Blocked diisocyanates as reactive coupling agents: Application to pine fiber-polypropylene composites

In this paper, composites from polypropylene and Kraft pulp (from Pinus radiata) were prepared. Phenyl isocyanate, unblocked and phenol blocked derivatives of 4,4`-methylenebis (phenyl isocyanate) (MDI) were used as coupling agents and the mechanical properties of the obtained composites analyzed. The results showed that the addition of such compatibilizers readily improved the tensile and flexural strengths of the composites. However, no significant variation in the mechanical properties was observed for composite formulations comprising different isocyanate compounds. Accordingly, the chemical structure of isocyanate derivatives did not affect extensively the mechanical properties of MDI-coupled pine fiber reinforced composites. These results were similar to those obtained in previous studies regarding the efficiency of organosilane coupling agents. In comparison to monoreactive isocyanates, the addition of MIDI increased considerably the mechanical properties of pine fiber-polypropylene composites. The mechanical anchoring of polymeric PP chains onto the irregular reinforcement surface supported this result. Non-isothermal DSC analysis showed a slowing effect of MDI on the crystallization kinetics of the coupled composites. This may have been the result of diminished polymer chain mobility in the matrix due to mechanical anchoring onto the fiber surface. Considering these results, the occurrence of strong bonds between the composite components was stated, rather than the unique existence of Van der Waals interactions among the non-polar structures. (c) 2008 Elsevier Ltd. All rights reserved.

Thermodynamic and topological instability approaches for forecasting glass-forming ability in the ternary Al-Ni-Y system

A thermodynamic approach to predict bulk glass-forming compositions in binary metallic systems was recently proposed. In this approach. the parameter gamma* = Delta H-amor/(Delta H-inter - Delta H-amor) indicates the glass-forming ability (GFA) from the standpoint of the driving force to form different competing phases, and Delta H-amor and Delta H-inter are the enthalpies for-lass and intermetallic formation, respectively. Good glass-forming compositions should have a large negative enthalpy for glass formation and a very small difference for intermetallic formation, thus making the glassy phase easily reachable even under low cooling rates. The gamma* parameter showed a good correlation with GFA experimental data in the Ni-Nb binary system. In this work, a simple extension of the gamma* parameter is applied in the ternary Al-Ni-Y system. The calculated gamma* isocontours in the ternary diagram are compared with experimental results of glass formation in that system. Despite sonic misfitting, the best glass formers are found quite close to the highest gamma* values, leading to the conclusion that this thermodynamic approach can lie extended to ternary systems, serving as a useful tool for the development of new glass-forming compositions. Finally the thermodynamic approach is compared with the topological instability criteria used to predict the thermal behavior of glassy Al alloys. (C) 2007 Elsevier B. V. All rights reserved.

Topological instability and electronegativity effects on the glass-forming ability of metallic alloys

The glass-forming ability (GFA) of metallic alloys is associated with a topological instability criterion combined with a new parameter based on the average electronegativity difference of an element and its surrounding neighbours. In this model, we assume that during solidification the glassy phase competes directly with the supersaturated solid solution having the lowest topological instability factor for a given composition. This criterion is combined with the average electronegativity difference among the elements in the alloy, which reflects the strength of the liquid. The GFA is successfully correlated with this combined criterion in several binary glass-forming systems.

Predicting glass-forming compositions in the Al-La and Al-La-Ni systems

In this work, a criterion considering the topological instability (lambda) and the differences in the electronegativity of the constituent elements (Delta e) was applied to the Al-La and Al-Ni-La systems in order to predict the best glass-forming compositions. The results were compared with literature data and with our own experimental data for the Al-La-Ni system. The alloy described in the literature as the best glass former in the Al-La system is located near the point with local maximum for the lambda.Delta e criterion. A good agreement was found between the predictions of the lambda.Delta e criterion and literature data in the Al-La-Ni system, with the region of the best glass-forming ability (GFA) and largest supercooled liquid region (Delta T(x)) coinciding with the best compositional region for amorphization indicated by the lambda.Delta e criterion. Four new glassy compositions were found in the Al-La-Ni system, with the best predicted composition presenting the best glass-forming ability observed so far for this system. Although the lambda.Delta e criterion needs further refinements for completely describe the glass-forming ability in the Al-La and Al-La-Ni systems, the results demonstrated that this criterion is a good tool to predict new glass-forming compositions. (C) 2010 Elsevier B. V. All rights reserved.

Effect of HMEC on the consolidation of cement pastes: Isothermal calorimetry versus oscillatory rheometry

Chemical admixtures increase the theological complexity of cement pastes owing to their chemical and physical interactions with particles, which affects cement hydration and agglomeration kinetics. Using oscillatory rheometry and isothermal calorimetry, this article shows that the cellulose ether HMEC (hydroxymethyl ethylcellulose), widely used as a viscosity modifying agent in self-compacting concretes and dry-set mortars, displayed a steric dispersant barrier effect during the first 2 h of hydration associated to a cement retarding nature, consequently reducing the setting speed. However, despite this stabilization effect, the polymer increased the cohesion strength when comparing cement particles with the same hydration degree. (C) 2009 Elsevier Ltd. All rights reserved.

Discoloration and fungal growth on three fiber cement formulations exposed in urban, rural and coastal zones

Three formulations of fiber cement were evaluated for fungal colonization and color change after five years of exposure in aging stations located in urban (Sao Paulo), rural (Pirassununga) and coastal (Rio Grande) zones in Brazil. The lowest color change and fungal colonization were registered in Rio Grande, which has a temperate climate, as opposed to Sao Paulo and Pirassununga, which are tropical. The highest fungal colonization was recorded in Sao Paulo, one of the most air polluted cities in Brazil. Pirassununga samples had an intermediate fungal colonization, in spite of showing the highest color change with visible dark spots on the surfaces. These spots were identified as cyanobacteria, which significantly contributed to the darkening of the specimens. The fiber cement formulation, varying in proportion of organic fibers such as poly (vinyl alcohol) and cellulose, was less significant for fungal bioreceptivity than the characteristics of the exposure site. The most frequent fungal genus found in the tropical climate, in both urban and rural zones, and the main one responsible for the higher records in Sao Paulo, was Scytalidiurn sp. which was registered for the first time on this building material in Brazil. (C) 2010 Elsevier Ltd. All rights reserved.

Residual stresses in TiN, DLC and MoS(2) coated surfaces with regard to their tribological fracture behaviour

Thin hard coatings on components and tools are used increasingly due to the rapid development in deposition techniques, tribological performance and application skills. The residual stresses in a coated surface are crucial for its tribological performance. Compressive residual stresses in PVD deposited TiN and DLC coatings were measured to be in the range of 0.03-4 GPa on steel substrate and 0.1-1.3 GPa on silicon. MoS(2) coatings had tensional stresses in the range of 0.8-1.3 on steel and 0.16 GPa compressive stresses on silicon. The fracture pattern of coatings deposited on steel substrate were analysed both in bend testing and scratch testing. A micro-scale finite element method (FEM) modelling and stress simulation of a 2 mu m TiN-coated steel surface was carried out and showed a reduction of the generated tensile buckling stresses in front of the sliding tip when compressive residual stresses of 1 GPa were included in the model. However, this reduction is not similarly observed in the scratch groove behind the tip, possibly due to sliding contact-induced stress relaxation. Scratch and bending tests allowed calculation of the fracture toughness of the three coated surfaces, based on both empirical crack pattern observations and FEM stress calculation, which resulted in highest values for TiN coating followed by MoS(2) and DLC coatings, being K(C) = 4-11, about 2, and 1-2 MPa M(1/2), respectively. Higher compressive residual stresses in the coating and higher elastic modulus of the coating correlated to increased fracture toughness of the coated surface. (C) 2009 Elsevier B.V. All rights reserved.

MEASUREMENT OF ELASTIC PROPERTIES OF MATERIALS BY THE ULTRASONIC THROUGH-TRANSMISSION TECHNIQUE

The elastic mechanical behavior of elastic materials is modeled by a pair of independent constants (Young`s modulus and Poisson`s coefficient). A precise measurement for both constants is necessary in some applications, such as the quality control of mechanical elements and standard materials used for the calibration of some equipment. Ultrasonic techniques have been used because wave velocity depends on the elastic properties of the propagation medium. The ultrasonic test shows better repeatability and accuracy than the tensile and indentation test. In this work, the theoretical and experimental aspects related to the ultrasonic through-transmission technique for the characterization of elastic solids is presented. Furthermore, an amorphous material and some polycrystalline materials were tested. Results have shown an excellent repeatability and numerical errors that are less than 3% in high-purity samples.

Characterization of mixed waste of granite and LD slag

This study focuses on the technical feasibility of the utilization of waste from the cutting of granite to adjust the chemical composition of slag from steelworks LD, targeting the addition of clinker Portland cement. For this, chemical characterization of the waste, its mixture and fusion was performed, obtaining a CaO/SiO(2) relationship of around 0.9 to 1.2 for the steelworks slag. We selected samples of the waste, mixed, melted and cooled in water and in the oven. Samples cooled in water, after examining with X-ray difractrograms, had been predominantly amorphous. For samples cooled in the furnace, which had vitreous, there was the presence of mineralogical phases Akermanita and Gehlenita, which is considered as the ideal stage for the mineral water activity of the slag. The adjustment of the chemical composition of the slag from steel works by the addition of waste granite was efficient, transforming the waste into a product that is the same as blast furnace slag and can be used in the manufacture of cement.

Influence of the rubbery phase on the crystallinity and thermomechanical properties of poly(3-hydroxybutyrate)/elastomer blends

Poly(3-hydroxybutyrate) (PHB) is a very promising biopolymer. In order to improve its processability and decrease its brittleness, PHB/elastomer blends can be prepared. In the work reported, the effect of the addition of a rubbery phase, i.e. ethylene - propylene-diene terpolymer (EPDM) or poly(vinyl butyral) (PVB), on the properties of PHB was studied. The effects of rubber type and of changing the PHB/elastomer blend processing method on the crystallinity and physical properties of the blends were also investigated. For blends based on PHB, the main role of EPDM is its nucleating effect evidenced by a decrease of crystallization temperature and an increase of crystallinity with increasing EPDM content regardless of the processing route. While EPDM has a weak effect on PHB glass transition temperature, PVB induces a marked decrease of this temperature thank to its plasticizer that swells the PHB amorphous phase. A promising solution to improve the mechanical properties of PHB seems to be the melt-processing of PHB with both plasticizer and EPDM. In fact, the plasticizer is more efficient than the elastomer in decreasing the PHB glass transition temperature and, because of the nucleating effect of EPDM, the decrease of the PHB modulus due to the plasticizer can be counterbalanced. (C) 2010 Society of Chemical Industry

Nanostructured diamond-like carbon films characterization

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by high-density plasma chemical vapor deposition Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films. micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp(3) hybridization degree (that is related with the structure and chemical composition) strongly depend on the substrate surface conditions The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films. (C) 2009 Elsevier B.V. All rights reserved.

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp(3) hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp(3) hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films. (C) 2008 Elsevier B.V. All rights reserved.

Electrical and Mechanical Properties of Post-annealed SiC(x)N(y) Films

Amorphous SiC(x)N(y) films have been deposited on (100) Si substrates by RF magnetron sputtering of a SiC target in a variable nitrogen-argon atmosphere. The as-deposited films were submitted to thermal anneling in a furnace under argon atmosphere at 1000 degrees C for 1 hour. Composition and structure of unannealed and annealed samples were investigated by RBS and FTIR. To study the electrical characteristics of SiC(x)N(y) films, Metal-insulator-semiconductor (MIS) structures were fabricated. Elastic modulus and hardness of the films were determined by nanoindentation. The results of these studies showed that nitrogen content and thermal annealing affect the electrical, mechanical and structural properties of SiC(x)N(y) films.

a-SiC : H anti-resonant layer ARROW waveguides

Over the last decades, anti-resonant reflecting optical waveguides (ARROW) have been used in different integrated optics applications. In this type of waveguide, light confinement is partially achieved through an anti-resonant reflection. In this work, the simulation, fabrication and characterization of ARROW waveguides using dielectric films deposited by a plasma-enhanced chemical vapor deposition (PECVD) technique, at low temperatures(similar to 300 degrees C), are presented. Silicon oxynitride (SiO(x)N(y)) films were used as core and second cladding layers and amorphous hydrogenated silicon carbide(a-SiC:H) films as first cladding layer. Furthermore, numerical simulations were performed using homemade routines based on two computational methods: the transfer matrix method (TMM) for the determination of the optimum thickness of the Fabry-Perot layers; and the non-uniform finite difference method (NU-FDM) for 2D design and determination of the maximum width that yields single-mode operation. The utilization of a silicon carbide anti-resonant layer resulted in low optical attenuations, which is due to the high refractive index difference between the core and this layer. Finally, for comparison purposes, optical waveguides using titanium oxide (TiO(2)) as the first ARROW layer were also fabricated and characterized.

Nitrogen doping of SiC thin films deposited by RF magnetron sputtering

Silicon carbide thin films (Si(x)C(y)) were deposited in a RF (13.56 MHz) magnetron sputtering system using a sintered SiC target (99.5% purity). In situ doping was achieved by introducing nitrogen into the electric discharge during the growth process of the films. The N(2)/Ar flow ratio was adjusted by varying the N(2) flow rate and maintaining constant the Ar flow rate. The structure, composition and bonds formed in the nitrogen-doped Si (x) C (y) thin films were investigated by X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), Raman spectroscopy and Fourier transform infrared spectrometry (FTIR) techniques. RBS results indicate that the carbon content in the film decreases as the N(2)/Ar flow ratio increases. Raman spectra clearly reveal that the deposited nitrogen-doped SiC films are amorphous and exhibited C-C bonds corresponding to D and G bands. After thermal annealing, the films present structural modifications that were identified by XRD, Raman and FTIR analyses.