Enhanced Chemical and Electrochemical Stability of Polyaniline-Based Layer-by-Layer Films

Polyaniline (PANI) has been widely used as an electroactive material in various applications including sensors, electrochromic devices, solar cells, electroluminescence, and electrochemical energy storage, owing to PANI’s unique redox properties. However, the chemical and electrochemical stability of PANI-based materials is not sufficiently high to maintain the performance of devices under many practical applications. Herein, we report a route to enhancing the chemical and electrochemical stability of PANI through layer-by-layer (LbL) assembly. PANI was assembled with different types of polyelectrolytes, and a comparative study between three different PANI-based layer-by-layer (LbL) films is presented here. Polyacids of different acidity and molecular structure, i.e., poly(acrylic acid) (PAA), polystyrene sulfonate (PSS), and tannic acid (TA), were used. The effect of polyacids’ acidity on film growth, conductivity, and chemical and electrochemical stability of PANI was investigated. The results showed that the film growth of the LbL system depended on the acidic strength of the polyacids. All LbL films exhibited improved chemical and electrochemical stability compared to PANI films. The doping level of PANI was strongly affected by the type of dopants, resulting in different chemical and electrochemical properties; the strongest polyacid (PSS) can provide the highest conductivity and chemical stability of conductive PANI. However, the electrochemical stability of PANI/PAA was found to be better than all the other films.

Porous Layer-by-Layer Films Assembled Using Polyelectrolyte Blend to Control Wetting Properties

Porous layer-by-layer (LbL) films have been employed for the implementation of superwetting surfaces, but they are limited to the LbL films consisting of only two oppositely charged polyelectrolytes. In this study, LbL films were assembled using a cationic polymer blend of branched poly(ethylene imine) (BPEI) and poly(allylamine hydrochloride) (PAH), and anionic poly(acrylic acid); they were then acid-treated at pH 1.8–2.0 to create a porous structure. The films of 100% BPEI exhibited a relatively smooth surface, whereas those of the 100% PAH exhibited porous surfaces. However, various surface morphologies were obtained when BPEI and PAH were blended. When coated with fluorinated silane, films with 50% and 100% PAH exhibited relatively higher water contact angles (WCAs). In particular, films with 50% PAH exhibited the highest WCA of 140–150° when treated at pH 1.8. These fluorinated films were further infused with lubricant oil to determine their feasibility as slippery surfaces. The water and oil sliding angles were in the range of 10–20° and 5–10°, respectively. Films prepared with the BPEI/PAH blend showed lower water slide angles than those prepared with 100% BPEI or PAH. Acid treatment of LbL films assembled using a polyelectrolyte blend can effectively control surface morphologies and can potentially be applied in superwetting.

Thermally Stimulated Desorption Optical Fiber-Based Interrogation System: An Analysis of Graphene Oxide Layers’ Stability

Thin graphene oxide (GO) film layers are being widely used as sensing layers in different types of electrical and optical sensor devices. GO layers are particularly popular because of their tuned interface reflectivity. The stability of GO layers is fundamental for sensor device reliability, particularly in complex aqueous environments such as wastewater. In this work, the stability of GO layers in layer-by-layer (LbL) films of polyethyleneimine (PEI) and GO was investigated. The results led to the following conclusions: PEI/GO films grow linearly with the number of bilayers as long as the adsorption time is kept constant; the adsorption kinetics of a GO layer follow the behavior of the adsorption of polyelectrolytes; and the interaction associated with the growth of these films is of the ionic type since the desorption activation energy has a value of 119 ± 17 kJ/mol. Therefore, it is possible to conclude that PEI/GO films are suitable for application in optical fiber sensor devices; most importantly, an optical fiber-based interrogation setup can easily be adapted to investigate in situ desorption via a thermally stimulated process. In addition, it is possible to draw inferences about film stability in solution in a fast, reliable way when compared with the traditional ones.

Selective Hydrogen Bonding Controls Temperature Response of Layer-by-Layer Upper Critical Solution Temperature Micellar Assemblies

This work establishes a correlation between the selectivity of hydrogen-bonding interactions and the functionality of micelle-containing layer-by-layer (LbL) assemblies. Specifically, we explore LbL films formed by assembly of poly(methacrylic acid)...

SISTEMA ROBÓTICO DE BAIXO CUSTO PARA PREPARAÇÃO DE FILMES POR LAYER-BY-LAYER

LOW-COST ROBOTIC SYSTEM FOR PREPARATION OF LAYER-BY-LAYER FILMS. Layer-by-Layer is an efficient technique for the deposition of thin films used in several devices such as sensors, solar cells, and other systems. A robotic system improves the process reproducibility, be a stand-alone system, and does not demand human participation during the deposition process. On the other hand, the commercially available equipment is expensive. In this work, we present a low-cost robotic system built by using materials commonly found that allows performing several bathing, drying steps and deposition cycles of the substrates necessary for the formation of LbL films. This technical note presents the electronic assembly scheme and the program developed for an experiment. The number of baths, the time necessary for the deposition, and repetitions to result in the formation of the desired film; can be easily modified in this program. The films prepared in this experiment were successfully employed for the preparation of compact layers for perovskite solar cells. Therefore, the equipment can be easily customized to the needs of each research group that uses it.

Towards the systematic design of multilayer O/W emulsions with tannic acid as an interfacial antioxidant

Three-step method optimizes multilayer emulsion for maximum tannic acid (TA) amount at surfaces. (1) TA–emulsifier bulk interactions assessed. (2) LbL films built for optimal TA presence. (3) Emulsions built as per LbL design and TA action evaluated.

Nanoparticles in Polyelectrolyte Multilayer Layer-by-Layer (LbL) Films and Capsules—Key Enabling Components of Hybrid Coatings

Originally regarded as auxiliary additives, nanoparticles have become important constituents of polyelectrolyte multilayers. They represent the key components to enhance mechanical properties, enable activation by laser light or ultrasound, construct anisotropic and multicompartment structures, and facilitate the development of novel sensors and movable particles. Here, we discuss an increasingly important role of inorganic nanoparticles in the layer-by-layer assembly—effectively leading to the construction of the so-called hybrid coatings. The principles of assembly are discussed together with the properties of nanoparticles and layer-by-layer polymeric assembly essential in building hybrid coatings. Applications and emerging trends in development of such novel materials are also identified.

Adsorption and Release of Rose Bengal on Layer-by-Layer Films of Poly(Vinyl Alcohol) and Poly(Amidoamine) Dendrimers Bearing 4-Carboxyphenylboronic Acid

Phenylboronic acid-bearing polyamidoamine dendrimer (PBA-PAMAM)/poly(vinyl alcohol) (PVA) multilayer films were prepared through the layer-by-layer (LbL) deposition of PBA-PAMAM solution and PVA solution. PBA-PAMAM/PVA films were constructed successfully through the formation of boronate ester bonds between the boronic acid moiety in PBA and 1,3-diol units in PVA. When the (PBA-PAMAM/PVA)5 films were immersed in rose bengal (RB) solution, RB was adsorbed onto the LbL films. The amount of RB adsorbed was higher in the LbL films immersed in acidic solution than in basic solution. The release of RB from the LbL films was also promoted in the basic solution, while it was suppressed in the acidic solution. The boronic acid ester is oxidized to phenol by hydrogen peroxide (H2O2) and the carbon-boron bond is cleaved, so that the (PBA-PAMAM/PVA)5 films can be decomposed by immersion in H2O2 solution. Therefore, when RB-adsorbed (PBA-PAMAM/PVA)5 films were immersed in H2O2 solution, the release of RB was moderately promoted when the solution was weakly acidic.