Microstructure, mechanical properties and chemical degradation of brazed AISI 316 stainless steel/alumina systems

The main aims of the present study are simultaneously to relate the brazing parameters with: (i) the correspondent interfacial microstructure, (ii) the resultant mechanical properties and (iii) the electrochemical degradation behaviour of AISI 316 stainless steel/alumina brazed joints. Filler metals on such as Ag–26.5Cu–3Ti and Ag–34.5Cu–1.5Ti were used to produce the joints. Three different brazing temperatures (850, 900 and 950 °C), keeping a constant holding time of 20 min, were tested. The objective was to understand the influence of the brazing temperature on the final microstructure and properties of the joints. The mechanical properties of the metal/ceramic (M/C) joints were assessed from bond strength tests carried out using a shear solicitation loading scheme. The fracture surfaces were studied both morphologically and structurally using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The degradation behaviour of the M/C joints was assessed by means of electrochemical techniques. It was found that using a Ag–26.5Cu–3Ti brazing alloy and a brazing temperature of 850 °C, produces the best results in terms of bond strength, 234 ± 18 MPa. The mechanical properties obtained could be explained on the basis of the different compounds identified on the fracture surfaces by XRD. On the other hand, the use of the Ag–34.5Cu–1.5Ti brazing alloy and a brazing temperature of 850 °C produces the best results in terms of corrosion rates (lower corrosion current density), 0.76 ± 0.21 μA cm−2. Nevertheless, the joints produced at 850 °C using a Ag–26.5Cu–3Ti brazing alloy present the best compromise between mechanical properties and degradation behaviour, 234 ± 18 MPa and 1.26 ± 0.58 μA cm−2, respectively. The role of Ti diffusion is fundamental in terms of the final value achieved for the M/C bond strength. On the contrary, the Ag and Cu distribution along the brazed interface seem to play the most relevant role in the metal/ceramic joints electrochemical performance.

A simple approach to numerical modelling of propane combustion in fluidized beds

A mathematical model is proposed for the evolution of temperature, chemical composition, and energy release in bubbles, clouds, and emulsion phase during combustion of gaseous premixtures of air and propane in a bubbling fluidized bed. The analysis begins as the bubbles are formed at the orifices of the distributor, until they explode inside the bed or emerge at the free surface of the bed. The model also considers the freeboard region of the fluidized bed until the propane is thoroughly burned. It is essentially built upon the quasi-global mechanism of Hautman et al. (1981) and the mass and heat transfer equations from the two-phase model of Davidson and Harrison (1963). The focus is not on a new modeling approach, but on combining the classical models of the kinetics and other diffusional aspects to obtain a better insight into the events occurring inside a fluidized bed reactor. Experimental data are obtained to validate the model by testing the combustion of commercial propane, in a laboratory-scale fluidized bed, using four sand particle sizes: 400–500, 315–400, 250–315, and 200–250 µm. The mole fractions of CO2, CO, and O2 in the flue gases and the temperature of the fluidized bed are measured and compared with the numerical results.

Chemical composition and antioxidante activity of Tunisian Origanum glandulosum Desf. essential oil and volatile oil obtain by supercritical CO2 extraction

Dried flowers and leaves of Origanum glandulosum Desf. were submitted to hydrodistillation (HD) and supercritical fluid extraction with CO2 (SFE). The essential oils isolated by HD and volatile oils obtained by SFE were analysed by GC and GC/MS. Total phenolics content and antioxidant effectiveness were performed. The main components of the essential oils from Bargou and Nefza were: p-cymene (40.4% and 39%), thymol (38.7% and 34.4%) and γ- terpinene (12.3% and 19.2%), respectively. The major components obtain by SFE in the volatile oil, from Bargou and Nefza, were: p-cymene (32.3% and 36.2%), thymol (41% and 40%) and γ-terpinene (20.3% and 13.3%). Total phenolic content, expressed in gallic acid equivalent (GAE) g kg-1 dry weight, varied from 12 to 27 g kg-1 dw, and the ability to scavenge the DPPH radicals, expressed by IC50 ranged from 44 to143 mg L-1.

Chemical reaction network of flavylium ions in heterogeneous media

Dissertação apresentada para a obtenção do Grau de Doutor em Química, especialidade em Química-Física, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

Methyl syringate: An efficient phenolic mediator for bacterial and fungal laccases

The aim of the present work is to provide insight into the mechanism of laccase reactions using syringyl-type mediators. We studied the pH dependence and the kinetics of oxidation of syringyl-type phenolics using the low CotA and the high redox potential TvL laccases. Additionally, the efficiency of these compounds as redox mediators for the oxidation of non-phenolic lignin units was tested at different pH values and increasing mediator/non-phenolic ratios. Finally, the intermediates and products of reactions were identified by LC-MS and H-1 NMR. These approaches allow concluding on the (1) mechanism involved in the oxidation of phenolics by bacterial laccases, (2) importance of the chemical nature and properties of phenolic mediators, (3) apparent independence of the enzyme's properties on the yields of non-phenolics conversion, (4) competitive routes involved in the catalytic cycle of the laccase-mediator system with several new C-O coupling type structures being proposed.

Reactivity of syringyl and guaiacyl lignin units and delignification kinetics in the kraft pulping of eucalyptus globulus wood using Py-Gc-Ms/FID

Eucalyptus globulus sapwood and heartwood showed no differences in lignin content (23.0% vs. 23.7%) and composition: syringyl-lignin (17.9% vs. 18.0%) and guaiacyl-lignin (4.8% vs. 5.2%). Delignification kinetics of S- and G-units in heartwood and sapwood was investigated by Py-GC–MS/FID at 130, 150 and 170 °C and modeled as double first-order reactions. Reactivity differences between S and G-units were small during the main pulping phase and the higher reactivity of S over G units was better expressed in the later pulping stage. The residual lignin composition in pulps was different from wood or from samples in the initial delignification stages, with more G and H-units. S/G ratio ranged from 3 to 4.5 when pulp residual lignin was higher than 10%, decreasing rapidly to less than 1. The S/H was initially around 20 (until 15% residual lignin), decreasing to 4 when residual lignin was about 3%.

Hexachlorophene as a topically applied chemical for prophylaxis against Schistosoma mansoni infections in mice

Treatment of mouse tail skins with hexachlorophene (1.25% w/v) in absolute methanol or 70% isopropanol suppressed Schistosoma mansoni infections by more than 95% even when the application was performed up to three days prior to exposure to cercarial suspensions by tail immersion. Treatment with concentrations of 0.313% or higher one day prior to exposure provided at least 98% protection when the treated surface was not subjected to water washes of greater duration than 1/2 hour. Tail immersion application of 1.25% hexachlorophene one day prior to exposure still provided 87-92% protection after 3 hours water wash. Wipe application of 1.25% hexachlorophene three days prior to exposure still provided 93% protection following 3 hours water wash. High cercarial recoveries from exposure tubes at the end of exposure periods indicated high antipenetrant activity for hexachlorophene. Sufficient hexachlorophene leached from treated tail skins into the surrounding water to affect subsequently added cercariae so that they were no longer infective to untreated mice.

Incorporating sustainability into a chemical company’s modus operandi

The intent of this dissertation is to review relevant existing management systems and chemical industry initiatives to identify synergies, overlaps and gaps with Sustainability best practices, to map the barriers to the incorporation of Sustainability and formulate recommendations to facilitate execution of Sustainability practices within existing management systems. A chemical industry Sustainability survey was conducted through APEQ, the Portuguese association of chemical companies, which constitutes the first baseline on the topic for this national industry association. The commonly used international standards and the Responsible Care® (RC) initiative were cross-referenced against the United Nations Global Compact Assessment Tool. Guidance on how to incorporate Sustainability into a company‘s modus operandi was collapsed into Sustainability Playbooks. The survey revealed that 73% of the APEQ member companies that participated in the survey have a Sustainability Plan. Both large and small/medium APEQ member companies see the market not willing to pay extra for ‗greener‘ products as one of the main barriers. APEQ large enterprise see complexity of implementation and low return on investment as the other most significant barriers while small/medium enterprise respond that the difficulty to predict customer sustainability needs is the other most significant barrier. Amongst many other insights from this survey reported to APEQ, Life Cycle Assessment practices were found to have a low level of implementation and were also considered of low importance, thus identifying a very important opportunity in Sustainability practices to be addressed by APEQ. Two hundred and seventy three assessment points from United Nations Global Compact Assessment Tool plus five additional items were cross-referenced with international standard requirements. With the authorization of the intellectual property owners, the United Nations Global Compact Assessment Tool was modified to introduce actionable recommendations for each gap identified by management standard. This tool was automated to output specific recommendations for 63 possible combinations after simply selecting from a list of commonly used management standards and the RC initiative. Finally this modified tool was introduced into Playbooks for Incorporation of Sustainability at two levels: a ―Get Started Playbook‖ for beginners or small/medium size enterprise and an ―Advanced Playbook‖ as a second advancement stage or for large enterprise.

Study on the changes of soil chemical characteristics as result of prescribed fire

Every year, particularly during the summer period, the Portuguese forests are devastated by forest fire that destroys their ecosystems. So in order to prevent these forest fires, public and private authorities frequently use methods for the reduction of combustible mass as the prescribed fire and the mechanical vegetation pruning. All of these methods of prevention of forest fires alter the vegetation layer and/or soil [1-2]. This work aimed the study of the variation of some chemical characteristics of soil that suffered prescribed fire. The studied an area was located in the Serra of Cabreira (Figure 1) with 54.6 ha. Twenty sampling points were randomly selected and samples were collected with a shovel before, just after the prescribed fire, and 125 and 196 days after that event. The parameters that were studied were: pH, soil moisture, organic matter and iron, magnesium and potassium total concentration. All the analysis followed International Standard Methodologies. This work allowed to conclude that: a) after the prescribed fire; i) the pH remained practically equal to the the initial value; ii) occurred a slight increase of the average of the organic matter contents and iron total contents; b) at the end of the sampling period compared to the initial values; i) the pH didn´t change significantly; ii) the average of the contents of organic matter decreased; and iii) the average of the total contents of Fe, Mg and K increased.

Impact of prescribed fire on the chemical properties of soil

Prescribed fire is a common forest management tool used in Portugal to reduce the fuel load availability and minimize the occurrence of wildfires. In addition, the use of this technique also causes an impact to ecosystems. In this presentation we propose to illustrate some results of our project in two forest sites, both located in Northwest Portugal, where the effect of prescribed fire on soil properties were recorded during a period of 6 months. Changes in soil moisture, organic matter, soil pH and iron, were examined by Principal Component Analysis multivariate statistics technique in order to determine impact of prescribed fire on these soil properties in these two different types of soils and determine the period of time that these forest soils need to recover to their pre-fire conditions, if they can indeed recover. Although the time allocated to this study does not allow for a widespread conclusion, the data analysis clearly indicates that the pH values are positively correlated with iron values at both sites. In addition, geomorphologic differences between both sampling sites, Gramelas and Anjos, are relevant as the soils’ properties considered have shown different performances in time. The use of prescribed fire produced a lower impact in soils originated from more amended bedrock and therefore with a ticker humus covering (Gramelas) than in more rocky soils with less litter covering (Anjos) after six months after the prescribed fire occurrence.

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara‐a‐Velha: comparison with Venetian and façon‐de‐Venise production

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Conservação e Restauro,Área de especialização Cerâmica e Vidro

Real fábrica de vidros de Coina – Chemical analysis of archaeological glass fragments

Actas do 17º Congresso da Associação Internacional para a História do Vidro

Modelling of the kinetics of municipal solid waste composting in full-scale mechanical-biological treatment plants

A thesis submitted in fulfilment of the requirements for the Degree of Doctor of Philosophy in Sanitary Engineering in the Faculty of Sciences and Technology of the New University of Lisbon

Partial chemical characterization of antigenic preparations of chromoblastomycosis agents

Antigenic preparations (saline, methylic, metabolic and exoantigens) of four agents of chromoblastomycosis, Fonsecaea pedrosoi, Phialophora verrucosa, Cladophialophora (Cladosporium) carrionii and Rhinocladiella aquaspersa were obtained. Partial chemical characterization of these antigenic preparations was obtained by determination of the levels of total lipids, protein, and carbohydrates, and identification of the main sterols and carbohydrates. Methylic antigens presented the highest lipid contents, whereas metabolic antigens showed the highest carbohydrate content. Total lipid, protein, and carbohydrate levels were in the range of 2.33 to 2.00mg/ml, 0.04 to 0.02 mg/ml and 0.10 to 0.02 mg/ml, respectively, in the methylic antigens and in the range of 0.53 to 0.18mg/ml, 0.44 to 0.26mg/ml, and 1.82 to 1.02 mg/ml, respectively, in saline antigens. Total lipid, protein, and carbohydrate contents were in the range of 0.55 to 0.20mg/ml, 0.69 to 0.57mg/ml and 10.73 to 5.93mg/ml, respectively, in the metabolic antigens, and in the range of 0.55 to 0.15mg/ml, 0.62 to 0.20mg/ml and 3.55 to 0.42mg/ml, respectively, in the exoantigens. Phospholipids were not detected in the preparations. Saline and metabolic antigens and exoantigens presented hexose and the methylic antigen revealed additional pentose units in their composition. The UV light absorption spectra of the sterols revealed squalene and an ergosterol fraction in the antigens. The characterization of these antigenic preparations may be useful for serological evaluation of patients of chromoblastomycosis.