The Effect of the Mixtures of Photoinitiators in Polymerization Efficiencies

The photoinitiated polymerization of methyl methacrylate using the mixtures of camphorquinone (CQ) and acylphosphine oxides (monoacylphosphine oxide, MAPO or bisacylphosphine oxide,BAPO) was studied to determine the possible synergistic effects. The addition of the acylphosphines to CQ resulted in an increase of the polymerization rate compared with CQ alone. On the other hand, a significant decrease of the polymerization quantum yield is observed for the mixtures compared with the pure acylphosphines. Therefore, the increase in the polymerization efficiency of the two rnixtures studied, MAPO/CQ and BAPO/CQ (compared with CQ) can be traced to the larger light absorption range, rather than to the onset of new mechanisms. The presence of the coinitiator ethyl 4-dimethylaminobenzoate, EDB, always present in CQ formulations, has no effect at all on the rates of polymerization photoinitiated by the acylphosphine oxides. From the point of view of photopolymerization quantum yields, an antagonistic effect is observed because Of the energy transfer of the M more efficient initiator (MAPO or BAPO) to the less efficient one (CQ). (C) 2008 Wiley Periodicals, Inc. j Appl Polym Sci 112: 129-134, 2009

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.

The influence of moisture on the deformability of cement-polymer adhesive mortar

Adhesive mortars are widely used to set porcelain stoneware tiles on buildings because their bond strength and flexibility properties increase the cladding serviceability. However, their long-term performance is not well understood, mainly the degradation of the polymeric matrix. The influence of moisture content on the flexibility of six adhesive mortars is investigated, based on standard EN 12002. Four of them have defined formulations and the other two are commercial and are widely used to set porcelain stoneware tiles on building facades in Brazil. The results show that moisture content above 6% is sufficient to reduce 50% of the mortar deformability, but that the drying process allows it to recover to a value similar to that prior to saturation; a logarithmic function best fits the correlation between moisture content and flexibility; water immersion increases matrix rigidity. It is suggested that standards should consider flexibility tests on both dried and wet samples as a requirement for polymer-modified mortars. (C) 2010 Elsevier Ltd. All rights reserved.

Chemical composition of mixed construction and demolition recycled aggregates from the State of Sao Paulo

Construction and Demolition Waste (CDW) represents. about 50% of the total Brazilian municipal solid waste: thus, recycling represents huge benefits both in environmental and economic perspectives. Herein, the chemical characterization results of three samples from two different recycling plants from the State of Sao Paulo is prevented. The results demonstrated that the visual classification into grey and red is not related to the chemical composition but mostly to the grain size fraction. The chemical composition of the CDW varies according to the content of cement paste, natural aggregates (quartz sand or granite), red ceramic and clay. Furthermore, the production of recycled concrete aggregates requires two crushing stages to meet the technical standards. The sand fraction (below 4.8 mm) presents high grades of SiO(2), which indicates the liberation of cement paste to fines (< 0.15 mm). The fines have a great potential to be used in the cement industry.

Exploring the potential of functionally graded materials concept for the development of fiber cement

In this study we establish the concept of functionally graded fiber cement. We discuss the use of statistical mixture designs to choose formulations and present ideas for the production of functionally graded fiber cement components for Hatschek machines. The feasibility of producing functionally graded fiber cement by grading PVA fiber content has been experimentally evaluated. Thermogravimetric analysis (TG) was employed to assess fiber distribution profiles and four-point bending tests were applied to evaluate the mechanical performance of both conventional and graded composites. The results show that grading PVA fiber content is an effective way to produce functionally graded fiber cement, which allows for a reduction of the total fiber volume without a significant reduction on modulus of rupture of composite. TG tests were found adequate to assess the fiber content at different points in functionally graded fiber cements. (C) 2009 Elsevier Ltd. All rights reserved.

Sand bioconsolidation through the precipitation of calcium carbonate by two ureolytic bacteria

Two ureolytic strains, B. sphaericus LMG 22257 and Bacillus sp (I-001), were tested for their ability to consolidate sand by submitting them to two days` treatment using 10(7) viable cell concentrations of inocula and medium precipitation with calcium ions. The results showed that B. sphaericus LMG 22257 induced greater calcium carbonate formation. Both strains produced calcite and were able to consolidate sand. Tensile strength of consolidated sand was not a function of the amount of precipitated CaCO(3) but a linear function of the ratio bioconsolidation index (BC) defined as the ratio of CaCO(3) volume to initial sand porosity. A simple model to estimate the engineering benefits of consolidation is proposed. (C) 2011 Elsevier B.V. All rights reserved.

On the classification of mixed construction and demolition waste aggregate by porosity and its impact on the mechanical performance of concrete

The properties of recycled aggregate produced from mixed (masonry and concrete) construction and demolition (C&D) waste are highly variable, and this restricts the use of such aggregate in structural concrete production. The development of classification techniques capable of reducing this variability is instrumental for quality control purposes and the production of high quality C&D aggregate. This paper investigates how the classification of C&D mixed coarse aggregate according to porosity influences the mechanical performance of concrete. Concretes using a variety of C&D aggregate porosity classes and different water/cement ratios were produced and the mechanical properties measured. For concretes produced with constant volume fractions of water, cement, natural sand and coarse aggregate from recycled mixed C&D waste, the compressive strength and Young modulus are direct exponential functions of the aggregate porosity. Sink and float technique is a simple laboratory density separation tool that facilitates the separation of cement particles with lower porosity, a difficult task when done only by visual sorting. For this experiment, separation using a 2.2 kg/dmA(3) suspension produced recycled aggregate (porosity less than 17%) which yielded good performance in concrete production. Industrial gravity separators may lead to the production of high quality recycled aggregate from mixed C&D waste for structural concrete applications.

Cracking formation on the surface of extruded photodegraded polypropylene plates

The cracking formation during the photodegradation of polypropylene (PP) plates (1 mm thickness), with (PPOx) and without pro-oxidant [PP), has been investigated. The plates were produced by extrusion in an industrial production line and were exposed to ultraviolet radiation in the laboratory for periods of up to 480 hr. The samples were investigated by infrared spectroscopy- FTIR, optical light microscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed that the extension of photodegradation process is more intense for PPOx than for PP samples. For both samples, cracks were formed at the surface perpendicularly to the flow-lines. However the cracks frequency was different for both samples and sides of sample. The crack frequency was correlated with chain orientation, A(110); it was shown that lower degrees of orientation resulted in lower crack frequency. POLYM. ENG. SCI., 48:365-372, 2008. (c) 2007 Society of Plastics Engineers.

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

Effect of the processing conditions and the addition of trans-polyoctenylene rubber on the properties of natural rubber/styrene-butadiene rubber blends

In this study, the influence of the processing conditions and the addition of trans-polyoctenylene rubber (TOR) on Mooney viscosity, tensile properties, hardness, tearing resistance, and resilience of natural rubber/styrene-butadiene rubber blends was investigated. The results obtained are explained in light of dynamic mechanical and morphological analyses. Increasing processing time produced a finer blend morphology, which resulted in an improvement in the mechanical properties. The addition of TOR involved an increase in hardness, a decrease in tear resistance, and no effect on the resilience. It resulted in a large decrease in the Mooney viscosity and a slight decrease in the tensile properties if the components of the compounds were not properly mixed. The results indicate that TOR acted more as a plasticizer than a compatibilizer. (c) 2008 Wiley Periodicals, Inc.

Evaluation of plaque composition by intravascular ultrasound ""virtual histology"": the impact of dense calcium on the measurement of necrotic tissue

Aims: We aimed to evaluate if the co-localisation of calcium and necrosis in intravascular ultrasound virtual histology (IVUS-VH) is due to artefact, and whether this effect can be mathematically estimated. Methods and results: We hypothesised that, in case calcium induces an artefactual coding of necrosis, any addition in calcium content would generate an artificial increment in the necrotic tissue. Stent struts were used to simulate the ""added calcium"". The change in the amount and in the spatial localisation of necrotic tissue was evaluated before and after stenting (n=17 coronary lesions) by means of a especially developed imaging software. The area of ""calcium"" increased from a median of 0.04 mm(2) at baseline to 0.76 mm(2) after stenting (p<0.01). In parallel the median necrotic content increased from 0.19 mm(2) to 0.59 mm(2) (p<0.01). The ""added"" calcium strongly predicted a proportional increase in necrosis-coded tissue in the areas surrounding the calcium-like spots (model R(2)=0.70; p<0.001). Conclusions: Artificial addition of calcium-like elements to the atherosclerotic plaque led to an increase in necrotic tissue in virtual histology that is probably artefactual. The overestimation of necrotic tissue by calcium strictly followed a linear pattern, indicating that it may be amenable to mathematical correction.

Using bifurcations in the determination of lock-in ranges for third-order phase-locked loops

Transmission and switching in digital telecommunication networks require distribution of precise time signals among the nodes. Commercial systems usually adopt a master-slave (MS) clock distribution strategy building slave nodes with phase-locked loop (PLL) circuits. PLLs are responsible for synchronizing their local oscillations with signals from master nodes, providing reliable clocks in all nodes. The dynamics of a PLL is described by an ordinary nonlinear differential equation, with order one plus the order of its internal linear low-pass filter. Second-order loops are commonly used because their synchronous state is asymptotically stable and the lock-in range and design parameters are expressed by a linear equivalent system [Gardner FM. Phaselock techniques. New York: John Wiley & Sons: 1979]. In spite of being simple and robust, second-order PLLs frequently present double-frequency terms in PD output and it is very difficult to adapt a first-order filter in order to cut off these components [Piqueira JRC, Monteiro LHA. Considering second-harmonic terms in the operation of the phase detector for second order phase-locked loop. IEEE Trans Circuits Syst [2003;50(6):805-9; Piqueira JRC, Monteiro LHA. All-pole phase-locked loops: calculating lock-in range by using Evan`s root-locus. Int J Control 2006;79(7):822-9]. Consequently, higher-order filters are used, resulting in nonlinear loops with order greater than 2. Such systems, due to high order and nonlinear terms, depending on parameters combinations, can present some undesirable behaviors, resulting from bifurcations, as error oscillation and chaos, decreasing synchronization ranges. In this work, we consider a second-order Sallen-Key loop filter [van Valkenburg ME. Analog filter design. New York: Holt, Rinehart & Winston; 1982] implying a third order PLL The resulting lock-in range of the third-order PLL is determined by two bifurcation conditions: a saddle-node and a Hopf. (C) 2008 Elsevier B.V. All rights reserved.

Long-term aging of fiber-cement corrugated sheets - The effect of carbonation, leaching and acid rain

This paper studies the performance of fiber-cement corrugated sheets exposed to long-term weathering, exploring the effect of different environments on fiber-cement degradation. Fiber-cement corrugated sheets that had been exposed to weathering, and in place for more than 30-years, were collected from two different Brazilian cities (Sao Paulo and Criciuma). Mechanical properties (MOR, MOE and fracture toughness) were tested on samples removed from the corrugated sheets. Microstructure was evaluated by X-ray diffraction, SEM with EDS analysis, MIP and TG. The results show that the 37-year-old asbestos-cement corrugated sheets from Sao Paulo presented similar characteristics to those of the non-aged asbestos-cement readily available on the market place. Conversely, deterioration of the asbestos-cement from the industrial area of Criciuma is related to acidic attack, along with carbonation and leaching as a consequence of continued exposition to acid rain during several decades. This process resulted in higher porosity and lower mechanical strength, revealing that leaching mechanisms can have important effect on the performance of thin fiber-cement sheets. (c) 2007 Elsevier Ltd. All rights reserved.

Stress cracking and photodegradation behavior of polycarbonate. The combination of two major causes of polymer failure

This work investigates the effects of photodegradation on the environmental stress cracking resistance of polycarbonate (PC). Injection molded samples were exposed to the ultraviolet (UV) light for various times in the laboratory prior to solvent contact. The bars were then stressed with two different loads in a tensile testing machine under the presence of ethanol. During this period, the stress relaxation was monitored and, after unloading, the ultimate properties were evaluated. Complementary tests were done by size exclusion chromatography, UV-visible spectroscopy, scanning electron microscopy, and light microscopy. The results indicated that ethanol causes significant modification in PC, with extensive surface crazing as well as reduction in mechanical properties. The previous degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison with the undegraded ones. The synergist action of photodegradation and stress cracking in PC may be a consequence of the chemical changes caused by oxidation.

The impact of El Nino Southern Oscillation phases on off-season maize yield for a subtropical region of Brazil

In recent years, maize has become one of the main alternative crops for the autumn winter growing season in the central-western and southeastern regions of Brazil. However, water deficits, sub-optimal temperatures and low solar radiation levels are common problems that are experienced during this growing season by local farmers. One methodology to assess the impact of variable weather conditions on crop production is the use of crop simulation models. The goal of this study was to evaluate the effect of climate variability on maize yield for a subtropical region of Brazil. Specific objectives for this study were (1) to analyse the effect of El Nino Southern Oscillation (ENSO) on precipitation and air temperature for four locations in the state of Sao Paulo and (2) to analyse the impact of ENSO on maize grown off-season for the same four locations using a crop simulation model. For each site, historical weather data were categorised as belonging to one of three phases of ENSO: El Nino (warm sea surface temperature anomalies in the Pacific), La Nina (cool sea surface temperature anomalies) or neutral, based on an index derived from observed sea surface temperature anomalies. During El Nino, there is a tendency for an increase in the rainfall amount during May for the four selected locations, and also during April, mainly in three of the locations, resulting in an increase in simulated maize yield planted between February 15 and March 15. In general, there was a decrease in the simulated yield for maize grown off-season during neutral years. This study showed how a crop model can be used to assess the impact of climate variability on the yield of maize grown off-season in a subtropical region of Brazil. The outcomes of this study can be very useful for both policy makers and local farmers for agricultural planning and decision making. Copyright (C) 2009 Royal Meteorological Society