Avaliação da estabilidade térmica e oxidativa dos biodieseis de algodão, girassol, dendê e sebo bovino

The search for new sources of environmentally friendly energy is growing every day. Among these alternative energies, biodiesel is a biofuel that has had prominence in world production. In Brazil, law 11.097, determine that all diesel sold in the country must be made by mixing diesel/biodiesel. The latter called BX, , where X represents the percent volume of biodiesel in the diesel oil, as specified by the ANP. In order to guarantee the quality of biodiesel and its mixtures, the main properties which should be controlled are the thermal and oxidative stability. These properties depend mainly of the chemical composition on the raw materials used to prepare the biodiesel. This dissertation aims to study the overall thermal and oxidative stability of biodiesel derived from cotton seed oil, sunflower oil, palm oil and beef tallow, as well as analyze the properties of the blends made from mineral oil and biodiesel in proportion B10. The main physical-chemical properties of oils and animal fat, their respective B100 and blends were determined. The samples were characterized by infrared and gas chromatography (GC). The study of thermal and oxidative stability were performed by thermogravimetry (TG), pressure differential scanning calorimeter (PDSC) and Rancimat. The obtained biodiesel samples are within the specifications established by ANP Resolution number 7/2008. In addition, all the blends and mineral diesel analyzed presented in conformed withthe ANP Regularion specifications number 15/2006. The obtained results from TG curves data indicated that the cotton biodiesel is the more stable combustible. In the kinetic study, we obtained the following order of apparent activation energy for the samples: biodiesel from palm oil > sunflower biodiesel > tallow biodiesel > cotton biodiesel. In terms of the oxidative stability, the two methods studied showed that biodiesel from palm oil is more stable then the tallow. Within the B100 samples studied only the latter were tound to be within the standard required by ANP resolution N° 7. Testing was carried out according to the EN14112. This higher stability its chemical composition

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Aplicação de tratamentos eletroquímicos integrados para remediação de solos e águas contaminadas com petróleo e pesticidas

Electrochemical technologies have been proposed as a promising alternative for the treatment of effluents and contaminated soils. Therefore, the objective of this work was to study the treatment of contaminated soils and wastewaters using electrochemical technologies. Thus, the study regarding the scale-up of the electrochemical system with continuous flow treatment of wastewater of the petrochemical industry was investigated using platinum electrodes supported on titanium (Ti / Pt), and boron-doped diamond (BDD). The results clearly showed that under the operating conditions studied and electrocatalytic materials employed, the better removal efficiency was achieved with BDD electrode reducing the chemical oxygen demand (COD) from 2746 mg L-1 to 200 mg L-1 in 5 h consuming 56.2 kWh m-3 . The decontamination of soils and effluents by petrochemical products was evaluated by studying the effects of electrokinetic remediation for removal of total petroleum hydrocarbons (HTP) from contaminated soil with diesel. The efficiency of this process was dependent on the electrolyte used Na2SO4 (96.46%), citric acid (81.36%) and NaOH (68.03%) for 15 days. Furthermore, the effluent after treatment of the soil was treated by electrochemical oxidation, achieving a good elimination of the organic polluting load dissolved. Depending on the physical behavior of wastewater contaminated with oil (emulsified state); atrazine emulsified effluents were investigated. The main characteristics of the effluent produced during the washing of contaminated soil were studied, being dependent on the surfactant dosage used; which determined its electrolytic treatment with BDD. The electrochemical oxidation of emulsified effluent of atrazine was efficient, but the key to the treatment is reducing the size of micelles.

Desenvolvimento de métodos para quantificação de benzilpenicilina em medicamentos veterinários e seus resíduos em leite bovino e caprino por UFLC-DAD

The Benzylpenicillin (PENG) have been as the active ingredient in veterinary medicinal products, to increase productivity, due to its therapeutic properties. However, one of unfortunate quality and used indiscriminately, resulting in residues in foods exposed to human consumption, especially in milk that is essential to the diet of children and the ageing. Thus, it is indispensable to develop new methods able to detect this waste food, at levels that are toxic to human health, in order to contribute to the food security of consumers and collaborate with regulatory agencies in an efficient inspection. In this work, were developed methods for the quality control of veterinary drugs based on Benzylpenicillin (PENG) that are used in livestock production. Additionally, were validated methodologies for identifying and quantifying the antibiotic residues in milk bovine and caprine. For this, the analytical control was performed two steps. At first, the groups of samples of medicinal products I, II, III, IV and V, individually, were characterized by medium infrared spectroscopy (4000 – 600 cm-1). Besides, 37 samples, distributed in these groups, were analyzed by spectroscopy in the ultraviolet and near infrared region (UV VIS NIR) and Ultra Fast Liquid Chromatograph coupled to linear arrangement photodiodes (UFLC-DAD). The results of the characterization indicated similarities, between PENG and reference standard samples, primarily in regions of 1818 to 1724 cm-1 of ν C=O that shows primary amides features of PENG. The method by UFLC-DAD presented R on 0.9991. LOD of 7.384 × 10-4 μg mL-1. LOQ of 2.049 × 10-3 μg mL-1. The analysis shows that 62.16% the samples presented purity ≥ 81.21%. The method by spectroscopy in the UV VIS NIR presented medium error ≤ 8 – 12% between the reference and experimental criteria, indicating is a secure choice for rapid determination of PENG. In the second stage, was acquiring a method for the extraction and isolation of PENG by the addition of buffer McIlvaine, used for precipitation of proteins total, at pH 4.0. The results showed excellent recovery values PENG, being close to 92.05% of samples of bovine milk (method 1). While samples of milk goats (method 2) the recovery of PENG were 95.83%. The methods for UFLC-DAD have been validated in accordance with the maximum residue limit (LMR) of 4 μg Kg-1 standardized by CAC/GL16. Validation of the method 1 indicated R by 0.9975. LOD of 7.246 × 10-4 μg mL-1. LOQ de 2.196 × 10-3 μg mL-1. The application of the method 1 showed that 12% the samples presented concentration of residues of PENG > LMR. The method 2 indicated R by 0.9995. LOD 8.251 × 10-4 μg mL-1. LOQ de 2.5270 × 10-3 μg mL-1. The application of the method showed that 15% of the samples were above the tolerable. The comparative analysis between the methods pointed better validation for LCP samples, because the reduction of the matrix effect, on this account the tcalculs < ttable, caused by the increase of recovery of the PENG. In this mode, all the operations developed to deliver simplicity, speed, selectivity, reduced analysis time and reagent use and toxic solvents, particularly if compared to the established methodologies.

Desenvolvimento de métodos para quantificação de benzilpenicilina em medicamentos veterinários e seus resíduos em leite bovino e caprino por UFLC-DAD

The Benzylpenicillin (PENG) have been as the active ingredient in veterinary medicinal products, to increase productivity, due to its therapeutic properties. However, one of unfortunate quality and used indiscriminately, resulting in residues in foods exposed to human consumption, especially in milk that is essential to the diet of children and the ageing. Thus, it is indispensable to develop new methods able to detect this waste food, at levels that are toxic to human health, in order to contribute to the food security of consumers and collaborate with regulatory agencies in an efficient inspection. In this work, were developed methods for the quality control of veterinary drugs based on Benzylpenicillin (PENG) that are used in livestock production. Additionally, were validated methodologies for identifying and quantifying the antibiotic residues in milk bovine and caprine. For this, the analytical control was performed two steps. At first, the groups of samples of medicinal products I, II, III, IV and V, individually, were characterized by medium infrared spectroscopy (4000 – 600 cm-1). Besides, 37 samples, distributed in these groups, were analyzed by spectroscopy in the ultraviolet and near infrared region (UV VIS NIR) and Ultra Fast Liquid Chromatograph coupled to linear arrangement photodiodes (UFLC-DAD). The results of the characterization indicated similarities, between PENG and reference standard samples, primarily in regions of 1818 to 1724 cm-1 of ν C=O that shows primary amides features of PENG. The method by UFLC-DAD presented R on 0.9991. LOD of 7.384 × 10-4 μg mL-1. LOQ of 2.049 × 10-3 μg mL-1. The analysis shows that 62.16% the samples presented purity ≥ 81.21%. The method by spectroscopy in the UV VIS NIR presented medium error ≤ 8 – 12% between the reference and experimental criteria, indicating is a secure choice for rapid determination of PENG. In the second stage, was acquiring a method for the extraction and isolation of PENG by the addition of buffer McIlvaine, used for precipitation of proteins total, at pH 4.0. The results showed excellent recovery values PENG, being close to 92.05% of samples of bovine milk (method 1). While samples of milk goats (method 2) the recovery of PENG were 95.83%. The methods for UFLC-DAD have been validated in accordance with the maximum residue limit (LMR) of 4 μg Kg-1 standardized by CAC/GL16. Validation of the method 1 indicated R by 0.9975. LOD of 7.246 × 10-4 μg mL-1. LOQ de 2.196 × 10-3 μg mL-1. The application of the method 1 showed that 12% the samples presented concentration of residues of PENG > LMR. The method 2 indicated R by 0.9995. LOD 8.251 × 10-4 μg mL-1. LOQ de 2.5270 × 10-3 μg mL-1. The application of the method showed that 15% of the samples were above the tolerable. The comparative analysis between the methods pointed better validation for LCP samples, because the reduction of the matrix effect, on this account the tcalculs < ttable, caused by the increase of recovery of the PENG. In this mode, all the operations developed to deliver simplicity, speed, selectivity, reduced analysis time and reagent use and toxic solvents, particularly if compared to the established methodologies.

Avaliação da fidedignidade dos ensaios de esteróides fecais realizados no Laboratório de Medidas Hormonais do Departamento de Fisiologia da UFRN

NASCIMENTO, H. G. ; FERNANDES, L. C. ; SOUSA, M. B. C. . Avaliação da fidedignidade dos ensaios de esteróides fecais realizados no Laboratório de Medidas Hormonais do Departamento de Fisiologia da UFRN. Publica , v. 2, p. 39-48, 2006.

Diagnóstico das espécies ativas do plasma usado em tratamentos termoquímicos do titânio

Plasma diagnostics by Optical Emission Spectroscopy were performed for electrical discharge in three gas mixture respecting the combinations z N2 y Ar x H2, z N2 y Ar x O2 e z N2 y Ar x CH4, in which the indexes z and y systematically vary from 1 to 4 and x varies from 0 to 4, every one has dimension SCCM, resulting in 80 combinations. From the all obtained spectrums, the species CH (387,1 nm), N2+ (391,4 nm), Hβ (486,1 nm), Hα (656,3 nm), Ar (750,4 nm), O (777,4 nm) e O (842,6 nm) were analyzed because of their abundance and importance on the kinetic of reaction from the plasma to surface, besides their high dependences on the gases flows. Particularly interesting z, y and x combinations were chosen in order to study the influence of active species on the surface modification during the thermochemical treatment. From the mixtures N2 Ar O2 e N2 Ar CH4 were chosen three peculiar proportions which presented luminous intensity profile with unexpected maximum or minimum values, denominated as plasma anomaly. Those plasma concentrations were utilized as atmosphere of titanium treatment maintaining constant the control parameters pressure and temperature. It has been verified a relation among luminous intensity associated to N2+ and roughness, nanohardness and O atoms diffusion into the crystalline lattice of treated titanium and it has been seen which those properties becomes more intense precisely in the higher points found in the optical profile associated to the N2+ specie. Those parameters were verified for the mixture which involved O2 gas. For the mixture which involves CH4 gas, the relation was determinate by roughness, number of nitrogen and carbon atoms diffused into the titanium structure which presented direct proportionality with the luminous intensity referent to the N2+ and CH. It has been yet studied the formation of TiCN phases on the surface which presented to be essentially directly proportional to the increasing of the CH specie and inversely proportional to the increasing of the specie N2+

Tratamentos de fibras de carnaúba [copernicia prunífera (miller) h. e. moore] para o desenvolvimento de compósito biodegradável com matriz de polihidroxibutirato

The use of raw materials from renewable sources for production of materials has been the subject of several studies and researches, because of its potential to substitute petrochemical-based materials. The addition of natural fibers to polymers represents an alternative in the partial or total replacement of glass fibers in composites. In this work, carnauba leaf fibers were used in the production of biodegradable composites with polyhydroxybutyrate (PHB) matrix. To improve the interfacial properties fiber / matrix were studied four chemical treatments to the fibers..The effect of the different chemical treatments on the morphological, physical, chemical and mechanical properties of the fibers and composites were investigated by scanning electron microscopy (SEM), infrared spectroscopy, X-ray diffraction, tensile and flexural tests, dynamic mechanical analysis (DMA), thermogravimetry (TGA) and diferential scanning calorimetry (DSC). The results of tensile tests indicated an increase in tensile strength of the composites after the chemical treatment of the fibers, with best results for the hydrogen peroxide treated fibers, even though the tensile strength of fibers was slightly reduced. This suggests a better interaction fiber/matrix which was also observed by SEM fractographs. The glass transition temperature (Tg) was reduced for all composites compared to the pure polymer which can be attributed to the absorption of solvents, moisture and other low molecular weight molecules by the fibers

Influência de tratamentos térmicos no comportamento mecânico da blenda poli(metacrilato de metila) / poli(tereftalato de etileno) reciclado

Studies indicate that a variation in the degree of crystallinity of the components of a polymer blend influences the mechanical properties. This variation can be obtained by subjecting the blend to heat treatments that lead to changes in the spherulitic structure. The aim of this work is to analyze the influence of different heat treatments on the variation of the degree of crystallinity and to establish a relationship between this variation and the mechanical behavior of poly(methyl methacrylate)/poly(ethylene terephthalate) recycled (PMMA / PETrec) with and without the use of compatibilizer agent poly(methyl methacrylate-al-glycidyl methacrylate-al-ethyl acrylate) (MMAGMA- EA). All compositions were subjected to two heat treatments. T1 heat treatment the samples were treated at 130 ° C for 30 minutes and cooled in air. In T2, the samples were treated at 230 ° C for 5 minutes and cooled to approximately -10 ° C. The variation of the degree of crystallinity was determined by the proportional relationship between crystallinity and density, with the density measured by pycnometry. The mechanical behavior was verified by tensile tests with and without the presence of notches and pre-cracks, and by method of fracture toughness in plane strain (KIC). We used the scanning electron microscopy (SEM) to analyze the fracture surface of the samples. The compositions subjected to heat treatment T1, in general, showed an increase in the degree of crystallinity in tensile strength and a tendency to decrease in toughness, while compositions undergoing treatment T2 showed that the opposite behavior. Therefore, this work showed that heat treatment can give a polymer blend further diversity of its properties, this being caused by changes in the crystal structure