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.

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.

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.

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.

Polypropylene fiber-reinforced self-compacting concrete for the reconstruction of the cathedral of La Laguna, Canary Island, Spain

High performance materials are needed for the reconstruction of such a singular building as a cathedral, since in addition to special mechanical properties, high self compact ability, high durability and high surface quality, are specified. Because of the project’s specifications, the use of polypropylene fiber-reinforced, self-compacting concrete was selected by the engineering office. The low quality of local materials and the lack of experience in applying macro polypropylene fiber for structural reinforcement with these components materials required the development of a pretesting program. To optimize the mix design, performance was evaluated following technical, economical and constructability criteria. Since the addition of fibers reduces concrete self-compactability, many trials were run to determine the optimal mix proportions. The variables introduced were paste volume; the aggregate skeleton of two or three fractions plus limestone filler; fiber type and dosage. Two mix designs were selected from the preliminary results. The first one was used as reference for self-compactability and mechanical properties. The second one was an optimized mix with a reduction in cement content of 20 kg/m3and fiber dosage of 1 kg/m3. For these mix designs, extended testing was carried out to measure the compression and flexural strength, modulus of elasticity, toughness, and water permeability resistance

Failure locus of polypropylene nonwoven fabrics under in-plane biaxial deformation

The failure locus, the characteristics of the stress–strain curve and the damage localization patterns were analyzed in a polypropylene nonwoven fabric under in-plane biaxial deformation. The analysis was carried out by means of a homogenization model developed within the context of the finite element method. It provides the constitutive response for a mesodomain of the fabric corresponding to the area associated to a finite element and takes into account the main deformation and damage mechanisms experimentally observed. It was found that the failure locus in the stress space was accurately predicted by the Von Mises criterion and failure took place by the localization of damage into a crack perpendicular to the main loading axis.

Mechanical behavior and deformation micromechanisms of polypropylene nonwoven fabrics as a function of temperature and strain rate

The mechanical behavior and the deformation and failure micromechanisms of a thermally-bonded polypropylene nonwoven fabric were studied as a function of temperature and strain rate. Mechanical tests were carried out from 248 K (below the glass transition temperature) up to 383 K at strain rates in the range ≈10−3 s−1 to 10−1 s−1. In addition, individual fibers extracted from the nonwoven fabric were tested under the same conditions. Micromechanisms of deformation and failure at the fiber level were ascertained by means of mechanical tests within the scanning electron microscope while the strain distribution at the macroscopic level upon loading was determined by means of digital image correlation. It was found that the nonwoven behavior was mainly controlled by the properties of the fibers and of the interfiber bonds. Fiber properties determined the nonlinear behavior before the peak load while the interfiber bonds controlled the localization of damage after the peak load. The influence of these properties on the strength, ductility and energy absorbed during deformation is discussed from the experimental observations.

Inmovilización de TiO2 sobre polímeros transparentes en el UV-A para la eliminación fotocatalítica de tricloroetileno en aire

El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.

A constitutive model for the in-plane mechanical behavior of nonwoven fabrics

A constitutive model is presented for the in-plane mechanical behavior of nonwoven fabrics. The model is developed within the context of the finite element method and provides the constitutive response for a mesodomain of the fabric corresponding to the area associated to a finite element. The model is built upon the ensemble of three blocks, namely fabric, fibers and damage. The continuum tensorial formulation of the fabric response rigorously takes into account the effect of fiber rotation for large strains and includes the nonlinear fiber behavior. In addition, the various damage mechanisms experimentally observed (bond and fiber fracture, interfiber friction and fiber pull-out) are included in a phenomenological way and the random nature of these materials is also taken into account by means of a Monte Carlo lottery to determine the damage thresholds. The model results are validated with recent experimental results on the tensile response of smooth and notched specimens of a polypropylene nonwoven fabric.

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.