Determinació de la ubicació estructural dels ions Yb3+ i Nb3+ en Yb:RTP, Nb:RTP i (Nb,Yb):RTP

Estudi elaborat a partir d’una estada al Stony Brook University al juliol del 2006. El RbTiOPO4 (RTP) monocristal•lí és un material d' òptica no lineal molt rellevant i utilitzat en la tecnologia làser actual, químicament molt estable i amb unes propietats físiques molt destacades, entre elles destaquen els alts coeficients electro-òptics i l'alt llindar de dany òptic que presenta. En els últims anys s’està utilitzant tecnològicament en aplicacions d'òptica no lineal en general i electro-òptiques en particular. En alguns casos ja ha substituït, millorant prestacions, a materials tals com el KTP o el LNB(1). Dopant RTP amb ions lantànids (Ln3+) (2-4), el material es converteix en un material làser auto-doblador de freqüència, combinant les seves propietats no lineals amb les de matriu làser. El RTP genera radiació de segon harmònic (SHG) a partir d’un feix fonamental amb longituds d’ona inferiors a 990 nm, que és el límit que presenta el KTP.La determinació de la ubicació estructural i l’estudi de l'entorn local del ions actius làser és de fonamental importància per a la correcta interpretació de les propietats espectroscòpiques d’aquest material. Mesures de difracció de neutrons sobre mostra de pols cristal•lí mostren que els ions Nb5+ i Ln3+ només substitueixin posicions de Ti4+ (8-9). Estudis molt recents d'EPR (electron paramagnetic resonance) semblen indicar que quan la concentració d'ió Ln3+ es baixa, aquest ió presenta la tendència a substituir l'ió alcalí present a l'estructura (10).Després dels resultats obtinguts en el present treball a partir de la tècnica EXAFS a la instal•lació sincrotò del Brookhaven National Laboratory/State University of New York (Stony Brook) es pot concloure definitivament que els ions Nb s’ubiquen en la posició Ti (1) i que els ions Yb3+ es distribueixen paritariament en les dues posicions del Ti (1 i 2). Aquests resultats aporten una valuosa informació per a la correcta interpretació dels espectres, tant d’absorció com d’emissió, del material i per la avaluació dels paràmetres del seu comportament durant l'acció làser.

Efecte de l'estrès estructual sobre l'emissió estimulada (laseig) en capes epitaxials de KY0.8Yb0.2(WO4)2 i KLu0.8Yb0.2(WO4)2 crescudes sobre substractes de KY(WO4)2 i KLu(WO4)2

Projecte de recerca elaborat a partir d’una estada a la State University of New York a Stony Brook, EEUU, a l’agost i setembre del 2008. S’ha demostrat com està relacionada la diferència en el rendiment de lasejat de dos mostres altament dopades amb iterbi (20 at. %) de capes epitaxials de KY(WO4)2 (KYW) dopat amb Yb crescut sobre un substrat de KYW i de KLu(WO4)2 (KLuW) dopat amb Yb crescut sobre un substrat de KLuW, respectivament, amb la presència de estrès estructural en les capes epitaxials, investigat per Topografia de Feix Blanc de Raig X de Sincrotró. A partir dels resultats obtinguts, queda clar que les mostres que mostren una quantitat d'estrés estructural més gran, les epitaxies de KYW dopat amb Yb crescudes sobre substrats de KYW, duen a una eficiència més petita durant el lasejat, permetent establir una correlació directa entre l'existència i la magnitud d'aquest estrès estructural i la pèrdua del rendiment làser en aquestes capes epitaxial, que per altra banda, des del punt de vista espectroscòpic són equivalents.

Elaboració de membranes de fibra buida modificades amb nanopartícules metàl·liques per aplicacions catalítiques

Investigación producida a partir de una estancia en la Université Paul Sabatier, Toulouse III - CNRS, entre 2007 y 2009. Durante los últimos años la investigación centrada en nuevos materiales de tamaño nanoscòpico (nanopartículas, quantum dots, nanotubos de carbono,...) ha experimentado un crecimiento considerable debido a las especiales propiedades de los "nanoobjetos" con respecto a magnetismo, catálisis, conductividad eléctrica, etc ... Sin embargo, hoy en día todavía existen pocas aplicaciones de las nanopartículas en temas medioambientales. Uno de los motivos de esta situación es la posible toxicidad de los nanoobjetos, pero existe también una dificultad tecnológica dado que las nanopartículas tienden a agregarse y es muy difícil manipularlas sin que pierdan sus propiedades especiales. Así, aunque la preparación de materiales catalíticos nanoestructurados es muy interesante, es necesario definir nuevas estrategias para prepararlos. Este proyecto de investigación tiene como objetivo principal la preparación de nuevas membranas catalíticas con nanopartículas metálicas en el interior para aplicaciones de tratamiento de agua. La innovación principal de este proyecto consiste en que las nanopartículas no son introducidas en la matriz polimérica una vez preformadas sino que se hacen crecer en el interior de la matriz polimérica mediante una síntesis intermatricial. El único requisito es que la matriz polimérica contenga grupos funcionales capaces de interaccionar con los precursores de las nanopartículas. Una vez finalizado el proyecto se puede afirmar que se han logrado parte de los objetivos planteados inicialmente. Concreamente ha quedado demostrado que se pueden sintetizar nanopartículas metálicas de metales nobles (platino y paladio) en membranas de fibra hueca de micro- y ultrafiltración siguiendo dos metodologías diferentes: modificación fotoquímica de polímeros y deposición de multicapas de polielectrolitos. Los nuevos materiales son efectivos en la catálisis de reducción de un compuesto modelo (4-nitrofenol con borohidruro de sodio) y, en general, los resultados han sido satisfactorios. Sin embargo, se ha puesto de manifiesto que el uso de un reactivo que genera hidrógeno gas en contacto con la solución acuosa dificulta enormemente la implementación de la reacción catalítica al ser el medio de la membrana una matriz porosa. Así, como conclusión principal se puede decir que se han encontrado las limitaciones de esta aproximación y se sugieren dos posibilidades de continuidad: la utilización de las membranas sintetizadas en contactores gas-líquido o bien el estudio y optimización del sistema de membrana en configuración de membranas planas, un objetivo más asequible dada su menor complejidad. Esta investigación se ha realizado en el seno del “Laboratoire de Génie Chimique” de Toulouse y del Departamento de Química de la Michigan State University y ha sido posible gracias a un proyecto financiado por la “Agence National pour la Recherce” y al programa PERMEANT entre el CNRS y la NSF.

Building Capacity in Developing Countries : OER for Food Safety

The Food Safety Knowledge Network (FSKN) was developed through the collaboration of Michigan State University and a professional network of international food industry retailers and manufacturers. The key objective of the FSKN project is to provide technical resources, in a cost effective way, in order to promote food safety in developing countries and for small and less developed companies. FSKN uses a competency based model including a framework, OERs, and assessments. These tools are being used to support face-to-face training, fully online training, and to gauge the learning outcomes of a series of pilot groups which were held in India, Egypt, and China.

AgShare : Building Community and Content with Multiple Partners

Michigan State University and OER Africa are creating a win-win collaboration of existing organizations for African publishing, localizing, and sharing of teaching and learning materials that fill critical resource gaps in African MSc agriculture curriculum. By the end of the 18-month planning and pilot initiative, African agriculture universities, faculty, students, researchers, NGO leaders, extension staff, and farmers will participate in building AgShare by demonstrating its benefits and outcomes and by building momentum and support for growth.

Acoustic properties of polypropylene composites reinforced with stone groundwood

Currently, acoustic isolation is one of the problems raised with building construction in Spain. The publication of the Basic Document for the protection against noise of the Technical Building Code has increased the demand of comfort for citizens. This has created the need to seek new composite materials that meet the new required acoustical building codes. In this paper we report the results of the newly developed composites that are able to improve the acoustic isolation of airborne noise. These composites were prepared from polypropylene (PP) reinforced with mechanical pulp fibers from softwood (Pinus radiata). Mechanical and acoustical properties of the composites from mechanical pulp (MP) and polypropylene (PP) have been investigated and compared to fiberglass (FG) composites. MP composites had lower tensile properties compared with FG composites, although these properties can be improved by incorporation of a coupling agent. The results of acoustical properties of MP composites were reported and compared with the conventional composites based on fiberglass and gypsum plasterboards. Finally, we suggest the application of MP composites as a light-weight building material to reduce acoustic transmitions

Management of corn stalk waste as reinforcement for polypropylene injection moulded composites

The main objective of this study was the management of corn stalk waste as reinforcement for polypropylene (PP) injection moulded composites as an alternative to wood flour and fibers. In the first step, corn stalk waste was subjected to various treatments, and four different corn stalk derivatives (flour and fibers) able to be used as reinforcement of composite materials were prepared and characterized. These derivatives are corn stalk flour, thermo-mechanical, semi-chemical, and chemical fibers. They were characterized in terms of their yield, lignin content, Kappa number, fiber length/diameter ratio, fines, coarseness, viscosity, and the length at the break of a standard sheet of paper. Results showed that the corn stalk derivatives have different physico-chemical properties. In the second step, the prepared flour and fibers were explored as a reinforcing element for PP composites. Coupled and non-coupled PP composites were prepared and tested for tensile properties. For overall trend, with the addition of a coupling agent, tensile properties of composites significantly improved, as compared with non-coupled samples. In addition, a morphological study revealed the positive effect of the coupling agent on the interfacial bonding. The composites prepared with semichemical fiber gave better results in comparison with the rest of the corn stalk derivatives due to its chemical characteristics

Mean intrinsic tensile properties of stone groundwood fibers from softwood

Stone groundwood (SGW) is a fibrous matter commonly prepared in a high yield process, and mainly used for papermaking applications. In this work, the use of SGW fibers is explored as reinforcing element of polypropylene (PP) composites. Due to its chemical and superficial features, the use of coupling agents is needed for a good adhesion and stress transfer across the fiber-matrix interface. The intrinsic strength of the reinforcement is a key parameter to predict the mechanical properties of the composite and to perform an interface analysis. The main objective of the present work was the determination of the intrinsic tensile strength of stone groundwood fibers. Coupled and non-coupled PP composites from stone groundwood fibers were prepared. The influence of the surface morphology and the quality at interface on the final properties of the composite was analyzed and compared to that of fiberglass PP composites. The intrinsic tensile properties of stone groundwood fibers, as well as the fiber orientation factor and the interfacial shear strength of the current composites were determined

Stone-ground wood pulp-reinforced polypropylene composites: water uptake and thermal properties

Two of the drawbacks of using natural-based composites in industrial applications are thermal instability and water uptake capacity. In this work, mechanical wood pulp was used to reinforce polypropylene at a level of 20 to 50 wt. %. Composites were mixed by means of a Brabender internal mixer for both non-coupled and coupled formulations. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to determine the thermal properties of the composites. The water uptake behavior was evaluated by immersion of the composites in water until an equilibrium state was reached. Results of water absorption tests revealed that the amount of water absorption was clearly dependent upon the fiber content. The coupled composites showed lower water absorption compared to the uncoupled composites. The incorporation of mechanical wood pulp into the polypropylene matrix produced a clear nucleating effect by increasing the crystallinity degree of the polymer and also increasing the temperature of polymer degradation. The maximum degradation temperature for stone ground wood pulp–reinforced composites was in the range of 330 to 345 ºC

Study of chemical modification of alkaline lignin by the glyoxalation reaction

In this study, glyoxalated alkaline lignins with a non-volatile and non-toxic aldehyde, which can be obtained from several natural resources, namely glyoxal, were prepared and characterized for its use in wood adhesives. The preparation method consisted of the reaction of lignin with glyoxal under an alkaline medium. The influence of reaction conditions such as the molar ratio of sodium hydroxide-to-lignin and reaction time were studied relative to the properties of the prepared adducts. The analytical techniques used were FTIR and 1H-NMR spectroscopies, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Results from both the FTIR and 1H-NMR spectroscopies showed that the amount of introduced aliphatic hydroxyl groups onto the lignin molecule increased with increasing reaction time and reached a maximum value at 10 h, and after they began to decrease. The molecular weights remained unchanged until 10 h of reaction time, and then started to increase, possibly due to the repolymerization reactions. DSC analysis showed that the glass transition temperature (Tg) decreased with the introduction of glyoxal onto the lignin molecule due to the increase in free volume of the lignin molecules. TGA analysis showed that the thermal stability of glyoxalated lignin is not influenced and remained suitable for wood adhesives. Compared to the original lignin, the improved lignin is reactive and a suitable raw material for adhesive formula

The suitability of steam exploded vitis vinifera and alkaline lignin for the manufacture of fiberboard

The main objective of this study was to explore the suitability of Vitis vinifera as a raw material and alkaline lignin as a natural binder for fiberboard manufacturing. In the first step, Vitis vinifera was steam- exploded through a thermo-mechanical vapor process in a batch reactor, and the obtained pulp was dried, ground, and pressed to produce the boards. The effects of pretreatment factors and pressing conditions on the chemical composition of the fibers and the physico-mechanical properties of binderless fiberboards were evaluated, and the conditions that optimize these properties were found. A response surface method based on a central composite design and multiple-response optimization was used. The variables studied and their respective variation ranges were: pretreatment temperature (Tr: 190-210ºC), pretreatment time (tr: 5-10 min), pressing temperature (Tp: 190-210ºC), pressing pressure (Pp: 8-16MPa), and pressing time (tp: 3-7min). The results of the optimization step show that binderless fiberboards have good water resistance and weaker mechanical properties. In the second step, fiberboards based on alkaline lignin and Vitis vinifera pulp produced at the optimal conditions determined for binderless fiberboards were prepared and their physico-mechanical properties were tested. Our results show that the addition of about 15% alkaline lignin leads to the production of fiberboards that fully meet the requirements of the relevant standard specifications

Synthesis and characterization of kraft lignin-based epoxy resins

Epoxidization is an interesting way to develop a new application of lignin and therefore to improve its application potential. In this work, kraft lignin-based epoxy resins were obtained by the epoxidization reaction, using the kraft lignin recovered directly from pulping liquor and modified by a methylolation reaction. The methylolated lignins were obtained by the reaction of original kraft lignin with formaldehyde and glyoxal, which is a less volatile and less toxic aldehyde. 1H-NMR spectroscopy showed that methylolated kraft lignin has more hydroxymethyl groups than glyoxalated kraft lignin. For the epoxidization reaction we studied the influence of the lignin:NaOH (w/w) ratio, temperature, and time of the reaction on the properties of the prepared epoxidized lignins. The structures of lignin-based epoxy resins were followed by epoxy index test and FTIR spectroscopy. Optimal conditions were obtained for lignin-based epoxy resin produced at lignin/NaOH = 1/3 at 70 ºC for 3h. Thermogravimetry analysis (TGA) revealed that the epoxidization enhances the thermal stability of lignins and may allow a wider temperature range for applications with lignin epoxy-PF blends

Tensile strength characteristics of polypropylene composites reinforced with stone groundwood fibers from softwood

The behavior of stone groundwood / polypropylene injection-molded composites was evaluated with and without coupling agent. Stone groundwood (SGW) is a fibrous material commonly prepared in a high yield process and mainly used for papermaking applications. In this work, the use of SGW fibers was explored as a reinforcing element of polypropylene (PP) composites. The surface charge density of the composite components was evaluated, as well as the fiber’s length and diameter inside the composite material. Two mixing extrusion processes were evaluated, and the use of a kinetic mixer, instead of an internal mixer, resulted in longer mean fiber lengths of the reinforcing fibers. On the other hand, the accessibility of surface hydroxyl groups of stone groundwood fibers was improved by treating the fibers with 5% of sodium hydroxide, resulting in a noticeable increase of the tensile strength of the composites, for a similar percentage of coupling agent. A new parameter called Fiber Tensile Strength Factor is defined and used as a baseline for the comparison of the properties of the different composite materials. Finally the competitiveness of stone groundwood / polypropylene / polypropylene-co-maleic anhydride system, which compared favorably to sized glass-fiber / polypropylene GF/PP and glass-fiber / polypropylene / polypropylene-co-maleic anhydride composite formulations, was quantified by means of the fiber tensile strength factor

Characterization of alkaline lignins for use in penol-formaldehyde and epoxy resins

Besides polyurethanes and polyesters, phenolic and epoxy resins are the most prominent applications for technical lignins in thermosetting materials. To evaluate the potential application of lignin raw materials in phenol formaldehyde and epoxy resins, three types of alkaline lignins were characterized in terms of their structures and thermal properties. The lignin samples analyzed were kraft lignin (LIG-1), soda–rice straw lignin (LIG-2), and soda-wheat straw lignin (LIG-3). FTIR and 1H-NMR methods were used to determine their structure. Gel permeation chromatography (GPC) was used to determine the molecular weight distribution (MWD). Differential scanning calorimetry (DSC) was used to measure the glass transition temperature (Tg), and thermogravimetric analysis (TGA) to determine the thermal stability of lignin samples. Results showed that kraft lignin (LIG-1) has moderate hydroxyl-group content, is rich in G-type units, and has good thermal stability. These properties make it more suitable for direct use in phenol formaldehyde resins, and it is therefore a good raw material for this purpose. The alkaline soda-rice straw lignin (LIG-2) with a high hydroxyl-group content and excellent thermal stability is most suited to preparing lignin-based epoxy resin

Preparation and properties of starch-based biopolymers modified with difunctional isocyanates

The present work reports on the preparation of thermoplastic starch (TPS) modified in situ with a diisocyanate derivative. Evidence of the condensation reaction between the hydroxyl groups of starch and glycerol with the isocyanate function (NCO) was confirmed by FTIR analysis. The evolution of the properties of the ensuing TPS, in term of mechanical properties, microstructure, and water sensitivity, was investigated using tensile mechanical, dynamic mechanical thermal analysis (DMTA), X-ray diffraction (XRD), and water uptake. The results showed that the addition of isocyanate did not affect the crystallinity of the TPS and slightly reduced the water uptake of the material. The evolution of the mechanical properties with ageing became less pronounced by the addition of the isocyanate as their amount exceeded 4 to 6wt%.