Dielectric relaxation dynamics of high-temperature piezoelectric polyimide copolymers

Polyimide co-polymers have been prepared based on different diamines as co-monomers: a diamine without CN groups and a novel synthesized diamine with two CN groups prepared by polycondensation reaction followed by thermal cyclodehydration. Dielectric spectroscopy measurements were performed and the dielectric complex function, ac conductivity and electric modulus of the co-polymers were investigated as a function of CN group content in the frequency range from 0.1 Hz to 107 Hz at temperatures from 25 to 260 °C. For all samples and temperatures above 150ºC, the dielectric constant increases with increasing temperature due to increaseing conductivity. The α-relaxation is just detected for the sample without CN groups, being this relaxation overlapped by the electrical conductivity contributions in the remaining samples. For the copolymer samples and the polymer with CN groups an important Maxwell-Wagner-Sillars contribution is detected. The mechanisms responsible for the dielectric relaxation, conduction process and electric modulus response have been discussed as a function of the CN groups content present in the samples.

Ion exchange dependent electroactive phase content and electrical properties of poly(vinylidene fluoride)/Na(M)Y composites

Different metal-ion exchanged NaY zeolite, Na(M)Y, were used to prepare poly(vinylidene fluoride) based composites by solvent casting and melting crystallization. The effect of different metal ion-exchanged zeolites on polymer crystallization and electrical properties was reported. Cation-framework interactions and hydration energy of the cations determined that K+ is the most efficient exchanged ion in NaY zeolite, followed by Cs+ and Li+. The electroactive phase crystallization strongly depends on the ions present in the zeolite, leading to variations of the surface energy characteristics of the Na(M)Y zeolites and the polymer chain ability of penetration in the zeolite. Thus, Na(Li)Y and NaY induces the complete electroactive -phase crystallization of the crystalline phase of PVDF, while Na(K)Y only induces it partly and Na(Cs)Y is not able to promote the crystallization of the electroactive phase. Furthermore, different ion size/weigh and different interaction with the zeolite framework results in significant variations in the electrical response of the composite. In this way, iinterfacial polarization effects in the zeolite cavities and zeolite-polymer interface, leads to strong increases of the dielectric constant on the composites with lightest ions weakly bound to the zeolite framework. Polymer composite with Na(Li)Y show the highest dielectric response, followed by NaY and Na(K)Y. Zeolite Na(Cs)Y contribute to a decrease of the dielectric constant of the composite. The results show the relevance of the materials for sensor development.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Experimental analysis of the cyclic response of traditional timber joints and their influence on the seismic capacity of timber frame structures

Timber connections represent the crucial part of a timber structure and a great variability exists in terms of types of connections and mechanisms. Taking as case study the widespread traditional timber frame structures, in particular the Portuguese Pombalino buildings, one of the most common timber connection is the half-lap joint. Connections play a major role in the overall behaviour of a structure, particularly when assessing their seismic response, since damage is concentrated at the connections. For this reason, an experimental campaign was designed and distinct types of tests were carried out on traditional half-lap joints to assess their in-plane response. In particular, pull-out and in-plane cyclic tests were carried out on real scale unreinforced connections. Subsequently, the connections were retrofitted, using strengthening techniques such as self-tapping screws, steel plates and GFRP sheets. The tests chosen were meant to capture the hysteretic behaviour and dissipative capacity of the connections and characterise their response and, therefore, their influence on the seismic response of timber frame walls, particularly concerning their uplifting and rotation capacity, that could lead to rocking in the walls. In this paper, the results of the experimental campaign are presented in terms of hysteretic curves, dissipated energy and equivalent viscous damping ratio. Moreover, recommendations are provided on the most appropriate retrofitting solutions.

Numerical Assessment of the out-of-plane response of a brick masonry structure without box behaviour

This paper presents the assessment of the out-of-plane response due to seismic loading of a masonry structure without rigid diaphragm. This structure corresponds to real scale brick masonry specimen with a main façade connected to two return walls. Two modelling approaches were defined for this evaluation. The first one consisted on macro modelling, whereas the second one on simplified micro modelling. As a first step of this study, static nonlinear analyses were conducted to the macro model aiming at evaluating the out-of-plane response and failure mechanism of the masonry structure. A sensibility analyses was performed in order to assess the mesh size and material model dependency. In addition, the macro models were subjected to dynamic nonlinear analyses with time integration in order to assess the collapse mechanism. Finally, these analyses were also applied to a simplified micro model of the masonry structure. Furthermore, these results were compared to experimental response from shaking table tests. It was observed that these numerical techniques simulate correctly the in-plane behaviour of masonry structures. However, the

Effect of environmental ageing on the numerical response of FRP-strengthened masonry walls

Recent durability studies have shown the susceptibility of bond in fiber-reinforced polymer (FRP) strengthened masonry components to hygrothermal exposures. However, it is not clear how this local material degradation affects the global behavior of FRP-strengthened masonry structures. This study addresses this issue by numerically investigating the nonlinear behavior of FRP-masonry walls after aging in two different environmental conditions. A numerical modeling strategy is adopted and validated with existing experimental tests on FRP-strengthened masonry panels. The model, once validated, is used for modeling of four hypothetical FRP-strengthened masonry walls with different boundary conditions, strengthening schemes, and reinforcement ratios. The nonlinear behavior of the walls is then simulated before and after aging in two different environmental conditions. The degradation data are taken from previous accelerated aging tests. The changes in the failure mode and nonlinear response of the walls after aging are presented and discussed.

Poly-N-acetyl glucosamine expression in Staphylococcus epidermidis biofilm cells affects the immune response and promotes tissue pathology in infected hosts

Staphylococcus epidermidis is a biofilm - forming bacterium and a leading etiological agent of nosocomial infections. The ability to establish biofilms on indwelling medical devices is a key virulence factor for this bacterium. Still, the influence of poly - N - acetyl glucosamine (PNAG), the major component of the extracellular biofilm matrix, in the host immune response has been scarcely studied. Here, t h is influence was assessed in mice challenged i.p. with PNAG - p roducing (WT) and isogenic - mutant lacking PNAG (M10) bacteria grown in biofilm - inducing conditions. Faster bacterial clearance was observed in the mice infected with WT bacteria than in M10 - infected counterparts , which w as accompanied by earlier neutrophil recruitment and higher IL - 6 production. Interestingly, in the WT - infected mice, but not in those infected with M10 , elevated serum IL - 10 was detected . To further study the effe ct of PNAG in the immune response, mice were primed with WT or M10 biofilm bacteria and subsequently infected with WT biofilm - released cells. WT - primed mice presented a higher frequency of splenic IFN - γ + and IL - 17 + CD4 + T cells, and more severe liver patho logy than M10 - primed counterparts. Nevertheless, T reg cells obtained from the WT - primed mice presented a higher suppressive function than those obtained from M10 - primed mice. This effect was abrogated when IL - 10 - deficient mice were similarly primed and infected indicating that PNAG promotes the differentiati on of highly suppressive T reg cells by a mechanism dependent on IL - 10. Altogether, these results provide evidence help ing explain ing the coexistence of inflammation and bacterial persistence often observed in biofilm - originated S. epidermidis infections

Attachment style impacts behavior and early oculomotor response to positive, but not negative, pictures

The present study investigated whether oculomotor behavior is influenced by attachment styles. The Relationship Scales Questionnaire was used to assess attachment styles of forty-eight voluntary university students and to classify them into attachment groups (secure, preoccupied, fearful, and dismissing). Eye-tracking was recorded while participants engaged in a 3-seconds free visual exploration of stimuli presenting either a positive or a negative picture together with a neutral picture, all depicting social interactions. The task consisted in identifying whether the two pictures depicted the same emotion. Results showed that the processing of negative pictures was impermeable to attachment style, while the processing of positive pictures was significantly influenced by individual differences in insecure attachment. The groups highly avoidant regarding to attachment (dismissing and fearful) showed reduced accuracy, suggesting a higher threshold for recognizing positive emotions compared to the secure group. The groups with higher attachment anxiety (preoccupied and fearful) showed differences in automatic capture of attention, in particular an increased delay preceding the first fixation to a picture of positive emotional valence. Despite lenient statistical thresholds induced by the limited sample size of some groups (p < 0.05 uncorrected for multiple comparisons), the current findings suggest that the processing of positive emotions is affected by attachment styles. These results are discussed within a broader evolutionary framework.

Determination of the magnetostrictive response of nanoparticles via magnetoelectric measurements

It is successfully demonstrated that nanoparticle’s magnetostriction can be accurately determined based on the magnetoelectric effect measured on polymeric-composite materials. This represents a novel, simple and versatile method for the determination of particle’s magnetostriction at their nano-sized and dispersed state, which is, up to date, a difficult and imprecise task.

Dielectric relaxation and ferromagnetic resonance in magnetoelectric (Polyvinylidene-fluoride)/ferrite composites

In this work the dielectric properties and ferromagnetic resonance of Polyvinylidene- uoride embedded with 10 wt. % of NiFe2O4 or Ni0.5Zn0.5Fe2O4 nanoparticles are presented. The mechanisms of the dielectric relaxation in these two composites do not differ from each other. For more precise characterization of the dielectric relaxation, a two dimensional distribution of relaxation times was calculated from the temperature dependencies of the complex dielectric permittivity. The results obtained from the 2D distribution and the mean relaxation time are found to be consistent. The dynamics of the dielectric permittivity is described by the Arrhenius law. The energy and attempt time of the dielectric relaxators lie in a narrow energy and time region thus proving that the single type chains of polymer are responsible for a dispersion. The magnetic properties of the composites were investigated using the fer- romagnetic resonance. A single resonance line was observed for both samples. From the temperature dependence (100 K - 310 K) of the resonance eld and linewidth, the origin of the observed line was attributed to the NiFe2O4 and Ni0.5Zn0.5Fe2O4 superparamagnetic nanoparticles. By measuring lms at dif- ferent orientations with respect to the external magnetic eld, the angular dependence of the resonance was observed, indicating the magnetic dipolar in-plane interactions.

Size effects on the magnetoelectric response on PVDF/Vitrovac 4040 laminate composites

Tri-layered and bi-layered magnetoelectric (ME) flexible composite structures of varying geometries and sizes consisting on magnetostrictive Vitrovac and piezoelectric poly(vinylidene fluoride) (PVDF) layers were fabricated by direct bonding. From the ME measurements it was determined that tri-layered composites structures (magnetostrictive-piezoelectric-magnetostrictive type), show a higher ME response (75 V.cm-1.Oe-1) than the bi-layer structure (66 V.cm 1.Oe-1). The ME voltage coefficient decreased with increasing longitudinal size aspect ratio between PVDF and Vitrovac layers (from 1.1 to 4.3), being observed a maximum ME voltage coefficient of 66 V.cm-1.Oe-1. It was also observed that the composite with the lowest transversal aspect ratio between PVDF and Vitrovac layers resulted in better ME performance than the structures with higher transversal size aspect ratios. It was further determined an intimate relation between the Vitrovac PVDF Area Area ratio and the ME response of the composites. When such ratio values approach 1, the ME response is the largest. Additionally the ME output value and magnetic field response was controlled by changing the number of Vitrovac layers, which allows the development of magnetic sensors and energy harvesting devices.

Mechanical vs. electrical hysteresis of carbon nanotube/styrene-butadiene-styrene composites and their influence in the electromechanical response

The interesting properties of thermoplastics elastomers can be combined with carbon nanotubes (CNT) for the development of large strain piezoresistive composites for sensor applications. Piezoresistive properties of the composites depend on CNT content, with the gauge factor increasing for concentrations around the percolation threshold, mechanical and electrical hysteresis. The SBS copolymer composition (butadiene/styrene ratio) influences the mechanical and electrical hysteresis of composites and, therefore, the piezoresistive response. This work reports on the electrical and mechanical response of CNT/SBS composites with 4%wt nanofiller content, due to the larger electromechanical response. C401 and C540 SBS copolymers with 80% and 60% butadiene content, respectively have been selected. The copolymer with larger amount of soft phase (C401) shows a rubber-like mechanical behavior, with mechanical hysteresis increasing linearly with strain until 100% strain. The copolymer with the larger amount of hard phase (C540) just shows rubber-like behavior for low strains. The piezoresistive sensibility is similar for both composites for low strains, with a GF≈ 5 for 5% strain. The electrical hysteresis shows opposite behavior than the mechanical hysteresis, increasing with strain for both composites, but with higher increase for softer copolymer, C401. The GF increases with increasing strain, but this increase is larger for composites with lower amounts of soft phase due to the distinct initial modulus and deformation of the soft and hard phases of the copolymer. The soft phase shows larger strain under a given stress than the harder phase and the conductive pathway rearrangements in the composites are different for both phases, the harder copolymer (C540) showing higher piezoresistive sensibility, GF≈ 18, for 20% strain.

Energy harvesting performance of BaTiO3/poly(vinylidene fluoride-trifluoroethylene) spin coated nanocomposites

The energy harvesting efficiency of poly(vinylidene fluoride-trifluoroethylene) spin coated films and its nanocomposites with piezoelectric BaTiO3 have been investigated as a function of ceramic filler size and content. It is found that the best energy harvesting performance of ~0.28 W is obtained for the nanocomposite samples with 20% filler content of 10 nm size particles and for 5% filler content for the 100 and 500 nm size fillers. For the larger filler average sizes, the power decreases for filler contents above 5% due to increase of the mechanical stiffness of the samples. Due to the similar dielectric characteristics of the samples, the performance is mainly governed by the mechanical response. The obtained power values, easy processing and the low cost and robustness of the polymer, allow the implementation of the material for micro and nanogenerator applications.

Terahertz response of patterned epitaxial graphene

We study the interaction between polarized terahertz (THz) radiation and micro-structured large-area graphene in transmission geometry. In order to efficiently couple the radiation into the two-dimensional material, a lateral periodic patterning of a closed graphene sheet by intercalation doping into stripes is chosen. We observe unequal transmittance of the radiation polarized parallel and perpendicular to the stripes. The relative contrast, partly enhanced by Fabry-Perot oscillations reaches 20 %. The effect even increases up to 50 % when removing graphene stripes in analogy to a wire grid polarizer. The polarization dependence is analyzed in a large frequency range from < 80 GHz to 3 THz, including the plasmon-polariton resonance. The results are in excellent agreement with theoretical calculations based on the electronic energy spectrum of graphene and the electrodynamics of the patterned structure

RNA-seq analysis of the Quercus suber root response to drought

Dissertação de mestrado em Plant Molecular Biology, Biotechnology and Bioentrepreneurship