Evaluating the reinforcement of inorganic fullerene-like nanoparticles in thermoplastic matrices by depth-sensing indentation

The reinforcing effect of inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles in two different polymer matrices, isotactic polypropylene (iPP) and polyphenylene sulfide (PPS), has been investigated by means of dynamic depth-sensing indentation. The hardness and elastic modulus enhancement upon filler addition is analyzed in terms of two main contributions: changes in the polymer matrix nanostructure and intrinsic properties of the filler including matrix-particle load transfer. It is found that the latter mainly determines the overall mechanical improvement, whereas the nanostructural changes induced in the polymer matrix only contribute to a minor extent. Important differences are suggested between the mechanisms of deformation in the two nanocomposites, resulting in a moderate mechanical enhancement in case of iPP (20% for a filler loading of 1%), and a remarkable hardness increase in case of PPS (60% for the same filler content). The nature of the polymer amorphous phase, whether in the glassy or rubbery state, seems to play here an important role. Finally, nanoindentation and dynamic mechanical analysis measurements are compared and discussed in terms of the different directionality of the stresses applied.

Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites

Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries.

Evaluation of APD and SiPM Matrices as Sensors for Monolithic PET Detector Block

Gamma detectors based on monolithic scintillator blocks coupled to APDs matrices have proved to be a good alternative to pixelated ones for PET scanners. They provide comparable spatial resolution, improve the sensitivity and make easier the mechanical design of the system. In this study we evaluate by means of Geant4-based simulations the possibility of replacing the APDs by SiPMs. Several commercial matrices of light sensors coupled to LYSO:Ce monolithic blocks have been simulated and compared. Regarding the spatial resolution and linearity of the detector, SiPMs with high photo detection efficiency could become an advantageous replacement for the APDs

Medidas autosemejantes en el plano, momentos y matrices de Hessenberg

La tesis MEDIDAS AUTOSEMEJANTES EN EL PLANO, MOMENTOS Y MATRICES DE HESSENBERG se enmarca entre las áreas de la teoría geométrica de la medida, la teoría de polinomios ortogonales y la teoría de operadores. La memoria aborda el estudio de medidas con soporte acotado en el plano complejo vistas con la óptica de las matrices infinitas de momentos y de Hessenberg asociadas a estas medidas que en la teoría de los polinomios ortogonales las representan. En particular se centra en el estudio de las medidas autosemejantes que son las medidas de equilibrio definidas por un sistema de funciones iteradas (SFI). Los conjuntos autosemejantes son conjuntos que tienen la propiedad geométrica de descomponerse en unión de piezas semejantes al conjunto total. Estas piezas pueden solaparse o no, cuando el solapamiento es pequeño la teoría de Hutchinson [Hut81] funciona bien, pero cuando no existen restricciones falla. El problema del solapamiento consiste en controlar la medida de este solapamiento. Un ejemplo de la complejidad de este problema se plantea con las convoluciones infinitas de distribuciones de Bernoulli, que han resultado ser un ejemplo de medidas autosemejantes en el caso real. En 1935 Jessen y A. Wintner [JW35] ya se planteaba este problema, lejos de ser sencillo ha sido estudiado durante más de setenta y cinco años y siguen sin resolverse las principales cuestiones planteadas ya por A. Garsia [Gar62] en 1962. El interés que ha despertado este problema así como la complejidad del mismo está demostrado por las numerosas publicaciones que abordan cuestiones relacionadas con este problema ver por ejemplo [JW35], [Erd39], [PS96], [Ma00], [Ma96], [Sol98], [Mat95], [PS96], [Sim05],[JKS07] [JKS11]. En el primer capítulo comenzamos introduciendo con detalle las medidas autosemejante en el plano complejo y los sistemas de funciones iteradas, así como los conceptos de la teoría de la medida necesarios para describirlos. A continuación se introducen las herramientas necesarias de teoría de polinomios ortogonales, matrices infinitas y operadores que se van a usar. En el segundo y tercer capítulo trasladamos las propiedades geométricas de las medidas autosemejantes a las matrices de momentos y de Hessenberg, respectivamente. A partir de estos resultados se describen algoritmos para calcular estas matrices a partir del SFI correspondiente. Concretamente, se obtienen fórmulas explícitas y algoritmos de aproximación para los momentos y matrices de momentos de medidas fractales, a partir de un teorema del punto fijo para las matrices. Además utilizando técnicas de la teoría de operadores, se han extendido al plano complejo los resultados que G. Mantica [Ma00, Ma96] obtenía en el caso real. Este resultado es la base para definir un algoritmo estable de aproximación de la matriz de Hessenberg asociada a una medida fractal u obtener secciones finitas exactas de matrices Hessenberg asociadas a una suma de medidas. En el último capítulo, se consideran medidas, μ, más generales y se estudia el comportamiento asintótico de los autovalores de una matriz hermitiana de momentos y su impacto en las propiedades de la medida asociada. En el resultado central se demuestra que si los polinomios asociados son densos en L2(μ) entonces necesariamente el autovalor mínimo de las secciones finitas de la matriz de momentos de la medida tiende a cero. ABSTRACT The Thesis work “Self-similar Measures on the Plane, Moments and Hessenberg Matrices” is framed among the geometric measure theory, orthogonal polynomials and operator theory. The work studies measures with compact support on the complex plane from the point of view of the associated infinite moments and Hessenberg matrices representing them in the theory of orthogonal polynomials. More precisely, it concentrates on the study of the self-similar measures that are equilibrium measures in a iterated functions system. Self-similar sets have the geometric property of being decomposable in a union of similar pieces to the complete set. These pieces can overlap. If the overlapping is small, Hutchinson’s theory [Hut81] works well, however, when it has no restrictions, the theory does not hold. The overlapping problem consists in controlling the measure of the overlap. The complexity of this problem is exemplified in the infinite convolutions of Bernoulli’s distributions, that are an example of self-similar measures in the real case. As early as 1935 [JW35], Jessen and Wintner posed this problem, that far from being simple, has been studied during more than 75 years. The main cuestiones posed by Garsia in 1962 [Gar62] remain unsolved. The interest in this problem, together with its complexity, is demonstrated by the number of publications that over the years have dealt with it. See, for example, [JW35], [Erd39], [PS96], [Ma00], [Ma96], [Sol98], [Mat95], [PS96], [Sim05], [JKS07] [JKS11]. In the first chapter, we will start with a detailed introduction to the self-similar measurements in the complex plane and to the iterated functions systems, also including the concepts of measure theory needed to describe them. Next, we introduce the necessary tools from orthogonal polynomials, infinite matrices and operators. In the second and third chapter we will translate the geometric properties of selfsimilar measures to the moments and Hessenberg matrices. From these results, we will describe algorithms to calculate these matrices from the corresponding iterated functions systems. To be precise, we obtain explicit formulas and approximation algorithms for the moments and moment matrices of fractal measures from a new fixed point theorem for matrices. Moreover, using techniques from operator theory, we extend to the complex plane the real case results obtained by Mantica [Ma00, Ma96]. This result is the base to define a stable algorithm that approximates the Hessenberg matrix associated to a fractal measure and obtains exact finite sections of Hessenberg matrices associated to a sum of measurements. In the last chapter, we consider more general measures, μ, and study the asymptotic behaviour of the eigenvalues of a hermitian matrix of moments, together with its impact on the properties of the associated measure. In the main result we demonstrate that, if the associated polynomials are dense in L2(μ), then necessarily follows that the minimum eigenvalue of the finite sections of the moments matrix goes to zero.

Modelado de Cadenas Cinemáticas mediante Matrices de Desplazamiento. Una alternativa al método de Denavit-Hartenberg

En este trabajo se presenta un método para el modelado de cadenas cinemáticas de robots que salva las dificultades asociadas a la elección de los sistemas de coordenadas y obtención de los parámetros de Denavit-Hartenberg. El método propuesto parte del conocimiento de la posición y orientación del extremo del robot en su configuración de reposo, para ir obteniendo en qué se transforman éstas tras los sucesivos movimientos de sus grados de libertad en secuencia descendente, desde el más alejado al más cercano a su base. Los movimientos son calculados en base a las Matrices de Desplazamiento, que permiten conocer en que se transforma un punto cuando éste es desplazado (trasladado o rotado) con respecto a un eje que no pasa por el origen. A diferencia del método de Denavit-Hartenberg, que precisa ubicar para cada eslabón el origen y las direcciones de los vectores directores de los sistemas de referencia asociados, el método basado en las Matrices de Desplazamiento precisa solo identificar el eje de cada articulación, lo que le hace más simple e intuitivo que aquel. La obtención de las Matrices de Desplazamiento y con ellas del Modelo Cinemático Directo a partir de los ejes de la articulación, puede hacerse mediante algunas simples operaciones, fácilmente programables.

New inorganic nanotube polymer nanocomposites: Improved thermal, mechanical and tribological properties in isotactic polypropylene incorporating INT-MoS2.

Environmentally friendly molybdenum disulfide (INT-MoS2) inorganic nanotubes were introduced into an isotactic polypropylene (iPP) polymer matrix to generate novel nanocomposite materials through an advantageous melt-processing route. The effects of INT-MoS2 content on the thermal, mechanical and tribological properties were investigated. The incorporation of INT-MoS2 generates notable performance enhancements through reinforcement effects, highly efficient nucleation activity and excellent lubricating ability in comparison with other nanoparticle fillers such as nanoclays, carbon nanotubes, silicon nitrides and halloysite nanotubes. It was shown that these INT-MoS2 nanocomposites can provide an effective balance between performance, cost effectiveness and processability, and should be of some interest in the area of multifunctional polymer nanocomposite materials.

Tuning the properties of carbon fiber-reinforced poly (phenylene sulphide) laminates via incorporation of inorganic fullerene-like WS2 nanoparticles

Novel carbon fiber (CF)-reinforced poly(phenylene sulphide) (PPS) laminates incorporating inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles were prepared via melt-blending and hot-press processing. The influence of the IF-WS2 on the morphology, thermal, mechanical and tribological properties of PPS/CF composites was investigated. Efficient nanoparticle dispersion within the matrix was attained without using surfactants. A progressive rise in thermal stability was found with increasing IF-WS2 loading, as revealed by thermogravimetric analysis. The addition of low nanoparticle contents retarded the crystallization of the matrix, whereas concentrations equal or higher than 1.0 wt% increased both the crystallization temperature and degree of crystallinity compared to those of PPS/CF. Mechanical tests indicated that with only 1.0 wt% IF-WS2 the flexural modulus and strength of PPS/CF improved by 17 and 14%, respectively, without loss in toughness, ascribed to a synergistic effect between the two fillers. A significant enhancement in the storage modulus and glass transition temperature was also observed. Moreover, the wear rate and coefficient of friction strongly decreased, attributed to the lubricant role of the IF-WS2 combined with their reinforcing effect. These inorganic nanoparticles show great potential to improve the mechanical and tribological properties of conventional thermoplastic/CF composites for structural applications.

Rheological and tribological properties of poly(phenylene sulphide) and poly(ether ether ketone) composites incorporating carbon nanotubes and inorganic nanoparticles: a comparative study

The rheological and tribological properties of single-walled carbon nanotube (SWCNT)-reinforced poly(phenylene sulphide) (PPS) and poly(ether ether ketone) (PEEK) nanocomposites prepared via melt-extrusion were investigated. The effectiveness of employing a dual-nanofiller strategy combining polyetherimide (PEI)-wrapped SWCNTs with inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles for property enhancement of the resulting hybrid composites was evaluated. Viscoelastic measurements revealed that the complex viscosity ?, storage modulus G?, and loss modulus G? increased with SWCNT content. In the low-frequency region, G? and G? became almost independent of frequency at higher SWCNT loadings, suggesting a transition from liquid-like to solid-like behavior. The incorporation of increasing IF-WS2 contents led to a progressive drop in ? and G? due to a lubricant effect. PEEK nanocomposites showed lower percolation threshold than those based on PPS, ascribed to an improved SWCNT dispersion due to the higher affinity between PEI and PEEK. The SWCNTs significantly lowered the wear rate but only slightly reduced the coefficient of friction. Composites with both nanofillers exhibited improved wear behavior, attributed to the outstanding tribological properties of these nanoparticles and a synergistic reinforcement effect. The combination of SWCNTs with IF-WS2 is a promising route for improving the tribological and rheological performance of thermoplastic nanocomposites.

Inorganic hydrophobic coatings: Surfaces mimicking the nature

Added value products are being developed in ceramic industry. Different optical effects as bright metallic shine or new functionalities as hydrophobicity or bactericide characteristics are the new properties searched on the tiles. In this study, we prepare glassy coatings for tiles based on copper pigment by a conventional industrial process. The obtained coatings present different aesthetical aspects, including bright metallic aspect which confers a high decorative value to the tile. Furthermore, these metallic coatings present hydrophobic properties with contact angles with water as high as 115 degrees and also bactericide characteristics. Superficial microstructure and nanoparticles were found in the bactericide-hydrophobic samples, resembling the surface of hydrophobic leaf surfaces. This structure was formed by the crystallization of CuO nanoparticles as Tenorite due to the copper saturation of the glassy matrix at the surface of the coatings.

Polypropylene/glass fiber hierarchical composites incorporating inorganic fullerene-like nanoparticles for advanced technological applications

Novel isotactic polypropylene (iPP)/glass fiber (GF) laminates reinforced with inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles as environmentally friendly fillers have been successfully fabricated by simple melt-blending and fiber impregnation in a hot-press without the addition of any compatibilizer. The influence of IF-WS2 concentration on the morphology, viscosity. and thermal and mechanical behavior of the hierarchical composites has been investigated. Results revealed an unprecedented 62 °C increase in the degradation temperature of iPP/GF upon addition of only 4.0 wt % IF-WS2. The coexistence of both micro- and nanoscale fillers resulted in synergistic effects on enhancing the stiffness, strength, crystallinity, thermal stability, glass transition (Tg) and heat distortion temperature (HDT) of the matrix. The approach used in this work is an efficient, versatile, scalable and economic strategy to improve the mechanical and thermal behavior of GF-reinforced thermoplastics with a view to extend their use in advanced technological applications. This new type of composite materials shows great potential to improve the efficiency and sustainability of many forms of transport.

Inorganic Nanoparticle-Modified Poly(Phenylene Sulphide)/ Carbon Fiber Laminates: Thermomechanical Behaviour

Carbon fiber (CF)-reinforced high-temperature thermoplastics such as poly(phenylene sulphide) (PPS) are widely used in structural composites for aerospace and automotive applications. The porosity of CF-reinforced polymers is a very important topic for practical applications since there is a direct correlation between void content and mechanical properties. In this study, inorganic fullerene-like tungsten disulphide (IF-WS2) lubricant nanoparticles were used to manufacture PPS/IF-WS2/CF laminates via melt-blending and hot-press processing, and the effect of IF-WS2 loading on the quality, thermal and mechanical behaviour of the hybrid composites was investigated. The addition of IF-WS2 improved fiber impregnation, resulting in lower degree of porosity and increased delamination resistance, compression and flexural properties; their reinforcement effect was greater at temperatures above the glass transition (Tg). IF-WS2 contents higher than 0.5 wt % increased Tg and the heat deflection temperature while reduced the coefficient of thermal expansion. The multiscale laminates exhibited higher ignition point and notably reduced peak heat release rate compared to PPS/CF. The coexistence of micro- and nano-scale fillers resulted in synergistic effects that enhanced the stiffness, strength, thermal conductivity and flame retardancy of the matrix. The results presented herein demonstrate that the IF-WS2 are very promising nanofillers to improve the thermomechanical properties of conventional thermoplastic/CF composites.

Mechanical and thermal behaviour of isotactic polypropylene reinforced with inorganic fullerene-like WS2 nanoparticles: Effect of filler loading and temperature

The thermal and mechanical behaviour of isotactic polypropylene (iPP) nanocomposites reinforced with different loadings of inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles was investigated. The IF-WS2 noticeably enhanced the polymer stiffness and strength, ascribed to their uniform dispersion, the formation of a large nanoparticle?matrix interface combined with a nucleating effect on iPP crystallization. Their reinforcement effect was more pronounced at high temperatures. However, a drop in ductility and toughness was found at higher IF-WS2 concentrations. The tensile behaviour of the nanocomposites was extremely sensitive to the strain rate and temperature, and their yield strength was properly described by the Eyring s equation. The activation energy increased while the activation volume decreased with increasing nanoparticle loading, indicating a reduction in polymer chain motion. The nanoparticles improved the thermomechanical properties of iPP: raised the glass transition and heat deflection temperatures while decreased the coefficient of thermal expansion. The nanocomposites also displayed superior flame retardancy with longer ignition time and reduced peak heat release rate. Further, a gradual rise in thermal conductivity was found with increasing IF-WS2 loading both in the glassy and rubbery states. The results presented herein highlight the benefits and high potential of using IF-nanoparticles for enhancing the thermomechanical properties of thermoplastic polymers compared to other nanoscale fillers.

Development of novel melt-processable biopolymer nanocomposites based on poly(L-lactic acid) and WS2 inorganic nanotubes.

The use of tungsten disulphide inorganic nanotubes (INT-WS2) offers the opportunity to produce novel and advanced biopolymer-based nanocomposite materials with excellent nanoparticle dispersion without the need for modifiers or surfactants via conventional melt blending. The study of the non-isothermal melt-crystallization kinetics provides a clear picture of the transformation of poly(L-lactic acid) (PLLA) molecules from the non-ordered to the ordered state. The overall crystallization rate, final crystallinity and subsequent melting behaviour of PLLA were controlled by both the incorporation of INT-WS2 and the variation of the cooling rate. In particular, it was shown that INT-WS2 exhibits much more prominent nucleation activity on the crystallization of PLLA than other specific nucleating agents or nano-sized fillers. These features may be advantageous for the enhancement of mechanical properties and process-ability of PLLA-based materials. PLLA/INT-WS2 nanocomposites can be employed as low cost biodegradable materials for many eco-friendly and medical applications, and the exceptional crystallization behaviour observed opens new perspectives for scale-up and broader applications.

Hierarchical and hybrid polymer nanocomposites based on carbon nanotubes and inorganic fullerene type nanoparticles

The influence of singlewalled carbon nanotubes (SWCNT) and inorganic fullerenelike tungsten disulfide nanoparticles (IFWS2) on the morphology and thermal, mechanical and electrical performance of multifunctional fibrereinforced polymer composites has been investigated. Significant improvements were observed in stiffness, strength and toughness in poly (ether ether ketone) (PEEK) / (SWCNT) / glass fibre (GF) laminates when a compatibilizer was used for wrapping the CNTs. Hybrid poly(phenylene sulphide) (PPS)/IFWS2/ carbon fibre (CF) reinforced polymer composites showed improved mechanical and tribological properties attributed to a synergetic effect between the IF nanoparticles and CF.

Thermoplastic Polymer Nanocomposites Based on Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes

Using inorganic fullerene-like (IF) nanoparticles and inorganic nanotubes (INT) in organic-inorganic hybrid composite, materials provide the potential for improving thermal, mechanical, and tribological properties of conventional composites. The processing of such high-performance hybrid thermoplastic polymer nanocomposites is achieved via melt-blending without the aid of any modifier or compatibilizing agent. The incorporation of small quantities (0.1-4 wt.%) of IF/INTs (tungsten disulfide, IF-WS2 or molybdenum disulfide, MoS2) generates notable performance enhancements through reinforcement effects and excellent lubricating ability in comparison with promising carbon nanotubes or other inorganic nanoscale fillers. It was shown that these IF/INT nanocomposites can provide an effective balance between performance, cost effectiveness, and processability, which is of significant importance for extending the practical applications of diverse hierarchical thermoplastic-based composites.