Influence of the Type of Quaternary Ammonium Salt Used in the Organic Treatment of Montmorillonite on the Properties of Poly(Styrene-co-Butyl Acrylate)/Layered Silicate Nanocomposites Prepared by In Situ Miniemulsion Polymerization

Hybrid latices of poly(styrene-co-butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer-MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 3658-3669, 2011

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

Thermal and mechanical characteristics of polyurethane/curaua fiber composites

Polyurethane composites reinforced with curaua fiber at 5, 10 and 20% mass/mass proportions were prepared by using the conventional melt-mixing method. The influence of curaua fibers on the thermal behavior and polymer cohesiveness in polyurethane matrix was evaluated by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). This specific interaction between the fibers and the hard segment domain was influenced by the behavior of the storage modulus E` and the loss modulus EaEuro(3) curves. The polyurethane PU80 is much stiffer and resistant than the other composites at low temperatures up to 70A degrees C. All samples were thermoplastic and presented a rubbery plateau over a wide temperature range above the glass transition temperature and a thermoplastic flow around 170A degrees C.

Instrumented indentation testing of an epoxy adhesive used in automobile body assembling

Instrumented indentation has been used to investigate the mechanical properties of BETAMATE 1496 (R) Epoxy adhesive. The properties of the adhesive were analyzed by measuring its hardness and its Young`s modulus in samples extracted from six different positions of the front door of a commercial passenger vehicle in two phases of processing: after application of the adhesive in the door assembling (""pre-cured"" state) and after final cure in the painting oven (""cured"" state). Special attention was given to setting the optimal parameters (""creep"" time and unloading time step) for the instrumented indentation testing for the present application. Young`s modulus values around 1.1 +/- 0.2 GPa and hardness values around 0.15 +/- 0.05 GPa were obtained for all samples, irrespective of the variation of the indentation parameters in the testing procedure and of the relative position of the adhesive in the door frame in both states. (C) 2008 Elsevier Ltd. All rights reserved.

Linear viscoelasticity of styrenic block copolymers-clay nanocomposites

In this work, the rheological behavior of block copolymers with different morphologies (lamellar, cylindrical, spherical, and disordered) and their clay-containing nanocomposites was studied using small amplitude oscillatory shear. The copolymers studied were one asymmetric starblock styrene-butadiene-styrene copolymer and four styrene-ethylene/butylenes-styrene copolymers with different molecular architectures, one of them being modified with maleic anhydride. The nanocomposites of those copolymers were prepared by adding organophilic clay using three different preparation techniques: melt mixing, solution casting, and a hybrid melt mixing-solution technique. The nanocomposites were characterized by X-ray diffraction and transmission electron microscopy, and their viscoelastic properties were evaluated and compared to the ones of the pure copolymers. The influence of copolymer morphology and presence of clay on the storage modulus (G`) curves was studied by the evaluation of the changes in the low frequency slope of log G` x log omega (omega: frequency) curves upon variation of temperature and clay addition. This slope may be related to the degree of liquid- or solid-like behavior of a material. It was observed that at temperatures corresponding to the ordered state, the rheological behavior of the nanocomposites depended mainly on the viscoelasticity of each type of ordered phase and the variation of the slope due to the addition of clay was small. For temperatures corresponding to the disordered state, however, the rheological behavior of the copolymer nanocomposites was dictated mostly by the degree of clay dispersion: When the clay was well dispersed, a strong solid-like behavior corresponding to large G` slope variations was observed.

Transient and Steady-State Analysis of the Affine Combination of Two Adaptive Filters

In this paper, we propose an approach to the transient and steady-state analysis of the affine combination of one fast and one slow adaptive filters. The theoretical models are based on expressions for the excess mean-square error (EMSE) and cross-EMSE of the component filters, which allows their application to different combinations of algorithms, such as least mean-squares (LMS), normalized LMS (NLMS), and constant modulus algorithm (CMA), considering white or colored inputs and stationary or nonstationary environments. Since the desired universal behavior of the combination depends on the correct estimation of the mixing parameter at every instant, its adaptation is also taken into account in the transient analysis. Furthermore, we propose normalized algorithms for the adaptation of the mixing parameter that exhibit good performance. Good agreement between analysis and simulation results is always observed.

Anomalous compressibility of ferropericlase throughout the iron spin cross-over

The thermoelastic properties of ferropericlase Mg(1-x)Fe(x)O (x = 0.1875) throughout the iron high-to-low spin cross-over have been investigated by first principles at Earth`s lower mantle conditions. This cross-over has important consequences for elasticity such as an anomalous bulk modulus (K(S)) reduction. At room temperature the anomaly is somewhat sharp in pressure but broadens with increasing temperature. Along a typical geotherm it occurs across most of the lower mantle with a more significant K(S) reduction at approximate to 1,400-1,600 km depth. This anomaly might also cause a reduction in the effective activation energy for diffusion creep and lead to a viscosity minimum in the mid-lower mantle, in apparent agreement with results from inversion of data related with mantle convection and postglacial rebound.

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.

Improving the tracking capability of adaptive filters via convex combination

As is well known, Hessian-based adaptive filters (such as the recursive-least squares algorithm (RLS) for supervised adaptive filtering, or the Shalvi-Weinstein algorithm (SWA) for blind equalization) converge much faster than gradient-based algorithms [such as the least-mean-squares algorithm (LMS) or the constant-modulus algorithm (CMA)]. However, when the problem is tracking a time-variant filter, the issue is not so clear-cut: there are environments for which each family presents better performance. Given this, we propose the use of a convex combination of algorithms of different families to obtain an algorithm with superior tracking capability. We show the potential of this combination and provide a unified theoretical model for the steady-state excess mean-square error for convex combinations of gradient- and Hessian-based algorithms, assuming a random-walk model for the parameter variations. The proposed model is valid for algorithms of the same or different families, and for supervised (LMS and RLS) or blind (CMA and SWA) algorithms.

A Class of Channels Resulting in Ill-Convergence for CMA in Decision Feedback Equalizers

This paper analyzes the convergence of the constant modulus algorithm (CMA) in a decision feedback equalizer using only a feedback filter. Several works had already observed that the CMA presented a better performance than decision directed algorithm in the adaptation of the decision feedback equalizer, but theoretical analysis always showed to be difficult specially due to the analytical difficulties presented by the constant modulus criterion. In this paper, we surmount such obstacle by using a recent result concerning the CM analysis, first obtained in a linear finite impulse response context with the objective of comparing its solutions to the ones obtained through the Wiener criterion. The theoretical analysis presented here confirms the robustness of the CMA when applied to the adaptation of the decision feedback equalizer and also defines a class of channels for which the algorithm will suffer from ill-convergence when initialized at the origin.

Avoiding Divergence in the Shalvi-Weinstein Algorithm

The most popular algorithms for blind equalization are the constant-modulus algorithm (CMA) and the Shalvi-Weinstein algorithm (SWA). It is well-known that SWA presents a higher convergence rate than CMA. at the expense of higher computational complexity. If the forgetting factor is not sufficiently close to one, if the initialization is distant from the optimal solution, or if the signal-to-noise ratio is low, SWA can converge to undesirable local minima or even diverge. In this paper, we show that divergence can be caused by an inconsistency in the nonlinear estimate of the transmitted signal. or (when the algorithm is implemented in finite precision) by the loss of positiveness of the estimate of the autocorrelation matrix, or by a combination of both. In order to avoid the first cause of divergence, we propose a dual-mode SWA. In the first mode of operation. the new algorithm works as SWA; in the second mode, it rejects inconsistent estimates of the transmitted signal. Assuming the persistence of excitation condition, we present a deterministic stability analysis of the new algorithm. To avoid the second cause of divergence, we propose a dual-mode lattice SWA, which is stable even in finite-precision arithmetic, and has a computational complexity that increases linearly with the number of adjustable equalizer coefficients. The good performance of the proposed algorithms is confirmed through numerical simulations.

Laboratory evaluation of recycled construction and demolition waste for pavements

The wide production of construction and demolition waste and its illegal deposition are serious current problems in Brazil. This research proposes to evaluate the feasibility of using aggregate from recycled construction and demolition waste (RCDW) in pavement applications. A laboratory program was conducted by geotechnical characterization, bearing capacity and repeated load triaxial tests. The results show that the composition and the compactive effort influence on the physical characteristics of the RCDW aggregate. The compaction process has promoted a partial crushing and breakage of RCDW particles, changing the grain-size distribution and increasing the percentage of cubic grains. This physical change contributes to a better densification of the RCDW aggregate and consequently an improvement in bearing capacity, resilient modulus and resistance to permanent deformation. The results have shown that the RCDW aggregate may be utilized as coarse base and sub-base layer for low-volume roads. (C) 2010 Elsevier Ltd. All rights reserved.

Drying and autogenous shrinkage of pastes and mortars with activated slag cement

Activated slag cement (ASC) shows significantly higher shrinkage than ordinary Portland cement agglomerates. Cracking generated by shrinkage is one of the most critical drawbacks for broader applications of this promising alternative binder. This article investigates the relationship between ASC hydration, unrestrained drying and autogenous shrinkage of mortar specimens. The chemical and microstructure evolution due to hydration were determined on pastes by thermogravimetric analysis, conduction calorimetry and mercury porosimetry. Samples were prepared with ground blast furnace slag (BFS) activated with sodium silicate (silica modulus of 1.7) with 2.5, 3.5 and 4.5% of Na2O, by slag mass. The amount of activator is the primary influence on drying and autogenous shrinkage, and early hydration makes a considerable contribution to the total result, which increases with the amount of silica. Drying shrinkage occurred in two stages, the first caused by extensive water loss when the samples were exposed to the environment, and the second was associated with the hydration process and less water loss. Due to the refinement of ASC porous system, autogenous shrinkage is responsible for a significant amount of the total shrinkage. (C) 2007 Elsevier Ltd. All rights reserved.

Effects of mechanical properties, residual stress and indenter tip geometry on instrumented indentation data in thin films

In this work, an axisymmetric two-dimensional finite element model was developed to simulate instrumented indentation testing of thin ceramic films deposited onto hard steel substrates. The level of film residual stress (sigma(r)), the film elastic modulus (E) and the film work hardening exponent (n) were varied to analyze their effects on indentation data. These numerical results were used to analyze experimental data that were obtained with titanium nitride coated specimens, in which the substrate bias applied during deposition was modified to obtain films with different levels of sigma(r). Good qualitative correlation was obtained when numerical and experimental results were compared, as long as all film properties are considered in the analyses, and not only sigma(r). The numerical analyses were also used to further understand the effect of sigma(r) on the mechanical properties calculated based on instrumented indentation data. In this case, the hardness values obtained based on real or calculated contact areas are similar only when sink-in occurs, i.e. with high n or high ratio VIE, where Y is the yield strength of the film. In an additional analysis, four ratios (R/h(max)) between indenter tip radius and maximum penetration depth were simulated to analyze the combined effects of R and sigma(r) on the indentation load-displacement curves. In this case, or did not significantly affect the load curve exponent, which was affected only by the indenter tip radius. On the other hand, the proportional curvature coefficient was significantly affected by sigma(r) and n. (C) 2010 Elsevier B.V. All rights reserved.

Precursor system of liquid crystalline phase containing propolis microparticles for the treatment of periodontal disease: Development and characterization

Precursor systems of liquid crystalline phase were prepared using the surfactant PPG-5-Ceteth-20, isopropyl myristate, and water; gelatin microparticles containing propolis were then added into these systems. Homogeneity of dispersion, the in-system microparticle morphology, and sedimentation behavior of each formulation were evaluated. The rheological and mechanical properties (hardness, compressibility, and adhesiveness), the work of syringing, and the propolis release profile were also evaluated. All the formulations exhibited pseudoplastic flow and thixotropy, and they displayed storage modulus, loss modulus, dynamic viscosity, and loss tangent that depended on temperature, frequency, and composition. Mechanical properties varied significantly among the formulations being affected by changes in the composition and temperature. Raising the concentration of surfactant and adding propolis microparticles significantly decreased the work of syringing. The drug release was non-Fickian (anomalous) and there was no significant difference between the tested systems in the times required for 10%, 30%, and 50% release of the initial drug loading.