the number and size of particles before and after placing the samples. Results show that the initial efficiency of filters made from natural precursors is severely determined by the cutting direction and associated microstructure. In biomorphic Silicon Carbide derived from radially cut wood, the initial efficiency of the filter is higher than 95%. Nevertheless, when the cut of the wood is axial, the efficiency depends on the pore size and the permeability, reaching in some cases values in the range 70–90%. In this case, the presence of macropores in some of the samples reduces their efficiency as particle traps. In continuous operation, the accumulation of particles within the porous media leads to the formation of a soot cake, which improves the efficiency except in the case when extra-large pores exist. For all the samples, after a few operation cycles, capture efficiency was higher than 95%. These experimental results show the potential for developing filters for diesel boilers based on biomorphic Silicon Carbide.

December, 2017 | DOI: 10.1016/j.jenvman.2017.05.003

High temperature compressive strength and creep behavior of Si-Ti-C-O fiber-bonded ceramics

Vera, MC; Martinez-Fernandez, J; Singh, M; Ramirez-Rico, J
Journal of the European Ceramic Society, 37 (2017) 4442-4448


Fiber bonded silicon carbide ceramic materials provide cost-advantage over traditional ceramic matrix composites and require fewer processing steps. Despite their interest in extreme environment thermostructural applications no data on long term mechanical reliability other than static fatigue is available for them. We studied the high temperature compressive strength and creep behavior of a fiber bonded SiC material obtained by hot-pressing of Si Ti-C-O fibers. The deformation mechanism and onset of plasticity was evaluated and compared with other commercial SiC materials. Up to 1400 degrees C, plasticity is very limited and any macroscopic deformation proceeds by crack formation and damage propagation. A transient viscous creep stage is observed due to flow in the silica matrix and once steady state is established, a stress exponent n similar to 4 and an activation energy Q similar to 700 kJ mol(-1) are found. These results are consistent with previous data on creep of polymer derived SiC fibers and polycrystals.

December, 2017 | DOI: 10.1016/j.jeurceramsoc.2017.06.037

Effect of the crystal chemistry on the hydration mechanism of swelling micas

Pavon, E; Alba, MD; Castro, MA; Cota, A; Osuna, FJ; Pazos, MC
Geochimica et Cosmochimica Acta, 217 (2017) 231-239


Swelling and dehydration under minor changes in temperature and water vapor pressure is an important property that clays and clay minerals exhibit. In particular, their interlayer space, the solid-water interface and the layers' collapse and re-expansion have received much attention because it affects to the dynamical properties of interlayer cations and thus the transfer and fate of water and pollutants. In this contribution, the dehydration and rehydration mechanism of a swelling high-charge mica family is examined by in situ X-ray Diffraction. The effect of the aluminosilicate layer charge and the physicochemical properties of the interlayer cations on these processes are analyzed. The results showed that the dehydration temperature and the number of steps involved in this process are related to the layer charge of the silicate and the physicochemical properties of the interlayer cations. Moreover, the ability to adsorb water molecules in a confined space with high electric field by the interlayer cations does not only depend on their hydration enthalpy but also on the electrostatic parameters of these cations.

November, 2017 | DOI: 10.1016/j.gca.2017.08.028

Cellulose-polyhydroxylated fatty acid ester-based bioplastics with tuning properties: Acylation via a mixed anhydride system

Heredia-Guerrero, JA; Goldoni, L; Benitez, JJ; Davis, A; Ceseracciu, L; Cingolani, R; Bayer, IS; Heinze, T; Koschella, A; Heredia, A; Athanassiou, A
Carbohydrate Polymers, 173 (2017) 312-320


The synthesis of microcrystalline cellulose (MCC) and 9,10,16-hydroxyhexadecanoic (aleuritic) acid ester-based bioplastics was investigated through acylation in a mixed anhydride (trifluoroacetic acid (TFA)/trifluoroacetic acid anhydride (TFAA)), chloroform co-solvent system. The effects of chemical interactions and the molar ratio of aleuritic acid to the anhydroglucose unit (AGU) of cellulose were investigated. The degree of substitution (DS) of new polymers were characterized by two-dimensional solution-state NMR and ranged from 0.51 to 2.60. The chemical analysis by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the presence of aleuritate groups in the structure induces the formation of new H-bond networks. The tensile analysis and the contact angle measurement confirmed the ductile behavior and the hydrophobicity of the prepared bioplastics. By increasing the aleuritate amounts, the glass transition temperature decreased and the solubility of bioplastic films in most common solvents was improved. Furthermore, this new polymer exhibits similar properties compared to commercial cellulose derivatives.

October, 2017 | DOI: 10.1016/j.carbpol.2017.05.068

High-temperature thermal conductivity of biomorphic SiC/Si ceramics

Ramirez-Rico, J.; Singh, M.; Zhu, D.; Martinez-Fernandez, J.
Journal of Materials Science, 52 (2017) 10038-10046


Thermal conductivity of biomorphic SiC/Si, a silicon carbide + silicon containing two phase material, was evaluated using the laser steady-state heat flux method. These materials were processed via silicon melt infiltration of wood-derived carbon scaffolds. In this approach, heat flux was measured through the thickness when one side of the specimen was heated with a 10.6-A mu m CO2 laser. A thin mullite layer was applied to the heated surface to ensure absorption and minimize reflection losses, as well as to ensure a consistent emissivity to facilitate radiative loss corrections. The influence of the mullite layer was accounted for in the thermal conductivity calculations. The effect of microstructure and composition (inherited from the wood carbonaceous performs) on measured conductivity was evaluated. To establish a baseline for comparison, a dense, commercially available sintered SiC ceramic was also evaluated. It was observed that at a given temperature, thermal conductivity falls between that of single-crystal silicon and fine-grained polycrystalline SiC and can be rationalized in terms of the SiC volume fraction in biomorphic SiC/Si material.

September, 2017 | DOI: 10.1007/s10853-017-1199-y

Biomorphic ceramics from wood-derived precursors

Ramirez-Rico, J.; Martinez-Fernandez, J.; Singh, M.
International Materials Reviews, 62 (2017) Issue 8


Materials development is driven by microstructural complexity and, in many cases, inspired by biological systems such as bones, shells and wood. In one approach, one selects the main microstructural features responsible for improved properties and design processes to obtain materials with such microstructures (continuous-fibre-reinforced ceramics, porous ceramics, fibrous ceramic monoliths, etc.). In a different approach, it is possible to use natural materials directly as microstructural templates. Biomorphic ceramics are produced from natural and renewable resources (wood or wood-derived products). A wide variety of SiC-based ceramics can be fabricated by infiltration of silicon or silicon alloys into cellulose-derived carbonaceous templates, providing a low-cost route to advanced ceramic materials with near-net shape potential and amenable to rapid prototyping. These materials have tailorable microstructure and properties, and behave like ceramic materials manufactured by advanced ceramic processing approaches. This review aims to be a comprehensive description of the development of bioSiC ceramics: from wood templates and their microstructure to potential applications of bioSiC materials.

August, 2017 | DOI: 10.1080/09506608.2017.1354429

Cutin from agro-waste as a raw material for the production of bioplastics

Heredia-Guerrero, JA; Heredia, A; Dominguez, E; Cingolani, R; Bayer, IS; Athanassiou, A; Benitez, JJ
Journal of Experimental Botany, 68 (2017) 5401-5410


Cutin is the main component of plant cuticles constituting the framework that supports the rest of the cuticle components. This biopolymer is composed of esterified bi- and trifunctional fatty acids. Despite its ubiquity in terrestrial plants, it has been underutilized as raw material due to its insolubility and lack of melting point. However, in recent years, a few technologies have been developed to obtain cutin monomers from several agro-wastes at an industrial scale. This review is focused on the description of cutin properties, biodegradability, chemical composition, processability, abundance, and the state of art of the fabrication of cutin-based materials in order to evaluate whether this biopolymer can be considered a source for the production of renewable materials.

August, 2017 | DOI: 10.1093/jxb/erx272

New insights into surface-functionalized swelling high charged micas: Their adsorption performance for non-ionic organic pollutants

Pazos, MC; Castro, MA; Cota, A; Osuna, FJ; Pavon, E; Alba, MD
Journal of Industrial and Engineering Chemistry, 52 (2017) 179-186


The major components of the wastewater from the petroleum refineries are benzene, toluene and phenol and one of the techniques applied to the treatment of effluents is sorption using organo-functionalized clay. The materials exploited in the present study are a family of surface-functionalized synthetic micas and their sorption capacities for non-ionic organic pollutants are analyzed. The organo-functionalization of their surface provides them the capacity to sorb effectively non-ionic pollutants in the interface. Their adsorption performance is a function of the alkylamonium properties such as the chain length, the mass fraction and the organization of the organic cation in the interlayer space of the micas.

August, 2017 | DOI: 10.1016/j.jiec.2017.03.042

Cs+ immobilization by designed micaceous adsorbent under subcritical conditions

Osuna, FJ; Cota, A; Pavon, E; Pazos, MC; Alba, MD
Applied Clay Science, 143 (2017) 293-299


The adsorption of Cs+ by clay minerals is a complicate process, being cation exchange and frayed-edge sites the major mechanisms that govern it. However, environmental variables have a significant impact on the process. In this work, the influence of the temperature and time in the cesium adsorption capacity of Na-Mica-n (n = 2 and 4) have been explored under subcritical conditions. Those synthetic micas were able to immobilize cations Cs+ combining adsorption at nonspecific sites, at specific sites and chemical reaction. The distribution constant of Cs+ was larger in the Na-Mica-2 denoting a higher concentration of specific adsorption sites when layer charge decreased.

July, 2017 | DOI: 10.1016/j.clay.2017.03.041

Failure mode and effect analysis of a large scale thin-film CIGS photovoltaic module

Delgado-Sanchez, JM; Sanchez-Cortezon, E; Lopez-Lopez, C; Aninat, R; Alba, MD
Engireering failure analysis, 76 (2017) 55-60


The efficiency of thin-film CIGS based cells at the laboratory scale is now getting closer to conventional Silicon technologies. As a consequence, the long-term stability of CIGS is now one of the main challenges left to address in order to assess its potential as an alternative for photovoltaic plants. This paper reports an overview of the critical risks for the commercial viability of the CIGS thin-film technology. The key causes of the potential failures of this technology are determined through the Failure Mode Analysis and Effects (FMEA) methodology. To validate the results obtained from the FMEA, aging tests and outdoor monitoring were also carried out. Based on the results obtained, we argue that the encapsulation material is the main cause of degradation in CIGS modules. 

June, 2017 | DOI: 10.1016/j.engfailanal.2017.02.004

Features of electrical properties of BE-C(Fe) biocarbons carbonized in the presence of an Fe-containing catalyst

Popov, VV; Orlova, TS; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the Solid State


The effect of partial graphitization on electrical and galvanomagnetic properties of BE-C(Fe) biomorphic carbons produced by beech wood carbonization at temperatures of 850-1600A degrees C in the presence of an iron-containing catalyst is studied. The use of an Fe catalyst at D cent (carb) ae<yen> 1000A degrees C leads to the formation of nanoscale graphite-phase inclusions; its total volume and nanocrystallite sizes increase with D cent (carb). The data on the carrier concentration and mobility are obtained. It was shown that partially graphitized BE-C(Fe) carbons with D cent (carb) ae<yen> 1000A degrees C in the conductivity type and magnetoresistance features relate to highly disordered metal systems whose conductivity can be described taking into account the contribution of quantum corrections, mainly the correction caused by the electron-electron interaction. It is shown that nonmonotonic dependences of the Hall constant R on the magnetic field are characteristic of BE-C(Fe) samples with 1000 ae<currency> D cent (carb) < 1600A degrees C, which is most probably caused by the contribution of various carrier groups, i.e., electrons and holes. In BE-C(Fe) samples with D cent (carb) = 1600A degrees C, the Hall coefficient corresponds to the metal state, which is associated with conducting medium homogenization resulting from the formation of a significant graphite phase volume.

April, 2017 | DOI: 10.1134/S1063783417040205

Precision and accuracy of stress measurement with a portable X-ray machine using an area detector

Lee, SY; Ling, JJ; Wang, SH; Ramirez-Rico, J
Journal of Applied Crystallography, 50 (2017) 131-144


The use of portable X-ray stress analyzers, which utilize an area detector along with the newly adopted 'cos alpha' or full-ring fitting method, has recently attracted increasing interest. In laboratory conditions, these measurements are fast, convenient and precise because they employ a single-exposure technique that does not require sample rotation. In addition, the effects of grain size and orientation can be evaluated from the Debye ring recorded on the area detector prior to data analysis. The accuracy of the measured stress, however, has been questioned because in most cases just a single reflection is analyzed and the sample-to-detector distances are relatively short. This article presents a comprehensive analysis of the uncertainty associated with a state-of-the-art commercial portable X-ray device. Annealed ferrite reference powders were used to quantify the instrument precision, and the accuracy of the stress measurement was tested by in situ tensile loading on 1018 carbon steel and 6061 aluminium alloy bar samples. The results show that the precision and accuracy are sensitive to the instrument (or sample) tilt angle (0) as well as to the selected hkl reflection of the sample. The instrument, sample and data analysis methods all affect the overall uncertainty, and each contribution is described for this specific portable X-ray system. Finally, on the basis of the conclusions reached, desirable measurement/analysis protocols for accurate stress assessments are also presented.

February, 2017 | DOI: 10.1107/S1600576716018914

Front contact optimization of industrial scale CIGS solar cells for low solar concentration using 2D physical modeling

Delgado-Sanchez, JM; Lopez-Gonzalez, JM; Orpella, A; Sanchez-Cortezon, E; Alba, MD; Lopez-Lopez, C; Alcubilla, R
Renewable Energy, 101 (2017) 90-95


Cu(In,Ga)Se-2 (CIGS) technology is one of the best absorber materials with record efficiencies among photovoltaic thin-film technologies (22.3% at lab scale and 16% at large commercial module). Although research on this material was originally motivated by low-cost, glass-glass applications focusing to fixed photovoltaic structures, the high efficiency values make CIGS an interesting alternative for low concentration systems. In this paper a 2D model for Cu(In,Ga)Se-2 (CIGS) solar cells under low solar concentration is described and contrasted with experimental data. Using simulation, the effect of front electric contact design parameters: finger width, finger separation, and number of buses are analyzed for solar concentrations from 1 up to 10 suns. Efficiency maps allowing front contact grid optimization are shown and analyzed for each concentration factor (Cx), assessing the viability of CIGS solar cells for low concentration applications, where commercial CIGS solar cells may exhibit 35% of electrical power increases with proper front grid optimization under low concentration respect to conventional grid design. 

January, 2017 | DOI: 10.1016/j.renene.2016.08.046

Insolubilization and thermal stabilization of a long-chain polyester by noncatalyzed melt-polycondensation synthesis in air

Benitez, JJ; Heredia-Guerrero, JA; Cruz-Carrillo, MA; Barthel, MJ; Knicker, HE; Heredia, A
Journal of Applied Polymer Science, 134 (2017) 1 art 44350


Self-standing films of poly(-hydroxyl hexadecanoic acid) [poly(-OHC16)] have been prepared by noncatalyzed melt-polycondensation in air at 150, 175, and 200 degrees C. Poly(-OHC16)s obtained are characterized as polyesters by infrared spectroscopy (FT-IR) and solid state magic angle spinning C-13 nuclear magnetic resonance (C-13 MAS-NMR). Structurally, poly(-OHC16)s are quite crystalline as revealed by wide angle X-ray diffraction (WAXD). The presence of oxygen in the reaction atmosphere causes a mild oxidation in the form of peroxyester species, tentatively at the interphase between poly(-OHC16) crystallites, and the structure amorphization. The interfacial peroxyester phase ends up in the encapsulation of the polyester grains and provides a barrier towards the action of solvents. Thermal stabilization and insolubility resulting from the synthesis conditions used are interesting features to prepare solvent and heat resistant poly(-OHC16) coatings. Thus, a few microns thick poly(-OHC16) layer has been fabricated on aluminum foil and its resistivity towards a chloroform:methanol (1:1, v:v) mixture has been confirmed.

December, 2016 | DOI: 10.1002/app.44350


Microstructure, elastic, and inelastic properties of biomorphic carbons carbonized using a Fe-containing catalyst

Orlova, TS; Kardashev, BK; Smirnov, BI; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the Solid State, 58 (2016) 2481-2487


The microstructure and amplitude dependences of the Young’s modulus E and internal friction (logarithmic decrement δ), and microplastic properties of biocarbon matrices BE-C(Fe) obtained by beech tree carbonization at temperatures Tcarb = 850–1600°C in the presence of an iron-containing catalyst are studied. By X-ray diffraction analysis and transmission electron microscopy, it is shown that the use of Fe-catalyst during carbonization with Tcarb ≥ 1000°C leads to the appearance of a bulk graphite phase in the form of nanoscale bulk graphite inclusions in a quasi-amorphous matrix, whose volume fraction and size increase with Tcarb. The correlation of the obtained dependences E(Тcarb) and δ(Tcarb) with microstructure evolution with increasing Тcarb is revealed. It is found that E is mainly defined by a crystalline phase fraction in the amorphous matrix, i.e., a nanocrystalline phase at Тcarb < 1150°C and a bulk graphite phase at Tcarb > 1300°C. Maximum values E = 10–12 GPa are achieved for samples with Тcarb ≈ 1150 and 1600°C. It is shown that the microplasticity manifest itself only in biocarbons with Tcarb ≥ 1300°C (upon reaching a significant volume of the graphite phase); in this case, the conditional microyield stress decreases with increasing total volume of introduced mesoporosity (free surface area).

December, 2016 | DOI: 10.1134/S1063783416120234

Manganese Dioxide Supported on Porous Biomorphic Carbons as Hybrid Materials for Energy Storage Devices

Gutierrez-Pardo, A; Lacroix, B; Martinez-Fernandez, J; Ramirez-Rico, J
ACS Applied Materials & Interfaces, 8 (2016) 30890-30898


A facile and low-cost method has been employed to fabricate MnO2/C hybrid materials for use as binder-free electrodes for supercapacitor applications. Biocarbon monoliths were obtained through pyrolysis of beech wood, replicating the microstructure of the cellulosic precursor, and serve as 3D porous and conductive scaffolds for the direct growth of MnO, nanosheets by a solution method. Evaluation of the experimental results indicates that a homogeneous and uniform composite material made of a carbon matrix exhibiting ordered hierarchical porosity and MnO, nanosheets with a layered nanocrystalline structure is obtained. The tuning of the MnO2 content and crystallite size via the concentration of KMnO4 used as impregnation solution allows to obtain composites that exhibit enhanced electrochemical behavior, achieving a capacitance of 592 F g(-1) in electrodes containing 3 wt % MnO2 with an excellent cyclic stability. The electrode materials were characterized before and after electrochemical testing.

November, 2016 | DOI: 10.1021/acsami.6b09361

Thermal conductivity of porous biomorphic SiC derived from wood precursors

Gomez-Martin, A; Orihuela, MP; Ramirez-Rico, J; Chacartegui, R; Martinez-Fernandez, J
Ceramics International, 42 (2016) 16220-16229


Biomorphic SiC is a SiC/Si composite made by the reactive infiltration of molten silicon by capillarity into a carbon preform from high-temperature pyrolysis of a wood porous precursor. When excess silicon is removed, a hierarchically porous SiC material with highly interconnected porosity is obtained. By choosing different wood precursors, different pore size distributions can be obtained thus tailoring the resulting properties. 

We study the thermal conductivity of porous biomorphic SiC from five different precursors, including a recycled wood product, in order to determine the microstructure-conductivity correlation. Here, we remove the excess of silicon by a high temperature capillary extraction-evaporation method. We used the laser flash technique to measure thermal diffusivity in the range similar to 300 K to 973 K, in order to determine the thermal conductivity. Thermal conductivities in the range 4-88 W/m K were achieved. The temperature, porosity, pore shape and orientation, and the treatment used to remove the remaining silicon all have a significant impact in the resulting thermal conductivity. We explain this influence in a first approximation in terms of a geometrical model.

November, 2016 | DOI: 10.1016/j.ceramint.2016.07.151

Enhancement of dielectric barrier layer properties by sol-gel and PECVD stacks

Lopez-Lopez, C; Menendez, MF; Menendez, LA; Menendez, A; Sanchez, P; Alba, MD; Sanchez-Cortezon, E; Delgado-Sanchez, JM
Surface and Coatings Technology, 305 (2016) 36-40


Thin-film PV modules grown on flexible, light weight, thermally stable and low cost substrates such as stainless steel foil, are an attractive product for solar market applications. When metal foils are used as substrate, it is essential to deposit a dielectric barrier layer to isolate electrically and chemically the thin-film solar cells from the substrate. In this work, SiOx stacks deposited on ‘rough’ stainless steel by a combination of a new sol-gel formulation and a Plasma Enhanced Chemical Vapor Deposition (PECVD) deposition step are reported as a suitable dielectric barrier layer candidate. Using these SiOx multilayers, a smooth and homogeneous film was achieved. X-ray diffraction (XRD) analysis showed that back contact of the solar cell (based on Molybdenum) is not affected by the presence of the barrier layer. Moreover, according to X-ray photoelectron spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) measurements, this approach led to excellent barrier layer properties against the diffusion of impurities from the stainless steel. A complete electrical characterization of these dielectric barrier layers was also carried out showing good electrical insulation.

November, 2016 | DOI: 10.1016/j.surfcoat.2016.07.085

Permeability and mechanical integrity of porous biomorphic SiC ceramics for application as hot-gas filters

Gomez-Martin, A.; Orihuela, M. P.; Becerra, J. A.; Martinez-Fernandez, J.; Ramirez-Rico, J.
Materials & Design, 107 (2016) 450-460


Biomorphic SiC is a biotemplated material fabricated by Si melt-infiltration of carbon preforms from wood pyrolysis. In this work, porous bioSiC ceramics from five different wood precursors, with porosities between 45 and 72% were studied for their feasibility in filtering applications.

Gas permeability and mechanical stability were investigated as a function of the microstructure of the starting wood precursor. Air-permeation performance at room temperature was measured for a range of flow rates, and the permeability constants were assessed by fitting of Forchheimer's equation to the experimental data. Darcian permeabilities were achieved in the range 10− 11–10− 12 m2, while inertial terms were in the range 10− 7–10− 8 m, showing a correlation with the average pore size and orientation of the larger channels. Regarding the mechanical stability, maximum compressive strength values were reached in the range of 3–115 MPa.

These results improve our understanding of the ways in which the microstructure influences permeability and mechanical robustness, enabling the device requirements to be tailored by selecting the wood precursor. It was also shown that these materials are promising for hot-gas filtering applications.

October, 2016 | DOI: 10.1016/j.matdes.2016.06.060

Monolithic supports based on biomorphic SiC for the catalytic combustion of hydrogen

Arzac, G. M.; Ramirez-Rico, J.; Gutierrez-Pardo, A.; Jimenez de Haro, M. C.; Hufschmidt, D.; Martinez-Fernandez, J.; Fernandez, A.
RSC Advances, 6 (2016) 66373-66384


Catalytic hydrogen combustion was studied with H-2/air mixtures in conditions that simulate the H-2 concentration of the exhaust gases from fuel cells (3-4% v/v H-2 in air). Pt-impregnated monoliths based on porous biomorphic SiC (bio-SiC) substrates were employed for the first time for this reaction. Capillary forces were exploited for the incipient impregnation of supports with H2PtCl6 solutions. Freeze drying permitted us to obtain a homogeneous distribution of the active phase reducing accumulation at the monolith's outer shell. The supports and catalysts were characterized from a structural and thermal point of view. Catalytic tests were performed in a homemade reactor fed with up to 1000 ml min(-1) H-2/air mixtures and a diffusional regime (non-isothermal) was achieved in the selected conditions. Catalyst loading was tested in the range of 0.25-1.5 wt% Pt and 100% conversion was achieved in all cases. Temperatures were recorded at different points of the monoliths during the reaction showing anisotropic thermal behavior for selected bio-SiC substrates. These effects are of interest for heat management applications and were explained in correlation with thermal conductivity measurements performed on the supports. Pt-impregnated monoliths were also tested in less than 100% conversion conditions (1% v/v H-2 in air) and in powder form in kinetic conditions for comparative purposes.

September, 2016 | DOI: 10.1039/c6ra09127j

Sliding wear resistance of porous biomorphic sic ceramics

Lopez-Robledo, MJ; Gomez-Martin, A; Ramirez-Rico, J; Martinez-Fernandez, J
International Journal of Refractory Metals & Hard Materials, 59 (2016) 26-31


Porous biomorphic SiC ceramics were fabricated from four different wood precursors, three natural woods and one recycled wood product, by reactive infiltration of molten silicon into a carbon preform obtained from wood pyrolysis. Sliding wear resistance when sliding against a Si3N4 ball in air was studied. Tribological experiments were done with a pin-on-disk apparatus, under normal loads of 1 and 2 N, at a sliding velocity of 100 mm/s. The wear properties and the volume fraction of porosity were correlated. A commercial sintered SiC ceramic was also tested for comparison. The measured values of friction coefficient were in the range reported in literature for monolithic SiC ceramics under similar dry contact conditions. Two concurrent wear mechanisms are taking place: abrasion from the SiC debris and soft ploughing. The presence of an oxide tribolayer was assessed using energy dispersive X-ray analysis. Wear rates were found to scale with the composite porosity.

September, 2016 | DOI: 10.1016/j.ijrmhm.2016.05.004

Electrochemical Energy Storage Applications of CVD Grown Niobium Oxide Thin Films

Fiz, Raquel; Appel, Linus; Gutierrez-Pardo, Antonio; Ramirez-Rico, Joaquin; Mathur, Sanjay
ACS Applied Materials & Interfaces, 8 (2016) 21423–21430


We report here on the controlled synthesis, characterization, and electrochemical properties of different polymorphs of niobium pentoxide grown by CVD of new single-source precursors. Nb2O5 films deposited at different temperatures showed systematic phase evolution from low-temperature tetragonal (TT-Nb2O5, T-Nb2O5) to high temperature monoclinic modifications (H–Nb2O5). Optimization of the precursor flux and substrate temperature enabled phase-selective growth of Nb2O5 nanorods and films on conductive mesoporous biomorphic carbon matrices (BioC). Nb2O5 thin films deposited on monolithic BioC scaffolds produced composite materials integrating the high surface area and conductivity of the carbonaceous matrix with the intrinsically high capacitance of nanostructured niobium oxide. Heterojunctions in Nb2O5/BioC composites were found to be beneficial in electrochemical capacitance. Electrochemical characterization of Nb2O5/BioC composites showed that small amounts of Nb2O5 (as low as 5%) in conjunction with BioCarbon resulted in a 7-fold increase in the electrode capacitance, from 15 to 104 F g–1, while imparting good cycling stability, making these materials ideally suited for electrochemical energy storage applications.

August, 2016 | DOI: 10.1021/acsami.6b03945

Thermal conductivity of Fe graphitized wood derived carbon

Ramirez-Rico, J; Gutierrez-Pardo, A; Martinez-Fernandez, J; Popov, VV; Orlova, TS
Materials & Design, 99 (2016) 528-534


Graphitic porous carbon materials from pyrolysis of wood precursors were obtained by means of a nanosized Fe catalyst, and their microstructure and electrical and thermal transport properties investigated. Thermal and electrical conductivity of graphitized carbon materials increase with the pyrolysis temperature, indicating a relationship between the degree of graphitization and thus in crystallite size with transport properties in the resulting carbon scaffolds. Evaluation of the experimental results indicate that thermal conductivity is mainly through phonons and increases with the temperature in Fe-catalyzed carbons suggesting that the mean free path of phonons in the material is small and defect scattering dominates over phonon-phonon interactions in the range from room temperature to 800 °C.

June, 2016 | DOI: 10.1016/j.matdes.2016.03.070

Stress measurement using area detectors: a theoretical and experimental comparison of different methods in ferritic steel using a portable X-ray apparatus

Ramirez-Rico, J; Lee, SY; Ling, JJ; Noyan, IC
Journal of Materials Science, 51 (2016) 5343-5355


Using area detectors for stress determination by diffraction methods in a single exposure greatly simplifies the measurement process and permits the design of portable systems without complex sample cradles or moving parts. An additional advantage is the ability to see the entire or a large fraction of the Debye ring and thus determine texture and grain size effects before analysis. The two methods most commonly used to obtain stress from a single Debye ring are the so-called cosαcos⁡αand full-ring fitting methods, which employ least-squares procedures to determine the stress from the distortion of a Debye ring by probing a set of scattering vector simultaneously. The widely applied sin2ψsin2⁡ψ method, in contrast, requires sample rotations to probe a different subset of scattering vector orientations. In this paper, we first present a description of the different methods under the same formalism and using a unified set of coordinates that are suited to area detectors normal to the incident beam, highlighting the similarities and differences between them. We further characterize these methods by means of in situ measurements in carbon steel tube samples, using a portable detector in reflection geometry. We show that, in the absence of plastic flow, the different methods yield basically the same results and are equivalent. An analysis of possible sources of errors and their impact in the final stress values is also presented.

June, 2016 | DOI: 10.1007/s10853-016-9837-3

Biological strategy for the fabrication of highly ordered aragonite helices: the microstructure of the cavolinioidean gastropods

Checa, AG; Macias-Sanchez, E; Ramirez-Rico, J
Scientific Reports, 6 (2016) article number 25989


The Cavolinioidea are planktonic gastropods which construct their shells with the so-called aragonitic helical fibrous microstructure, consisting of a highly ordered arrangement of helically coiled interlocking continuous crystalline aragonite fibres. Our study reveals that, despite the high and continuous degree of interlocking between fibres, every fibre has a differentiated organic-rich thin external band, which is never invaded by neighbouring fibres. In this way, fibres avoid extinction. These intra-fibre organic-rich bands appear on the growth surface of the shell as minuscule elevations, which have to be secreted differentially by the outer mantle cells. We propose that, as the shell thickens during mineralization, fibre secretion proceeds by a mechanism of contact recognition and displacement of the tips along circular trajectories by the cells of the outer mantle surface. Given the sizes of the tips, this mechanism has to operate at the subcellular level. Accordingly, the fabrication of the helical microstructure is under strict biological control. This mechanism of fibre-by-fibre fabrication by the mantle cells is unlike that any other shell microstructure.

May, 2016 | DOI: 10.1038/srep25989

Biodegradable polyester films from renewable aleuritic acid: surface modifications induced by melt-polycondensation in air

Benitez, JJ; Heredia-Guerrero, JA; de Vargas-Parody, MI; Cruz-Carrillo, MA; Morales-Florez, V; de la Rosa-Fox, N; Heredia, A
Journal of Physics D-Applied Physics, 49 (2016) 175601


Good water barrier properties and biocompatibility of long-chain biopolyesters like cutin and suberin have inspired the design of synthetic mimetic materials. Most of these biopolymers are made from esterified mid-chain functionalized.-long chain hydroxyacids. Aleuritic (9,10,16-trihydroxypalmitic) acid is such a polyhydroxylated fatty acid and is also the major constituent of natural lac resin, a relatively abundant and renewable resource. Insoluble and thermostable films have been prepared from aleuritic acid by melt-condensation polymerization in air without catalysts, an easy and attractive procedure for large scale production. Intended to be used as a protective coating, the barrier's performance is expected to be conditioned by physical and chemical modifications induced by oxygen on the air-exposed side. Hence, the chemical composition, texture, mechanical behavior, hydrophobicity, chemical resistance and biodegradation of the film surface have been studied by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM), nanoindentation and water contact angle (WCA). It has been demonstrated that the occurrence of side oxidation reactions conditions the surface physical and chemical properties of these polyhydroxyester films. Additionally, the addition of palmitic acid to reduce the presence of hydrophilic free hydroxyl groups was found to have a strong influence on these parameters.

May, 2016 | DOI: 10.1088/0022-3727/49/17/175601

Strength and microplasticity of biocarbons prepared by carbonization in the presence of a catalyst

Shpeizman, VV; Orlova, TS; Smirnov, BI; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the Solid State, 58 (2016) 703-710


The microdeformation has been investigated under uniaxial compression of beech-derived biocarbons partially graphitized during carbonization in the presence of a Ni- or Fe-containing catalyst. The strength and ultimate fracture strain have been determined at different temperatures of carbonization of the samples in the absence or in the presence of a catalyst. It has been shown using high-precision interferometry that the deformation of biocarbon samples under uniaxial loading occurs through jumps (in magnitude and rate of deformation) with axial displacements in the nanometer and micrometer ranges. The use of a catalyst leads to a decrease in the size of nanometer-scale jumps and in the number of micrometer-scale jumps. The standard deviations of the strain rate on loading steps from the smooth average dependence of the strain rate on the displacement have been calculated for micrometer-scale jumps. A similar characteristic for nanometer- scale jumps has been determined from the distortion of the shape of beats in the primary interferogram. It has been shown that the variation in the standard deviation of the strain rate with a change in the carbonization temperature is similar to the corresponding dependence of the ultimate fracture strain.

April, 2016 | DOI: 10.1134/S1063783416040223

Active metal brazing of silicon nitride ceramics using a Cu-based alloy and refractory metal interlayers

Fernandez, JM; Asthana, R; Singh, M; Valera, FM
Ceramics International, 42 (2016) 5447-5454


Silicon nitride/silicon nitride joints with refractory metal (W and Mo) interlayers were vacuum brazed using an active braze, Cu-ABA (Cu-3Si-2Al-2.25Ti, wt%), and two interlayer arrangements in a double-lap offset configuration: Si3N4/Cu-ABA/W/Cu-ABA/Mo/Cu-ABA/Si3N4 and Si3N4/Cu-ABA /Si3N4. Titanium segregated at the Si3N4/Cu-ABA and Mo/Cu-ABA interfaces, but not at the W/Cu-ABA interface. The room-temperature compression-shear strength values of Si3N4/Cu-ABA/Si3N4 and Si3N4/Cu-ABA/W/Cu-ABA/Mo/Cu-ABA/Si3N4 joints were 118 +/- 24 MPa and 22 +/- 5 MPa, respectively. Elevated-temperature compression tests showed that Si3N4/Cu-ABA/Si3N4 joints had strength of 31 +/- 6 MPa at 1023 K and 17 +/- 3 MPa at 1073 K. Likewise, Si3N4/Cu-ABA/W/Cu-ABA/Mo/Cu-ABA/Si3N4 joints had strength of 19 +/- 4 MPa at 1023 K and 13 +/- 3 MPa at 1073 K. Knoop microhardness profiles revealed hardness gradients across the joints. The effect of joint microstructure and test configuration on the mechanical behavior is discussed.

March, 2016 | DOI: 10.1016/j.ceramint.2015.12.087

Influence of temperature and time on the Eu3+ reaction with synthetic Na-Mica-n (n=2 and 4)

Garcia-Jimenez, MJ; Cota, A; Osuna, FJ; Pavon, E; Alba, MD
Chemical Engineering Journal, 284 (2016) 1174-1183


Bentonite is accepted as the best clay material for the engineered barrier of Deep Geological Repositories (DGRs). The performance of clay as the main component of the engineered barrier in the DGR has been intensively studied and the structure of the selected clay mineral play a crucial role. In this sense, a new family of synthetic swelling silicates, Na-Mica-n, with tuned layer charge (n) values between 2.0 and 4.0 per unit cell has recently been synthesized and a general synthetic method has been reported. These swelling high-charge micas could be highly valuable for the decontamination of harmful cations. The ability of these micas to immobilize Eu3+ under subcritical conditions has been probed. The adsorption was in both non-specific sites (cation exchange mechanism) and specific sites (chemical reaction or surface defects adsorption). Moreover, its adsorption capacity, under the same conditions is higher than in saponite and far superior to the bentonites. 

January, 2016 | DOI: 10.1016/j.cej.2015.09.077

Thermal conductivity of partially graphitized biocarbon obtained by carbonization of medium-density fiberboard in the presence of a Ni-based catalyst

Orlova, TS; Parfen'eva, LS; Smirnov, BI; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the Solid State, 58 (2016) 208-214


The thermal conductivity k and resistivity rho of biocarbon matrices, prepared by carbonizing medium-density fiberboard at T (carb) = 850 and 1500A degrees C in the presence of a Ni-based catalyst (samples MDF-C( Ni)) and without a catalyst (samples MDF-C), have been measured for the first time in the temperature range of 5-300 K. X-ray diffraction analysis has revealed that the bulk graphite phase arises only at T (carb) = 1500A degrees C. It has been shown that the temperature dependences of the thermal conductivity of samples MDFC- 850 and MDF-C-850(Ni) in the range of 80-300 K are to each other and follow the law of k(T) similar to T (1.65), but the use of the Ni-catalyst leads to an increase in the thermal conductivity by a factor of approximately 1.5, due to the formation of a greater fraction of the nanocrystalline phase in the presence of the Ni-catalyst at T (carb) = 850A degrees C. In biocarbon MDF-C-1500 prepared without a catalyst, the dependence is k(T) similar to T (1.65), and it is controlled by the nanocrystalline phase. In MDF-C-1500(Ni), the bulk graphite phase formed increases the thermal conductivity by a factor of 1.5-2 compared to the thermal conductivity of MDF-C-1500 in the entire temperature range of 5-300 K; k(T = 300 K) reaches the values of similar to 10 W m(-1) K-1, characteristic of biocarbon obtained without a catalyst only at high temperatures of T (carb) = 2400A degrees C. It has been shown that MDF-C-1500(Ni) in the temperature range of 40aEuro'300 K is characterized by the dependence, k(T) similar to T (1.3), which can be described in terms of the model of partially graphitized biocarbon as a composite of an amorphous matrix with spherical inclusions of the graphite phase.

January, 2016 | DOI: 10.1134/S1063783416010236


Impact of hydrothermal treatment of FEBEX and MX80 bentonites in water, HNO3 and Lu(NO3)(3) media: Implications for radioactive waste control

Osuna, FJ; Chain, P; Cota, A; Pavon, E; Alba, MD
Applied Clay Science, 118 (2015) 48-55


Engineered barriers of deep geological repositories (DGR) are commonly constructed with bentonite. FEBEX and MX80 bentonites have been selected by different countries as reference materials for the sealing of repositories; however, their chemical reactivity with high-level long-lived radioactive wastes (HLRW) under subcritical conditions had not been explored before. The hydrothermal stability in neutral and acid media and chemical reactivity in contact with an actinide analogous compound were both studied. The long-range and short-range structural changes were analyzed by X-ray diffraction, nuclear magnetic resonance and scanning electron microscopy. Both bentonites have exhibited a good stability in neutral and acid media and have generated a new phase immobilizing the actinide analogous compound. The extent of the chemical reaction is higher in MX80 bentonite than in FEBEX bentonite. 

December, 2015 | DOI: 10.1016/j.clay.2015.08.036

Specific features of the electrical properties in partially graphitized porous biocarbons of beech wood

Popov, VV; Orlova, TS; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the solid state, 57 (2015) 1746-1751


The electrical and galvanomagnetic properties of partially graphitized highly porous bioC(Ni) biocarbon matrices produced by pyrolysis (carbonization) of beech wood at temperatures T (carb) = 850-1600A degrees C in the presence of a Ni-containing catalyst have been studied in comparison with their microstructural features. The temperature dependences of the resistivity, the magnetoresistance, and the Hall coefficient have been measured in the temperature range of 4.2-300 K in magnetic fields to 28 kOe. It has been shown that an additional graphite phase introduction into samples with T (carb) a parts per thousand yen 1000A degrees C results in an increase in the carrier mobility by a factor of 2-3, whereas the carrier (hole) concentration remains within similar to 10(20) cm(-3), as in biocarbons obtained without catalyst. An analysis of experimental data has demonstrated that the features of the conductivity and magnetoresistance of these samples are described by quantum corrections related to their structural features, i.e., the formation of a globular graphite phase of nano- and submicrometer sizes in the amorphous matrix. The quantum corrections to the conductivity decrease with increasing carbonization temperature, which indicates an increase in the degree of structure ordering and is in good agreement with microstructural data.

September, 2015 | DOI: 10.1134/S1063783415090280

Viability of adding gypsum and calcite for remediation of metal-contaminated soil: laboratory and pilot plant scales

Gonzalez-Nunez, R; Alba, MD; Vidal, M; Rigol, A
International Journal of Environmental Science and Technology, 12 (2015) 2697-2710


The effect of adding waste materials (gypsum and calcite) for the remediation of a soil contaminated by pyritic minerals was examined. Materials were characterised in terms of their acid neutralisation capacity (ANC), sorption capacity and structural components. Their effect on the contaminant leaching in soil + material mixtures over a wide range of pH was also evaluated. Results at laboratory and pilot plant scales were compared to account for the potential variability in the material efficiency when applied at larger scale. The use of gypsum permitted its valorisation, although calcite was a more effective amendment because its addition led to a greater increase in the pH and acid neutralisation capacity, and thus in the sorption capacity in the resulting soil + material mixture. In the same way, when the combination of gypsum + calcite was added to the soil, it led to an increase in the pH from 2.5 to 6.9 and in the ANC from −86 to 1,513 meq/kg. As a result, the concentration of extractable heavy metals and As was reduced, and they were successfully immobilised both at laboratory and at pilot plant scales. Thus, the use of these materials induced a significant reduction in the contaminant mobility and permitted the valorisation of waste materials.

August, 2015 | DOI: 10.1007/s13762-014-0671-3

Uranium immobilization by FEBEX bentonite and steel barriers in hydrothermal conditions

Villa-Alfageme, M; Hurtado, S; El Mrabet, S; Pazos, MC; Castro, MA; Alba, MD
Chemical Engineering Journal, 269 (2015) 279-287


FEBEX clay is considered a reference material in engineered barriers for safe storage of nuclear waste and uranium is a minor component of high-level radioactive waste (HLRW) and a main component of the spent nuclear fuel (SNF). Here, the kinetics of reaction of uranium with FEBEX was investigated in addition to the uranium immobilisation ability and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with UO22+ and tetravalent actinide simulator ZrO2+, also present in HLRW. The quantification of the reaction was performed through gamma spectrometry of uranium. Two mechanisms for UO22+ retention by FEBEX were detected: adsorption and formation of stable and insoluble new phases. The structural analyses performed using ZrO2+, confirmed the uranium adsorption and the presence of new phases, ZrO2 and Zr(SiO4), that emphasise the existence of a chemical reaction with the bentonite. The analysis of the velocity of reaction uranium-clay minerals revealed temperature dependence. An exponential fitting suggested that the removal of uranium from solution at temperatures over 200 °C could be completed in less than a year. For lower temperatures, several years are needed. Milliequivalents of UO22+ immobilised by the clay depended on temperature and time and were over cation exchange capacity (CEC) of FEBEX even at 100 °C (reaching 600% of CEC). The reaction with steel, also temperature dependent, was finally analysed. At 200 °C 40–70% of uranium reacted with steel. But only 30–15% reacted at 300 °C and 100 °C. The reactions provide a stable immobilisation mechanism for uranium even when its sorption and swelling capacities fail. Our experiments will be of particular interest for very deep borehole disposals were higher temperatures and pressures are expected.

June, 2015 | DOI: 10.1016/j.cej.2015.01.134

Self-Assembling of Tetradecylammonium Chain on Swelling High Charge Micas (Na-Mica-3 and Na-Mica-2): Effect of Alkylammonium Concentration and Mica Layer Charge

Pazos, MC; Cota, A; Osuna, FJ; Pavon, E; Alba, MD
Langmuir, 31 (2015) 4394-4401


A family of tetradecylammonium micas is synthesized using synthetic swelling micas with high layer charge (NanSi8-nAln,Mg6F4O20 center dot XH2O, where n = 2 and 3) exchanged with tetradecylammonium cations. The molecular arrangement of the surfactant is,elucidated on the basis of XRD patterns and DTA. The ordering conformation of the surfactant molecules into the interlayer space of Micas is investigated by IR/FT, C-13, Al-27, and Si-29 MAS NMR. The structural arrangement of the tetradecylammonium cation in the interlayer space of high-charge micas is more sensitive to the effect of the mica layer charge at high concentration. The surfactant arrangement is found to follow the bilayer-paraffin model for all values of layer charge and surfactant concentration. However, at initial concentration below the mica CEC, a lateral monolayer is also observed. The amount of ordered conformation all-trans is directly proportional to the layer charge and surfactant concentration.

April, 2015 | DOI: 10.1021/acs.langmuir.5b00224

Pectin-Lipid Self-Assembly: Influence on the Formation of Polyhydroxy Fatty Acids Nanoparticles

Guzman-Puyol, Susana; Jesus Benitez, Jose; Dominguez, Eva; Bayer, Ilker Sefik; Cingolani, Roberto; Athanassiou, Athanassia; Heredia, Antonio; Heredia-Guerrero, Jose Alejandro
Plos One, 10 (2015) e0124639


Nanoparticles, named cutinsomes, have been prepared from aleuritic (9,10,16-trihidroxipalmitic) acid and tomato fruit cutin monomers (a mixture of mainly 9(10), 16-dihydroxypalmitic acid (85%, w/w) and 16-hydroxyhexadecanoic acid (7.5%, w/w)) with pectin in aqueous solution. The process of formation of the nanoparticles of aleuritic acid plus pectin has been monitored by UV-Vis spectrophotometry, while their chemical and morphological characterization was analyzed by ATR-FTIR, TEM, and non-contact AFM. The structure of these nanoparticles can be described as a lipid core with a pectin shell. Pectin facilitated the formation of nanoparticles, by inducing their aggregation in branched chains and favoring the condensation between lipid monomers. Also, pectin determined the self-assembly of cutinsomes on highly ordered pyrolytic graphite (HOPG) surfaces, causing their opening and forming interconnected structures. In the case of cutin monomers, the nanoparticles are fused, and the condensation of the hydroxy fatty acids is strongly affected by the presence of the polysaccharide. The interaction of pectin with polyhydroxylated fatty acids could be related to an initial step in the formation of the plant biopolyester cutin.

April, 2015 | DOI: 10.1371/journal.pone.0124639

Effect of catalytic graphitization on the electrochemical behavior of wood derived carbons for use in supercapacitors

Gutierrez-Pardo, A; Ramirez-Rico, J; Cabezas-Rodriguez, R; Martinez-Fernandez, J
Journal of Power Sources, 278 (2015) 18-26


Porous graphitic carbons were successfully obtained from wood precursors through pyrolysis using a transition metal as catalyst. Once the catalyst is removed, the resulting material mimics the microstructure of the wood and presents high surface area, open and interconnected porosity and large pore volume, high crystallinity and good electrical conductivity, making these carbons interesting for electrochemical devices. Carbons obtained were studied as electrodes for supercapacitors in half cell experiments, obtaining high capacitance values in a basic media (up to 133 F g−1 at current densities of 20 mA g−1 and 35 F g−1 at current densities of 1 A g−1). Long-cycling experiments showed excellent stability of the electrodes with no reduction of the initial capacitance values after 1000 cycles in voltammetry.

March, 2015 | DOI: 10.1016/j.jpowsour.2014.12.030

Synthesis temperature effect on Na-Mica-4 crystallinity and heteroatom distribution

Naranjo, M; Castro, MA; Cota, A; Osuna, FJ; Pavon, E; Alba, MD
Microporous and Mesoporous Materials, 204 (2015) 282-288


The discovery of swelling brittle mica, Na-Mica-4, has been one of the most significant advances in the pursuit for a material with high ion-exchange capacity. For technical applications, the control of the phase evolution during the synthesis is crucial. The main aim of this study was to investigate the effect of Na-Mica-4 synthesis temperature on the crystalline phase evolution, Si–Al distribution in the tetrahedral sheet, the Al occupancy between tetrahedral and octahedral sites and their effects on the interlayer space composition. The synthesis temperature range between 600 °C and 900 °C was explored. At low temperature (600 °C), the precursors were transformed in a low-charged swelling 2:1 phyllosilicate, saponite type, which was progressively aluminum enriched with temperature. The high-charged swelling mica was completely formed at 700 °C, although a minor anhydrous contribution remained up to 850 °C. Up to 800 °C, silicates and fluorides secondary phases were detected as a minor contribution.

March, 2015 | DOI: 10.1016/j.micromeso.2014.11.026

Sliding wear resistance of sintered SiC-fiber bonded ceramics

Vera, MC; Ramirez-Rico, J; Martinez-Fernandez, J; Singh, M
International Journal of Refractory Metals & Hard Materials, 49 (2015) 232-239


Advanced SiC-based ceramics and fiber reinforced composites are interesting materials for a wide variety of applications involving sliding wear conditions because of their excellent thermomechanical properties. The microstructure and wear resistance of sintered SiC fiber bonded ceramics (SA Tyrannohex) were studied. The material is composed of SiC-fibers in two orientations, with polygonal cross sections and cores having higher carbon content than their surroundings, as observed with SEM. A thin layer of C exists between the fibers. This layer has been found to be a turbostratic-layered structure oriented parallel to the fiber surface. XRD shows that the material is highly crystalline and composed mostly of β-SiC. Unlubricated wear behavior of the SA-Tyrannohex material when sliding against a Si3N4 ball in air at room temperature was evaluated. Experiments were performed using a pin on disk apparatus, under different normal loads of 2, 5 and 10 N at sliding speeds of 25, 50, 100 mm/s. A decrease of the friction coefficient with load was found due to the presence of the turbostratic carbon layer between the fibers. Wear rates of the order of 100 mm3/MJ were obtained, independently of sliding speed. Microfracture of the fibers is the main wear mechanism.

March, 2015 | DOI: 10.1016/j.ijrmhm.2014.06.020

Sliding wear resistance of biomorphic SiC ceramics

Vera, MC; Ramirez-Rico, J; Martinez-Fernandez, J; Singh, M
International Journal of Refractory Metals & Hard Materials, 49 (2015) 327-333


Biomorphic SiC ceramics were fabricated from four different wood precursors and their Knoop hardness and sliding wear resistance when sliding against a Si3N4 ball in air were studied. Tribological experiments were performed using a pin on disk apparatus, under normal loads of 2 and 5 N, at a sliding speed of 100 mm/s. The effects of specimen porosity and microstructure on measured wear were evaluated. A commercial sintered silicon carbide ceramic was also tested for comparison. Small differences in friction coefficient comparable to monolithic SiC ceramics were obtained. Several concurrent wear mechanisms are taking place: microfracture, plastic deformation in the Si phase and oxidation of the Si and/or SiC phase. The presence of an oxide tribolayer was assessed using fluorescence microscopy. Wear rates were found to scale with SiC content and depend on residual porosity in the composite.

March, 2015 | DOI: 10.1016/j.ijrmhm.2014.07.004

Microstructure, elastic and inelastic properties of partially graphitized biomorphic carbons

Orlova, TS; Kardashev, BK; Smirnov, BI; Gutierrez-Pardo, A; Ramirez-Rico, J; Martinez-Fernandez, J
Physics of the Solid State, 57 (2015) 586-591


The microstructural characteristics and amplitude dependences of the Young's modulus E and internal friction (logarithmic decrement delta) of biocarbon matrices prepared by beech wood carbonization at temperatures T (carb) = 850-1600A degrees C in the presence of a nickel-containing catalyst have been studied. Using X-ray diffraction and electron microscopy, it has been shown that the use of a nickel catalyst during carbonization results in a partial graphitization of biocarbons at T (carb) a parts per thousand yen 1000A degrees C: the graphite phase is formed as 50- to 100-nm globules at T (carb) = 1000A degrees C and as 0.5- to 3.0-mu m globules at T (carb) = 1600A degrees C. It has been found that the measured dependences E(T (carb)) and delta(T (carb)) contain three characteristic ranges of variations in the Young's modulus and logarithmic decrement with a change in the carbonization temperature: E increases and delta decreases in the ranges T (carb) < 1000A degrees C and T (carb) > 1300A degrees C; in the range 1000 < T (carb) < 1300A degrees C, E sharply decreases and delta increases. The observed behavior of E(T (carb)) and delta(T (carb)) for biocarbons carbonized in the presence of nickel correlates with the evolution of their microstructure. The largest values of E are obtained for samples with T (carb) = 1000 and 1600A degrees C. However, the samples with T (carb) = 1600A degrees C exhibit a higher susceptibility to microplasticity due to the presence of a globular graphite phase that is significantly larger in size and total volume.

March, 2015 | DOI: 10.1134/S106378341503018X

Polyester Films Obtained by Noncatalyzed Melt-Condensation Polymerization of Aleuritic (9,10,16-Trihydroxyhexadecanoic) Acid in Air

Benitez, JJ; Heredia-Guerrero, JA; Guzman-Puyol, S; Dominguez, E; Heredia, A
Journal of Applied Polymer, 132 (2015) Art. 41328


To mimic nontoxic and fully biodegradable biopolymers like the plant cutin, polyester films from a natural occurring fatty polyhydroxyacid like aleuritic (9,10,16-trihydroxyhexadecanoic) acid have been prepared by noncatalyzed melt-polycondensation at moderate temperature (150 degrees C) directly in air. The course of the reaction has been followed by infrared spectroscopy, C-13 magic angle spinning nuclear magnetic resonance spectroscopy, differential scanning calorimetry and X-ray diffraction and well differentiated stages are observed. First, a high conversion esterification reaction leads to an amorphous rubbery, infusible, and insoluble material whose structure is made out of ester linkages mostly involving primary hydroxyls and partially branched by minor esterification with secondary ones. Following the esterification stage, the cleavage of vicinal secondary hydroxyls and further oxidation to carboxylic acid is observed at the near surface region of films. New carboxylic groups created also undergo esterification and generate cross-linking points within the polymer structure. Additionally, and despite the harsh preparation conditions used, very little additional side reaction like peroxidation and dehydration are observed. Results demonstrate the feasibility of polyester films fabrication from a reference fatty polyhydroxyacid like aleuritic acid by noncatalyzed melt-polycondensation directly in air. The methodology can potentially be extended to similar natural occurring hydroxyacids to obtain films and coatings to be used, for instance, as nontoxic and biodegradable food packaging material.

February, 2015 | DOI: 10.1002/app.41328

Long-Chain Polyhydroxyesters from Natural Occurring Aleuritic Acid as Potential Material for Food Packaging

Benitez, JJ; Heredia-Guerrero, JA; Guzman-Puyol, S; Dominguez, E; Heredia, A
Soft Materials, 13 (2015) 5-11


Fatty polyhydroxyesters (C≥16) are present in nature as barrier polymers like cutin in some protective tissues of higher plants. The mimicry of these biopolymers is regarded as a strategy to design nontoxic and fully biodegradable food packaging films and coatings. To obtain cutin inspired materials we have used a natural occurring polyhydroxylated monomer like aleuritic (9,10,16-trihydroxypalmitic) acid and a direct and scalable synthesis route consisting in the noncatalyzed melt-condensation polymerization in air. To reduce the number of hydroxyl groups and to increase hydrophobicity, palmitic acid has been used as a capping agent. Aleuritic-palmitic polyhydroxyesteres films have been obtained and characterized.

January, 2015 | DOI: 10.1080/1539445X.2014.993476


Ceramic Barrier Layers for Flexible Thin Film Solar Cells on Metallic Substrates: A Laboratory Scale Study for Process Optimization and Barrier Layer Properties

Delgado-Sanchez, JM; Guilera, N; Francesch, L; Alba, MD; Lopez, L; Sanchez, E
ACS Applied Materials & Interfaces, 6 (2014) 18543-18549


Flexible thin film solar cells are an alternative to both utility-scale and building integrated photovoltaic installations. The fabrication of these devices over electrically conducting low-cost foils requires the deposition of dielectric barrier layers to flatten the substrate surface, provide electrical isolation between the substrate and the device, and avoid the diffusion of metal impurities during the relatively high temperatures required to deposit the rest of the solar cell device layers. The typical roughness of low-cost stainless-steel foils is in the hundred-nanometer range, which is comparable or larger than the thin film layers comprising the device and this may result in electrical shunts that decrease solar cell performance. This manuscript assesses the properties of different single-layer and bilayer structures containing ceramics inks formulations based on Al2O3, AlN, or Si3N4 nanoparticles and deposited over stainless-steel foils using a rotogravure printing process. The best control of the substrate roughness was achieved for bilayers of Al2O3 or AlN with mixed particle size, which reduced the roughness and prevented the diffusion of metals impurities but AlN bilayers exhibited as well the best electrical insulation properties.

November, 2014 | DOI: 10.1021/am504923z

Enhanced activity of clays and its crucial role for the activity in ethylene polymerization

Camejo-Abreu, C; Tabernero, V; Alba, MD; Cuenca, T; Terreros, P
Journal of Molecular Catalysis A-Chemical, 393 (2014) 96-104


This paper presents a study of the effects of different treatments on the polymerization activity of modified clays as cocatalysts. To achieve this goal, an intercalating cation was introduced into two smectites and these clays were then modified with trimethyl aluminium. The results for ethylene polymerization, when a zirconocene complex was used as catalyst, and the structure analysis, allow us to obtain interesting deductions about the generation mode of the active species. All active materials employed as support activators presented aluminium in a pentahedral environment together with acidic hydrogen atoms. These two features were detected only after TMA treatment and they seem to be crucial elements in active cocatalyst generation. Moreover, a material without structural aluminium displayed the best activity pointing to the new aluminium species generated in the solid matrix as the determining factor for the activity. We proposed a synergic effect between Lewis acid aluminium centres and acidic Bronsted protons that generate the SiOHAl groups that activate the zirconium compound.

November, 2014 | DOI: 10.1016/j.molcata.2014.05.030

Quantification and comparison of the reaction properties of FEBEX and MX-80 clays with saponite: Europium immobilisers under subcritical conditions

Villa-Alfageme, M; Hurtado, S; Castro, MA; El Mrabet, S; Orta, MM; Pazos, MC; Alba, MD
Applied Clay Science, 101 (2014) 10-15


The evaluation of the retention mechanisms in FEBEX and MX-80 bentonites, selected as reference materials to construct engineered barriers, carries major implications in the safe storage of immobilisation capacity through a recently discovered chemical retention mechanism and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with immobilisation capacity through a recently discovered chemical retention mechanism and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with Eu(NO3)3 (151Eu and 153Eu, with 52.2% 153Eu) and spiked with radioactive 152Eu for the quantification of the reactions. Results were compared with saponite as the reference smectite. The strong dependence of the reaction parameters with temperature and time was quantified and the reaction velocity was evaluated. The velocity follows these trends: 240 days are needed for the total retention of europium for temperatures over 200 °C; below 150 °C, significantly longer reaction times, on the order of three years, are required to complete the reaction. Clays do not influence velocity rates, but the retention capacity of bentonites remains lower than for saponite. At 300 °C, the milliequivalents retained by the three clays are consistently over CEC. The structural analyses reveal not only adsorption of europium but also the presence of Eu(OH)3 precipitation and Eu2SiO3 confirming the existence of a chemical reaction.

November, 2014 | DOI: 10.1016/j.clay.2014.08.012

Characterization of porous graphitic monoliths from pyrolyzed wood

Gutierrez-Pardo, A; Ramirez-Rico, J; de Arellano-Lopez, AR; Martinez-Fernandez, J
Journal of Materials Science, 49 (2014) 7688-7696


Porous graphitic carbons were obtained from wood precursors using Ni as a graphitization catalyst during pyrolysis. The structure of the resulting material retains that of the original wood precursors with highly aligned, hierarchical porosity. Thermal characterization was performed by means of thermogravimetry and differential scanning calorimetry, and the onset temperature for graphitization was determined to be similar to 900 A degrees C. Structural and microstructural characterization was performed by means of electron microscopy, electron and x-ray diffraction, and Raman spectroscopy. The effect of maximum pyrolysis temperature on the degree of graphitization was assessed. No significant temperature effect was detected by means of Raman scattering in the range of 1000-1400 A degrees C, but at temperatures over the melting point of the catalyst, the formation of graphite grains with long-range order was detected.

November, 2014 | DOI: 0.1007/s10853-014-8477-8

Direct evidence of Lowenstein's rule violation in swelling high-charge micas

Pavon, E; Osuna, FJ; Alba, MD; Delevoye, L
Chemical Communications, 53 (2014) 6984-6986


The structure of high-charged micas, Na-n-micas (n = 2 and 4), a family of synthetic silicates with a wide range of applications, was investigated through the use of 17O solid-state NMR at natural abundance in order to preserve quantitative spectral information. The use of a very high-field and highly sensitive probehead, together with 17O NMR literature data allowed for the detection of an isolated signal at 26 ppm, assigned partially to AlOAl, as evidence of the violation of Lowenstein's rule for Na-4-mica.

July, 2014 | DOI: 10.1039/C4CC01632G

Biomimetic polymers of plant cutin: an approach from molecular modeling

San-Miguel, MA; Oviedo, J; Heredia-Guerrero, JA; Heredia, A; Benitez, JJ
Journal of Molecular Modeling, 20 (2014) 2329


Biomimetics of materials is based on adopting and reproducing a model in nature with a well-defined functionality optimized through evolution. An example is barrier polymers that protect living tissues from the environment. The protecting layer of fruits, leaves, and non-lignified stems is the plant cuticle. The cuticle is a complex system in which the cutin is the main component. Cutin is a biopolyester made of polyhydroxylated carboxylic acids of 16 and 18 carbon atoms. The biosynthesis of cutin in plants is not well understood yet, but a direct chemical route involving the self-assembly of either molecules or molecular aggregates has been proposed. In this work, we present a combined study using experimental and simulation techniques on self-assembled layers of monomers selectively functionalized with hydroxyl groups. Our results demonstrate that the number and position of the hydroxyl groups are critical for the interaction between single molecules and the further rearrangement. Also, the presence of lateral hydroxyl groups reinforces lateral interactions and favors the bi-dimensional growth (2D), while terminal hydroxyl groups facilitate the formation of a second layer caused by head–tail interactions. The balance of 2D/3D growth is fundamental for the plant to create a protecting layer both large enough in 2D and thick enough in 3D.

July, 2014 | DOI: 10.1007/s00894-014-2329-y

Infrared and Raman spectroscopic features of plant cuticles: a review

Heredia-Guerrero, JA; Benitez, JJ; Dominguez, E; Bayer, IS; Cingolani, R; Athanassiou, A; Heredia, A
Frontiers in Plant Science, 25 (2014)


The cuticle is one of the most important plant barriers. It is an external and continuous lipid membrane that covers the surface of epidermal cells and whose main function is to prevent the massive loss of water. The spectroscopic characterization of the plant cuticle and its components (cutin, cutan, waxes, polysaccharides and phenolics) by infrared and Raman spectroscopies has provided significant advances in the knowledge of the functional groups present in the cuticular matrix and on their structural role, interaction and macromolecular arrangement. Additionally, these spectroscopies have been used in the study of cuticle interaction with exogenous molecules, degradation, distribution of components within the cuticle matrix, changes during growth and development and characterization of fossil plants.

June, 2014 | DOI: 10.3389/fpls.2014.00305

Influence of the synthesis parameter on the interlayer and framework structure of lamellar octadecyltrimethylammonium kanemite

Corredor, JI; Cota, A; Pavon, E; Osuna, FJ; Alba, MD
Applied Clay Science, 95 (2014) 9-17


Inorganic–organic nanostructures, used as host materials for selective adsorption of functional molecules and as mesostructured material precursors, can be constructed by the interlayer modification of inorganic layered materials with surfactants. The formation mechanism is mainly determined by the surfactant assemblies in the 2D limited space. In this paper, a detailed structural analysis of the lamellar mesophases prepared from kanemite, a lamellar silicate, and octadecyltrimethylammonium (ODTMA) under various conditions was reported. The adsorbed amount of ODTMA and the long and short range structural orders were explored by TGA, XRD, IR/FT and MAS NMR spectroscopies. The results revealed that ODTMA molecules were efficiently intercalated in the interlayer space of kanemite and, in all synthesis conditions, an ordered lamellar structure was obtained. The ODTMA adsorption in kanemite caused changes not only in the interlayer space but also in the silicate framework, where five-member rings were formed. The characteristics of the final products were influenced by the synthesis conditions, although the separation mode, filtration or centrifugation, was not relevant. Therefore, the adsorption conditions of ODTMA in kanemite will contribute to the design of novel layered materials with potential environmental and technological use.

June, 2014 | DOI: 10.1016/j.clay.2014.02.030

Biomechanical properties of the tomato (Solanum lycopersicum) fruit cuticle during development are modulated by changes in the relative amounts of its components

Espana, L; Heredia-Guerrero, JA; Segado, P; Benitez, JJ; Heredia, A; Dominguez, E
New Phytologist, 202 (3) (2014) 790-802


attenuated total reflectance–Fourier transform infrared (ATR-FTIR);biomechanics;cuticle;cutin;flavonoids;tomato (Solanum lycopersicum) fruit


- In this study, growth-dependent changes in the mechanical properties of the tomato (Solanum lycopersicum) cuticle during fruit development were investigated in two cultivars with different patterns of cuticle growth and accumulation.

- The mechanical properties were determined in uniaxial tensile tests using strips of isolated cuticles. Changes in the functional groups of the cuticle chemical components were analysed by attenuated total reflectance–Fourier transform infrared (ATR-FTIR).

- The early stages of fruit growth are characterized by an elastic cuticle, and viscoelastic behaviour only appeared at the beginning of cell enlargement. Changes in the cutin:polysaccharide ratio during development affected the strength required to achieve viscoelastic deformation. The increase in stiffness and decrease in extensibility during ripening, related to flavonoid accumulation, were accompanied by an increase in cutin depolymerization as a result of a reduction in the overall number of ester bonds.

- Quantitative changes in cuticle components influence the elastic/viscoelastic behaviour of the cuticle. The cutin:polysaccharide ratio modulates the stress required to permanently deform the cuticle and allow cell enlargement. Flavonoids stiffen the elastic phase and reduce permanent viscoelastic deformation. Ripening is accompanied by a chemical cleavage of cutin ester bonds. An infrared (IR) band related to phenolic accumulation can be used to monitor changes in the cutin esterification index.

May, 2014 | DOI: 10.1111/nph.12727

Thermal conductivity at the amorphous-nanocrystalline phase transition in beech wood biocarbon

Parfen'eva, LS; Orlova, TS; Smirnov, BI; Smirnov, IA; Misiorek, H; Jezowski, A; Ramirez-Rico, J
Physica of the Solid State, 56 (2014) 1071-1080


High-porosity samples of beech wood biocarbon (BE-C) were prepared by pyrolysis at carbonization temperatures T carb = 650, 1300, and 1600°C, and their resistivity ρ and thermal conductivity κ were studied in the 5–300 and 80–300 K temperature intervals. The experimental results obtained were evaluated by invoking X-ray diffraction data and information on the temperature dependences ρ(T) and κ(T) for BE-C samples prepared at T carb = 800, 1000, and 2400°C, which were collected by the authors earlier. An analysis of the κ(T carb) behavior led to the conclusion that the samples under study undergo an amorphous-nanocrystalline phase transition in the interval 800°C < T carb < 1000°C. Evaluation of the electronic component of the thermal conductivity revealed that the Lorentz number of the sample prepared at T carb = 2400°C exceeds by far the classical Sommerfeld value, which is characteristic of metals and highly degenerate semiconductors.

May, 2014 | DOI: 10.1134/S1063783414050229

Effect of clays and metal containers in retaining Sm3+ and ZrO2+ and the process of reversibility

El Mrabet, S; Castro, MA; Hurtado, S; Orta, MM; Pazos, MC; Villa-Alfageme, M; Alba, MD
American Mineralogist, 99 (4) (2014) 696-703


Knowledge and understanding about radionuclides retention processes on the materials composing the engineered barrier (clay mineral and metallic container waste) are required to ensure the safety and the long-term performance of radioactive waste disposal. Therefore, the present study focuses on the competitiveness of clay and the metallic container in the process of adsorption/desorption of the radionuclides simulators of Am3+ and UO22+. For this purpose, a comparative study of the interaction of samarium (chosen as chemical analog for trivalent americium) and zirconyl (as simulator of uranyl and tetravalent actinides) with both FEBEX bentonite and metallic container, under subcritical conditions, was carried out. The results revealed that the AISI-316L steel container, chemical composition detailed in Table 1, immobilized the high-radioactive waste (HRW), even during the corrosion process. The ZrO2+ was irreversibly adsorbed on the minireactor surface. In the case of samarium SEM/EDX analysis revealed the formation of an insoluble phase of samarium silicate on the container surface. There was no evidence of samarium diffusion through the metallic container. Samarium remained adsorbed by the container also after desorption experiment with water. Therefore, steel canister is actively involved in the HRW immobilization.

April, 2014 | DOI: 10.2138/am.2014.4665

A new route of synthesis of Na-Mica-4 from sodalite

Naranjo, M; Castro, MA; Cota, A; Pavon, E; Pazos, MC; Alba, MD
Microporous and Mesoporous Materials, 188 (2014) 176-180


Synthesis of Na-Mica-4 has been achieved by a “mix and calcine” method using sodalite and magnesium fluoride as the only precursors. Previous research found sodalite as a key intermediate reaction product in the formation of Na-Mica-4 when the NaCl melt method was employed. Similarities in structure, chemical composition and cation distribution in products using the proposed method and the NaCl melt method are described and suggest that Na-Mica-4 is a very stable product. The use of sodalite as precursor provokes microporous formation in the final mica. The absence of excess Na leads to a lower particle size and to the presence of less impurity in the calcined product. Different sodalites could be used in the synthesis of different Na-Mica-4 with presumably different physicochemical properties.

March, 2014 | DOI: 10.1016/j.micromeso.2013.12.004

Effect of carbonization temperature on the microplasticity of wood-derived biocarbon

Shpeizman, VV; Orlova, TS; Kardashev, BK; Smirnov, BI; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the Solid State, 56 (2014) 538-545


The uniaxial compression strength under stepped loading and the 325-nm-stepped deformation rate of biocarbon samples obtained by carbonization of beech wood at different temperatures in the 600–1600°C range have been measured using high-precision interferometry. It has been shown that the strength depends on the content of nanocrystalline phase in biocarbon. The magnitude of deformation jumps at micro- and nanometer levels and their variation with a change in the structure of the material and loading time have been determined. For micro- and nanometer-scale jumps, standard deviations of the differences between the experimentally measured deformation rate at loading steps and its magnitude at the smoothed fitting curve have been calculated, and the correlation of the error with the deformation prior to destruction has been shown. The results obtained have been compared with the previously published data on measurements of the elastic properties and internal friction of these materials.

March, 2014 | DOI: 10.1134/S1063783414030305

New Bio-Ceramization Processes Applied to Vegetable Hierarchical Structures for Bone Regeneration: An Experimental Model in Sheep

Filardo, G; Kon, E; Tampieri, A; Cabezas-Rodriguez, R; Di Martino, A; Fini, M; Giavaresi, G; Lelli, M; Martinez-Fernandez, J; Martini, L; Ramirez-Rico, J; Salamanna, F; Sandri, M; Sprio, S; Marcacci, M
Tissue Engineering Part A, 20 (2014) 763-773


Bone loss is still a major problem in orthopedics. The purpose of this experimental study is to evaluate the safety and regenerative potential of a new scaffold based on a bio-ceramization process for bone regeneration in long diaphyseal defects in a sheep model. The scaffold was obtained by transformation of wood pieces into porous biomorphic silicon carbide (BioSiC®). The process enabled the maintenance of the original wood microstructure, thus exhibiting hierarchically organized porosity and high mechanical strength. To improve cell adhesion and osseointegration, the external surface of the hollow cylinder was made more bioactive by electrodeposition of a uniform layer of collagen fibers that were mineralized with biomimetic hydroxyapatite, whereas the internal part was filled with a bio-hybrid HA/collagen composite. The final scaffold was then implanted in the metatarsus of 15 crossbred (Merinos-Sarda) adult sheep, divided into 3 groups: scaffold alone, scaffold with platelet-rich plasma (PRP) augmentation, and scaffold with bone marrow stromal cells (BMSCs) added during implantation. Radiological analysis was performed at 4, 8, 12 weeks, and 4 months, when animals were sacrificed for the final radiological, histological, and histomorphometric evaluation. In all tested treatments, these analyses highlighted the presence of newly formed bone at the bone scaffolds' interface. Although a lack of substantial effect of PRP was demonstrated, the scaffold+BMSC augmentation showed the highest value of bone-to-implant contact and new bone growth inside the scaffold. The findings of this study suggest the potential of bio-ceramization processes applied to vegetable hierarchical structures for the production of wood-derived bone scaffolds, and document a suitable augmentation procedure in enhancing bone regeneration, particularly when combined with BMSCs.

February, 2014 | DOI: 10.1089/ten.tea.2013.0108

Interaction of Hydrated Cations with Mica-n (n = 2, 3 and 4) Surface

Pavon, E; Castro, MA; Cota, A; Osuna, FJ; Pazos, MC; Alba, MD
Journal of Physical Chemistry C, 118 (2014) 2115-2121


High charged swelling micas, with layer charge between 2 and 4, have been found to readily swell with water, and complete cation exchange (CEC) can be achieved. Because of their high CEC, applications like radioactive cation fixation or removal of heavy metal cations from wastewater were proposed. Their applicability can be controlled by the location of the interlayer cation in a confined space with a high electric field. In synthetic brittle micas, the interlayer cation has a low water coordination number; therefore, their coordination sphere would be completed by the basal oxygen of the tetrahedral layer as inner-sphere complexes (ISC). However, no direct evidence of these complexes formation in brittle micas has been reported yet. In this contribution, we mainly focus on the understanding the mechanisms that provoke the formation of ISC in high charge swelling micas, Mica-n. A whole series of cations (X) were used to explore the influence of the charge and size of the interlayer cation. Three brittle swelling micas, Mica-n (n = 4, 3 and 2), were selected in order to analyze the influence of the layer charge in the formation of ISC. The contribution of the ISC has been analyzed thorough the evolution of the 060 reflection and the changes in the short-range order of the tetrahedral cations will be followed 29Si and 27Al MAS NMR. The results showed that ISC was favored in X-Mica-4 and that provoked a high distortion angle between the Si–Al tetrahedra. When the content of aluminum decreases, the electrostatic forces between the layers are relaxed, and the hydrated cations did not interact so strongly with the tetrahedral sheet, having the opportunity to complete their hydration sphere.

January, 2014 | DOI: 10.1021/jp4110695

Competitive effect of the metallic canister and clay barrier on the sorption of Eu3+ under subcritical conditions

El Mrabet, S; Castro, MA; Hurtado, S; Orta, MM; Pazos, MC; Villa-Alfageme, M; Alba, MD
Applied Geochemistry, 40 (2014) 25-31


An in depth knowledge and understanding of high activity radionuclide (HLRW) immobilization processes on the materials composing the engineered barrier (clay and metallic canister) is required to ensure the safety and the long-term performance of radioactive waste disposal procedures. Therefore, the aim of this study was to understand the mechanisms involved in the retention of Eu3+ by two components of the multibarrier system, the bentonite barrier and the canister. As such, a comparative study of the interaction of trivalent Eu3+, used to simulate trivalent actinides, with both bentonite and a metallic canister has been undertaken in this work. To this end, we designed a minireactor into which the bentonite was introduced and compacted. The minireactor-bentonite system was then submitted to a hydrothermal reaction with a 7.9 × 10−2 M solution of Eu3+ at 300 °C for 4.5 days. SEM and XRD results revealed that both bentonite and the container were involved in the immobilization of europium by the formation of insoluble europium silicate phases. The presence of europium silicate adsorbed on the surface of the metallic canister indicates the competitive effect of both components of the engineered barrier (bentonite and metallic canister) in HLRW immobilization. These results suggested that the canister could play a role in the HLRW immobilization even during its corrosion process.

January, 2014 | DOI: j.apgeochem.2013.10.014


Modeling Macro-Sized, High Aspect Ratio Through-Hole Filling by Multi-Component Additive-Assisted Copper Electrodeposition

Childers, AS; Johnson, MT; Ramirez-Rico, J; Faber, KT
Journal of the Electrochemical Society, 160 (2013) D3093-D3102


A multi-element, time-dependent model is used to examine additive-assisted copper electroplating in macro-channels. This model is an adaptation of the work of Akolkar and Landau [J. Electrochem. Soc., 156, D351 (2009)], used to describe plating in micro-vias for integrated circuits. Using their method for describing species movement in the channel, the model has been expanded to include transport and adsorption limitations of the inhibitor and accelerator, as well as the copper ions in solution. The model is used to investigate copper plating as an infiltration method across many size scales and aspect ratios. Biomorphic graphite scaffolds produced from wood are used as a representative system and the results of a two-additive bath are used to characterize the behavior of the additives and determine the effectiveness of the plating. The results indicate that at macro-scales, channel dimensions play an increasingly important role in dictating the behavior of additive-assisted plating. Because additive systems are designed to establish differential surface coverage within the channel, the success of which is determined by the additive's rates of diffusion and adsorption, certain size scale/aspect ratio combinations preclude such coverage. A guide for sample geometries that may be successfully infiltrated with a two-additive bath is provided.

December, 2013 | DOI: 10.1149/2.018312jes

Thermal conductivity of wood-derived graphite and copper–graphite composites produced via electrodeposition

Johnson, MT; Childers, AS; Ramirez-Rico, J; Wang, H; Faber, KT
Composites Part A: Applied Science and Manufaturing, 63 (2013) 182-189


The thermal conductivity of wood-derived graphite and graphite/copper composites was studied both experimentally and using finite element analysis. The unique, naturally-derived, anisotropic porosity inherent to wood-derived carbon makes standard porosity-based approximations for thermal conductivity poor estimators. For this reason, a finite element technique which uses sample microstructure as model input was utilized to determine the conductivity of the carbon phase independent of porosity. Similar modeling techniques were also applied to carbon/copper composite microstructures and predicted conductivities compared well to those determined via experiment.

October, 2013 | DOI: 10.1016/j.compositesa.2013.06.009

In situ imaging and strain determination during fracture in a SiC/SiC ceramic matrix composite

Ramirez-Rico, J; Stolzenburg, F; Almer, JD; Routbort, JL; Singh, D; Faber, KT
Scripta Materialia, 69 (2013) 497-500


A combined imaging and microdiffraction technique using high-energy synchrotron X-rays is described and used to reveal microstructure, damage and strain evolution around notches in SiC/SiC composites. This technique allows for monitoring the material for cracks while loading and mapping the strain distribution in fibers and matrix with a resolution of tens of microns. We show that at current resolutions this technique is capable of measuring the strain distribution near crack tips in ceramic matrix composites and observe load transfer effects.

October, 2013 | DOI: 10.1016/j.scriptamat.2013.05.032

Structure-mediated transition in the behavior of elastic and inelastic properties of beach tree bio-carbon

Kardashev, BK; Orlova, TS; Smirnov, BI; Gutierrez, A; Ramirez-Rico, J
Physics of the Solid State, 55 (2013) 1884-1891


Microstructural characteristics and amplitude dependences of the Young modulus E and of internal friction (logarithmic decrement δ) of bio-carbon matrices prepared from beech tree wood at different carbonization temperatures T carb ranging from 600 to 1600°C have been studied. The dependences E(T carb) and δ(T carb) thus obtained revealed two linear regions of increase of the Young modulus and of decrease of the decrement with increasing carbonization temperature, namely, ΔE ∼ AΔT carb and Δδ ∼ BΔT carb, with A ≈ 13.4 MPa/K and B ≈ −2.2 × 10−6 K−1 for T carb < 1000°C and A ≈ 2.5 MPa/K and B ≈ −3.0 × 10−7 K−1 for T carb > 1000°C. The transition observed in the behavior of E(T carb) and δ(T carb) at T carb = 900–1000°C can be assigned to a change of sample microstructure, more specifically, a change in the ratio of the fractions of the amorphous matrix and of the nanocrystalline phase. For T carb < 1000°C, the elastic properties are governed primarily by the amorphous matrix, whereas for T carb > 1000°C the nanocrystalline phase plays the dominant part. The structurally induced transition in the behavior of the elastic and microplastic characteristics at a temperature close to 1000°C correlates with the variation of the physical properties, such as electrical conductivity, thermal conductivity, and thermopower, reported in the literature.

September, 2013 | DOI: 10.1134/S1063783413090151

Monolayer arrangement of fatty hydroxystearic acids on graphite: Influence of hydroxyl groups

Medina, S; Benitez, JJ; Castro, MA; Cerrillos, C; Millan, C; Alba, MD
Thin Solid Films, 539 (2013) 194-200


Previous studies have indicated that long-chain linear carboxylic acids form commensurate packed crystalline monolayers on graphite even at temperatures above their melting point. This study examines the effect on the monolayer formation and structure of adding one or more secondary hydroxyl, functional groups to the stearic acid skeleton (namely, 12-hydroxystearic and 9,10-dihydroxystearic acid). Moreover, a comparative study of the monolayer formation on recompressed and monocrystalline graphite has been performed through X-ray diffraction (XRD) and Scanning Tunneling Microscopy (STM), respectively. The Differential Scanning Calorimetry (DSC) and XRD data were used to confirm the formation of solid monolayers and XRD data have provided a detailed structural analysis of the monolayers in good correspondence with obtained STM images. DSC and XRD have demonstrated that, in stearic acid and 12-hydroxystearic acid adsorbed onto graphite, the monolayer melted at a higher temperature than the bulk form of the carboxylic acid. However, no difference was observed between the melting point of the monolayer and the bulk form for 9,10-dihydroxystearic acid adsorbed onto graphite. STM results indicated that all acids on the surface have a rectangular p2 monolayer structure, whose lattice parameters were uniaxially commensurate on the a-axis. This structure does not correlate with the initial structure of the pure compounds after dissolving, but it is conditioned to favor a) hydrogen bond formation between the carboxylic groups and b) formation of hydrogen bonds between secondary hydroxyl groups, if spatially permissible. Therefore, the presence of hydroxyl functional groups affects the secondary structure and behavior of stearic acid in the monolayer.

July, 2013 | DOI: 10.1016/j.tsf.2013.05.053

Evaluation of rare earth on layered silicates under subcritical conditions: Effect of the framework and interlayer space composition

Chain, P; Cota, A; El Mrabet, S; Pavon, E; Pazos, MC; Alba, MD
Chemical Geology, 347 (2013) 208-216


Clay-based minerals are considered to be an important component in backfill barriers due to both their ability to seal and adsorb radioactive waste and to interact chemically with it under subcritical conditions. Herein, we describe a systematic study of the properties of layered silicates that could affect their hydrothermal reactivity, namely type of layers, octahedral occupancy, origin and total amount of the layer charge, and nature of the interlayer cation. The silicates studied were selected on the basis of their different characteristics associated with these properties and were treated hydrothermally at 300 °C for 48 h in a 7.3 · 10− 2 M Lu(NO3)3 · 3.6H2O solution. The final products were analyzed by X-ray diffraction and solid-state NMR spectroscopy. All the layered silicates studied were found to be able to generate a Lu2Si2O7 phase after hydrothermal treatment under subcritical conditions, thereby confirming the participation of a chemical mechanism of the clay barrier generating phases being stables with temperature and pH conditions. However, the extent of this reaction depends to a large extent on the physicochemical properties of the framework and the interlayer space composition, such as the presence or absence of an octahedral sheet, the degree of occupancy of this sheet, and the origin and total layer charge. Therefore, this study allows tuning the clay mineral framework characteristic that favors the rare earth cations (as trivalent actinide simulator) immobilization.

June, 2013 | DOI: 10.1016/j.chemgeo.2013.03.006

Solution Properties of the System ZrSiO4–HfSiO4: A Computational and Experimental Study

Cota, Agustin; Burton, Benjamin P.; Chain, Pablo; Pavon, Esperanza; Alba, Maria D.
Journal of Physical Chemistry C, 117 (2013) 10013-10019


ZrSiO4 and HfSiO4 are of considerable interest because of their low thermal expansions, thermal conductivities, and the optical properties of HfSiO4. In addition, silicate phases of both are studied as model radioactive waste disposal materials. Previous first principles calculations reported near ideal mixing in the Zr1–xHfxSiO4 system, with a very weak propensity for phase separation. Density functional theory (DFT)/cluster-expansion first principles calculations presented in this work indicate near ideal mixing with a very weak propensity for ordering. Zr1–xHfxSiO4 samples (x = 0, 0.25, 0.5, 0.75, and 1.0) were synthesized from intimate stoichiometric mixtures of constituent-oxides and annealing at 1823 K for 20 days in a platinum crucible. Samples were characterized by X-ray diffraction (XRD; Rietveld analysis) and 29Si MAS NMR. The XRD data exhibited a pronounced negative deviation from Vegard’s law in the excess volume of mixing, and the 29Si MAS NMR spectra also suggest nonideal mixing. Given the very weak energetics that favor cation ordering, it is clear that there must be some other cause(s) for the observed deviations from ideal mixing behavior.

May, 2013 | DOI: 10.1021/jp401539g

Synthesis and characterization of kanemite from fluoride-containing media: Influence of the alkali cation

Corredor, JI; Cota, A; Pavon, E; Alba, MD
American Mineralogist, 98 (2013) 1000-1007


Kanemite belongs to the group of naturally occurring sodium silicate minerals that was first found in Kanem, at the edge of the Lake Chad, and has been synthesized in different ways from NaOH-SiO2 mixtures and used as precursor for the design of microporous and mesoporous materials. The fluoride route to the synthesis of microporous materials is based on the substitution of OH− anions by fluoride anions, which may subsequently also play a mineralizing role, and gives rise to materials with higher hydrophobicity and thermal and hydrothermal stability. Moreover, F− plays an important role in the incorporation of framework heteroatoms, thereby affecting the activity of the final material. The aim of this study was to synthesize fluorokanemite using different synthetic routes and different F− source. The final product was characterized by a combination of methods that provided information regarding the incorporation of fluorine into the framework and the short- and long-range structural order of the fluorosilicate. Kanemite with water content close to ideal was obtained in all cases. The washing process was found to have no effect in the long- or short-range structural order of the layer framework, although it did affect the structure of the cation in the interlayer space of kanemite. The mineralizing agent therefore appears to be the key to the synthesis. Furthermore, it governs the resulting kanemite structure by controlling the formation of hydrogen bonds in the framework, and therefore the degree of lamellar structure condensation.

May, 2013 | DOI: 10.2138/am.2013.4372

Effects of thermal and mechanical treatments on montmorillonite homoionized with mono- and polyvalent cations: Insight into the surface and structural changes

Fernandez, M; Alba, MD; Sanchez, RMT
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 423 (2013) 1-10


Smectite is a family of clay minerals that have important applications. In the majority of these clay minerals, the hydrated interlayer cations play a crucial role on the properties of the clay. Moreover, many studies have revealed that both thermal and grinding treatments affect the MMT structure and that interlayer cations play an important role in the degradation of the structure, primarily after mechanical treatment. In this study, the effects of these treatments on MMTs homoionized with mono (Na+, Li+ or K+) or polyvalent (Ca2+ or Al3+) cations were analyzed by the combination of a set of techniques that can reveal the difference of bulk phenomena from those produced on the surface of the particles. The thermal and mechanical (in an oscillating mill) treatments affected the framework composition and structure of the MMT, and the thermal treatment caused less drastic changes that the mechanical one. The effect of the interlayer cations is primarily due to the oxidation state and, to the size of the cations, which also influenced the disappearance of aluminum in the MMT tetrahedral sheet. These treatments caused a decrease in the surface area and an increase in the particle agglomeration and the isoelectric point. Both treatments caused the leaching of the framework aluminum. Furthermore, the mechanical treatment induced structural defects, such as the breakup of the particles, which favored the dehydroxylation and the increase of the isoelectric points of the montmorillonites.

April, 2013 | DOI: 10.1016/j.colsurfa.2013.01.040

Joining and interface characterization of in situ reinforced silicon nitride

Asthana, R; Singh, M; Martinez-Fernandez, J
Journal of Alloys and Compounds, 552 (2013) 137-145


Copper-base active metal interlayers were used to bond in situ reinforced silicon nitride (Honeywell AS800) at 1317 K for 5 and 30 min in vacuum. The joints were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), electron back scattered diffraction (EBSD), and transmission electron microscopy (TEM). A Ti-rich interaction zone (∼3.0–3.5 μm thick) formed at the Si3N4/braze interface. This reaction layer grew toward the inner part of the joint with a featureless microstructure, creating a strong bond. Regions of a Ti-rich phase were frequently found next to the reaction layer but surrounded by the Cu alloy. Extensive Ti and Si enrichments were noted at the interface but there was no evidence of interfacial segregation of Y, La, and Sr (from Y2O3, La2O3 and SrO, added as sintering aids). The reaction layer thickness and composition did not change when brazing time increased from 5 min to 30 min suggesting rapid growth kinetics in the early stages of reaction. The joints were crack-free and showed features associated with plastic deformation, which indicated that the metal interlayer accommodated strain associated with CTE mismatch. The inner part of the joint consisted of highly textured large grains of the braze alloy.

March, 2013 | DOI: 10.1016/j.jallcom.2012.09.104

Hydration properties of synthetic high-charge micas saturated with different cations: An experimental approach

Pavon, E; Castro, MA; Naranjo, M; Orta, MM; Pazos, MC; Alba, MD
American Mineralogist, 98 (2013) 394-400


An understanding of the interaction mechanisms between exchangeable cations and layered silicates is of interest from both a basic and an applied point of view. Among 2:1 phyllosilicates, a new family of swelling high-charge synthetic micas has been shown to be potentially useful as decontaminant. However, the location of the interlayer cations, their acidity and the water structure in the interlayer space of these silicates are still unknown. The aim of this paper was therefore to study the hydration state of the interlayer cations in the interlayer space of high-charge expandable micas and to evaluate the effect that this hydration has on the swelling and acidity behavior of these new materials. To achieve these objectives, three synthetic micas with different charge density total layer charges (ranging between 2 and 4 per unit cell) and with five interlayer cations (Na+, Li+, K+, Mg2+, and Al3+) were synthesized and their hydration state, interlayer space, and acidity analyzed by DTA/TG, XRD, and 1H MAS NMR spectroscopy. The results showed that the hydration state depends on both the layer charge and the nature of the interlayer cation. A high participation of the inner-sphere complexes in the highly charged confined space has been inferred and proposed to induce Brønsted acidity in the solid.

March, 2013 | DOI: 10.2138/​am.2013.4217

Heat capacity of Bio-SiC and SiC/Si ecoceramics prepared from white eucalyptus, beech, and sapele tree wood

Smirnov, IA; Smirnov, BI; Orlova, TS; Wlosewicz, D; Hackemer, A; Misiorek, H; Mucha, J; Jezowski, A; Ramirez-Rico, J; Martinez-Fernandez, J
Physics of the Solid State, 55 (2013) 454-460


This paper reports on measurement of the heat capacity at constant pressure C p of silicon bio-carbide prepared within the 5–300 K temperature interval from beech tree wood (bio-SiC(BE)), and within 80–300 K, from tree wood of sapele (bio-SiC(SA)), as well as SiC/Si ecoceramics of beech, sapele, and white eucalyptus wood. It has been shown that in bio-SiC(BE) the measured heat capacity contains a significant contribution of surface heat capacity, whose magnitude decreases with increasing temperature. Of the ecoceramics, only SiC/Si(SA) characterized by a high enough porosity has revealed a small contribution to the heat capacity coming from its surface component. The experimental results obtained are discussed.

February, 2013 | DOI: 10.1134/S1063783413020285

Thermopower of Bio-SiC and SiC/Si ecoceramics prepared from sapele tree wood

Smirnov, IA; Smirnov, BI; Orlova, TS; Sulkovski, C; Misiorek, H; Muha, J; Jezowski, A; Ramirez-Rico, J; Martinez-Fernandez, J
Physics of the Solid State, 55 (2013) 54-59


The thermopower coefficients of bio-SiC and SiC/Si ecoceramics prepared from sapele tree wood have been measured in the temperature interval 5–300 K. The measurements have been performed both along and perpendicular to empty (bio-SiC), as well as empty and partially silicon-filled (SiC/Si) channels in the samples. In bio-SiC, a contribution to thermopower associated with electron drag by phonons has been shown to exist within the temperature interval 5–200 (250) K. No such effect is realized in SiC/Si. This is assumed to derive from the presence in this material of heavily doped silicon embedded in SiC channels and the dominant part it plays in the behavior of the thermopower of this ceramics. The results obtained for the thermopower are compared with the available data for bio-SiC prepared from white eucalyptus tree wood and heavily doped bismuth.

February, 2013 | DOI: 10.1134/S1063783413010307


Chemical–physical characterization of isolated plant cuticles subjected to low-dose γ-irradiation

Heredia-Guerrero, Jose A; de Lara, Rocio; Dominguez, Eva; Heredia, Antonio; Benavente, Juana; Benitez, Jose J
Chemistry and physics of lipids, 165 (2012) 803-808


Isolated tomato fruit cuticles were subjected to low dose (80 Gy) γ-irradiation, as a potential methodology to prevent harvested fruit and vegetables spoilage. Both irradiated and non-irradiated samples have been morphologically and chemically characterized by scanning electron (SEM), atomic force (AFM), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopies. Additionally, electrochemical measurements comprising membrane potential and diffusive permeability were carried out to detect modifications in transport properties of the cuticle as the fruit primary protective membrane. It has been found that low dose γ-irradiation causes some textural changes on the surface but no significant chemical modification. Texture modification is found to be due to a partial removal of outermost (epicuticular) waxes which is accompanied by mild changes of electrochemical parameters such as the membrane fixed charge, cation transport number and salt permeability. The modification of such parameters indicates a slight reduction of the barrier properties of the cuticle upon low dose γ-irradiation.

December, 2012 | DOI: 10.1016/j.chemphyslip.2012.10.003

Microstructural and high-temperature mechanical characteristics of nickel oxide/zirconia composites for solid oxide fuel cells

Oliva-Ramirez, M.; Huaman-Mamani, F. A.; Jimenez-Melendo, M.
Fuel Processing Technology, 103 (2012) 45-50


NiO/8YSZ (8 mol% Y 2O 3-stabilized ZrO 2) composites with different NiO contents (10, 20 and 40 mol%) have been fabricated by a conventional route of mechanical mixing of NiO and 8YSZ powders and sintering at 1500 °C for 10 h in air. The resulting microstructures have been characterized by electron microscopy. In 10 and 20 mol% NiO/8YSZ, the composite is formed by isolated NiO particles surrounded by zirconia matrix grains; this phase is interconnected in the 40 mol% NiO/8YSZ composite. Mechanical tests at constant strain rate and at constant load were conducted on these materials at temperatures of up to 1350 °C. Different behaviors were found depending on the percolation of the NiO phase. Microstructural observations after deformation are essential to understand the overall mechanical behavior of the composites.

November, 2012 | DOI: 10.1016/j.fuproc.2011.09.013

Effect of ytterbium doping on the microstructure and plastic deformation of BaCeO3 perovskite oxide

Jimenez-Melendo, M; Vaquero-Aguilar, C; Huaman-Mamani, FA
Fuel Processing Technology, 103 (2012) 146-150


Trivalent cation-doped barium cerate perovskites are attractive materials for clean-energy applications, in particular solid oxide fuel cells, due to their singular proton conductivity in wet environments. Furthermore, these devices operate at high temperatures, where creep and other deformation processes determine the lifetime and overall performance. In this work, the structural and microstructural characteristics of undoped and ytterbium-doped (1 to 10 at.%) BaCeO 3 polycrystals produced by solid state reaction have been investigated. A single orthorhombic perovskite phase was found after sintering in air at 1500 °C for 10 h. The microstructure shows a complex evolution with doping: the average grain size firstly decreases with increasing Yb content up to 5 at.%, and then increases with further Yb additions. The high-temperature mechanical properties have been studied in compression between 1100 and 1250 °C in air at constant initial strain rate. The creep strength increases with increasing Yb content. Extended steady states of deformation were attained at lower strain rates and higher temperatures when increasing doping amount.

November, 2012 | DOI: 10.1016/j.fuproc.2011.10.005

Creep strength of nickel oxide/zirconia composites under different environmental atmospheres

M. Jiménez-Melendo; F.A. Huamán-Mamani
Solid State Ionics, 225 (2012) 471-475


NiO/8YSZ (8 mol% Y2O3-stabilized cubic ZrO2) and NiO/3YTZP (3 mol% Y2O3-stabilized tetragonal ZrO2) composites with different NiO contents have been fabricated by a conventional route of mechanical mixing of NiO and zirconia powders and sintering at 1500 °C for 10 h in air. The resulting microstructures have been characterized by electron microscopy. The composites show a duplex microstructure formed by equiaxed grains of NiO and ZrO2, without any intermediate phase. Compressive mechanical tests at constant strain rate were carried out at temperatures between 1150 and 1350 °C under different environments: air, inert (Ar) and reducing (5% H2/95% Ar) atmospheres. The overall creep behavior of the composites is essentially controlled by the zirconia matrix, due to the softness of the NiO phase in the experimental conditions used in this study. The creep strength is not affected by oxygen partial pressure. However, a large decrease in creep resistance under reducing conditions was observed in samples submitted to in situ redox cycling.

October, 2012 | DOI: 10.1016/j.ssi.2012.02.011

High-temperature plastic deformation mechanisms of ytterbium-doped barium cerate proton conductor

M. Jiménez-Melendo
Solid State Ionics, 225 (2012) 286-290


The enhanced proton conductivity exhibited by trivalent cation-doped barium cerate perovskites makes these materials excellent candidates for electrochemical applications, in particular as electrolytes for solid oxide fuel cells. These devices operate at elevated temperatures, where creep and other deformation processes influence the overall efficiency and lifetime. In this work, the high-temperature plastic deformation mechanisms of fine-grained 5 at.% Yb-doped BaCeO3 polycrystals produced by conventional solid-state reaction has been investigated by means of compressive tests at constant load between 1150 and 1250 °C in air. The creep curves show an unusual sigmoidal behavior, followed by extended steady states of deformation. Grain boundary sliding is the main deformation mechanism, characterized by a stress exponent n of 2, as found in other fine-grained superplastic ceramics and metals.

October, 2012 | DOI: 10.1016/j.ssi.2012.03.031

Electrical resistivity and thermal conductivity of SiC/Si ecoceramics prepared from sapele wood biocarbon

Parfen'eva, LS; Orlova, TS; Smirnov, BI; Smirnov, IA; Misiorek, H; Mucha, J; Jezowski, A; Pardo, AG; Rico, JR
Physics of the Solid State, 54 (2012) 2132-2141


Samples of β-SiC/Si ecoceramics with a silicon concentration of ∼21 vol % have been prepared using a series of consecutive procedures (carbonization of sapele wood biocarbon, synthesis of high-porosity biocarbon with channel-type pores, infiltration of molten silicon into empty channels of the biocarbon, formation of β-SiC, and retention of residual silicon in channels of β-SiC). The electrical resistivity ρ and thermal conductivity κ of the β-SiC/Si ecoceramic samples have been measured in the temperature range 5–300 K. The values of ρ Si chan(T) and κ Si chan(T) have been determined for silicon Sichan located in β-SiC channels of the synthesized β-SiC/Si ecoceramics. Based on the performed analysis of the obtained results, the concentration of charge carriers (holes) in Sichan has been estimated as p ∼ 1019 cm−3. The factors that can be responsible for such a high value of p have been discussed. The prospects for practical application of β-SiC/Si ecoceramics have been considered.

October, 2012 | DOI: 10.1134/S1063783412100289

Microstructure and high-temperature mechanical behavior of melt-growth Al2O3/Er3Al5O12/ZrO2 ternary eutectic composites

Huaman-Mamani, FA; Jimenez-Melendo, M; Mesa, MC; Oliete, PB
Journal of Alloys and Compounds, 536 (2012) S527-S531


The microstructural and high-temperature mechanical characteristics of directionally solidified rods of Al2O3–Er3Al5O12–ZrO2 ternary eutectic oxides processed by the laser-heated floating zone method at different growth rates have been investigated. The eutectic microstructure displayed an entangled three-dimensional network of Al2O3 and Er3Al5O12 phases of similar sizes, elongated along the growth direction; the minority zirconia phase formed small fibers into the alumina phase. The interphase spacing is reduced with increasing solidification rate, changing about 2 μm down to 200 nm. These microstructural features are essentially the same exhibited by Al2O3–Y3Al5O12–ZrO2 composites processed by the same technique. Compressive deformation tests performed at 1400 °C at constant strain rate showed that the creep resistance decreased when increasing the growth rate due to the refinement of the microstructure.

September, 2012 | DOI: 10.1016/j.jallcom.2012.01.105

High-temperature mechanical characteristics of NiO/3YTZP composites

Jimenez-Melendo, M; Oliva-Ramirez, M; Huaman-Mamani, FA
Journal of Alloys and Compounds, 536 (2012) S472-S476


NiO/3YTZP (3 mol% Y2O3-stabilized tetragonal ZrO2) composites with 40 mol% NiO (26 vol% NiO) have been fabricated by mechanical mixing of NiO and 3YTZP powders and sintering at 1500 °C for 10 h in air. The resulting microstructures have been characterized by electron microscopy. Compressive mechanical tests at constant strain rate were conducted on these materials at temperatures between 1150 and 1350 °C in air. The σ–ɛ curves display extended secondary creep regimes without signals of macroscopic failure. The composite creep behavior is characterized by a stress exponent n = 2 and an activation energy for flow Q = 490 kJ/mol. The overall creep behavior of the composites is essentially controlled by the zirconia matrix, due to the softness of the NiO phase in the experimental conditions used in this study.

September, 2012 | DOI: 10.1016/j.jallcom.2011.11.040

Effects of the presence of Fe(0) on the sorption of lanthanum and lutetium mixtures in smectites

Galunin, E; Alba, MD; Santos, MJ; Vidal, M
Applied Clay Science, 65-66 (2012) 162-172


The sorption of La and Lu mixtures was examined in two bentonites after incubation for three months at 20 and 80 °C with Fe(0), as a laboratory approach to evaluate the effects of waste canister corrosion in a deep repository on the performance of clay engineered barriers. The sorption/desorption parameters were determined from batch tests in two ionic media: deionized water and, to consider the additional effect of cement leachates, 0.02 mol L− 1 Ca.

Results from XRD analyses showed the formation of crystalline FeO(OH), goethite, in a few samples and the degradation of the bentonites due to Fe(0) oxidation during incubation. Moreover, the EDX spectra showed that the lanthanides were sorbed primarily at smectite sites, although sorption onto goethite was also observed, whereas Fe(0) particles did not contribute to lanthanide sorption. The formation of goethite could explain the high Kd values measured in a few scenarios (e.g., those with single solutions or mixtures with the lowest initial concentration of the competitive lanthanide in which high affinity sites governed sorption), with up to 3-fold increases over the values obtained without Fe incubation. However, at higher lanthanide concentration, Kd values decreased or remained constant compared to the samples without Fe incubation, which could be explained by bentonite degradation. In the Ca medium, as much as 5 times lower Kd values were obtained, because of the competitive effect of the Ca ions, especially for Lu in the MX80 bentonite. This indicated that the small number of high affinity sites had been diminished.

The sorption data were satisfactorily fitted to a two-solute Langmuir model. In addition, Kd values correlated well with desorption data, which showed that the larger the decrease in Kd, the larger the increase in sorption reversibility. It is suggested that corrosion products from the metal canister might compromise the long-term radionuclide retention of the clay-engineered barriers.

September, 2012 | DOI: 10.1016/j.clay.2012.06.011

Thermal conductivity of high-porosity heavily doped biomorphic silicon carbide prepared from sapele wood biocarbon

Parfen'eva, LS; Orlova, TS; Smirnov, BI; Smirnov, IA; Misiorek, H; Mucha, J; Jezowski, A; Cabezas-Rodriguez, R; Ramirez-Rico, J
Physics of the Solid State, 54 (2012) 1732-1739


The electrical resistivity and thermal conductivity of high-porosity (~52 vol %, channel-type pores) bio-SiC samples prepared from sapele wood biocarbon templates have been measured in the temperature range 5-300 K. An analysis has been made of the obtained results in comparison with the data for bio-SiC samples based on beech and eucalyptus, as well as for polycrystalline β-SiC. The conclusion has been drawn that the electrical resistivity and thermal conductivity of bio-SiC samples based on natural wood are typical of heavily doped polycrystalline β-SiC.

August, 2012 | DOI: 10.1134/S1063783412080240

Biomimetic mineralization of calcium phosphate on a functionalized porous silicon carbide biomaterial

Dey, A; van den Hoogen, CJ; Rosso, M; Lousberg, N; Hendrix, MMRM; Friedrich, H; Ramirez-Rico, J; Zuilhof, H; de With, G; Sommerdijk, NAJM
ChemPlusChem, 77 (2012) 694-699


Porous biomorphic silicon carbide (bioSiC) is a structurally realistic, high-strength, and biocompatible material which is promising for application in load-bearing implants. The deposition of an osteoconductive coating is essential for further improvement of its integration with the surrounding tissue. A new strategy towards biomimetic calcium phosphate coatings on bioSiC is described. X-ray photoelectron spectroscopy (XPS) analysis shows that using 10-undecenoic acid methyl ester a covalently bound monolayer can be synthesized on the surface of the bioSiC. After hydrolysis it exposes carboxylic acid groups that promote the selective nucleation and growth of a very well-defined crystalline layer of calcium phosphate. The resulting calcium phosphate coating is characterized by X-ray diffraction and electron microscopy techniques. Further, ion beam imaging is employed to quantify the mineral deposition meanwhile, three-dimensional dual-beam imaging (FIB/SEM) is used to visualize the bioSiC/mineral interface. The monolayer is show to actively induce the nucleation of a well-defined and highly crystalline mixed octacalcium phosphate/hydroxyapatite (OCP/HAP) coating on implantable bioSiC substrates with complex geometry. The mild biomimetic procedure, in principle, allows for the inclusion of bioactive compounds that aid in tissue regeneration. Moreover, the mixed OCP/HAP phase will have a higher solubility compared to HAP, which, in combination with its porous structure, is expected to render the coating more reabsorbable than standard HAP coatings.

August, 2012 | DOI:

Synthetic high-charge organomica: Effect of the layer charge and alkyl chain length on the structure of the adsorbed surfactants

Pazos, MC; Castro, MA; Orta, MM; Pavon, E; Rios, JSV; Alba, MD
Langmuir, 28 (2012) 7325-7332


A family of organomicas was synthesized using synthetic swelling micas with high layer charge (NanSi8-nAlnMg6F4O20 center dot XH2O, where n = 2, 3, and 4) exchanged with dodecylammonium and octadecylammonium cations. The molecular arrangement of the surfactant was elucidated on the basis on XRD patterns and DTA. The ordering conformation of the surfactant molecules into the interlayer space of micas was investigated by C-13, Al-27, and Si-29 MAS NMR The arrangement of alkylammonium ions in these high-charge synthetic micas depends on the combined effects of the layer charge of the mica and the chain length of the cation. In the organomicas with dodecylammonium, a transition from a parallel layer to a bilayer-paraffin arrangement is observed when the layer charge of the mica increases. However, when octadecylammonium is the interlayer cation, the molecular arrangement of the surfactant was found to follow the bilayer-paraffin model for all values of layer charge. The amount of ordered conformation all-trans is directly proportional of layer charge.

May, 2012 | DOI: 10.1021/la300153e

Remediation of metal-contaminated soils with the addition of materials - Part II: Leaching tests to evaluate the efficiency of materials in the remediation of contaminated soils

Gonzalez-Nunez, R; Alba, MD; Orta, MM; Vidal, M; Rigol, A
Chemosphere, 87 (2012) 829-837


The effect of the addition of materials on the leaching pattern of As and metals (Cu, Zn, Ni, Pb, and Cd) in two contaminated soils was investigated. The examined materials included bentonites, silicates and industrial wastes, such as sugar foam, fly ashes and a material originated from the zeolitization of fly ash. Soil + material mixtures were prepared at 10% doses. Changes in the acid neutralization capacity, crystalline phases and contaminant leaching over a wide range of pHs were examined by using pHstat leaching tests. Sugar foam, the zeolitic material and MX-80 bentonite produced the greatest decrease in the leaching of pollutants due to an increase in the pH and/or the sorption capacity in the resulting mixture. This finding suggests that soil remediation may be a feasible option for the reuse of non-hazardous wastes.

May, 2012 | DOI: 10.1016/j.chemosphere.2012.01.015

Interfacial characterization of silicon nitride/silicon nitride joints brazed using Cu-base active metal interlayers

Singh, M; Fernandez, JM; Asthana, R; Rico, JR
Ceramics Intenational, 38 (2012) 2793-2802


Silicon nitride/silicon nitride joints were vacuum brazed at 1317 K for 5 min and 30 min using ductile Cu-base active metal interlayers. The joints were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), electron back scattered diffraction (EBSD), and transmission electron microscopy (TEM). An inhomogeneous Ti-rich reaction layer (similar to 2-3 mu m thick) formed in 5 min at the Si3N4/braze interface. The inhomogeneity disappeared after brazing for 30 min and was replaced with a compact and featureless reaction zone. TEM studies revealed fine grains in the reaction layer, and larger grains in the inner part of the joint interfaces. The joints were crack-free and presented features associated with plastic deformation, which indicated accommodation of strain associated with CTE mismatch. Electron Backscatter diffraction (EBSD) revealed a highly textured braze alloy interlayer and its crystallographic orientation was determined. The formation of additional phases at the joint interface during brazing is discussed.

May, 2012 | DOI: 10.1016/j.ceramint.2011.11.050

Residual stresses in Al2O3-ZrO 2 (3mol.% Y2O3) directionally solidified eutectic ceramics as a function of temperature

Ramirez-Rico, J; Martinez-Fernandez, J; Pena, JI; Singh, D; Routbort, J
Materials Science and Engineering A, 541 (2012) 61-66


Directionally solidified eutectics are in situ composites grown from the melt. Due to the differences in the thermoelastic properties of the different phases present in the material, these composites often exhibit residual stresses that can affect their mechanical properties. In this work we use neutron diffraction to investigate residual stresses in Al 2O 3-ZrO 2 eutectic composites as a function of temperature, for samples processed at two different growth rates, 10mm/h and 750mm/h. Our results show that the stress-free temperature is in the range of 1200±200°C. We explain the experimental observations based on the thermoelastic properties of the phases in the material and confirm our measurements using a simple, self-consistent model.

April, 2012 | DOI: 10.1016/j.msea.2012.02.001

Electrostatic Induced Molecular Tilting in Self-Assembled Monolayers of n-Octadecylamine on Mica

Oviedo, J; San-Miguel, MA; Heredia-Guerrero, JA; Benitez, JJ
Journal of Physical Chemistry C, 116 (2012) 7099-7105


Self-assembled monolayers of n-octadecylamine on mica (ODA/mica SAMs) have been investigated by atomic force microscopy (AFM) and by attenuated total reflectance infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopies. Topographic data characterizes a stable configuration with the alkyl skeleton tilted approximate to 46 degrees from the surface normal that is rationalized according to a well established structural alkyl chain packing model. Extended contact with air increases molecular tilting up to approximate to 58 degrees. ATR-FTIR and XPS reveal the presence of protonated amino groups within the monolayer and its increment upon exposure to air. The transition between both tilted states is explained assuming the protonation reaction as the driving force and introducing a model to evaluate an electrostatic repulsions term in the overall cohesive energy balance of the system. ODA molecules in the self-assembled monolayer respond to their spontaneous protonation by atmospheric water by tilting as a mechanism to relax the repulsions between -NH3+ heads.

March, 2012 | DOI: 10.1021/jp300829g

Effect of oxidation on the compressive strength of sintered SiC-fiber bonded ceramics

Ramirez-Rico, J; Martinez-Fernandez, J; Singh, M
Materials Science and Engineering A, 534 (2012) 394-399


The compressive strength of SiC-fiber bonded ceramics obtained from hot-pressed amorphous Si-Al-C-O fibers and its degradation by high temperature exposure to an oxidizing environment was studied. Compressive strength was measured at room temperature as a function of strain rate, orientation, and oxidation temperature. Weight loss was monitored as a function of exposure time in atmospheric air at temperatures ranging from 800 to 1600°C, for times ranging from 0.5 to 5. h. Room-temperature compressive strength had a moderate decrease after exposures at 800°C associated to carbon burnout; increased for exposures in the range 1000-1500°C due to a defect-blunting action of the silica scale; and decreased significantly at 1600°C due to extensive surface recession.

February, 2012 | DOI: 10.1016/j.msea.2011.11.085


Remediation of metal-contaminated soils with the addition of materials – Part I: Characterization and viability studies for the selection of non-hazardous waste materials and silicates

R. González-Núñez, M.D. Alba, M.M. Orta, M. Vidal, A. Rigol
Chemosphere, 85 (2011) 1511-1517


Contamination episodes in soils require interventions to attenuate their impact. These actions are often based on the addition of materials to increase contaminant retention in the soil and to dilute the contaminant concentration. Here, non-hazardous wastes (such as sugar foam, fly ash and a material produced by the zeolitization of fly ash) and silicates (including bentonites) were tested and fully characterized in the laboratory to select suitable materials for remediating metal-contaminated soils. Data from X-ray fluorescence (XRF), N2 adsorption/desorption isotherms, X-ray diffraction (XRD) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM–EDX) analyses revealed the chemical composition, specific surface area and the phases appearing in the materials. A pH titration test allowed the calculation of their acid neutralization capacity (ANC). The metal sorption and desorption capacities of the waste materials and silicates were also estimated. Sugar foam, fly ash and the zeolitic material were the best candidate materials. Sugar foam was selected because of its high ANC (17 000 meq kg−1), and the others were selected because of their larger distribution coefficients and lower sorption reversibilities than those predicted in the contaminated soils.

November, 2011 | DOI: 10.1016/j.chemosphere.2011.09.042

Application of the solid state NMR to the study of the alcohol/alkane mixtures adsorption onto graphite

María D. Alba, Miguel A. Castro, Stuart M. Clarke, Santiago Medina, Loic Messe, Carmen Millán
Solid State Nuclear Magnetic Resonance, 40 (2011) 138-143


The mixing of molecules adsorbed from solution to different interfaces has both industrial and academic relevance and the mixing behaviour at the interface is a key to understanding for example, that the surface tension of a mixture of two surfactants is lower than either of the two pure materials and many other effects. In this paper, we report, for the first time, the application of Solid State NMR to the study of alkane/alcohol mixtures, in a range of relative size ratio between 0 and 0.35, adsorbed onto graphite at high, multilayer coverage. Moreover, this paper evaluated, for the first time, the utility of the combined used of 1H and 2H NMR for: (i) determining the surface composition and (ii) making a theoretical approach to the sorption isotherm. A variety of preferential adsorption behaviour is reported. Preferential adsorption of the longer molecule (decane vs. heptanol) from a mixture has been observed. However, if both components are of similar length, the alcohol is preferentially adsorbed (heptanol vs. octane and octanol vs. octane). Finally, a linear relation between the relative size ratio and the amount of alcohol at monolayer coverage is observed.

November, 2011 | DOI: 10.1016/j.ssnmr.2011.11.002

Structure, Electrical Resistivity, and Thermal Conductivity of Beech Wood Biocarbon Produced at Carbonization Temperatures below 1000 degrees C

Parfen'eva, LS; Orlova, TS; Kartenko, NF; Smirnov, BI; Smirnov, IA; Misiorek, H; Jezowski, A; Muha, J; Vera, MC
Physics of the Solid State, 53 (2011) 2398-2407


This paper reports on measurements of the thermal conductivity. and the electrical resistivity. in the temperature range 5-300 K, and, at 300 K, on X-ray diffraction studies of high-porosity (with a channel pore volume fraction of similar to 47 vol %) of the beech wood biocarbon prepared by pyrolysis (carbonization) of tree wood in an argon flow at the carbonization temperature T(carb) = 800 degrees C. It has been shown that the biocarbon template of the samples studied represents essentially a nanocomposite made up of amorphous carbon and nanocrystallites-"graphite fragments" and graphene layers. The sizes of the nanocrystallites forming these nanocomposites have been determined. The dependences rho(T) and kappa(T) have been measured for the samples cut along and perpendicular to the tree growth direction, thus permitting determination of the magnitude of the anisotropy of these parameters. The dependences rho(T) and kappa(T), which have been obtained for beech biocarbon samples prepared at T(carb) = 800 degrees C, are compared with the data amassed by us earlier for samples fabricated at T(carb) = 1000 and 2400 degrees C. The magnitude and temperature dependence of the phonon thermal conductivity of the nanocomposite making up the beech biocarbon template at T(carb) = 800 degrees C have been found.

November, 2011 | DOI: 10.1134/S1063783411110230

Structure and Chemical State of Octadecylamine Self-Assembled Monolayers on Mica

Benitez, JJ; San-Miguel, MA; Dominguez-Meister, S; Heredia-Guerrero, JA; Salmeron, M
Journal of Physical Chemistry C, 115 (40) (2011) 19716-19723


Structural and chemical data on n-octadecylamine self-assembled monolayers on mica (ODA/mica SAMs) have been obtained from ATR-FTIR and XPS spectroscopies. The analysis of the methylene modes concludes that alkylamine molecules are arranged in a rigid and well-ordered packing. Besides, the magnitude of the splitting of the methylene scissoring deflection is consistent with a molecular tilted configuration within the self-assembled layer, as already reported from topographic AFM data. Molecular dynamics simulations have supported this conclusion. XPS has revealed the presence of an important fraction of protonated amino groups (-NH3+) even in freshly prepared ODA/mica SAMs in air at RT. Two sources of protonation are proposed: (i) the acid-base reaction of (-NH2) end groups with the water adlayer on the surface of hydrophilic mica and (ii) the formation of an alkylamonium alkylcarbamate by a fast reaction with the atmospheric CO2 dissolved in such water adlayer. Though the water induced amino protonation is hypothetical, the presence of carbamate is univocally confirmed by ATR-FTIR. Upon extended contact with air (ripening) the conformational ordering in ODA/mica SAMs is slightly improved. Besides, further amino group protonation takes place with no additional carbamate formation. The process is described by a tentative mechanism in which protons are transferred from water molecules at the edges of SAMs islands to the inside. On the other side, carbamation is hindered by the steric effect of CO2 molecules trying to penetrate the close packed structure of octadecylamine molecules.

October, 2011 | DOI: 10.1021/jp203871g

Evolution of Phases and Al–Si Distribution during Na-4-Mica Synthesis

María D. Alba, Miguel A. Castro, Moisés Naranjo, M. Mar Orta, Esperanza Pavón, and M. Carolina Pazos
Journal of Physical Chemistry C, 2011, 115 (41), pp 20084–20090


Na-4-mica, a highly charged fluorophlogopite, has recently attracted much attention because of its unique combination of high charge (four charges per unit cell) and its swelling and cation-exchange properties. The ability to improve the properties of this mica depends on gaining knowledge about its phase evolution during the calcination process. For the synthesis, the stoichiometric powder mixture (4SiO 2/2Al 2O 3/6MgF 2/8NaCl) was heated to 900 °C for 0-600 h. The obtained solids were characterized by X-ray fluorescence (XRF); X-ray diffraction (XRD); scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis; 29Si, 27Al, and 23Na magic-angle-spinning MAS NMR spectroscopy; and thermogravimetric/differential thermal analysis (TG/DTA). The results showed that the precursors are rapidly (t < 3 h) transformed into sodalite, Al 6Na 8(SiO 4) 6Cl 2, and a 2:1 phyllosilicate. For t = 7.5 h, the amount of 2:1 phyllosilicate increased as a result of the decomposition of sodalite, with a progressive incorporation of aluminum in the 2:1 phyllosilicate being observed. For t = 7.5 h, synthesis of Na-4-mica was considered to be complete, as the material remained essentially unaltered for the next 15 h. For t = 30 h, the mica started to decompose, and for very long reaction times (t ≥ 300 h), only forsterite and a carnegierite phase were present.

October, 2011 | DOI: 10.1021/jp207408h

The effect of polymorphic structure on the structural and chemical stability of yttrium disilicates

Evgeny Galunin, Miquel Vidal and María D. Alba
American Mineralogist, 96 (2011) 1512-1520


Under pressure and temperature conditions like those found in deep geological repositories (DGRs), rare-earth cations may react with silicates to form rare-earth disilicates. This study establishes the stability range of yttrium disilicates in response to changes in pH. The α, β, γ, and δ polymorphs of Y2Si2O7 were synthesized by the sol-gel process at temperatures between 1100 and 1650 °C and subjected to pHstat leaching tests. By measuring the Y and Si leaching rates and monitoring the transformation of the crystalline and amorphous phases, we showed that yttrium disilicates were stable at pH > 5. At pH < 5, the pH stability sequence was consistent with the temperature-dependent stabilities of Y2Si2O7 phases, with the δ polymorph showing the lowest leaching rates. Because rare-earth compounds can be used as a proxy for analogous actinide hosts, the results of this study can be used to predict the performance of engineered barriers in DGR.

October, 2011 | DOI: 10.2138/​am.2011.3659

Structural elucidation of Β-(Y,Sc)2Si2O 7: Combined use of 89Y MAS NMR and powder diffraction

Allix, M., Alba, M.D., Florian, P., Fernandez-Carrion, A.J., Suchomel, M.R., Escudero, A., Suard, E., Becerro, A.I.
Journal of Applied Crystallography, 44 (2011) 846-852


Although the structures of pure Sc2Si2O7 and &#914;-Y2Si 2O7 have been described in the literature using the C2/m space group, 29Si magic angle spinning (MAS) NMR measurements of the intermediate members of the Sc2Si2O7-&#914;- Y2Si2O7 system indicate a lowering of the symmetry to the C2 space group. Indeed, these compositions exhibit a unique Si crystallographic site and an Si-O-Si angle lower than 180°, incompatible with the C2/m space group. C2 is the only possible alternative. Space group Cm can be discarded with regard to its two different Si sites per unit cell. Moreover, 89Y MAS NMR data have revealed the existence of two different Y sites in the structure of the intermediate members of the Sc 2Si2O7-&#914;-Y2Si2O 7 system, confirming the lowering of the symmetry to the C2 space group. The viability of the C2 model has therefore been tested and confirmed by refinement of synchrotron and neutron powder diffraction data for the different members of the system. The structural evolutions across the Sc 2Si2O7-&#914;-Y2Si2O 7 system are discussed.

August, 2011 | DOI: 10.1107/S0021889811021303

Formation of organo-highly charged mica

Alba, M.D. , Castro, M.A., Orta, M.M., Pavón, E., Pazos, M.C., Valencia Rios, J.S.
Langmuir, 16 (2011) 9711-9718


The interlayer space of the highly charged synthetic Na-Mica-4 can be modified by ion-exchange reactions involving the exchange of inorganic Na + cations by surfactant molecules, which results in the formation of an organophilic interlayer space. The swelling and structural properties of this highly charged mica upon intercalation with n-alkylammonium (RNH 3) + cations with varying alkyl chain lengths (R = C12, C14, C16, and C18) have been reported. The stability, fine structure, and evolution of gaseous species from alkylammonium Mica-4 are investigated in detail by conventional thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), in situ X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (MAS NMR) techniques. The results clearly show the total adsorption of n-alkylammonium cations in the interlayer space which expands as needed to accommodate intercalated surfactants. The surfactant packing is quite ordered at room temperature, mainly involving a paraffin-type bilayer with an all-trans conformation, in agreement with the high density of the organic compounds in the interlayer space. At temperatures above 160 °C, the surfactant molecules undergo a transformation that leads to a liquid-like conformation, which results in a more disordered phase and expansion of the interlayer space.

August, 2011 | DOI: 10.1021/la200942u

Solid solubility of Yb2Si2O7 in β-, γ- And δ-Y2Si2O7

Fernández-Carrión, A.J., Alba, M.D., Escudero, A., Becerro, A.I.
Journal of Solid State Chemistry, 184 (2011) 1882-1889


This paper examines the structural changes with temperature and composition in the Yb2Si2O7–Y2Si2O7 system; members of this system are expected to form in the intergranular region of Si3N4 and SiC structural ceramics when sintered with the aid of Yb2O3 and Y2O3 mixtures. A set of different compositions have been synthesised using the sol–gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1650 °C during different times. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of Yb2Si2O7 in β-Y2Si2O7 and γ-Y2Si2O7. Although Yb2Si2O7 shows a unique stable polymorph (β), Yb3+ is able to replace Y3+ in γ-Y2Si2O7 and δ-Y2Si2O7 at high temperatures and low Yb contents. IR results confirm the total solid solubility in the system and suggest a constant SiOSi angle of 180° in the Si2O7 unit across the system. The temperature–composition diagram of the system, obtained from powder XRD data, is dominated by the β-RE2Si2O7 polymorph, with γ-RE2Si2O7 and δ-RE2Si2O7 showing reduced stability fields. The diagram is in accordance with Felsche's diagram if average ionic radii are assumed for the members of the solid solution at any temperature, as long as the β–γ phase boundary is slightly shifted towards higher radii.

July, 2011 | DOI: 10.1016/j.jssc.2011.05.034

Compressive strength degradation in ZrB2-based ultra-high temperature ceramic composites

Ramirez-Rico, J; Bautista, MA; Martinez-Fernandez, J; Singh, M
Journal of the European Ceramic Society, 31 (2011) 1345-1352


The high temperature compressive strength behavior of zirconium diboride (ZrB2)-silicon carbide (SiC) particulate composites containing either carbon powder or SCS-9a silicon carbide fibers was evaluated in air. Constant strain rate compression tests have been performed on these materials at room temperature, 1400, and 1550°C. The degradation of the mechanical properties as a result of atmospheric air exposure at high temperatures has also been studied as a function of exposure time. The ZrB2-SiC material shows excellent strength of 3.1±0.2GPa at room temperature and 0.9±0.1GPa at 1400°C when external defects are eliminated by surface finishing. The presence of C is detrimental to the compressive strength of the ZrB2-SiC-C material, as carbon burns out at high temperatures in air. As-fabricated SCS-9a SiC fiber reinforced ZrB2-SiC composites contain significant matrix microcracking due to residual thermal stresses, and show poor mechanical properties and oxidation resistance. After exposure to air at high temperatures an external SiO2 layer is formed, beneath which ZrB2 oxidizes to ZrO2. A significant reduction in room temperature strength occurs after 16-24h of exposure to air at 1400°C for the ZrB2-SiC material, while for the ZrB2-SiC-C composition this reduction is observed after less than 16h. The thickness of the oxide layer was measured as a function of exposure time and temperatures and the details of oxidation process has been discussed.

June, 2011 | DOI: 10.1016/j.jeurceramsoc.2010.05.020

Electrical properties of biomorphic SiC ceramics and SiC/Si composites fabricated from medium density fiberboard

T.S. Orlova, V.V. Popov, J. Quispe Cancapa, D. Hernández Maldonado, E. Enrique Magarino, F.M. Varela Feria, A. Ramírez de Arellano, J. Martínez Fernández
Journal of the European Ceramic Society, 31 (2011) 1317-1323


A study has been made of the dependences of the electrical resistivity and the Hall coefficient on the temperature in the range 1.8–1300 K and on magnetic fields of up to 28 kOe for the biomorphic SiC/Si (MDF-SiC/Si) composite and biomorphic porous SiC (MDF-SiC) based upon artificial cellulosic precursor (MDF – medium density fiberboards). It has been shown that electric transport in MDF-SiC is effected by carriers of n-type with a high concentration of ∼1020 cm−3 and a low mobility of ∼0.4 cm2 V−1 s−1. The specific features in the conductivity of MDF-SiC are explained by quantum effects arising in disordered systems and requiring quantum corrections to conductivity. The TEM studies confirmed the presence of disordering structural features (nanocrystalline regions) in MDF-SiC. The conductivity of MDF-SiC/Si composite originates primarily from Si component in the temperature range 1.8–500 K and since ∼500 to 600 K the contribution of MDF-SiC matrix becomes dominant.

June, 2011 | DOI: 10.1016/j.jeurceramsoc.2010.06.015

High-temperature mechanical behavior of polycrystalline yttrium-doped barium cerate perovskite

Vaquero-Aguilar, C; Lopez-Robledo, MJ; Martinez-Fernandez, J; Real, C; Jimenez-Melendo, M
Journal of the European Ceramic Society, 31 (2011) 1333-1338


The high-temperature mechanical properties of the mixed ionic-electronic conductor perovskite BaCe0.95Y0.05O3−δ with average grain size of 0.40 μm have been studied in compression between 1100 and 1300 °C in air at different initial strain rates. The true stress–true strain curves display an initial stress drop, followed by an extended steady-state stage. As the temperature decreases and/or the strain rate increases, there is a transition to a damage-tolerant strain-softening stage and eventually to catastrophic failure. Analysis of mechanical and microstructural data revealed that grain boundary sliding is the primary deformation mechanism. The strength drop has been correlated with the growth of ultrafine grains during deformation, already present at grain boundaries and triple grain junctions in the as-fabricated material.

June, 2011 | DOI: 10.1016/j.jeurceramsoc.2010.05.023

Microstructural and mechanical evaluation of a Cu-based active braze alloy to join silicon nitride ceramics

Singh, M; Asthana, R; Varela, FM; Martinez-Fernandez, J
Journal of the European Ceramic Society, 31 (2011) 1309-1316


Self-joining of St. Gobain Si3N4 (NT-154) using a ductile Cu–Al–Si–Ti active braze (Cu-ABA) was demonstrated. A reaction zone (∼2.5–3.5 μm thick) developed at the interface after 30 min brazing at 1317 K. The interface was enriched in Ti and Si. The room temperature compressive shear strengths of Si3N4/Si3N4 and Inconel/Inconel joints (the latter created to access baseline data for use with the proposed Si3N4/Inconel joints) were 140 ± 49 MPa and 207 ± 12 MPa, respectively. High-temperature shear tests were performed at 1023 K and 1073 K, and the strength of the Si3N4/Si3N4 and Inconel/Inconel joints were determined. The joints were metallurgically well-bonded for temperatures above 2/3 of the braze solidus. Scanning and transmission electron microscopy studies revealed a fine grain microstructure in the reaction layer, and large grains in the inner part of the joint with interfaces being crack-free. The observed formation of Ti5Si3 and AlN at the joint interface during brazing is discussed.

June, 2011 | DOI: 10.1016/j.jeurceramsoc.2010.07.022

Microstructural and mechanical evaluation of porous biomorphic silicon carbide for high temperature filtering applications

Bautista, MA; Cancapa, JQ; Fernandez, JM; Rodriguez, MA; Singh, M
Journal of the European Ceramic Society, 31 (2011) 1325-1332


Biomorphic SiC (bioSiC) is a low cost SiC/Si composite obtained by melt infiltration of carbon preforms obtained from the pyrolysis of cellulose precursors. The porosity and pore size distribution of bioSiC can be tailored for specific applications by adequate selection of the wood precursor. Natural and artificial industrial woods were explored as possible bioSiC precursors. Silicon was removed by chemical etching. Relevant microstructural parameters such as pore size distribution, total porosity, and permeability were characterized. Since the filtration process involves large pressure gradients along the material at high temperatures, mechanical properties of porous bioSiC from the different precursors were evaluated at room temperature and 800 °C. The feasibility of porous bioSiC as a filtration material for high temperature gasification processes is discussed in terms of these properties. MDF-bioSiC is shown to be a promising material for such applications because of its good mechanical properties, interconnected porosity, pore sizes, and permeability.

June, 2011 | DOI: 10.1016/j.jeurceramsoc.2010.06.014

Structure and support induced structure disruption of soft nanoparticles obtained from hydroxylated fatty acids

Heredia-Guerrero, JA; San-Miguel, MA; Luna, M; Dominguez, E; Heredia, A; Benitez, JJ
Soft Matter, 7 (2011) 4357-4363


Soft and spherical nanoparticles, named as cutinsomes, have been prepared from concentrated 9(10),16-dihydroxypalmitic acid (diHPA) in aqueous solution. After isolation, cutinsomes have been chemically and structurally characterized by ATR-FTIR, TEM and dynamic atomic force microscopy (dynamic AFM). The nanoparticle can be described as a lipidic, liquid-like and mostly esterified core surrounded by a polar shell of carboxylate/carboxylic acid molecules. Molecular dynamic (MD) simulations have been used to support this model. The structural stability of soft cutinsomes has been tested by deposition on both non-polar (HOPG) and polar (mica) flat substrates. It has been found that the magnitude of the interaction between the polar shell of cutinsomes and the support determines their structure conservation or its spreading or rupture and spill out of the liquid-like content. The structural consistence of these nanoparticles as a function of the polarity of substrate is of interest in elucidating the formation mechanism of cutin, the most abundant biopolyester in nature and a very interesting biomaterial to be mimetized.

May, 2011 | DOI: 10.1039/c0sm01545h

Interaction of Eu-isotopes with saponite as a component of the engineered barrier

María D. Alba, Miguel A. Castro, P. Chaín, Santiago Hurtado, M. Mar Orta, M. Carolina Pazos and María Villa
Applied Clay Science, 52 (2011) 253-257


Bentonite is accepted as the best clay material in the engineered barrier of deep geological repositories (DGRs) for radioactive waste disposal. In recent years, the interactions between a wide range of rare-earth (REE) cations and smectites have been studied. A combined study of stable europium and radioactive isotopes is reported here. Saponite was subjected to hydrothermal reactions with stable and radioactive (152Eu) europium ions under subcritical conditions. The structural changes of saponite were evaluated by XRD and SEM. The effect of temperature and reaction time on the changes was quantified by measuring 152Eu through gamma spectrometry. The reaction between europium and saponite was a first-order reaction. The presence of Eu in the precipitate in an amount much higher than the cation exchange capacity of saponite confirmed participation of chemical reactions or surface adsorption in the europium immobilization, even at temperatures as low as 150 °C. The reaction rate constant indicated that an 8- to 9-month period was needed for the completion, without significant changes, of the europium/saponite chemical reaction under the subcritical conditions of 200 °C and 350 °C.

May, 2011 | DOI: 10.1016/j.clay.2011.02.027

Stability of Rare-Earth Disilicates: Ionic Radius Effect

Galunin, E; Alba, MD; Vidal, M
Journal of the American Ceramic Society, 94 (2011) 1568–1574


Rare-earth (RE) disilicates, of general formula RE2Si 2O7, are one of the products of the chemical reaction between RE (elements), which are actinide simulators, and the silicates used in the engineered barrier systems of deep geological repositories (DGPs). The aim of this paper is to establish the stability range of the disilicate phase as function of the nature of the RE (RE=Sc, Lu, or Y) and examine whether this phase would permit RE leaching under experimental conditions simulating those of the DGP. The &#946;-polymorphs of the RE disilicates were synthesized by the sol-gel method and subsequently submitted to a pHstat leaching test. The rates of RE and Si leaching were measured and the transformation of the crystalline and amorphous phases was examined by X-ray powder diffraction and nuclear magnetic resonance techniques. The results indicate that the disilicate phases were stable within a wide range of pH, their stability being related to the hydrated ratio of the RE. Disilicate stability increased with the ionic radius of the RE. As a result, the Sc disilicate was stable throughout the pH range tested, whereas Y and Lu disilicate leaching was only observed at pH<4. Thus, it was confirmed that the formation of the disilicate phases could contribute to the confinement of radioactive wastes in engineered barriers.

May, 2011 | DOI: 10.1111/j.1551-2916.2010.04272.x

Bulk and Adsorbed Monolayer Phase Behavior of Binary Mixtures of Undecanoic Acid and Undecylamine: Catanionic Monolayers

Sun, C; Bojdys, MJ; Clarke, SM; Harper, LD; Jefferson, A; Castro, MA; Medina, S
Langmuir, 27 (2011) 3626-3637


Differential scanning calorimetry (DSC) and X-ray powder diffraction (PXRD) have been used to determine the phase behavior of the binary mixtures of undecanoic acid (A) and undecylamine (B) in the bulk. In addition, we report DSC data that indicates very similar behavior for the solid monolayers of these materials adsorbed on the surface of graphite. The two species are found to form a series of stoichiometric complexes of the type AB, A2B, and A 3B on the acid rich side of the phase diagram. Interestingly, no similar series of complexes is evident on the amine rich side. As a result of this complexation, the solid monolayers of the binary mixtures exhibit a very pronounced enhancement in stability relative to the pure adsorbates.

April, 2011 | DOI: 10.1021/la1048198

Structural, chemical surface and transport modifications of regenerated cellulose dense membranes due to low-dose γ-radiation

Vazquez, MI; Heredia-Guerrero, JA; Galan, P; Benitez, JJ; Benavente, J
Materials Chemistry and Physics, 126 (2011) 734-740


Modifications caused in commercial dense regenerated cellulose (RC) flat membranes by low-dose &#947;-irradiation (average photons energy of 1.23 MeV) are studied. Slight structural, chemical and morphological surface changes due to irradiation in three films with different RC content were determined by ATR-FTIR, XRD, XPS and AFM. Also, the alteration of their mechanical elasticity has been studied. Modification of membrane performance was determined from solute diffusion coefficient and effective membrane fixed charge concentration obtained from NaCl diffusion measurements. Induced structural changes defining new and effective fracture propagation directions are considered to be responsible for the increase of fragility of irradiated RC membranes. The same structural changes are proposed to explain the reduction of the membrane ion permeability through a mechanism involving either ion pathways elongation and/or blocking.

April, 2011 | DOI: 10.1016/j.matchemphys.2010.12.051

The biophysical design of plant cuticles: an overview

Dominguez, E; Heredia-Guerrero, JA; Heredia, A
New Phytologist, 189 (2011) 938-949


The outer surfaces of epidermal cell walls are impregnated with an extracellular matrix called the cuticle. This composite matrix provides several functions at the interface level that enable plants to thrive in different habitats and withstand adverse environmental conditions. The lipid polymer cutin, which is the main constituent of the plant cuticle, has some unique biophysical properties resulting from its composition and structure. This review summarizes the progress made towards understanding the biophysical significance of this biopolymer with special focus on its structural, thermal, biomechanical, and hydric properties and relationships. The physiological relevance of such biophysical properties is discussed in light of existing knowledge on the plant cuticle.

March, 2011 | DOI: 10.1111/j.1469-8137.2010.03553.x

Blocking of grain reorientation in self-doped alumina materials

Suarez, M; Fernandez, A; Menendez, JL; Ramirez-Rico, J; Torrecillas, R
Scripta Materialia, 64 (2011) 517-520


Alumina nanoparticles 10-20 nm in diameter were nucleated on alumina particles, 150 nm average diameter, by a colloidal route followed by calcination. It is shown that after sintering, the final grain size is up to 20% smaller due to the addition of the alumina nanoparticles. Electron backscattered diffraction analysis shows that whereas a correlation in the relative crystalline orientations between neighbouring grains exists in the pure materials, the addition of alumina nanoparticles results in a random crystalline orientation.

March, 2011 | DOI: 10.1016/j.scriptamat.2010.11.031

Monolayer structures of alkyl aldehydes: Odd-membered homologues

Phillips, TK; Clarke, SM; Bhinde, T; Castro, MA; Millan, C; Medina, S
Thin Solid Films, 519 (2011) 3123-3127


Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C7, C9 and C11) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C11 homologue is determined to have a plane group of either p2, pgb or pgg, and for the C7 homologue the p2 plane group is preferred.

March, 2011 | DOI: 10.1016/j.tsf.2010.12.084

Examination of competitive lanthanide sorption onto smectites and its significance in the management of radioactive waste

Galunin, E; Alba, MD; Santos, MJ; Abrao, T; Vidal, M
Journal of Hazardous Materials, 186 (2011) 1930-1941


The competitive effect of La and Lu (analogues of radionuclides appearing in radioactive waste) in the sorption in four smectites was examined. Sorption and desorption distribution coefficients (Kd; Kd,des), and desorption rates (Rdes) were determined from batch tests in two media: deionized water and, to consider the influence of cement leachates, 0.02molL-1 Ca. The competitive effect was lower when high-affinity sites were available, as in the water medium at the lowest range of initial lanthanide concentration, with high Kd for La and for Lu (5-63×104Lkg-1). Lower Kd was measured at higher initial concentrations and in the Ca medium, where Lu showed a stronger competitive effect. This was confirmed by fitting the sorption data to a two-solute Langmuir isotherm. The desorption data indicated that sorption was virtually irreversible for the scenarios with high sorption, with an excellent correlation between Kd and Kd,des (R2 around 0.9 for the two lanthanides). Assuming that radioactive waste is a mixture of radionuclides, and that Ca ions will be provided by the cement leachates, this would reduce the retention capacity of clay engineered barriers.

February, 2011 | DOI: 10.1016/j.jhazmat.2010.12.098


Bioactivation of biomorphous silicon carbide bone implants

Will J, Hoppe A, Muller FA, Raya CT, Fernandez JM, Greil P
Acta Biomaterialia, 6 (2010) 448-4494


Wood-derived silicon carbide (SiC) offers a specific biomorphous microstructure similar to the cellular pore microstructure of bone. Compared with bioactive ceramics such as calcium phosphate, however, silicon carbide is considered not to induce spontaneous interface bonding to living bone. Bioactivation by chemical treatment of biomorphous silicon carbide was investigated in order to accelerate osseointegration and improve bone bonding ability. Biomorphous SiC was processed from sipo (Entrandrophragma utile) wood by heating in an inert atmosphere and infiltrating the resulting carbon replica with liquid silicon melt at 1450 °C. After removing excess silicon by leaching in HF/HNO3 the biomorphous preform consisted of &#946;-SiC with a small amount (approximately 6 wt.%) of unreacted carbon. The preform was again leached in HCl/HNO3 and finally exposed to CaCl2 solution. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared analyses proved that oxidation of the residual carbon at the surface induced formation of carboxyl [COO-] groups, which triggered adsorption of Ca2+, as confirmed by XPS and inductively coupled plasma optical emission spectroscopy measurements. A local increase in Ca2+ concentration stimulated in vitro precipitation of Ca5(PO 4)3OH (HAP) on the silicon carbide preform surface during exposure to simulated body fluid, which indicates a significantly increased bone bonding activity compared with SiC.

December, 2010 | DOI: 10.1016/j.actbio.2010.06.036

Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica

Heredia-Guerrero, JA; San-Miguel, MA; Sansom, MSP; Heredia, A; Benitez, JJ
Physical Chemistry Chemical Physics, 12 (2010) 10423-10428


Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica from solution has been studied using AFM, ATR-FTIR and MD simulations. The goal of this study is to define the role of hydroxyl groups in the interaction between molecules as reference data to understand the mechanism of formation of synthetic and natural biopolyesters from polyhydroxylated long chain carboxylic acids. In a confined structure, such as the one imposed by a vertically self-assembled layer on mica, aleuritic acid has a tendency to adopt a monolayer configuration ruled by the lateral interactions between molecules via the two secondary hydroxyl groups. This (2D) growth competes with the multilayer formation (3D), which is conditioned by the terminal primary hydroxyl group. As the self-assembly spatial constraint is relaxed, MD has shown that the structure tends to become an amorphous and crosslinked phase that can be characterized by topographic and friction force AFM data.

September, 2010 | DOI: 10.1039/c0cp00163e

Steering the Self-Assembly of Octadecylamine Monolayers on Mica by Controlled Mechanical Energy Transfer from the AFM Tip

Benitez, JJ; Heredia-Guerrero, JA; Salmeron, M
Journal of Physical Chemistry C, 114 (2010) 12630-12634


We have studied the effect of mechanical energy transfer from the tip of an atomic force microscope on the dynamics of self-assembly of monolayer films of octadecylamine on mica. The formation of the self-assembled film proceeds in two successive stages, the first being a fast adsorption from solution that follows a Langmuir isotherm. The second is a slower process of island growth by aggregation of the molecules dispersed on the surface. We found that the dynamics of aggregation can be altered substantially by the addition of mechanical energy into the system through controlled tip surface interactions. This leads to both the creation of pinholes in existing islands as a consequence of vacancy concentration and to the assembly of residual molecules into more compact islands.

July, 2010 | DOI: 10.1021/jp102813s

Sc-45 Spectroscopy of Solids: Interpretation of Quadrupole Interaction Parameters and Chemical Shifts

Alba, MD; Chain, P; Florian, P; Massiot, D
Journal of Physical Chemistry C, 114 (2010) 12125-12132


The aims of the present study is to describe for the first time the Sc-45 MAS NMR spectra of X-2-Sc2SiO5 and C-Sc2Si2O7, to combine the spectroscopic information with the structures published from diffraction data, and to propose a rational interpretation of the chemical shifts and quadrupolar parameters. For that purposed, we have correlated the experimental quadrupole coupling parameters of Sc-45 determined for a number of scandium compounds to those found by a simple electrostatic calculation and we have found that the isotropic chemical shift of the Sc-45 is linearly correlated to the shift parameter, calculated by bond-valence theory. We also show that a simple point charge calculation can approximate the electric field gradient to a sufficiently good approximation that it provides a valuable mean to assign the NMR spectra.

July, 2010 | DOI: 10.1021/jp1036525

Self-assembly of supramolecular lipid nanoparticles in the formation of plant biopolyester cutin

Dominguez, E; Heredia-Guerrero, JA; Benitez, JJ; Heredia, A
Molecular Biosystems, 6 (2010) 948-950


The implication of a self-assembly process in the early stages of cutin biosynthesis has been shown by means of antibodies raised against polyhydroxy fatty acid nanoparticles (cutinsomes).

June, 2010 | DOI: 10.1039/b927186d

Structural characterization of polyhydroxy fatty acid nanoparticles related to plant lipid biopolyesters

Heredia-Guerrero, JA; Dominguez, E; Luna, M; Benitez, JJ; Heredia, A
Chemistry and Physics of Lipids, 163 (2010) 329-333


In the present work, we report the physico-chemical properties and structural characteristics of special polyhydroxy fatty acid nanoparticles after their fusion by means of attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electronic microscopy (SEM), atomic force microscopy (AFM), and light microscopy. All the characteristics and properties investigated have an important degree of similarity to the native plant cutin, the main biopolymer present in the plant cuticles. The supramolecular organization of these polymerized prime nanoparticles after their interaction on cellulose substrate and isolated cuticle samples, simulating the in vivo conditions in epidermal plant cells, strongly suggests a growth of these nanoparticles after a self-assembly process.

March, 2010 | DOI: 10.1016/j.chemphyslip.2010.01.006

Application of Micro-X-ray Fluorescence Analysis for the Characterization of Industrial Wastes

Alba, MD; Aparicio, P; Benitez, JM; Castro, MA; Diaz, M; Orta, MM
Industrial & Engineering Chemistry Research, 49 (2010) 2348-2352


The issue of how to improve product quality and product yield in a short period of time is becoming more critical in many industries. Thus, shorter delay times between laboratory analysis and process correction are important in process control. Elimination of sample handling and operator Manipulation is desirable. The present article proposes micro-X-ray fluorescence (mu XRF) as an economical control method for industrial product quality with a minimum time cost. Samples from different industrial processes have been chosen and analyzed by XRF and mu XRF, The results show that the two techniques give similar results and that mu XRF allows the waste to be classified and is able to detect problems in the production process.

March, 2010 | DOI: 10.1021/ie901716w

Lanthanide sorption on smectitic clays in presence of cement leachates

Galunin, E; Alba, MD; Santos, MJ; Abrao, T; Vidal, M
Geochimica et Cosmochimica Acta, 74 (2010) 862-875


Due to their potential retention capacity, clay minerals have been proposed for use in the engineered barriers for the storage of high-level radioactive actinides in deep geological waste repositories. However, there is still a lack of data on the sorption of actinides in clays in conditions simulating those of the repositories. The present article examines the sorption of two lanthanides (actinide analogues) in a set of smectitic clays (FEBEX bentonite, MX80 bentonite, hectorite, saponite, Otay montmorillonite, and Texas montmorillonite). Distribution coefficients (K-d) were determined in two media: water and 0.02 mol L-1 Ca, the latter representing the cement leachates that may modify the chemical composition of the water in contact with the clay. The K-d values of the lanthanides used in the experiments (La and Lu) varied greatly (25-50 000 L kg(-1)) depending on the ionic medium (higher values in water than in the Ca medium), the initial lanthanide concentration (up to three orders of magnitude decrease inversely with lanthanide concentration), and the examined clay (up to one order of magnitude for the same lanthanide and sorption medium). Freundlich and Langmuir isotherms were used to fit sorption data to allow comparison of the sorption parameters among smectites. The model based on the two-site Langmuir isotherms provided the best fit of the sorption data, confirming the existence of sorption sites with different binding energies. The sites with higher sorption affinity were about 6% of the total sorption capacity in the water medium, and up to 17% in the Ca medium, although in this latter site sorption selectivity was lower. The wide range of K-d values obtained regarding the factors examined indicated that the retention properties of the clays should also be considered when selecting a suitable clay for engineered barriers.

February, 2010 | DOI: 10.1016/j.gca.2009.11.003


Reversibility of La and Lu sorption onto smectites: Implications for the design of engineered barriers in deep geological repositories

Galunin, E; Alba, MD; Aviles, MA; Santos, MJ; Vidal, M
Journal of Hazardous Materials, 172 (2009) 1198-1205


The sorption reversibility of La and Lu (considered as actinide analogues) onto a set of smectites (bentonite FEBEX; hectorite, HEC; MX80; saponite, SAP; Otay montmorillonite, SCa-3; and Texas montmorillonite, STx-1) was studied to estimate actinide retention by smectites that are candidates for use as engineered barriers in deep geological repositories. The sorption distribution coefficients (K d) and the reversibility parameters (desorption distribution coefficients (K d,des), adjusted distribution coefficients (K d,adj), and desorption rates (R des)) were determined from batch tests in two ionic media: deionized water and Ca 0.02 mol L -1. The latter simulates possible conditions due to the presence of concrete leachates. The results varied greatly depending on the ionic medium, the lanthanide concentration and the clay structure. The high values of K d,des obtained (up to 1.1 × 10 5 and 9.2 × 10 4 L kg -1 for La and Lu in water, and 2.8 × 10 4 and 4.1 × 10 4 L kg -1 for La and Lu in the Ca medium) indicate the suitability of the tested smectites for lanthanide (and therefore, actinide) retention. Based on all the data, SCa-3, HEC and FEBEX clays are considered the best choices for water environments, whereas in Ca environments the suitable clays depended on the lanthanide considered.

December, 2009 | DOI: 10.1016/j.jhazmat.2009.07.124

Synthesis and characterization of a plant cutin mimetic polymer

Heredia-Guerrero, JA; Heredia, A; Garcia-Segura, R; Benitez, JJ
Polymer, 50 (2009) 5633-5637


A mimetic polymer of plant cutin have been synthesized from 9,10,16-trihydroxyhexadecanoic (aleuritic) acid through a low temperature polycondensation reaction. Reaction conditions (solvent, catalyst, temperature, etc…) were studied and modified to optimize yield and product characteristics. The resulting polyaleurate polymer was characterized by Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD) and solid state 13C-Cross Polarization/Magic Angle Spinning Nuclear Magnetic Resonance (13C-CP/MAS NMR). Mechanical and hydrodynamic properties were also investigated. In the average, the product obtained is physically and chemically very similar to plant cutin (a hydrophobic polyester). However, a more detailed analysis of results reveals that polyaleurate framework is more rigid than natural cutin and with additional larger short-range ordered domains. Also, the synthetic polymer displays slightly different mechanical properties with respect to natural cutin. Additional hydrogen bonding within the framework of polyaleurate is considered to be responsible for such experimental observations.

November, 2009 | DOI: 10.1016/j.polymer.2009.10.018

The hydrothermal conversion of kaolinite to kalsilite: Influence of time, temperature, and pH

Becerro, AI; Escudero, A; Mantovani, M
American Mineralogist, 94 (2009) 11-12


Kalsilite (the low-temperature form of KAlSiO4) is used as the precursor of leucite, an important component in porcelain-fused-to-metal and ceramic-restoration systems, and it has also been proposed as a high-thermal expansion ceramic for bonding to metals. The present study reports the hydrothermal synthesis and characterization of pure kalsilite from kaolinite in subcritical conditions, as well as the characterization of the intermediate products by means of XRD, 29Si and 27Al MAS NMR, IR, SEM, and TEM. Effects of time, temperature, and pH on the reaction products are analyzed. The experimental data indicate that pure kalsilite is obtained after hydrothermal treatment of kaolinite at 300 °C for 12 h in 0.5 M KOH solution. Longer reaction times increase the crystallinity of the structure, whereas lower reaction times give rise to the metastable ABW-type KAlSiO4 polymorph. Lower temperatures are not sufficient to produce kalsilite, but zeolite W is obtained instead as the unique reaction product. Finally, the pH of the aqueous solution in contact with kaolinite is an important parameter for the synthesis of kalsilite, which must be ≥13.70.

November, 2009 | DOI: 10.2138/am.2009.3284

Hydrothermal Synthesis of Kalsilite: A Simple and Economical Method

Becerro, AI; Mantovani, M; Escudero, A
Journal of the American Ceramic Society, 92 (2009) 2204-2206


This study reports a simple method to synthesize pure kalsilite (KAlSiO4) using readily available precursors, kaolinite and KOH solution, after only 12 h of hydrothermal treatment in mild conditions. A structural refinement has been carried out using the Rietveld method to obtain unit cell parameters, and the 29Si and 27Al magic angle spinning nuclear magnetic resonance spectra have shown the purity and complete Si/Al ordering of the kalsilite structure obtained. Finally, the morphology of the particles has been analyzed by scanning electron microscopy.

October, 2009 | DOI: 10.1111/j.1551-2916.2009.03232.x

Rare-earth disilicate formation under Deep Geological Repository approach conditions

Alba, MD; Chain, P; Orta, MM
Applied Clay Science, 46 (2009) 63-68


The Deep Geological Repository (DGR) concept involves the placement of long-lived radioactive waste in rooms excavated deep. The major responsibility of the disposal safety falls on the Engineered Barrier System (EBS). The main constituent of EBS is bentonite that prevents the release of radiactive nuclei by physical and chemical mechanisms. The physical mechanism is expected to fault with the weathering of the bentonite while the chemical mechanisms have been only proved at 300 °C. It is the aim of this paper to explore the feasibility of the chemical mechanism at temperatures closer to the DGP conditions and to shed light on the mechanism of transformation of the argillaceous materials of the EBS in rare-earth disilicate phases. Saponite was submitted to hydrothermal reaction at 175 °C and 150 °C with different solutions of REE3+ cations (REE = Sc, Lu, Y, Sm, Nd and La). The products were analyzed by XRD, NMR and electron microscopy. At conditions close to the DGP, the saponite was able to form rare-earth silicates. The formation of the disilicate phase, as final product, needs a set of stages and oxyorthosilicate as precursor.

September, 2009 | DOI: 10.1016/j.clay.2009.07.012

Mineralogical stability of phyllosilicates in hyperalkaline fluids: Influence of layer nature, octahedral occupation and presence of tetrahedral Al

Becerro, AI; Mantovani, M; Escudero, A
American Mineralogist, 94 (2009) 1187-1197


Mineralogical changes in a set of phyllosilicates, differing in their layer nature, chemical composition, octahedral character, and Al content of the tetrahedral sheet, were analyzed after hydrothermal reaction in an alkaline solution. The composition of the alkaline solution was selected to simulate the first stage of cement degradation [NaOH-KOH-Ca(OH)2]. The reaction products have been analyzed by XRD, 29Si and 27Al MAS NMR spectroscopy, SEM/EDX, and TEM. The results indicate that the main factor influencing the stability of the clays is the occupation of the octahedral sheet such that all trioctahedral members withstand the alkaline attack, whereas most of the dioctahedral clays suffer a complete dissolution and crystallization of new phases. Second, clays with Al in the tetrahedral sheet of their layers are shown to be less stable than those with a pure Si tetrahedral sheet.

August, 2009 | DOI: 10.2138/am.2009.3164

Stability of phyllosilicates in Ca(OH)2 solution: Influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity

Mantovani, M; Escudero, A; Alba, MD; Becerro, AI
Applied Geochemistry, 24 (2009) 1251-1260


This paper presents the results of a comprehensive investigation of the interaction of layered silicates with Ca(OH)2 in hydrothermal conditions. The study is intended to evaluate the stability of the clay buffer in radioactive waste repositories, at the intermediate stages of concrete leaching, when the pH is controlled by the dissolution of portlandite. The influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity will be assessed by analysing the behaviour of a set of well-selected phyllosilicates and using the combined capabilities of 29Si and 27Al MAS-NMR spectroscopy, powder X-ray diffraction and SEM/EDX. The results show that the main factor affecting the stability of the clay is the octahedral occupation, so that trioctahedral phyllosilicates are much more stable than dioctahedral ones. The nature and expandability of the layer does not seem to much influence the stability of the clay, so that a 2:1 expandable phyllosilicate shows the same stability as a chemically analogous 1:1 non-expandable phyllosilicate. However other factors like the poor crystallinity of the starting material or the presence of Al in the tetrahedral sheet of trioctahedral phyllosilicates weaken the clay structure in alkaline conditions and favour the transformation towards other phases.

July, 2009 | DOI: 10.1016/j.apgeochem.2009.03.012

Chemical Reactions in 2D: Self-Assembly and Self-Esterification of 9(10),16-Dihydroxypalmitic Acid on Mica Surface

Heredia-Guerrero, JA; San-Miguel, MA; Sansom, MSP; Heredia, A; Benitez, JJ
Langmuir, 25 (2009) 6869-6874


9(10),16-Dihydroxypalmitic acid (diHPA) is a particularly interesting polyhydroxylated fatty acid (1) because it is the main monomer of cutin, the most abundant biopolyester in nature, and (2) because the presence of a terminal and a secondary hydroxyl group in midchain positions provides an excellent model to study their intermolecular interactions in a confined phase such as self-assembled layers. In this study we have combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy, as well as molecular dynamics (MD) simulations to conclude that the self-assembling of diHPA molecules on mica is a layer by layer process following a Brunauer−Emmett−Teller (BET) type isotherm and with the first layer growing much faster than the rest. Interactions between secondary hydroxyls reinforce the cohesive energy of the monolayer, while the presence of the terminal hydroxyl group is necessary to trigger the multilayered growth. Besides, XPS and ATR-FT-IR spectroscopies clearly indicate that spontaneous self-esterification occurs upon self-assembling. The esterification reaction is a prerequisite to propose a self-assembly route for the biosynthesis of cutin in nature. Molecular dynamics simulations have shown that internal molecular reorganization within the self-assembled layers provides the appropriate intermolecular orientation to facilitate the nucleophilic attack and the release of a water molecule required by the esterification reaction.

June, 2009 | DOI: 10.1021/la9001412

Cutin synthesis: A slippery paradigm

Heredia, A; Heredia-Guerrero, JA; Dominguez, E; Benitez, JJ
Biointerphases, 4 (2009) P1-P3


Despite its biological importance, the mechanism of construction of cutin, the polymer matrix of plant cuticles, has not yet been elucidated. Recently, progress on lipid barrier formation of polymers such as cutin and suberin has been recently reviewed by Pollard et al. In their review the authors state that the ubiquitous cutin is the least understood of the plant extracellular polymers and that major questions about cutin structure and its macromolecular assembly remain to be resolved. At the time this paper was being published our research group has developed a new hypothesis on plant cutin synthesis.

March, 2009 | DOI: 10.1116/1.3063816

Preferential Adsorption from Binary Mixtures on Graphite: The n-Decane−n-Heptan-1-ol System

Alba, MD; Castro, MA; Clarke, S; Medina, S; Messe, L; Millan, C; Orta, MM; Perdigon, AC
Journal of Physical Chemistry C, 113 (2009) 3176-3180


The competitive adsorption of n-decane and n-heptan-1-ol adsorbed from the binary liquid mixture onto graphite has been studied using differential scanning calorimetry, incoherent quasielastic neutron scattering, and 1H and 2H nuclear magnetic resonance. A solid monolayer is identified at all bulk solution compositions with a melting temperature that varies with bulk composition in a manner resembling the bulk behavior. Incoherent elastic neutron scattering, IQNS, and nuclear magnetic resonance, NMR, data indicate that decane is preferentially adsorbed onto the surface over most of the composition range, heptanol being the principal surface component only at very high heptanol concentrations. NMR is proved, for the first time, to be an efficient tool to provide independent information on each component of the system.

February, 2009 | DOI: 10.1021/jp8072014

Synthesis of MCM-22 zeolites of different Si/Al ratio and their structural, morphological and textural characterisation

Delitala, C; Alba, MD; Becerro, AI; Delpiano, D; Meloni, D; Musu, E; Ferino, I
Microporous and Mesoporous Materials, 118 (2009) 1-10


MCM-22 zeolites with Si/Al in the 9–46 range were synthesised in rotating autoclave and characterised by X-ray diffraction, 1H, 29Si and 27Al magic angle spinning nuclear magnetic resonance, scanning electron microscopy and nitrogen physisorption. For the Si/Al = 21, 30 and 46 samples both X-ray diffraction and scanning electron microscopy revealed the crystallisation of pure MCM-22. Besides the latter, crystals of ferrierite also formed during the synthesis of the Si/Al = 9 sample. Based on the 1H MAS NMR spectra of dehydrated samples, the different proton species present on the MCM-22 samples were determined and quantified. Information about the incorporation of Al ions into the zeolite framework, as well as on the preferential crystallographic sites occupied in dependence on the Si/Al ratio of the sample, was obtained by 27Al MAS NMR spectroscopy. From 29Si MAS NMR spectra, differences in the degree of crystallinity of the samples were assessed, the results being in agreement with the diffraction data. Nitrogen physisorption runs revealed the microporous nature of the adsorbents, with a supermicropore to ultramicropore volume ratio in good agreement, for the best crystallised samples, with the porous structure with supercages and sinusoidal channels of the ideal MCM-22 crystal.

February, 2009 | DOI: 10.1016/j.micromeso.2008.07.047

Liquid-phase thiophene adsorption on MCM-22 zeolites. Acidity, adsorption behaviour and nature of the adsorbed products

Delitala, C; Cadoni, E; Delpiano, D; Meloni, D; Alba, MD; Becerro, AI; Ferino, I
Microporous and Mesoporous Materials, 118 (2009) 11-20


The liquid-phase adsorption of thiophene from thiophene/iso-octane solutions has been investigated in batch conditions at room temperature and atmospheric pressure on MCM-22 zeolites with Si/Al in the 9–46 range. Thiophene adsorption was found to occur in two steps whatever the Si/Al ratio of the adsorbent. The presence of ferrierite besides the MCM-22 phase caused a significant loss of the adsorption performance. For pure MCM-22 samples, the Si/Al ratio influenced the adsorption performance. Based on the acid properties of the samples, investigated by adsorption microcalorimetry of ammonia, the adsorption features were interpreted by assuming that positively charged species were originated during the first step; these species underwent successive reaction with weakly adsorbed species formed in the second step, leading to heavy molecular weight organosulphur compounds. Direct evidence for the occurrence of reactive adsorption of thiophene involving its transformation into heavy molecular weight organosulphur compounds was obtained by GC/MS investigation of the nature of the adsorbed material recovered after the adsorption experiments. The peculiar structure of MCM-22 zeolites made possible the formation of long-sized organosulphur compounds. Due to the mechanism by which thiophene is transformed (i.e. progressive addition of other thiophene molecules), the size of the resulting products was found to depend also on the concentration of the weakly adsorbed thiophene molecules able to interact with those already activated through protonation.

February, 2009 | DOI: 10.1016/j.micromeso.2008.08.008

Synthesis, Rietveld Analysis, and Solid State Nuclear Magnetic Resonance of X2-Sc2SiO5

Alba, MD; Chain, P; Gonzalez-Carrascosa, T
Journal of the American Ceramic Society, 92 (2009) 487-490


Compounds containing rare earths are of increasing technological interest especially because of their unique mechanical, magnetic, electrical, and optical properties. Among them, rare earth oxyorthosilicates are attractive scintillators for γ- and X-ray spectroscopy and detection. However, there are many structural aspects of those compounds that are not clear. In this research, the structure parameters for Sc2Si2O5, X2-polymorph, have been refined from powder X-ray diffraction (XRD) data and the 29Si MAS NMR spectrum is reported for the first time. X2-Sc2SiO5 polymorph was synthesized by the sol–gel method and characterized by XRD and 29Si MAS NMR. The XRD pattern was indexed in a monoclinic unit cell with space group I2/c; the resulting unit cell parameters were a=9.9674(2) Å, b=6.4264(9) Å, c=12.0636(2) Å, and β=103.938(1)°. The 29Si MAS NMR spectrum showed a unique signal at −79.5 ppm, compatible with the unique Si crystallographic site in the unit cell. Finally, the band valence method has been applied to the calculation of a “shift parameter,” which is correlated with the NMR chemical shift.

February, 2009 | DOI: 10.1111/j.1551-2916.2008.02877.x

Phase separation of carboxylic acids on graphite surface at submonolayer regime

Alba, MD; Bickerstaffe, AK; Castro, MA; Clarke, SM; Medina, S; Millan, C; Orta, MM; Pavon, E; Perdigon, AC
The European Physical Journal Special Topics, 167 (2009) 151-156


Mixing behaviour of solid crystalline monolayers adsorbed onto graphite from different mixtures of undecanoic and dodecanoic acids at submonolayer coverage has been investigated. X-ray diffraction measurements have been collected from a variety of compositions as a function of temperature. An extensive phase separation is found for all the compositions – the scattering patterns characteristic of the pure material crystalline structures being preserved across the entire composition range. The temperature dependence of the monolayer melting points and their depression is also clearly indicative of separation of the two surface components, in clear contrast to that expected if the two carboxylic acids mixed ideally in the monolayer.

February, 2009 | DOI: 10.1140/epjst/e2009-00951-6

José María Delgado Sánchez
Estrategia de Optimización de Dispositivos Fotovoltaicos de Lámina Delgada desde la Microestructura a la Macroestructura

Director/s: María Dolores Alba Carranza
Universidad de Sevilla
Wednesday, 18 February, 2015

José Alejandro Heredia Guerrero
Autoensamblaje molecular y síntesis de materiales biomiméticos a partir de hidroxiácidos derivados de cutinas vegetales

Director/s: José Jesús Benítez Jiménez y Antonio Heredia Bayona
Universidad de Málaga
Friday, 28 October, 2011

Moisés Naranjo Muñoz
Síntesis y reactividad de silicatos laminares de alta carga

Director/s: Miguel Angel Castro Arroyo
Universidad de Sevilla
Friday, 25 June, 2010

Pablo Chain Villar
Síntesis hidrotermal de disilicatos de tierras raras a partir de silicatos laminares. Un mecanismo inmovilizador de residuos radioactivos de alta actividad

Director/s: María Dolores Alba Carranza
Universidad de Sevilla
Tuesday, 18 December, 2007

Alberto Escudero Belmonte
Síntesis y caracterización estructural de sistemas binarios de disilicatos de tierras raras

Director/s: Ana Isabel Becerro Nieto
Universidad de Sevilla
Monday, 9 July, 2007