Probing the dependence of the properties of cellulose acetates and their films on the degree of biopolymer substitution: use of solvatochromic indicators and thermal analysis

Although cellulose acetates, CAs, are extensively employed there is scant information about the systematic dependence of their properties on their degree of substitution, DS; this is the subject of the present work. Nine CAs samples, DS from 0.83 to 3.0 were synthesized; their films were prepared. The following solvatochromic probes have been employed in order to determine the empirical polarity, E (T)(33); ""acidity, alpha""; ""basicity, beta"", and ""dipolarity/polarizability, pi*"" of the casted films: 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl) phenolate, WB; 4-nitroaniline; 4-nitroanisole; 4-nitro-N,N-dimethylaniline; 2,6-diphenyl-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, RB. Additionally, two systems, ethanol plus ethyl acetate (EtOH-EtAc), and cellulose plus cellulose triacetate, CTA, were employed as models for CAs of different DS. Regarding the model systems, the following was observed: (i) For EtOH-EtAc, the dependence of all solvatochromic parameters on the ""equivalent-DS"" of the binary mixture was non-linear because of preferential solvation; (ii) The dependence of E (T)(33) on equivalent DS of the cellulose-CTA films is linear, but the slope is smaller than that of the corresponding plot for CAs. This is attributed to the more efficient hydrogen bonding in the model system, a conclusion corroborated by IR measurements. The dependence of solvatochromic parameters of CAs on their DS is described by the simple equations; a consequence of the substitution of the OH by the ester group. The thermal properties of bulk CAs samples were investigated by DSC and TGA; their dependence on DS is described by simple equations. The relevance of these data to the processing and applications of CAs is briefly discussed.

Economia evolucionária e path dependence do investimento externo japonês: um estudo do Leste Asiático no período pré Segunda Guerra Mundial

A abertura da economia e o reinício das relações econômicas japonesas com o exterior e o processo de industrialização da economia japonesa na Era Meiji levaram o Japão a investir no exterior. Os investimentos japoneses no exterior cresceram preponderantemente no Leste Asiático, concentrando-se nessa área até o término da Segunda Guerra Mundial. A tese mostra que existem restrições de caráter institucional e histórico, que impõem limitações às empresas quanto ao leque de opções para investirem no exterior. Uma vez que as empresas japonesas fizeram a opção, impostas por aquelas restrições, de investir no Leste Asiático, feedbacks positivos, propiciados pelos eventos históricos e institucionais, geraram auto-reforços, levando a um resultado de inflexibilidade - lock-in - para sair dessa região. A tese comprova que explicar os investimentos externos japoneses pelo modelo de economia evolucionária, através do processo de path dependence, que incorpora o caráter institucional e histórico, é mais plausível do que as interpretações convencionais.

The effects of commodity dependence on the brazilian economy: a test of the dutch disease hypothesis

A doença holandesa tornou-se amplamente conhecida na década de 1960, quando a descoberta repentina de reservatórios de gás natural em território holandês, na região do mar do norte, transformou o país em uma economia rica em recursos. A desagradável consequência que proveio da recém-adquirida abundância de commodities foi o declínio da próspera indústria holandesa, que perdeu sua competitividade devido à valorização do florim holandês, como consequência do aumento do influxo de capital estrangeiro no país. Desde então este fenômeno tem sido observado em diversos países que possuem abundância de commodities. O objetivo desta tese é aplicar o modelo da doença holandesa ao Brasil, já que a maior economia da América latina poderá também ter de encarar a ameaça de se tornar prisioneira da “armadilha das commodities”, devido à sua abundância de recursos naturais. O autor revisa a bibliografia básica abordando o tema geral da doença holandesa e dá enfoque a estudos realizados anteriormente no Brasil. Além disso, os quatro maiores sintomas que caracterizam a doença holandesa são testados: (1) valorização das taxas de câmbio do real, (2) declínio do setor industrial, (3) crescimento do setor de serviços, e (4) aumento dos salários. Todos estes sintomas foram observados e podem ser comprovados através das abordagens de cointegração ou de correlação, com exceção do sintoma número dois. Ainda que estes resultados sejam significativos, há muito outros fatores determinantes que influenciam o desenvolvimento dos sintomas examinados, motivo pelo qual futuros estudos serão necessários para se obtiver conclusões definitivas sobre como o Brasil é afetado pela doença holandesa.

Dependence of the electrical conductivity and elastomeric properties on sample preparation of blends of polyaniline and natural rubber

Blend films (free-standing) containing 20% in volume of polyaniline (PANI) in 80% of natural rubber (NR) were fabricated by casting in three different ways: (1) adding PANI-EB (emeraldine base) dissolved in N-methyl-2-pyrrolidone (NMP) to the latex (NRL), (2) adding PANI-EB dissolved in in-cresol to NR dissolved in xylol (NRD), (3) overlaying the surface of a pure NR cast film with a PANI layer grown by in situ polymerization (NRO). All the films were immersed into HCl solution to achieve the primary doping (protonation) of PANI before the characterization. The main goal here was to investigate the elastomeric and electrical conductivity properties for each blend, which may be applied as pressure and deformation sensors in the future. The characterization was carried out by optical microscopy, dc conductivity, vibrational spectroscopy (infrared absorption and Raman scattering), thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile stress-strain curves. The results suggest that the NRL blend is the most suitable in terms of mechanical and electrical properties required for applications in pressure and deformation sensors: a gain of conductivity without losing the elastomeric property of the rubber. (c) 2005 Wiley Periodicals, Inc.

Resonant excitation of Mn local vibrational modes in the higher order Raman spectra of nanocrystalline Ga(1-x)Mn(x)N films

The effect of manganese on the vibrational properties of Ga(1-x)Mn(x)N (0 <= x <= 0.18) films has been investigated by Raman scattering using 488.0 and 632.8 nm photon excitations. The first-order transverse and longitudinal optical GaN vibrational bands were observed in the whole composition range using both excitations, while the corresponding overtones, as well as a prominent peak located in 1238 cm(-1) (153.5 meV) were only observed in the Mn-containing films under 488.0 nm excitation. We propose that the peak observed at 1238 cm(-1) is due to resonant Mn local vibrational modes, the excitation process being related to electronic transitions involving the Mn acceptor band.

Optical and electrical properties of polymerizing plasmas and their correlation with DLC film properties

Diamond-like carbon (DLC) films were grown from radiofrequency plasmas of acetylene-argon mixtures, at different excitation powers, P. The effects of this parameter on the plasma potential, electron density, electron temperature, and plasma activity were investigated using a Langmuir probe. The mean electron temperature increased from about 0.5 to about 7.0 eV while the mean electron density decreased from about 1.2x10(9) to about 0.2x10(9) cm(-3) as P was increased from 25 to 150 W. Both the plasma potential and the plasma activity were found to increase with increasing P. Through actinometric optical emission spectrometry, the relative concentrations of CH, [CH], and H, [H], in the discharge were mapped as a function of the applied power. A rise in [H] and a fall in [CH] with increasing P were observed and are discussed in relation to the plasma characteristics and the subimplantation model. The optical properties of the films were calculated from ultraviolet-visible spectroscopic data; the surface resistivity was measured by the two-point probe method. The optical gap, E(G), and the surface resistivity, rho(s), fall with increasing P. E(G) and rho(s) are in the ranges of about 2.0-1.3 eV and 10(14)-10(16) Omega/square, respectively. The plasma power also influences the film self-bias, V(b), via a linear dependence, and the effect of V(b) on ion bombardment during growth is addressed together with variation in the relative densities of sp(2) and sp(3) bonds in the films as determined by Raman spectroscopy.

Experimental analysis of harmonic distortions in the excitation currents of double-excited three-phase transformers

This paper shows the results of experimental investigations of three-phase banks composed of single-phase transformers and three-phase three-limb core transformers under simultaneous alternating and direct current excitations, for several winding connections. Harmonic analysis of excitation currents for different de saturation levels is performed.