Marcelo A. Pereira-da-Silva

The morphology of layer-by-layer films of polymer/polyelectrolyte studied by atomic force microscopy

Layer-by-layer (LBL) films of a semiconducting polymer (POMA) alternated with a polyelectrolyte (PVS), adsorbed onto silicon oxide, mica, ITO/glass, Au/Cr/glass, hydrophilic and hydrophobic glass were studied by atomic force microscopy (AFM). The samples were characterized LBL with the AFM operating in the contact, friction and tapping modes, which allowed us to determine their morphological surface properties such as roughness, mean grain size, grain boundaries and power spectrum density. Their film thickness was measured by AFM using the tip as a scraping tool. Surface roughness increases with the number of bilayers until a constant value is reached. This is in agreement with the observed increase in the adsorbed amount (per layer) of POMA as the number of bilayers is increased, which also saturates after several bilayers. It is shown that the 3D growth behaviour indicates a similar microscopic mechanism for all systems under study, pointing to a stochastic growth process of the Eden model type, but strongly influenced by initial roughness and water affinity of the virgin substrates. The crystalline or amorphous nature of the substrates does not seem to influence the growth process.

Impact of bleaching pine fibre on the fibre/cement interface

The goal of this article was to evaluate the surface characteristics of the pine fibres and its impact on the performance of fibre–cement composites. Lower polar contribution of the surface energy indicates that unbleached fibres have less hydrophilic nature than the bleached fibres. Bleaching the pulp makes the fibres less stronger, more fibrillated and permeable to liquids due to removal the amorphous lignin and its extraction from the fibre surface. Atomic force microscopy reveals these changes occurring on the fibre surface and contributes to understanding the mechanism of adhesion of the resulting fibre to cement interface. Scanning electron microscopy shows that pulp bleaching increased fibre/cement interfacial bonding, whilst unbleached fibres were less susceptible to cement precipitation into the fibre cavities (lumens) in the prepared composites. Consequently, bleached fibre-reinforced composites had lower ductility due to the high interfacial adhesion between the fibre and the cement and elevated rates of fibre mineralization.

Enhanced Sensitivity of Gas Sensor Based on Poly(3-hexylthiophene) Thin-Film Transistors for Disease Diagnosis and Environment Monitoring

Electronic devices based on organic thin-film transistors (OTFT) have the potential to supply the demand for portable and low-cost gadgets, mainly as sensors for in situ disease diagnosis and environment monitoring. For that reason, poly(3-hexylthiophene) (P3HT) as the active layer in the widely-used bottom-gate/bottom-contact OTFT structure was deposited over highly-doped silicon substrates covered with thermally-grown oxide to detect vapor-phase compounds. A ten-fold organochloride and ammonia sensitivity compared to bare sensors corroborated the application of this semiconducting polymer in sensors. Furthermore, P3HT TFTs presented approximately three-order higher normalized sensitivity than any chemical sensor addressed herein. The results demonstrate that while TFTs respond linearly at the lowest concentration values herein, chemical sensors present such an operating regime mostly above 2000 ppm. Simultaneous alteration of charge carrier mobility and threshold voltage is responsible for pushing the detection limit down to units of ppm of ammonia, as well as tens of ppm of alcohol or ketones. Nevertheless, P3HT transistors and chemical sensors could compose an electronic nose operated at room temperature for a wide range concentration evaluation (1–10,000 ppm) of gaseous analytes. Targeted analytes include not only biomarkers for diseases, such as uremia, cirrhosis, lung cancer and diabetes, but also gases for environment monitoring in food, cosmetic and microelectronics industries.

Titanium surface topography after brushing with fluoride and fluoride-free toothpaste simulating 10 years of use.

OBJECTIVES To conduct a controlled study contrasting titanium surface topography after procedures that simulated 10 years of brushing using toothpastes with or without fluoride. METHODS Commercially pure titanium (cp Ti) and Ti-6Al-4V disks (6 mm Ø×4 mm) were mirror-polished and treated according to 6 groups (n=6) as a function of immersion (I) or brushing (B) using deionised water (W), fluoride-free toothpaste (T) and fluoride toothpaste (FT). Surface topography was evaluated at baseline (pretreatment) and post-treatment, using atomic force microscope in order to obtain three-dimensional images and mean roughness. Specimens submitted to immersion were submerged in the vehicles without brushing. For brushed specimens, procedures were conducted using a linear brushing machine with a soft-bristled toothbrush. Immersion and brushing were performed for 244 h. IFT and BFT samples were analysed under scanning electron microscope with Energy-Dispersive X-ray Spectroscopy (EDS). Pre and post-treatment values were compared using the paired Student T-test (α=.05). Intergroup comparisons were conducted using one-way ANOVA with Tukey post-test (α=.05). RESULTS cp Ti mean roughness (in nanometers) comparing pre and post-treatment were: IW, 2.29±0.55/2.33±0.17; IT, 2.24±0.46/2.02±0.38; IFT, 2.22±0.53/1.95±0.36; BW, 2.22±0.42/3.76±0.45; BT, 2.27±0.55/16.05±3.25; BFT, 2.27±0.51/22.39±5.07. Mean roughness (in nanometers) measured in Ti-6Al-4V disks (pre/post-treatment) were: IW, 1.79±0.25/2.01±0.25; IT, 1.61±0.13/1.74±0.19; IFT, 1.92±0.39/2.29±0.51; BW, 2.00±0.71/2.05±0.43; BT, 2.37±0.86/11.17±2.29; BFT, 1.83±0.50/15.73±1.78. No significant differences were seen after immersions (p>.05). Brushing increased the roughness of cp Ti and of Ti-6Al-4V (p<.01); cp Ti had topographic changes after BW, BT and BFT treatments whilst Ti-6Al-4V was significantly different only after BT and BTF. EDS has not detected fluoride or sodium ions on metal surfaces. CONCLUSIONS Exposure to toothpastes (immersion) does not affect titanium per se; their use during brushing affects titanium topography and roughness. The associated effects of toothpaste abrasives and fluorides seem to increase roughness on titanium brushed surfaces.

Bending of Layer-by-Layer Films Driven by an External Magnetic Field

We report on optimized architectures containing layer-by-layer (LbL) films of natural rubber latex (NRL), carboxymethyl-chitosan (CMC) and magnetite (Fe3O4) nanoparticles (MNPs) deposited on flexible substrates, which could be easily bent by an external magnetic field. The mechanical response depended on the number of deposited layers and was explained semi-quantitatively with a fully atomistic model, where the LbL film was represented as superposing layers of hexagonal graphene-like atomic arrangements deposited on a stiffer substrate. The bending with no direct current or voltage being applied to a supramolecular structure containing biocompatible and antimicrobial materials represents a proof-of-principle experiment that is promising for tissue engineering applications in biomedicine.

On the Performance Degradation of Poly(3-Hexylthiophene) Field-Effect Transistors

Polymeric transistor degradation was investigated on bottom and top gate structures. Shelf-lifetime studies in both kinds of devices demonstrate an accelerated increase in effective charge carrier mobility, threshold voltage, and off current in modulus when poly(3-hexylthiophene) (P3HT) is exposed to atmospheric gases. Although P3HT is underneath PMMA dielectric and gold gate electrode films, electrical parameters degradation can be only delayed by 100 h. Therefore, only glass encapsulation of the active area is capable of effectively preventing current modulation decrease after exposure to atmospheric gases. Differently from their bottom-gate counterparts, capped top-gate TFTs clearly present negative threshold voltage and positive hysteresis. An interface with reduced deep traps concentration and electrical characterization influence on shallow traps filling are believed to play a significant role in these top-gate P3HT/PMMA transistors under operating conditions. Alternating gate voltage stress along 3000 cycles provides evidence of electrical sweep as a cause of performance degradation. Similarly, dc gate bias stress monitored for 127 min can impair current modulation and shifts threshold voltage depending on its sign. Finally, reversibility of both kinds of stress points that shallow traps are the major problem in these capped devices.

Experimental and computational investigation of reduced graphene oxide nanoplatelets stabilized in poly(styrene sulfonate) sodium salt

The production of large-area interfaces and the use of scalable methods to build up designed nanostructures generating advanced functional properties are of high interest for many materials science applications. Nevertheless, large-area coverage remains a major problem even for pristine graphene, and here we present a hybrid, composite graphene-like material soluble in water that can be exploited in many areas such as energy storage, electrodes fabrication, selective membranes and biosensing. Graphene oxide (GO) was produced by the traditional Hummers’ method being further reduced in the presence of poly(styrene sulfonate) sodium salt (PSS), thus creating stable reduced graphene oxide (rGO) nanoplatelets wrapped by PSS (GPSS). Molecular dynamics simulations were carried out to further clarify the interactions between PSS molecules and rGO nanoplatelets, with calculations supported by Fourier transform infrared spectroscopy analysis. The intermolecular forces between rGO nanoplatelets and PSS lead to the formation of a hybrid material (GPSS) stabilized by van der Waals forces, allowing the fabrication of high-quality layer-by-layer (LbL) films with poly(allylamine hydrochloride) (PAH). Raman and electrical characterizations corroborated the successful modifications in the electronic structures from GO to GPSS after the chemical treatment, resulting in (PAH/GPSS) LbL films four orders of magnitude more conductive than (PAH/GO).

Analysis of the Early Stages and Evolution of Dental Enamel Erosion

The aim of this study was to evaluate by atomic force microscopy (AFM) the early phases and evolution of dental enamel erosion caused by hydrochloric acid exposure, simulating gastroesophageal reflux episodes. Polished bovine enamel slabs (4x4x2 mm) were selected and exposed to 0.1 mL of 0.01 M hydrochloric acid (pH=2) at 37 ?#61472;?#61616;C using five different exposure intervals (n=1): no acid exposure (control), 10 s, 20 s, 30 s and 40 s. The exposed area was analyzed by AFM in 3 regions to measure the roughness, surface area and morphological surface. The data were analyzed qualitatively. Roughness started as low as that of the control sample, Rrms=3.5 nm, and gradually increased at a rate of 0.3 nm/s, until reaching Rrms=12.5 nm at 30 s. After 40 s, the roughness presented increment of 0.40 nm only. Surface area (SA) increased until 20 s, and for longer exposures, the surface area was constant (at 30 s, SA=4.40 μm2 and at 40 s, SA=4.43 μm2). As regards surface morphology, the control sample presented smaller hydroxyapatite crystals (22 nm) and after 40 s the crystal size was approximately 60 nm. Short periods of exposure were sufficient to produce enamel demineralization in different patterns and the morphological structure was less affected by exposure to hydrochloric acid over 30 s.

Analysis of polyaniline films using atomic force microscopy

This work presents a morphological study of polyaniline (PANI) films, chemically and electrochemically synthesised over ITO (Indium Tin Oxide covered glass) substratum using atomic force microscopy (AFM). From AFM images we calculate the fractal dimension of the polyaniline formed films using power spectral density (PSD) and the box counting method (roughness versus scale). As a result it is shown that the fractality obtained by PSD are in good agreement with box counting.

Thickness and roughness measurements in poly(o-methoxyaniline) layer-by-layer films using AFM

Atomic force microscopy (AFM) was employed to monitor the buildup of layer-by-layer films of poly(o-methoxyaniline) (POMA) and poly(ethenesulfonic acid) (PVS) onto several substrates. Using the contact mode of an AFM, we produced a furrow on the film, which was made possible because the film material was less stiff than the substrate and the silicon tip. Film thickness could then be measured using the tapping mode. The thickness and adsorbed amount of POMA/PVS increased linearly after several bilayers had been deposited, while the roughness increased with the number of bilayers until reaching a saturation value. This behavior was attributed to the ability of these polymers to aggregate, which was confirmed by an analysis of grain sizes.