Abstract This work provides a convenient strategy for preparation of conducting polycaprolactone (PCL)/polyaniline (PAni) nanofibers, useful for development of optoelectronic sensors and devices. PCL/PAni nanofibers were obtained by electrospinning technique and characterized by SEM, FTIR, thermal analysis, and DC electrical conductivity. The influence of the experimental conditions in the electrospinning process, such as the applied voltage, on the nanofiber morphology was discussed in detail. Incorporation of PAni into PCL nanofibers significantly increased the electrical conductivity from a non-detectable level for the neat PCL to 0.032 ± 0.022 S/cm for the nanofibers containing 7.5 wt.% PAni. Therefore, electrospun PCL/PAni nanofiber mats presented optical and electrical properties, that awaken the possibility of applications for these materials as acid-base sensors and electrochromic devices.
Graphical Abstract Abstract Polymers are a class of soft materials with numerous and versatile mechanical and chemical properties that can be tuned specific to their application. Agriculture is an expanding area due to the requirement for indispensable food to meet the demands of a growing global population. Consequently, development of technology to improve the quality of the soil and agriculture manages is still under development. Intelligent agricultural supplies (controlled or slow release agrochemicals and superabsorbents) and biosorbents contribute to an expanding niche using technology from polymers. This review elucidates the state-of-the-art and will discuss some important aspects of using polymers in intelligent fertilizers, as well as superabsorbent, biosorbent and biodegradation processes in agriculture that are environmentally, technically, socially, and economically sustainable.
ABSTRACT: Agriculture has sought ways to increase food production to meet global demands, intensifying dependence on natural resources. An alternative for intensive production has relied on the use of “smart” fertilizers that release nutrients in a controlled manner. Biodegradable polymers containing fertilizers has presented economic and environmental advantages when applied to the soil, as they release water and nutrients gradually to the environment without leaving residues. The objective of this study was to monitor the behavior of chitosan-clay hybrid microspheres, used as potassium nitrate soil ferti-releaser in lettuce cultivation. The experiment consisted of two treatments: (i) application of ferti-releasing chitosan-clay microspheres and (ii) use of conventional fertilization. Both treatments were monitored with TDR probes to measure electrical conductivity and soil moisture. The results indicate that both moisture and electrical conductivity are higher in soils treated with the ferti-releasing material. In addition, there was a gradual and homogenous release if compared to the conventional fertilization. The statistical analysis showed that the microspheres were efficient mainly for the controlled nitrogen release.
The use of controlled release fertilizers is a trend for improving productivity, reducing costs and environmental pollution. Such materials release gradually the nutrients to the plant in order to supply its requirement and are an alternative to improve fertilization. The preparation of a microsphere from natural materials (chitosan and montmorilonite clay) added with nutrients, according to the needs of plants nutritional, is one of the main motivations of this work. The addition of lamellar silicates as natural clays is a promising alternative to increase water and chemical compounds sorption capacity. In the present chitosan/montmorilonite clay composites were prepared via inversion phase and thermal, structural and morphologically studies were performed. The release of the KNO3 was realized in water using conductimetry and time domain reflectometry technique was used to monitor the in situ release in soil. Double coated microspheres provide the better nutrient encapsulation and a swelling of 200% was observed. The release was influenced by pH and fast release was observed for pH 4 and 5.5. According to the soil tests a slow release was observed since the KNO3 delivery was accompanied during 60 days showing higher values in the first ten days and a constant value until 60 days.
Hybrid materials based on polyaniline (PAni) were obtained by in situ polymerization of aniline with chitosan and/or organically modified clay (nanomer I-24) in HCl. The samples were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and direct current (DC) electrical conductivity. Thin films of PAni, PAni-clay, PAni-chitosan and PAni-chitosan-clay were prepared by casting a solution of each sample in N-methyl-2-pyrrolidone (NMP) onto indium tin oxide (ITO)/glass electrodes and their electrochromic properties were investigated. It was observed color variation from transparent yellow in the reduced state (E = -0.2 V vs. Ag/AgCl), green in the intermediate state (E = 0.5 V) and dark blue in the oxidized state (E = 0.8 V) for all samples. The color changes of each material in function of the applied potential were tracked using the Commission Internationale de l'Eclairage (CIE) system of colorimetry, in which the color change was much more significant for PAni-clay film.
Abstract In this work, conductive polymers were prepared based on polypyrrole (PPy) and its blends with epoxy resin. The chemical syntheses of PPy used two oxidants (Fe2(SO4)3 and FeCl3.6H2O) and two surfactants (DBSNa and DBSA). PPy samples and their blends were characterized by scanning electron microscopy, electrical conductivity by four points, and measurements of complex parameters of electric permittivity (ε) and magnetic permeability, in the frequency range of 8.2 to 12.4 GHz. The micrographs of the fractured surfaces show that the PPy synthetized in the presence of surfactants has particles with smaller diameters, and the oxidant sulfate favored the formation of elongated structures, called fillets. The analysis of the blends found a homogeneous distribution of PPy clusters in epoxy resin matrix, which did not favor the electrical conductivity of these materials. On the other hand, the measurements of the complex parameters of the permittivity show that the blends have increasing values when the PPy concentration is increased in the epoxy resin.
Abstract The aim of this work was modulate the emission properties and improve thermal stability of a conjugated polymer incorporated into an inorganic matrix. Hybrid material was prepared based on poly(9,9-dioctylfluorene-co-phenylene (PF) and montmorillonite (Na+Mt) clay using wet impregnation of 10, 30 and 50 wt.% of PF into Na+Mt and Na+Mt intercalated with ammonium quaternary salts (hexadecyltrimethylammonium — HDTMA) in a different proportions (OMt-1 and OMt-2). The materials were characterized by infrared and UV-Vis spectroscopy, fluorescence, X-ray diffratometry and thermogravimetry analysis. The results show that the presence of the clay alters the photoluminescent and thermal properties. Nevertheless, the degree of the clay organophilization and the clay content influences the luminescent properties due to the diverse interaction behavior between the polymer and clay. The sodium clay acted only as dispersing agent since no intercalation process occurs and the emission displacement is assigned to this behavior. In this case the PF emission displace from 402 to 395 nm. A nonlinear displacement is observed for PF/OMt-2 due the difficulties to conclude if the intercalation of the polymer occurs (379, 403 and 412 for hybrid with 10, 30 and 50%, respectively). For PF/OMt-1 a higher displacements for lower wavelength is observed due to intercalation of polymer chains and subsequent isolation in the interlamellar space, especially with material with 10 and 30% of PF in the hybrid material, whose displacement reached to 360 nm. All these results show that is possible to try to control the emission of the conjugated hybrid material changing the rate of the material.
In this work different samples of polypyrrole (PPy) were synthesized varying the combination of FeCl3 and Fe2(SO4)3 as oxidant agents and sodium dodecylbenzenesulfonate (DBSNa) and dodecylbenzenesulfonic acid (DBSA) as surfactants. Infrared spectroscopy analyses showed no significant differences in the chemical structures of synthesized PPy samples. However, thermogravimetric, electrical conductivity and X-ray diffraction analyses showed that the anionic surfactants favored the preparation of samples which are more thermally stable, conducting and with a more ordered crystallographic structure. Reflectivity measurements of PPy/epoxy resin blends, in the frequency range from 8 to 12 GHz, showed microwave attenuation up to 95% of the incident radiation.
Neste trabalho diferentes amostras de polipirrol (PPi) foram sintetizadas variando a combinação dos oxidantes FeCl3 e Fe2(SO4)3 e dos surfactantes docecilbenzenosulfonato de sódio (DBSNa) e ácido dodecilbenzenosulfônico (DBSA). Análises por espectroscopia na região do infravermelho não apresentam diferenças significativas na estrutura química das amostras de PPi sintetizadas. No entanto, análises termogravimétricas, de condutividade elétrica e de difração de raios X mostram que os surfactantes aniônicos favorecem a obtenção de amostras mais estáveis termicamente, condutoras e ordenadas cristalograficamente. Medidas de refletividade de blendas de PPi com resina epóxi, na faixa de 8 a 12 GHz, mostram valores de atenuação de micro-ondas de até 95% da radiação incidente.
Two imidazolium-based ionic liquids (C4MIMTf2N and C4MIMBF4) were used to verify their influence on polyaniline (PANI) and nitrile rubber (NBR)/PANI blend properties and the vulcanization process. High conductivity values were observed for PANI-C4MIMTf2N samples and no interference was found for the C4MIMBF4 samples. These materials were added to NBR by mechanical mixing. Based on the torque results, the presence of C4MIMBF4 does not protect the vulcanization reaction of NBR with PANI as performed by C4MIMTf2N. The highest conductivity value was obtained with 7 wt. % of PANI-DSBA-C4MIMTf2N (10-6 S/cm). This result is attributed to the more effective interaction of PANI and NBR phases promoted by the ionic liquid.
Composite materials have attracted the attention of numerous researchers due to the distinct properties shown by this class of materials and the mineral clay used in their synthesis. In this study, conductive composites were obtained by mixing polyaniline (PAni) with clay (kaolinite and montmorillonite). The aniline was polymerized in a medium with clay and the powder was characterized by X ray diffraction, electrical conductivity and morphology. The results suggest PAni chain linearization in a kaolinite medium. The addition of montmorillonite resulted in PAni chain linearization and intercalation of mineral clay, although the montmorillonite was not pretreated. The PAni-clay composites showed an electrical conductivity of 0.01 S.cm-1, which appeared not to be influenced by the amount of clay used.
It is a known fact that the adequate combination of components and experimental conditions may produce materials with specific requirements. This study presents the effect of carbon fiber fabric impregnation with polyaniline conducting polymer aiming at the radar absorbing material processing. The experiments consider the sample preparation with one and two impregnations. The prepared samples were evaluated by reflectivity measurements, in the frequency range of 8-12 GHz and scanning electron microscopy analyses. The correlation of the results shows that the quantity of impregnated material influences the performance of the processed microwave absorber. This study shows that the proposed experimental route provides flexible absorbers with absorption values of the incident radiation close to 87%.
In this work, conducting paints based on blends of polyurethane and polyaniline in different proportions were prepared. The effects of both, polyaniline doping method and the blend processing time on the paint rheological behavior were evaluated. It was observed that the doping of the polyaniline with dodecylbenzene sulphonic acid (DBSA) by reactive processing (PAni-DBSA-pr) altered the paint complex viscosity due to the excess of the DBSA used in that doping process. This effect was observed during the rheological analyses by controlling the resting time of the prepared samples. FTIR analyses were carried out to verify possible interactions among the components of the mixture (polyurethane and polyaniline), suggesting that no chemical reactions occurred, but only physical interactions. It was also observed that samples containing 15% (w/w) of PAni-DBSA-pr attenuated nearly 48% of the incident electromagnetic radiation, at around 1112 GHz, showing the applying potential of this paint as radar absorbing material.
Neste trabalho preparou-se tintas condutoras baseadas em blendas de poliuretano contendo polianilina em diferentes proporções. Estudou-se as influências do método de dopagem da polianilina (PAni) e do tempo de processamento da mistura no comportamento reológico da tinta. Verificou-se que a dopagem, com o ácido dodecilbenzeno sulfônico (DBSA), por processamento reativo (PAni-DBSA-pr) afetou, de maneira mais acentuada, a viscosidade da tinta devido, principalmente, ao excesso de ácido dopante presente nessa amostra. Esse efeito foi observado pelas análises reológicas devido às alterações nos valores de viscosidade complexa, controlando-se o tempo de repouso das misturas. Medidas espectrofotométricas na região do infravermelho foram realizadas para verificar a ocorrência de interações entre os componentes da mistura (o poliuretano e a polianilina), constatando-se que, possivelmente, não ocorreram ligações químicas, mas somente interações físicas. Observou-se também que, amostras contendo 15% (m/m) de PAni-DBSA-pr absorveram aproximadamente 48% da radiação eletromagnética incidente (8-12 GHz), indicando a viabilidade do uso desta tinta como material absorvedor de radiação.
In this work the EPDM elastomer was mixed with Polyaniline (PAni) doped with dodecilbenzene sulfonic acid (DBSA) using a molar ratio of 1:3 of PAni:DBSA. The EPDM mixture with 40%(w/w) of PAni-(DBSA)3 was carried out using an internal mixer chamber with two rotors coupled to a Haake Rheocord 90 at 150°C and 30 rpm. Aliquots were taken during the processing time of 5, 10, 20, 30 and 40 min, and the morphology was evaluated by SEM. The morphology of the blends markedly changes as a function of processing time, from a compact, at 5 min to a sponge-like morphology at 30 and 40 min. These differences influence the material properties, such as electromagnetic radiation absorption of radar absorbing materials (RAM).
Neste trabalho, o elastômero EPDM foi misturado à Polianilina (PAni) a qual foi dopada com ácido dodecilbenzeno sulfônico (DBSA) na razão molar 1:3. A mistura de EPDM contendo 40%(m/m) de PAni-(DBSA)3 foi realizada em um misturador interno de dois rotores, acessório do reômetro Haake Rheocord 90, a 150°C e 30 rpm. Foram recolhidas amostras em 5, 10, 20, 30 e 40 min de processamento e a morfologia foi avaliada por MEV. A análise microscópica da superfície da amostra mostrou fases completamente distintas em função do tempo de mistura, passando de uma estrutura de duas fases compacta (5 min) até o aparecimento de uma estrutura "tipo esponja" (30 e 40 min). Estas diferenças afetam as propriedades do material como, por exemplo, o comportamento de absorção de radiação eletromagnética de materiais absorvedores de radiação (MARE).
The search for new materials possessing magnetic and dieletric properties adequated to be used as radar absorbing materials has been of great importance. Among the materials under study, conducting polymers have been applied due to the possibility of variation of their conductivity with the frequency of the incident radiation. These research areas have been considered the state of the art in the processing of radar absorbing materials. The aim of this work is to present the large range of properties of the conducting polymers and their correlation with the potential application of these materials as electromagnetic radiation absorbers. Some results are also presented on blends of EPDM and 30-80% (w/w) of PAni-DBSA with thickness of 1 and 3 mm, analysed in the range of 8-12 GHz, which absorbed in the range of 50-90% of incident radiation.
A procura por novos materiais que possuam propriedades magnéticas e dielétricas adequadas ao uso em absorvedores de radiação eletromagnética é de grande importância. Dentre os materiais em estudo, os polímeros condutores têm sido aplicados como centros de absorção de radiação, devido à possibilidade de variação da sua condutividade com a freqüência da radiação das ondas incidentes, sendo esta pesquisa o estado da arte no processamento de materiais absorvedores de radiação (MAR). O objetivo deste trabalho é apresentar a ampla faixa de propriedades dos polímeros condutores, correlacionando-as com o potencial de aplicação destes materiais como aditivos no processamento de MAR. Uma breve análise dos resultados obtidos com uma blenda de EPDM contendo 30-80 %(m/m) de PAni-DBSA e espessuras de 1 e 3 mm, analisadas na faixa de 8-12 GHz, mostra que o material absorveu na faixa de 50 a 90% da radiação incidente.