Electric characterization of a hybrid composite based on POMA/P(VDF- TrFE)/Zn2SiO4 : Mn using impedance spectroscopy

Understanding the microscopic origin of the dielectric properties of disordered materials has been a challenge for many years, especially in the case of samples with more than one phase. For polar dielectrics, for instance, the Lepienski approach has indicated that the random free energy barrier model of Dyre must be extended. Here we analyse the dielectric properties of a polymer blend made up with the semiconducting poly(o-methoxyaniline) and poly( vinylidene fluoride-trifluorethylene) POMA/P(VDF-TrFE), and of a hybrid composite of POMA/P(VDF-TrFE)/Zn2SiO4:Mn. For the blend, the Lepienski model, which takes into account the rotation or stretching of electric dipoles, provided excellent fitting to the ac impedance data. Because two phases had to be assumed for the hybrid composite, we had to extend the Lepienski model to fit the data, by incorporating a second transport mechanism. The two mechanisms were associated with the electronic transport in the polymeric matrix and with transport at the interfaces between Zn2SiO4: Mn microparticles and the polymeric matrix, with the relative importance of the interfacial component increasing with the percentage of Zn2SiO4: Mn in the composite. The analysis of impedance data at various temperatures led to a prediction of the theoretical model of a change in morphology at 190 +/- 40 K, and this was confirmed experimentally with a differential scanning calorimetry experiment.

Composite Resin to Yttria Stabilized Tetragonal Zirconia Polycrystal Bonding: Comparison of Repair Methods

Purpose: The purpose of the current study was to evaluate different approaches for bonding composite to the surface of yttria stabilized tetragonal zirconia polycrystal (Y-TZP) ceramics.Methods: One hundred Y-TZP blocks were embedded in acrylic resin, had the free surface polished, and were randomly divided into 10 groups (n=10). The tested repair approaches included four surface treatments: tribochemical silica coating (TBS), methacryloxydecyldihidrogenphosphate (MDP)-containing primer/silane, sandblasting, and metal/zirconia primer. Alcohol cleaning was used as a "no treatment" control. Surface treatment was followed by the application (or lack thereof) of an MDP-containing resin cement liner. Subsequently, a composite resin was applied to the ceramic surface using a cylindrical mold (4-mm diameter). After aging for 60 days in water storage, including 6000 thermal cycles, the specimens were submitted to a shear test. Analysis of variance and the Tukey test were used for statistical analyses (alpha=0.05).Results: Surface treatment was a statistically significant factor (F=85.42; p<0.0001). The application of the MDP-containing liner had no effect on bond strength (p=0.1017). TBS was the only treatment that had a significantly positive effect on bond strength after aging.Conclusion: Considering the evaluated approaches, TBS seems to be the best surface treatment for Y-TZP composite repairs. The use of an MDP-containing liner between the composite and Y-TZP surfaces is not effective.

Evaluation by Free Vibration Method of Moisture Absorption Effects in Polyamide/Carbon Fiber Laminates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrochemistry of organometallic compounds. Part II. Oxidations of alkyl and aryl derivatives of bis(salicylaldehyde)ethylenediimine cobalt(III) in dimethylformamide

The influence of the axial organic ligand R on the electrochemical oxidation of the compounds [RCoIII(salen)DMF)], where salen is bis(salicylaldehyde)ethylenediimine, and R CH3, C2H5, n-C3H7, n-C4H9, s-C4H9, i-C4H9, CH2Cl, CF3CH2, c-C6H11CH2, c-C6H11, C6H5, C6H5CH2, p-CH3C6H4CH2, and p-NO2C6H4CH2, was studied by means of cyclic voltametry in dimethylformamide (DMF), 0.2 M in tetraethylammonium perchlorate (TEAP), at 25 and -20°C, with a platinum disc working electrode. The above-mentioned compounds can be classified according to their electrochemical behavior. (a) The complexes with R CH3, C2H5, n-C3H7, n-C4H9, c-C6H11CH2, and C6H5 undergo a reversible one-electron oxidation in the 10-50 V s-1 potential scan range. At slower scan rates, the oxidized product decomposes chemically. At -20°C, this chemical step is slow, and a reversible one-electron electrochemical oxidation is observed. (b) The compounds with R CH2Cl, C6H5CH2, p-CH3C6H4CH2 and p-NO2C6H4CH2 undergo a quasi-reversible one-electron oxidation at room temperaure. At -20°C, the electrochemical process becomes more complex. A following chemical reactions is coupled to the quasi-reversible one-electron transfer. Two reduction peaks are observed. (c) The compounds with R i-C4H9, s-C4H9, and c-C6H11 undergo a reversible one-electron oxidation at -20°C. At room temperature, the irreversible chemical reaction following the electron transfer step is too fast to allow the isolation of the electrochemical step. (d) At -20°C, the derivatives with R C2H5, c-C6H11 CH2 and c-C6H11 are adsorbed at the electrode surface. Evidence indicates that the reagent in these reactions is the pentacoordinated species [RCoIII(salen)]. A linear free-energy relationship between E1/2 (for reversible processes) and the Taft polar parameters o* was obtained with a slope of ρ* = 0.25 ± 0.03. As expected, the benzyl derivatives which present mesomeric effects do not fit this polar correlation. The rated of the electrochemical oxidation is also affected by the nature of the ligand R. For the ligands which are strong electron-withdrawing groups and for the benzyl derivatives, the rate of the electrochemical oxidation of the metal ion decreases at room temperature. At lower temperatures, it is suggested that the oxidation to the CoIV-R species is followed by a chemical reaction in which this complex is partly transformed into a CoIII(R*) species, which is reduced at a much more cathodic potential than the Co(IV) species. © 1979.

Second quantization approach to composite hadron interactions in quark models

Starting from the Fock space representation of hadron bound states in a quark model, a change of representation is implemented by a unitary transformation such that the composite hadrons are redescribed by elementary-particle field operators. Application of the unitary transformation to the microscopic quark Hamiltonian gives rise to effective hadron-hadron, hadron-quark, and quark-quark Hamiltonians. An effective baryon Hamiltonian is derived using a simple quark model. The baryon Hamiltonian is free of the post-prior discrepancy which usually plagues composite-particle effective interactions.

Piezoelectric effect in composite polyurethane-ferroelectric ceramics

Flexible and free-standing films of piezoelectric composites made up of lead zirconate titanate (PZT) ceramic powder dispersed in a castor oil-based polyurethane (PU) matrix were obtained by spin coating and characterized as materials for sensor applications. The piezoelectric coefficients d 31 and d 33 were measured with the usual technique. The piezoelectric charge constant d 33 yields values up to ≤24 pC/N, even at lower PZT content (33 vol%). Some desirable properties like piezoelectricity, flexibility and good mechanical resistance show this new material to be a good alternative for use as sensors and actuators.

Aesthetic posts and cores for metal-free restoration of endodontically treated teeth.

Utilization of contemporary post and core systems has facilitated the aesthetic restoration of endodontically treated teeth. Light transmission and biocompatibility have been enhanced by the introduction of metal-free post systems. The periodontal and endodontic status, root length, and histological structure of the devitalized teeth must be considered in order to achieve successful restoration following endodontic treatment. This article presents various restorative criteria for the aesthetic placement and buildup of post and core materials, as well as the preservation of maximum coronal and root structure.

Scanning electron microscope analysis of internal adaptation of materials used for pulp protection under composite resin restorations

Purpose: The aim of this study was to evaluate the interfacial microgap with different materials used for pulp protection. The null hypothesis tested was that the combination of calcium hydroxide, resin-modified glass ionomer, and dentin adhesive used as pulp protection in composite restorations would not result in a greater axial gap than that obtained with hybridization only. Materials and Methods: Standardized Class V preparations were performed in buccal and lingual surfaces of 60 caries-free, extracted human third molars. The prepared teeth were randomly assessed in six groups: (1) Single Bond (SB) (3M ESPE, St. Paul, MN, USA); (2) Life (LF) (Kerr Co., Romulus, MI, USA) + SB; (3) LF + Vitrebond (VT) (3M ESPE) + SB; (4) VT + SB; (5) SB + VT; (6) SB + VT + SB. They were restored with microhybrid composite resin Filtek Z250 (3M ESPE), according to the manufacturer's instructions. However, to groups 5 and 6, the dentin bonding adhesive was applied prior to the resin-modified glass ionomer. The specimens were then thermocycled, cross-sectioned through the center of the restoration, fixed, and processed for scanning electron microscopy. The specimens were mounted on stubs and sputter coated. The internal adaptation of the materials to the axial wall was analyzed under SEM with × 1,000 magnification. Results: The data obtained were analyzed with nonparametric tests (Kruskal-Wallis, p ≤ .05). The null hypothesis was rejected. Calcium hydroxide and resin-modified glass ionomer applied alone or in conjunction with each other (p < .001) resulted in statistically wider microgaps than occurred when the dentin was only hybridized prior to the restoration. ©2005 BC Decker Inc.

Influence of resin composite insertion technique in preparations with a high C-factor

Objective: To evaluate the marginal microleakage in enamel and dentin/cementum walls in preparations with a high C-factor, using 3 resin composite insertion techniques. The null hypothesis was that there is no difference among the 3 resin composite insertion techniques. Method and Materials: Standardized Class 5 cavities were prepared in the lingual and buccal aspects of 30 caries-free, extracted third molars. The prepared teeth were randomly assigned to 3 groups: (1) oblique incremental placement technique, (2) horizontal incremental placement technique, and (3) bulk insertion (single increment). The preparations were restored with a 1-bottle adhesive (Single Bond, 3M ESPE) and microhybrid resin composite (Z100, 3M ESPE). Specimens were isolated with nail varnish except for a 2-mm-wide rim around the restoration and thermocycled (1,000 thermal cycles, 5°C/55°C; 30-second dwell time). The specimens were immersed in an aqueous solution of 50 wt% silver nitrate for 24 hours, followed by 8 hours in a photo-developing solution and evaluated for microleakage using an ordinal scale of 0 to 4. The microleakage scores obtained from occlusal and gingival walls were analyzed with Wilcoxon and Kruskal-Wallis nonparametric tests. Results: The null hypothesis was accepted. The horizontal incremental placement technique, the oblique incremental technique, and bulk insertion resulted in statistically similar enamel and dentin microleakage scores. Conclusion: Neither the incremental techniques nor the bulk placement technique were capable of eliminating the marginal microleakage in preparations with a high C-factor.

Ultrasonic material characterization using diffraction-free PVDF receivers

This work describes the use of a large aperture PVDF receiver in the measurement of density of liquids and elastic constants of composite materials. The density measurement of several liquids is obtained with the accuracy of less than 0.2% using a conventional NDT emitter transducer and a 70-mm diameter, 52-μm P(VDF-TrFE) membrane with gold electrodes. The determination of the elastic constants of composite materials is based in the measurement of phase velocity. It is shown that the diffraction can lead to errors around 1% in the velocity measurement when using a pair of ultrasonic transducers (1MHz and 19mm diameter) operating in transmission-reception mode separated by a distance of 100 mm. This effect is negligible when using a pair of 10-MHz transducers. On the other hand, the dispersion at 10 MHz can result in errors of about 0.5%, measuring the velocity in composite materials. The use of an 80-mm diameter, 52-μm thick PVDF membrane receiver allows measuring the phase velocity without the diffraction effects.

Free radical entrapment and crystallinity of resin composites after accelerated aging as a function of the expiration date

This study evaluated the spin concentration and the crystallinity in different classifications of dental composites as a function of the material condition (new, aged and expired). Specimens were obtained according to the factors: composites: Filtek P60, Filtek Z250, Filtek Z350XT, and Filtek Silorane; and material conditions: new, aged, and expired. The syringe composites underwent an accelerated aging protocol (Arrhenius model). The magnetic properties of the composites were characterized using Electron Paramagnetic Resonance (EPR) and the concentration of spins (number of spins/mass) was calculated. The crystallinity of the composites tested was characterized with X-ray diffraction (XRD). Filtek P60 and Filtek Z250 presented similarities in terms of spin concentration and crystallinity, irrespective of the material condition. The aging protocol influenced the composite Filmic Z350XT that exhibited a significant increase in the spin concentration. Besides, lower intensity peaks of the organic matrix and amorphous silica were also observed for both aged and expired Filtek Z350XT. Although a significant lower spin concentration was observed for the silorane composite in comparison to that of the methacrylates, a decrease in the relative intensity of peaks of the amorphous region related to the organic components in the diffractograms was observed. The material conditions tested influence the crystallinity and the magnetic properties of the composites evaluated. (C) 2014 Elsevier Ltd. All rights reserved.

Investigations on PVP/Y3BO6:Eu3+, a red Luminescent composite for lighting devices based on near UV-LEDs

This work deals with a red phosphor. Y3BO6:Eu3+, and its corresponding poly(N-vinylpyrrolidone) (PVP)/Y3BO6:Eu3+ luminescent composite film suitable for applications in the next generation of Hg-free lamps based on near ultraviolet (UV) light emitting diodes (LEDs). Well crystallized samples of Y3BO6 powders with the Eu3+ content up to 20 mol% were prepared by the Pechini method. After structural, morphological and optical characterization, the best doping rate of Eu3+ in the matrix was determined to be 15 mol%. This optimal powder, which is highly friable, was easily ground into fine particles and homogeneously dispersed into a PVP polymer solution to give rise to a polymer phosphor composite. Structural and optical features of the composite film have been studied and compared to those of a pristine PVP film and Y3BO6:Eu3+ powder. All the characterization (XRD, SAXS, luminescence...) proved that the red phosphor particles are well incorporated into the polymer composite film which exhibited the characteristic red emission of Eu3+ under UV light excitation. Furthermore, photostability of the polymer/phosphor composite film under UV-LED irradiation was evaluated from exposure to accelerated artificial photoageing at wavelengths above 300 nm.

Otimização do processamento de partículas lead-free para aplicação em compósitos polímero/cerâmica com propriedades piezoelétrica e fotoluminescente

Pós-graduação em Química - IQ

Degree of conversion of nanofilled and microhybrid composite resins photo-activated by different generations of LEDs

Objective: This study aimed at evaluating the degree of conversion (DC) of four composite resins, being one nanofilled and 3 microhybrid resins, photo-activated with second- and third-generation light-emitting diodes (LEDs). Material and methods: Filtek (TM) Z350 nanofilled composite resins and Amelogen (R) Plus, Vit-l-escence (TM) and Opallis microhybrid resins were photo-activated with two second-generation LEDs (Radii-cal and Elipar Free Light (TM) 2) and one third-generation LED (Ultra-Lume LED 5) by continuous light mode, and a quartz halogen-tungsten bulb (QHT, control). After 24 h of storage, the samples were pulverized into fine powder and 5 mg of each material were mixed with 100 mg of potassium bromide (KBr). After homogenization, they were pressed, which resulted in a pellet that was evaluated using an infrared spectromer (Nexus 470, Thermo Nicolet) equipped with TGS detector using diffuse reflectance (32 scans, resolution of 4 cm(-1)) coupled to a computer. The percentage of unreacted carbon-carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1637 cm-1) against internal standard before and after curing of the specimen: aromatic C-C (peak at 1610 cm-1). Results: The ANOVA showed a significant effect on the interaction between the light-curing units (LCUs) and the composite resins (p<0.001). The Tukey's test showed that the nanofilled resin (Filtek (TM) Z350) and Opallis when photo-activated by the halogen lamp (QTH) had the lowest DC compared with the other microhybrid composite resins. The DC of the nanofilled resin (Filtek (TM) Z350) was also lower using LEDs. The highest degrees of conversion were obtained using the third-generation LED and one of second-generation LEDs (Elipar Free Light (TM) 2). Conclusions: The nanofilled resin showed the lowest DC, and the Vit-l-escence (TM) microhybrid composite resin showed the highest DC. Among the LCUs, it was not possible to establish an order, even though the second-generation LED Radii-cal provided the lowest DC.

Linking origin of the electric field-assisted beta-PbF2 crystallization in lead oxyfluoroborate glasses below T (g) to simultaneous cathode/anode-compensated electrochemical reactions

Full validation of the electrochemical mechanisms so far postulated as driving force of electric field-assisted non-spontaneous crystallization development in given glasses has suffered experimental restrictions. In this work, we looked into origin of this phenomenon in lead oxyfluoroborate glasses, resulting in beta-PbF2 growth even below the corresponding glass transition temperatures, through achieving a systematic study of not only Pt,Ag/Glass/Ag,Pt- but also Pt,Ag/Glass/YSZ:PbF2/Ag,Pt-type cells, where YSZ:PbF2 represents a two-phase system (formed by Y2O3-doped ZrO2 and PbF2). It is demonstrated that crystallization induction in these glasses involves Pb2+ ions reduction at the cathode, the phenomenon being, however, confirmed only when the F- ions were simultaneously also able to reach the anode for oxidation, after assuring either a direct glass-anode contact or percolation pathways for free fluoride migration across the YSZ:PbF2 mixtures. A further support of this account is that the electrochemically induced beta-PbF2 phase crystallizes showing ramified-like microstructure morphology that arises, accordingly, from development of electroconvective diffusion processes under electric field action.