Benzoxazine Resin/Carbon Nanotube Nanostructured Composite's Degradation Kinetic

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nonoxidative thermal degradation kinetic of polyamide 6,6 reinforced with carbon nanotubes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Kinetic model of poly(3-hydroxybutyrate) thermal degradation from experimental non-isothermal data

The non-isothermal data given by TG curves for poly(3-hydroxybutyrate) (PHB) were studied in order to obtain a consistent kinetic model that better represents the PHB thermal decomposition. Thus, data obtained from the dynamic TG curves were suitably managed in order to obtain the Arrhenius kinetic parameter E according to the isoconversional F-W-O method. Once the E parameters is found, a suitable logA and kinetic model (f(alpha)) could be calculated. Hence, the kinetic triplet (E +/- SD, logA +/- SD and f(alpha)) obtained for the thermal decomposition of PHB under non-isothermal conditions was E=152 +/- 4 kJ mol(-1), logA=14.1 +/- 0.2 s(-1) for the kinetic model, and the autocatalytic model function was: f(alpha)=alpha(m)(1-alpha)(n)=alpha(0.42)(1-alpha)(0.56).

Kinetic studies on clavulanic acid degradation

Clavulanic acid (CA), a potent beta-lactamase inhibitor, is very sensitive to pH and temperature. It is produced by Streptomyces clavuligerus and to optimize both the fermentation step and the downstream process, the expression of the hydrolysis kinetics has to be determined. In the present work the CA degradation rate from various sources was investigated at temperatures of 10, 20, 25, 30 and 40degreesC and PH values of 6.2 and 7.0. The results showed that first-order kinetics explained very well the hydrolysis kinetics and the Arrhenius equation could be applied to establish a relationship between the degradation rate constant and temperature, at both pHs. It has been observed that CA from fermentation medium was much more unstable than that from standard solution and from a commercially available medicine. Also, it was observed that CA was more stable at PH 6.2 than at pH 7.0, irrespective of the CA source. (C) 2004 Elsevier B.V. All rights reserved.

Biheterocyclic ligands: synthesis, characterization and coordinating properties of bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes with transition metal ions and their thermokinetic and biological studies

The Co(II), Ni(II) and Cu(II) metal ions complexes of Bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes (BATs) have been prepared and characterized by elemental analysis, conductivity measurements infrared, magnetic susceptibility, the electronic spectral data and thermal studies. Based on spectral and magnetic results, the ligands are tetradentate coordinating through the N and S-atoms of BATs; six-coordinated octahedral or distorted octahedral and some times four-coordinated square planar were proposed for these complexes. Activation energies computed for the thermal decomposition steps were compared. The ligands and their metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive, two gram-negative bacteria and two fungal species were found to vary from moderate to very strong.

Development of Elastomeric Hybrid Composite Based on Synthesised Manosilica and Short Nylon Fiber

Nanoscale silica was synthesized by precipitation method using sodium silicate and dilute hydrochloric acid under controlled conditions. The synthesized silica was characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), BET adsorption and X-Ray Diffraction (XRD). The particle size of silica was calculated to be 13 nm from the XRD results and the surface area was found to be 295 m2/g by BET method. The performance of this synthesized nanosilica as a reinforcing filler in natural rubber (NR) compound was investigated. The commercial silica was used as the reference material. Nanosilica was found to be effective reinforcing filler in natural rubber compound. Filler-matrix interaction was better for nanosilica than the commercial silica. The synthesized nanosilica was used in place of conventional silica in HRH (hexamethylene tetramine, resorcinol and silica) bonding system for natural rubber and styrene butadiene rubber / Nylon 6 short fiber composites. The efficiency of HRH bonding system based on nanosilica was better. Nanosilica was also used as reinforcing filler in rubber / Nylon 6 short fiber hybrid composite. The cure, mechanical, ageing, thermal and dynamic mechanical properties of nanosilica / Nylon 6 short fiber / elastomeric hybrid composites were studied in detail. The matrices used were natural rubber (NR), nitrile rubber (NBR), styrene butadiene rubber (SBR) and chloroprene rubber (CR). Fiber loading was varied from 0 to 30 parts per hundred rubber (phr) and silica loading was varied from 0 to 9 phr. Hexa:Resorcinol:Silica (HRH) ratio was maintained as 2:2:1. HRH loading was adjusted to 16% of the fiber loading. Minimum torque, maximum torque and cure time increased with silica loading. Cure rate increased with fiber loading and decreased with silica content. The hybrid composites showed improved mechanical properties in the presence of nanosilica. Tensile strength showed a dip at 10 phr fiber loading in the case of NR and CR while it continuously increased with fiber loading in the case of NBR and SBR. The nanosilica improved the tensile strength, modulus and tear strength better than the conventional silica. Abrasion resistance and hardness were also better for the nanosilica composites. Resilience and compression set were adversely affected. Hybrid composites showed anisotropy in mechanical properties. Retention in ageing improved with fiber loading and was better for nanosilica-filled hybrid composites. The nanosilica also improved the thermal stability of the hybrid composite better than the commercial silica. All the composites underwent two-step thermal degradation. Kinetic studies showed that the degradation of all the elastomeric composites followed a first-order reaction. Dynamic mechanical analysis revealed that storage modulus (E’) and loss modulus (E”) increased with nanosiica content, fiber loading and frequency for all the composites, independent of the matrix. The highest rate of increase was registered for NBR rubber.

Studies on Advanced Oxidation Processes for the Removal of Acetamiprid from Wastewater

Pollution of water with pesticides has become a threat to the man, material and environment. The pesticides released to the environment reach the water bodies through run off. Industrial wastewater from pesticide manufacturing industries contains pesticides at higher concentration and hence a major source of water pollution. Pesticides create a lot of health and environmental hazards which include diseases like cancer, liver and kidney disorders, reproductive disorders, fatal death, birth defects etc. Conventional wastewater treatment plants based on biological treatment are not efficient to remove these compounds to the desired level. Most of the pesticides are phyto-toxic i.e., they kill the microorganism responsible for the degradation and are recalcitrant in nature. Advanced oxidation process (AOP) is a class of oxidation techniques where hydroxyl radicals are employed for oxidation of pollutants. AOPs have the ability to totally mineralise the organic pollutants to CO2 and water. Different methods are employed for the generation of hydroxyl radicals in AOP systems. Acetamiprid is a neonicotinoid insecticide widely used to control sucking type insects on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, ornamental flowers. It is now recommended as a substitute for organophosphorous pesticides. Since its use is increasing, its presence is increasingly found in the environment. It has high water solubility and is not easily biodegradable. It has the potential to pollute surface and ground waters. Here, the use of AOPs for the removal of acetamiprid from wastewater has been investigated. Five methods were selected for the study based on literature survey and preliminary experiments conducted. Fenton process, UV treatment, UV/ H2O2 process, photo-Fenton and photocatalysis using TiO2 were selected for study. Undoped TiO2 and TiO2 doped with Cu and Fe were prepared by sol-gel method. Characterisation of the prepared catalysts was done by X-ray diffraction, scanning electron microscope, differential thermal analysis and thermogravimetric analysis. Influence of major operating parameters on the removal of acetamiprid has been investigated. All the experiments were designed using central compoiste design (CCD) of response surface methodology (RSM). Model equations were developed for Fenton, UV/ H2O2, photo-Fenton and photocatalysis for predicting acetamiprid removal and total organic carbon (TOC) removal for different operating conditions. Quality of the models were analysed by statistical methods. Experimental validations were also done to confirm the quality of the models. Optimum conditions obtained by experiment were verified with that obtained using response optimiser. Fenton Process is the simplest and oldest AOP where hydrogen peroxide and iron are employed for the generation of hydroxyl radicals. Influence of H2O2 and Fe2+ on the acetamiprid removal and TOC removal by Fenton process were investigated and it was found that removal increases with increase in H2O2 and Fe2+ concentration. At an initial concentration of 50 mg/L acetamiprid, 200 mg/L H2O2 and 20 mg/L Fe2+ at pH 3 was found to be optimum for acetamiprid removal. For UV treatment effect of pH was studied and it was found that pH has not much effect on the removal rate. Addition of H2O2 to UV process increased the removal rate because of the hydroxyl radical formation due to photolyis of H2O2. An H2O2 concentration of 110 mg/L at pH 6 was found to be optimum for acetamiprid removal. With photo-Fenton drastic reduction in the treatment time was observed with 10 times reduction in the amount of reagents required. H2O2 concentration of 20 mg/L and Fe2+ concentration of 2 mg/L was found to be optimum at pH 3. With TiO2 photocatalysis improvement in the removal rate was noticed compared to UV treatment. Effect of Cu and Fe doping on the photocatalytic activity under UV light was studied and it was observed that Cu doping enhanced the removal rate slightly while Fe doping has decreased the removal rate. Maximum acetamiprid removal was observed for an optimum catalyst loading of 1000 mg/L and Cu concentration of 1 wt%. It was noticed that mineralisation efficiency of the processes is low compared to acetamiprid removal efficiency. This may be due to the presence of stable intermediate compounds formed during degradation Kinetic studies were conducted for all the treatment processes and it was found that all processes follow pseudo-first order kinetics. Kinetic constants were found out from the experimental data for all the processes and half lives were calculated. The rate of reaction was in the order, photo- Fenton>UV/ H2O2>Fenton> TiO2 photocatalysis>UV. Operating cost was calculated for the processes and it was found that photo-Fenton removes the acetamiprid at lowest operating cost in lesser time. A kinetic model was developed for photo-Fenton process using the elementary reaction data and mass balance equations for the species involved in the process. Variation of acetamiprid concentration with time for different H2O2 and Fe2+ concentration at pH 3 can be found out using this model. The model was validated by comparing the simulated concentration profiles with that obtained from experiments. This study established the viability of the selected AOPs for the removal of acetamiprid from wastewater. Of the studied AOPs photo- Fenton gives the highest removal efficiency with lowest operating cost within shortest time.

População protozoários ciliados e degradabilidade ruminal em búfalos e bovinos zebuínos sob dieta à base de cana-de-açúcar

Três búfalos e três bovinos zebuínos adultos com cânulas ruminais foram alimentados à vontade com dieta de cana-de-açúcar fresca e picada, suplementada com 3 kg de concentrado/animal, durante 13 semanas. Após duas semanas de adaptação, amostras do conteúdo ruminal foram coletadas semanalmente, em dois tempos de amostragem: antes da alimentação e 40 minutos após para determinação da concentração e composição da fauna ruminal. Na quinta semana do experimento, os conteúdos ruminais foram misturados e reinoculados entre animais de mesma espécie e, na última semana, estimadas as degradabilidades in situ da MS, PB e FDN da cana-de-açúcar e MS e PB do concentrado. A concentração média de protozoários foi maior em bovinos, de 4,85 x 10(5)/mL, que em búfalos, de 3,82 x 10(5)/mL. As composições genéricas para Entodinium e subfamília Diplodiniinae foram 79,2 e 6,2% em bovinos e 32,0 e 54,9% em búfalos, respectivamente. Não houve interação significativa entre espécies animais e tempo de amostragem. Houve aumento da concentração média dos holotricos após 40 minutos da alimentação. As degradabilidades efetivas dos nutrientes estudados foram semelhantes entre as duas espécies animais, observando-se diferenças na cinética da degradação. Concluiu-se que os búfalos apresentaram menor concentração de ciliados no rúmen, maior composição de Diplodiniinae e menor de Entodinium que os bovinos; os holotricos exibiram capacidade de migração e seqüestro no rúmen em ambas as espécies; e as diferenças na fauna ruminal não influenciaram a degradabilidade efetiva dos nutrientes da cana-de-açúcar e do concentrado.

Estudo da cinética de cristalização e de degradação de compósitos nanoestruturados de poliamida 6,6/nanotubos de carbonos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation of Decomposition Kinetics of Poly (Ether-Ether-Ketone) by Thermogravimetric Analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo da cinética de degradação da resina benzoxazina e seus compósitos nanoestruturados

The benzoxaxine resin is a new class of thermoset phenolic resin, which is presenting, in the lasts decades, a great application in the aircraft industry due mainly to its excellent mechanical and thermal properties. This resin associates the mechanical properties of epoxy resin with the thermal and flame retardant properties of phenolic resin. In this context, they are considered polymers of high performance and they are excellent candidates to replace the current thermoset matrices used in the processing of high performance composites. Thus, in this study nanostructured composites Benzoxazine/CNT were produced at different concentrations of functionalized and non-functionalized CNT (0,1%; 0,5% and 1,0% w/w). The thermal stability of the benzoxazine resin and its nanostructured composites was studied using thermogravimetry (TGA) and degradation kinetic model Ozawa-Wall-Flynn (O-W-F). The thermal characterization also included differential scanning calorimetry (DSC) and dynamic-mechanical analysis, infrared spectroscopy with Fourier transform (FTIR) and scanning electron microscopy (SEM).The introduction of non-functionalized CNT at low concentrations resulted in nanostructured composites with better thermal properties in relation to the neat resin. For all cases, however, the dispersion of CNT in the matrix was ineffective

Estudo da cinética de degradação da resina benzoxazina e seus compósitos nanoestruturados

The benzoxaxine resin is a new class of thermoset phenolic resin, which is presenting, in the lasts decades, a great application in the aircraft industry due mainly to its excellent mechanical and thermal properties. This resin associates the mechanical properties of epoxy resin with the thermal and flame retardant properties of phenolic resin. In this context, they are considered polymers of high performance and they are excellent candidates to replace the current thermoset matrices used in the processing of high performance composites. Thus, in this study nanostructured composites Benzoxazine/CNT were produced at different concentrations of functionalized and non-functionalized CNT (0,1%; 0,5% and 1,0% w/w). The thermal stability of the benzoxazine resin and its nanostructured composites was studied using thermogravimetry (TGA) and degradation kinetic model Ozawa-Wall-Flynn (O-W-F). The thermal characterization also included differential scanning calorimetry (DSC) and dynamic-mechanical analysis, infrared spectroscopy with Fourier transform (FTIR) and scanning electron microscopy (SEM).The introduction of non-functionalized CNT at low concentrations resulted in nanostructured composites with better thermal properties in relation to the neat resin. For all cases, however, the dispersion of CNT in the matrix was ineffective

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

A mechanistic kinetic model for phenol degradation by the Fenton process

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards. (C) 2009 Elsevier B.V. All rights reserved.

Kinetic and thermodynamic investigation on clavulanic acid formation and degradation during glycerol fermentation by Streptomyces DAUFPE 3060

Clavulanic acid (CA) is a potent inhibitor of beta-lactamases, produced by some resistant pathogenic microorganisms, which allows efficient treatment of infectious diseases. The kinetic and thermodynamic parameters of CA production by a new isolate of Streptomyces DAUFPE 3060 and its degradation were evaluated. The effect of temperature on the system was investigated in the range 24-40 degrees C adopting an overall model accounting for (a) the Arrhenius-type formation of CA by fermentation, (b) the hypothetical reversible unfolding of the enzyme limiting the overall metabolism, and (c) the irreversible first-order degradation of CA. The higher rates of CA formation (k(CA) = 0,107 h(-1)) and degradation (k(d) = 0.062 h(-1)) were observed at 32 and 40 degrees C, respectively. The main thermodynamic parameters of the three above hypothesized events were estimated. In particular, the activation parameters of degradation (activation energy = 39.0 kJ/mol; Delta H(d)* = 36.5 kJ/mol; Delta S(d)* = -219.7 J/(mol K); Delta G(d)* = 103.5 kJ/mol) compare reasonably well with those reported in the literature for similar system without taking into account the other two events. (C) 2009 Elsevier Inc. All rights reserved.