HYDROLYTIC DEGRADATION BEHAVIOR OF PLLA NANOCOMPOSITES REINFORCED WITH MODIFIED CELLULOSE NANOCRYSTALS

Bionanocomposites derived from poly(L-Lactide) (PLLA) were reinforced with chemically modified cellulose nanocrystals (m-CNCs). The effects of these modified cellulose nanoparticles on the mechanical and hydrolytic degradation behavior of polylactide were studied. The m-CNCs were prepared by a method in which hydrolysis of cellulose chains is performed simultaneously with the esterification of hydroxyl groups to produce modified nanocrystals with ester groups. FTIR, elemental analysis, TEM, XRD and contact angle measurements were used to confirm and characterize the chemical modifications of the m-CNCs. These bionanocomposites gave considerably better mechanical properties than neat PLLA based on an approximately 100% increase in tensile strength. Due to the hydrophobic properties of the esterified nanocrystals incorporated into a polymer matrix, it was also demonstrated that a small amount of m-CNCs could lead to a remarkable decrease in the hydrolytic degradation rate of the biopolymer. In addition, the m-CNCs considerably delay the degradation of the nanocomposite by providing a physical barrier that prevents the permeation of water, which thus hinders the overall absorption of water into the matrix. The results obtained in this study show the nanocrystals can be used to reinforce polylactides and fine-tune their degradation rates in moist or physiological environments.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

Photoacoustic spectroscopy provides information about both amplitude and phase of the response of a system to an optical excitation process. This paper presents the studies of the phase in the electron transfer process between octaethylporphyn (OEP) and quinone molecules dispersed in a polymeric matrix. It was observed a tendency in the phase behavior to small values only in the spectral region near to 620 nm, while for shorter wavelength did not show any tendency. These measurements suggested that the electron transfer to acceptor occurred with the participation of octaethylporphyn singlet excited state.

Preparation and thermal behavior of mixture of basic carbonate and 4-dimethylaminocinnamylidenepyruvate with lanthanides (III) and yttrium (III) in the solid state

Solid Ln-OHCO3-DMCP compounds, where Ln represents lanthanides (III) and yttrium (III) ions and DMCP is the anion 4-dimethylaminocinnamylidenepyruvate, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), x-Ray diffraction powder patterns and elemental analysis have been used to characterize the compounds. The thermal stability as well as the thermal decomposition of these compounds were studied using an alumina crucible in an air atmosphere.

Amphoteric behavior of di-2-pyridyl ketone benzoylhydrazone in ethanol-water mixtures

The ligand di-2-pyridyl ketone benzoylhydrazone (DPKBH) is widely used for the determination of transition metal ions in environmental samples. Due to its low solubility in water it is used in aqueous-ethanol (1:1) solvent and for higher sensitivity the pH must be properly adjusted. The properties of DPKBH solutions must be known at different ethanol-water percentages in order to achieve higher sensitivity and/or selectivity for metal analysis. The acid-base behavior of this reagent in aqueous-ethanol solvent and the dissociation/ionization constants (pK1 and pK2) of DPKBH have been determined in different aqueous-ethanol solvent mixtures (10, 20, 30 and 50 % V/V of ethanol) from potentiometric titrations at 25.0 ± 0.1° C. As the amount of ethanol increases from 10 to 30% the pK1 and pK2 values increased, but they decreased in 50% of the organic solvent. The results are correlated with the medium composition and its effects.

Thermal behavior of corn starch granules modified by acid treatment at 30 and 50°C

Unprocessed native starches are structurally too weak and functionally too restricted for application in today's advanced food technologies. Processing is necessary to engender a range of functionality. Naturals or natives starches can be modified by using several methods physical, chemical, enzymatic or combined, according industrial purposes. In this work, native corn starch was hydrolyzed by hydrochloric acid solution and investigated by using thermoanalytical techniques (thermogravimetry - TG, differential thermal analysis - DTA and differential scanning calorimetry - DSC), as well as optical microscopy and X-ray diffractometry. After acid treatment at 30 and 50°C, a decrease of gelatinization enthalpy (ΔHgel) was verified. Optical microscopy and X-ray diffractometry allowed us to verify the granules contorn and rugosity typical of cereal starches.

Environmental behavior of soils and mixtures of soil-whitewash mud

The present study sought to observe the behavior of soils in natural state and in mixtures, in different ratios, with the industrial solid residue called whitewash mud. The work was conducted with samples of typical soils from the region of Alagoinhas, Bahia-Brazil. Wet chemical analysis and atomic absorption spectrophotometry were used in order to obtain the classification of the industrial solid residue. Solubilization and leaching tests were performed and X-ray diffraction and electron microscopy techniques were carried out. The results showed that the whitewash mud was classified as non-inert, but with great capacity of heavy metal retention largely owed to the kaolinite and goethite presence in the clay fraction of the soils, making it difficult to have heavy metals readily available for exchange.

COMPARISON BETWEEN WOOD DRYING DEFECT SCORES: SPECIMEN TESTING X ANALYSIS OF KILN-DRIED BOARDS

It is important to develop drying technologies for Eucalyptus grandis lumber, which is one of the most planted species of this genus in Brazil and plays an important role as raw material for the wood industry. The general aim of this work was to assess the conventional kiln drying of juvenile wood of three clones of Eucalyptus grandis. The specific aims were to compare the behavior between: i) drying defects indicated by tests with wood specimens and conventional kiln-dried boards; and ii) physical properties and the drying quality. Five 11-year-old trees of each clone were felled, and only flatsawn boards of the first log were used. Basic density and total shrinkage were determined, and the drying test with wood specimens at 100 °C was carried out. Kiln drying of boards was performed, and initial and final moisture content, moisture gradient in thickness, drying stresses and drying defects were assessed. The defect scoring method was used to verify the behavior between the defects detected by specimen testing and the defects detected in kiln-dried boards. As main results, the drying schedule was too severe for the wood, resulting in a high level of boards with defects. The behavior between the defects in the drying test with specimens and the defects of kiln-dried boards was different, there was no correspondence, according to the defect scoring method.

Behavior of chicks subjected to thermal challenge

In the first week of a chick life, broilers are very sensitive to different conditions outside their thermoneutral zone. Thus, the goal of this study was to evaluate the behaviors and productive responses of broilers subjected to conditions of thermal comfort or challenge at different intensities (27, 30, 33 and 36ºC) and durations (1, 2, 3 and 4 days starting on the second day of life). In the experiment, ten minutes of images from each hour of each treatment were analyzed to evaluate the key behaviors of the birds. Similar behavior at different dry-bulb air temperatures were identified by using Ward's method of cluster analysis. These behaviors were grouped by dendograms in which the similarity of these data was qualified. Feed intake, water intake and body mass of these animals were evaluated and used to support the observed behaviors. Thus, a similar huddling behavior was observed in the birds from the 2nd to the 5th day of life subjected to 27ºC and 30ºC, while at 30ºC and 33ºC the behavior of accessing feeders and drinkers was also similar. Chicks subjected to 33ºC presented the best performance, and at 30 and 36ºC showed intermediate development.

Non-linear analysis of laminated metal matrix composites by an integrated micro/macro-mechanical model

The present paper describes an integrated micro/macro mechanical study of the elastic-viscoplastic behavior of unidirectional metal matrix composites (MMC). The micromechanical analysis of the elastic moduli is based on the Composites Cylinder Assemblage model (CCA) with comparisons also draw with a Representative Unit Cell (RUC) technique. These "homogenization" techniques are later incorporated into the Vanishing Fiber Diameter (VFD) model and a new formulation is proposed. The concept of a smeared element procedure is employed in conjunction with two different versions of the Bodner and Partom elastic-viscoplastic constitutive model for the associated macroscopic analysis. The formulations developed are also compared against experimental and analytical results available in the literature.

Multiple scales analysis of nonlinear oscillations of a portal frame foundation for several machines

An analytical study of the nonlinear vibrations of a multiple machines portal frame foundation is presented. Two unbalanced rotating machines are considered, none of them resonant with the lower natural frequencies of the supporting structure. Their combined frequencies is set in such a way as to excite, due to nonlinear behavior of the frame, either the first anti-symmetrical mode (sway) or the first symmetrical mode. The physical and geometrical characteristics of the frame are chosen to tune the natural frequencies of these two modes into a 1:2 internal resonance. The problem is reduced to a two degrees of freedom model and its nonlinear equations of motions are derived via a Lagrangian approach. Asymptotic perturbation solutions of these equations are obtained via the Multiple Scales Method.

Thermalhydraulic behavior of electrically heated rod during a critical heat flux transient

In nuclear reactors, the occurrence of critical heat flux leads to fuel rod overheating with clad fusion and radioactive products leakage. To predict the effects of such phenomenon, experiments are performed using electrically heated rods to simulate operational and accidental conditions of nuclear fuel rods. In the present work, it is performed a theoretical analysis of the drying and rewetting front propagation during a critical heat flux experiment, starting with the application of an electrical power step from steady state condition. After the occurrence of critical heat flux, the drying front propagation is predicted. After a few seconds, a power cut is considered and the rewetting front behavior is analytically observed. Studies performed with various values of coolant mass flow rate show that this variable has more influence on the drying front velocity than on the rewetting one.

Effect of particle morphology on the mechanical and thermo-mechanical behavior of polymer composites

Fiber reinforced polymer composites have been used in many applications, such as in automobile, aerospace and naval industries, due basically to their high strength-to-weight and modulus-to-weight, among other properties. Even though particles are usually not able to lead to the level of reinforcement of fibers, particle reinforced polymer composites have been proposed for many new applications due to their low cost, easy fabrication and isotropic properties. In this work, polymer composites were prepared by incorporating glass particles of different morphologies on poly(aryl sulfones) matrices. Particles with aspect ratios equal to 1, 2.5 and 10 were used. The prepared composites were characterized using electron microscopy and thermal analysis. Mechanical properties of the composites were evaluated using a four-point bending test. The thermo-mechanical behavior of the obtained composites was also investigated. The results showed that the morphology of the particles alter significantly the mechanical properties of composites. Particles with larger values of aspect ratio led to large elastic modulus but low levels of strain at failure. This result was explained by modeling the thermo-mechanical behavior of the composites using a viscoelastic model. Parameters of the model, obtained from a Cole-Cole type of plot, demonstrated that interactions at the polymer-reinforcing agent interface were higher for composites with large aspect ratio particles. Higher levels of interactions at interfaces can lead to higher degrees of stress transfer and, consequently, to composites with large elastic modulus, as experimentally observed.

Experimental Analysis of Fracture Processes in Concrete

This paper draws on the basic problems related to the determination of parameters to characterize the structural behavior of concretes using Fracture Mechanics concepts. Experimental procedures and results are discussed.

Analysis of Regular and Irregular Dynamics of a Non Ideal Gear Rattling Problem

This paper presents a study on the dynamics of the rattling problem in gearboxes under non-ideal excitation. The subject has being analyzed by a number of authors such as Karagiannis and Pfeiffer (1991), for the ideal excitation case. An interesting model of the same problem by Moon (1992) has been recently used by Souza and Caldas (1999) to detect chaotic behavior. We consider two spur gears with different diameters and gaps between the teeth. Suppose the motion of one gear to be given while the motion of the other is governed by its dynamics. In the ideal case, the driving wheel is supposed to undergo a sinusoidal motion with given constant amplitude and frequency. In this paper, we consider the motion to be a function of the system response and a limited energy source is adopted. Thus an extra degree of freedom is introduced in the problem. The equations of motion are obtained via a Lagrangian approach with some assumed characteristic torque curves. Next, extensive numerical integration is used to detect some interesting geometrical aspects of regular and irregular motions of the system response.