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.

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.

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.

Novel poly(3-hydroxybutyrate) nanocomposites containing WS2 inorganic nanotubes with improved thermal, mechanical and tribological properties

Poly(3-hydroxybutyrate) (PHB) nanocomposites containing environmentally-friendly tungsten disulphide inorganic nanotubes (INTeWS2) have been successfully prepared by a simple solution blending method. The dynamic and isothermal crystallization studies by differential scanning calorimetry (DSC) demonstrated that the INTeWS2 exhibits much more prominent nucleation activity on the crystallization of PHB than specific nucleating agents or other nanoscale fillers. Both crystallization rate and crystallinity significantly increase in the nanocomposites compared to neat PHB. These changes occur without modifying the crystalline structure of PHB in the nanocomposites, as shown by wide-angle X-ray diffraction (WAXS) and infrared/Raman spectroscopy. Other parameters such as the Avrami exponent, the equilibrium melting temperature, global rate constant and the fold surface free energy of PHB chains in the nanocomposites were obtained from the calorimetric data in order to determine the influence of the INTeWS2 filler. The addition of INTeWS2 remarkably influences the energetics and kinetics of nucleation and growth of PHB, reducing the fold surface free energy by up to 20%. Furthermore, these nanocomposites also show an improvement in both tribological and mechanical (hardness and modulus) properties with respect to pure PHB evidenced by friction and nanoindentation tests, which is of important potential interest for industrial and medical applications.

Analysis of single and binary phases in cerium doped sodium bismuth titanate -Na0.5Bi0.5TiO3 materials

The pure and cerium doped sodium bismuth titanate inorganic powders were synthesized by solid state reaction method. The presence of rhombohedral phase was observed in cerium doped NBT compounds. At 1200 ºC, the 5% of cerium doped NBT compound forms single perovskite phase. The samples of x = 0.10 and 0.15 were heat treated to 1350 ºC, the binary phases with cerium and bismuth oxides were observed. The X-ray diffraction, fourier transform infrared spectroscopy, reflectance spectra, differential thermal analysis and thermo gravimetric analysis were used to analyze the various properties of samples. Moreover, the effects of cerium doping and calcining temperature on NBT samples were investigated. In this work we present our recent results on the synthesis and characterization of Ce doped sodium bismuth titanate materials.

Electrochemical Performance of Hierarchical Porous Carbon Materials Obtained from the Infiltration of Lignin into Zeolite Templates

Hierarchical porous carbon materials prepared by the direct carbonization of lignin/zeolite mixtures and the subsequent basic etching of the inorganic template have been electrochemically characterized in acidic media. These lignin-based templated carbons have interesting surface chemistry features, such as a variety of surface oxygen groups and also pyridone and pyridinic groups, which results in a high capacitance enhancement compared to petroleum-pitch-based carbons obtained by the same procedure. Furthermore, they are easily electro-oxidized in a sulfuric acid electrolyte under positive polarization to produce a large amount of surface oxygen groups that boosts the pseudocapacitance. The lignin-based templated carbons showed a specific capacitance as high as 250 F g−1 at 50 mA g−1, with a capacitance retention of 50 % and volumetric capacitance of 75 F cm−3 at current densities higher than 20 A g−1 thanks to their suitable porous texture. These results indicate the potential use of inexpensive biomass byproducts, such as lignin, as carbon precursors in the production of hierarchical carbon materials for electrodes in electrochemical capacitors.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

(Table 1) Mass-accumulation rates for the non-authigenic, inorganic, crystalline, eolian component of sediments recovered at DSDP Hole 62-463

Elevated regions in the central parts of ocean basins are excellent for study of accumulation of eolian material. The mass-accumulation rates of this sediment component appear to reflect changes in the influx of volcanic materials through the Early Cretaceous to Recent history of Deep Sea Drilling Project Site 463, on the Mid-Pacific Mountains. Four distinct episodes of eolian accumulation occurred during the Cretaceous: two periods of moderate accumulation, averaging about 0.2 to 0.3 g/cm**2/10**3 yr, 67 to 70.5 m.y. ago and 91 to 108 m.y. ago; a period of low accumulation, approximately 0.03 g/cm**2/10**3 yr, 70.5 to 90 m.y. ago; and a period of high accumulation, about 0.9 g/cm**2/10**3 yr, 109 to 117 m.y. ago (bottom of the hole). Much of the Cenozoic section is missing from Site 463. Upper Miocene to Recent sediments record an upward increase in accumulation rates, from less than 0.01 to about 0.044 g/cm**2/10**3 yr. The late Pliocene-Pleistocene peak may reflect the change to glacial-wind regimes, as well as an increase in volcanic source materials.

Molecular dynamics simulation of organic-inorganic nanocomposites: Layering behavior and interlayer structure of organoclays

Isothermal-isobaric (NPT) molecular dynamics simulation has been performed to investigate the layering behavior and structure of nanoconfined quaternary alkylammoniums in organoclays. This work is focused on systems consisting of two clay layers and a number of alkylammoniums, and involves the use of modified Dreiding force field. The simulated basal spacings of organoclays agree satisfactorily with the experimental results in the literature. The atomic density profiles in the direction normal to the clay surface indicate that the alkyl chains within the interlayer space of montmorillonite exhibit an obvious layering behavior. The headgroups of long alkyl chains are distributed within two layers close to the clay surface, whereas the distributions of methyl and methylene groups are strongly dependent on the alkyl chain length and clay layer charge. Monolayer, bilayer, and pseudo-trilayer structures are found in organoclays modified with single long alkyl chains, which are identical to the structural models based on the measured basal spacings. A pseudo-quadrilayer structure, for the first time to our knowledge, is also identified in organoclays with double long alkyl chains. In the mixture structure of paraffin-type and multilayer, alkyl chains do not lie flat within a single layer but interlace, and also jump to the next layer in pseudo-trilayer as well as next nearest layer in pseudo-quadrilayer.

Organic-inorganic poly(methyl methacrylate) hybrids with confined polyhedral oligosilsesquioxane macromonomers

We herein report the synthesis of organic-inorganic hybrid poly(methyl methacrylate) containing 1 polyhedral oligosilsesquioxanes. Octakis(3-hydroxypropyldimethylsiloxy)octasilsesquioxane (OHPS) was synthesized from octakis(hydridodimethylsiloxy)octasilsesquioxane [Si8O12(OSiMe2H)(8), Q(8)M(8)(H)] following literature procedures. Octakis(tnethacryloxypropyldimethylsiloxy) octasilsesquioxane (OMPS) was synthesized via the reaction of methacryloyl chloride or methacrylic acid anhydride with OHPS, with the latter giving improved purity. Polymerization of OMPS with methyl inethacrylate using a dibenzoylperoxide initiator gave a highly cross-linked polymer. Characterization of the polymer was performed using Fourier transform IR spectroscopy, Si-29 NMR, differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, and transmission electron microscopy with energy-dispersive X-ray analysis. The polymer was found to be largely homogeneous. Increasing the OMPS concentration in the polymer gave increased decomposition and glass transition temperatures.

Control of ordered structure and morphology of large-pore periodic mesoporous organosilicas by inorganic salt

Highly ordered rodlike periodic mesoporous organosilicas (PMO) were successfully synthesized using 1.2-bis(trimethoxysilyl)ethane as an precursor and triblock copolymer P123 as a template at low acid concentration and in the presence of inorganic salts (KCl). The role of acid and salt as well as the effects of synthesis temperature and reactant mole ratio in the control of morphology and the formation of ordered mesostructure was systematically examined. It was found that the addition of inorganic salt can dramatically expand the range of the synthesis parameters to produce highly ordered PMO structure and improve the quality of PMO materials. The morphology of PMOs was significantly dependent on the induction time for precipitation. The uniform PMO rods can only be synthesized in a narrow range of acid and salt concentrations. The results also show that the optimized salt concentration (I M) and low acidity (0.167 M) were beneficial to the formation of not only highly ordered mesostructure but also rodlike morphology. Increasing acidity resulted in fast hydrolysis reaction and short rod or plate-like particles. Highly ordered rod can also be prepared at low temperature (35 degrees C) with high salt amount (1.5 M) or high temperature (45 degrees C) with low salt amount (0.5 M). Optimum reactant molar composition at 40 degrees C is 0.035P123:8KCl:1.34HCI:444H(2)O:1.0bis(trimethoxysilyl)ethane. Lower or higher SiO2/PI23 ratio led to the formation of uniform meso-macropores or pore-blocking effect. (c) 2005 Elsevier Inc. All rights reserved.

Scavenging of halogen in recycling of halogen-based polymer materials

Pyrolytic recycling of materials for electronics and automotive is attractive because of the possibility of recovery of fuel and of precious metals from printed circuit. Due to the complexity of their composition an appropriate pre-treatment has to be performed in order to limit the evolution of dangerous halogen containing compounds which strongly impair the fuel quality. An advantageous pyrolysis approach implies the attempt of mineralisation of the organic bromine to the not volatile and harmless inorganic form using strong bases such as NaOH and KOH to reduce the amount of volatile and increasing the residue. The char stability is greatly variable depending on the substrate. Mg(OH)2 and Ca(OH)2 behave in a similar manner but to a lower extent. Carbonates and reducing agent such as LiAlH have been tested as well and their ability to scavenge bromine is discussed in terms of effectiveness and mechanism.

Bioactive organic/inorganic hybrids with improved mechanical performance

New sol-gel functionalized poly-ethylene glycol (PEGM)/SiO2-CaO hybrids were prepared with interpenetrating networks of silica and PEGM through the formation of Si-O-Si bonds. Bioactive and mechanical properties were investigated for a series of hybrids containing varying organic/inorganic ratios and PEG molecular weights. In contrast to the unmodified PEG/SiO2-CaO hybrids, which rapidly dissolved and crumbled, the epoxy modified hybrids exhibited good mechanical properties and bioactivity. The compressive strength and Young's modulus were greater for higher molecular weight PEGM hybrids (PEGM600 compared to PEGM300). Compressive strengths of 138 MPa and 81 MPa were found for the 50: 50 and 60: 40 organic/inorganic hybrid samples respectively, which are comparable with cortical bone. Young's modulus values of ∼800 MPa were obtained for the 50 : 50 and 60 : 40 organic/inorganic hybrids. Bioactivity tests were conducted by immersing the hybrids into simulated body fluid and observing the formation of apatite. Apatite formation was observed within 24 hours of immersion. PEGM600 hybrids showed enhanced apatite formation compared to PEGM300 hybrids. Increased apatite formation was observed with increasing organic/inorganic ratio. 70 : 30 and 60 : 40 hybrids exhibited the greatest apatite formation. All PEGM hybrids samples had good cell viability and proliferation. The 60 : 40 PEGM600 hybrids displayed the optimal combination of bioactivity and mechanical strength. The bioactivity of these hybrids, combined with the enhanced mechanical properties, demonstrate that these materials have significant potential for bone regeneration applications.