Electroactive and biocompatible fibrous
scaffolds have been prepared
and characterized using polyaniline (PAni) doped with dodecylbenzenesulfonic
acid (DBSA) combined with poly(lactic acid) (PLA) and PLA/poly(ethylene
glycol) (PEG) mixtures. The composition of simple and core–shell
fibers, which have been obtained by both uniaxial and coaxial electrospinning,
respectively, has been corroborated by Fourier-transform infrared
and micro-Raman spectroscopies. Morphological studies suggest that
the incorporation of PEG enhances the packing of PLA and PAni chains,
allowing the regulation of the thickness of the fibers. PAni and PEG
affect the thermal and electrical properties of the fibers, both decreasing
the glass transition temperature and increasing the electrical conductivity.
Interestingly, the incorporation of PEG improves the PAni-containing
paths associated with the conduction properties. Although dose response
curves evidence the high cytotoxicity of PAni/DBSA, cell adhesion
and cell proliferation studies on PLA/PAni fibers show a reduction
of such harmful effects as the conducting polymer is mainly retained
inside the fibers through favorable PAni···PLA interactions.
The incorporation of PEG into uniaxial fibers resulted in an increment
of the cell mortality, which has been attributed to its rapid dissolution
into the culture medium and the consequent enhancement of PAni release.
In opposition, the delivery of PAni decreases and, therefore, the
biocompatibility of the fibers increases when a shell coating the
PAni-containing system is incorporated through coaxial electrospinning.
Finally, morphological and functional studies using cardiac cells
indicated that these fibrous scaffolds are suitable for cardiac tissue
engineering applications.
Resumo: O conhecimento da estabilidade térmica da madeira e materiais celulósicos é um importante fator na utilização destes materiais de fontes naturais como carga de reforço em matrizes poliméricas. Entretanto, estes materiais possuem baixa resistência à degradação térmica causado principalmente pela presença de espécies voláteis que entram em ignição em baixas temperaturas. Características dessa natureza contribuem significativamente na limitação do uso de tais materiais como cargas de reforços em situações que exigem temperaturas mais elevadas. Neste trabalho é avaliada a degradação térmica de duas espécies de madeira, em atmosfera de nitrogênio, por meio de medidas termogravimétricas. Os parâmetros cinéticos de decomposição térmica foram estimados com o método proposto por Flynn-Wall-Ozawa (FWO). A Garapeira apresentou energia de ativação menor nas frações reação até 0,4. Na fração de reação de 0,9 foi observada a maior diferença de energia de ativação entre as espécies de madeira. O mecanismo de reação para duas espécies é basicamente controlado por difusão (D n ) até a fração de reação de 0,8, sendo que após segue cinética de terceira ordem (F 3 ). Palavras-chave: Madeira, degradação térmica, energia de ativação, reação no estado sólido.
Nonisothermal Degradation of Wood Using Thermogravimetric MeasurementsAbstract: The thermal stability of wood and cellulosic materials is an important factor for applications of these natural renewable materials as fillers for reinforcing polymeric matrices. However, these materials have low thermal stability caused mainly by species that ignite at low temperatures. These characteristics contribute significantly to limit their use in situations where higher temperatures are required. In this work, the thermal degradation of two kinds of wood (Pinus and Garapeira) was evaluated using thermogravimetric measurements under nitrogen atmosphere. The parameters of thermal decomposition kinetics were estimated using the Flynn-Wall-Ozawa (FWO) method. The Garapeira wood showed lower activation energy at reaction degrees below 0.5, probably due to the presence of volatiles compounds, such as oil and wax. The Pinus wood had different characteristics in the initial reaction degree (up to 0.4). After this point, however, Garapeira becomes more stable than Pinus due to the formation of more thermally stable species and because of the higher amount of lignin. Besides, the thermal degradation processes of both woods were found to be mainly controlled by diffusion (D n ) of volatile species at reaction degrees up to 0.8, achieving a third order (F 3 ) mechanism afterwards.
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