Alkali activated fuel ash and slag mixes:optimization study from paste to concrete building blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (pfa) from a UK power plant, ground granulated blast furnace slag (ggbs) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several pfa and ggbs combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of pfa/ggbs and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from pfa/ggbs combinations.

Highly CO2 sensitive extruded fluorescent plastic indicator film based on HPTS

Highly-sensitive optical fluorescent extruded plastic films are reported for the detection of gaseous and dissolved CO2. The pH-sensitive fluorescent dye used is 8-Hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS, PTS-) coated on the surface of hydrophilic fumed silica and the base is tetrabutylammonium hydroxide (TBAH). The above components are used to create an HPTS pigment (i.e. HPTS/SiO2/TBAH) with a high CO2 sensitivity (%CO2(S=1/2) = 0.16%) and fast 50% response (t50↓) = 2 s and recovery (t50↑) = 5 s times. Highly CO2-sensitive plastic films are then fabricated, via the extrusion of the HPTS pigment powder in low-density polyethylene (LDPE). As with the HPTS-pigment, the luminescence intensity (at 515 nm) and absorbance (at 475 nm) of the HPTS plastic film decreases as the %CO2 in the ambient gas phase increases. The HPTS plastic film exhibits a high CO2 sensitivity, %CO2(S=1/2), of 0.29%, but a response time ˂2 min and recovery time ˂40 min, which is slower than that of the HPTS pigment. The HPTS plastic film is very stable under ambient conditions, (with a shelf life ˃ six month when stored in the dark but under otherwise ambient conditions). Moreover, the HPTS-film is stable in water, salt solution and even in acid (pH=2), and in each of these media it can be used to detect dissolved CO2.

High temperature thermal stability investigations of ammonium sulphide passivated InGaAs and interface formation with Al2O3 studied by synchrotron radiation based photoemission

High resolution synchrotron radiation core level photoemission measurements have been used to undertake a comparative study ofthe high temperature thermal stability ofthe ammonium sulphide passivated InGaAs surface and the same surface following the atomic layer deposition (ALD) of an ultrathin (∼1 nm) Al2O3 layer. The solution based ex situ sulphur passivation was found to be effective at removing a significant amount of the native oxides and protecting the surface against re-oxidation upon air exposure. The residual interfacial oxides which form between sulphur passivated InGaAs and the ultrathin Al2O3 layer can be substantially removed at high temperature (up to 700 ◦C) without impacting on the InGaAs stoichiometry while significant loss of indium was recorded at this temperature on the uncovered sulphur passivated InGaAs surface.

High-temperature stability study of 1 nm Al2O3 deposited on InAs surfaces investigated by synchrotron radiation based photoemission spectroscopy

High-resolution soft x-ray photoemission spectroscopy (SXPS) has been used to study the high-temperature thermal stability of ultra-thin atomic layer deposited (ALD) Al2O3 layers (~1 nm) on sulfur passivated and native oxide covered InAs surfaces. While the arsenic oxides were removed from both interfaces following a 600 °C anneal, a residual indium oxide signal remained. No significant differences were observed between the sulfur passivated and native oxide surfaces other than the thickness of the interfacial oxide layer while the Al2O3 stoichiometry remained unaffected by the anneals. The energy band offsets were determined for the Al2O3 on the sulfur passivated InAs surface using both valence band edge and shallow core-level photoemission measurements.

Argilas aniónicas multifuncionais

O presente trabalho aborda a imobilização de vários complexos do tipo dioxomolibdénio(VI), dioxotungsténio(VI) e de cobre(II) em suportes do tipo hidróxidos duplos lamelares (LDHs). Numa primeira parte descrevem-se os suportes LDHs e a síntese e caracterização em solução e estado sólido de complexos catecolato cis-MoO2 e cis-WO2. Investigou-se depois a química de intercalação deste tipo de complexos, nomeadamente a influência dos LDHs percursores, temperatura de intercalação, excesso de anião e mudança de metal no complexo intercalado (M=Mo, W). De seguida foi estudada a imobilização de oxocomplexos de molibdénio(VI) num LDH com pilares de bipiridina dicarboxilato e procedeu-se à avaliação da sua aplicabilidade em reacções catalíticas de oxidação de álcoois e olefinas. Com o objectivo de desenvolver as aplicações dos LDHs com pilares foi estudada a imobilização de um complexo de cobre(II) neste material e avaliada a sua aplicação como catalizador na oxidação de substratos orgânicos.

Desenvolvimento e avaliação de um sistema de monitorização da corrosão electroquímica no betão armado

O presente trabalho teve como principal objectivo desenvolver e avaliar o desempenho de um sistema de monitorização da corrosão no betão armado. Para tal foram construídos dois provetes de classe 20/25, e outros dois de classe 30/35. Dentro desses quatro provetes foram instalados sensores de corrosão designados por Monicorr. Para cada classe de betão utilizaram-se dois tipos diferentes de contaminação, designadas por A e B. A contaminação do tipo A é feita adicionando durante a amassadura do betão uma solução aquosa de cloreto de cálcio a 4% em massa de cimento e sujeitando esses provetes a ciclos de condensação de 50h, durante um período de 1000h. A contaminação do tipo B é feita sujeitando os outros dois provetes de classes diferentes a ciclos de 100h de nevoeiro salino a 3% em massa de água, durante um período de 2000h. Para avaliar o desempenho do sistema de monitorização Monicorr foram comparados os valores da velocidade de corrosão instantânea por LPR, a resistividade do betão e o potencial de corrosão da armadura, obtidos pelo sistema Monicorr, com os obtidos por aparelhos utilizados para o mesmo efeito em laboratório. Paralelamente, estudou-se também a variação do potencial de corrosão da armadura em função da área oxidada. Para além disso desenvolveu-se um conjunto de pseudo referências de grafite dopada com diferentes percentagens de cimento e avaliou-se a sua estabilidade relativamente ao eléctrodo de calomelanos e óxido de managanês manganês em soluções de hidróxido de cálcio saturada e de betão armado contaminado com sais cloreto. Finalmente foram ainda desenvolvidas duas tarefas, a primeira relacionada com os resultados obtidos na medição da resistividade do betão armado pelas técnicas de dois pinos e quatro pinos, e a segunda com o desenvolvimento de um método rápido de contaminação do betão armado com dióxido de enxofre. Os resultados obtidos permitem concluir que: - o sistema de monitorização Monicorr apresenta um comportamento muito semelhante aos utilizados em laboratório para medir grandezas como o potencial de corrosão da armadura, resistividade do betão e velocidade de corrosão instantânea por LPR; - a monitorização das três grandezas atrás referidas pode ser uma ferramenta importante para permitir saber qual é o desenvolvimento corrosivo de uma estrutura de betão armado; os eléctrodos de grafite dopada com cimento apresentam uma elevada estabilidade nos meios testados tendo um desempenho muito semelhante à referência de manganês óxido de manganês para os mesmos meios. Relativamente à influência da área oxidada no potencial de corrosão da armadura não foi possível tirar conclusões. Foi possível, também, concluir que existe uma clara concordância entre as medições da resistividade do betão utilizando o método dos dois pinos e o método dos quatro pinos. Finalmente pode-se concluir que a metodologia desenvolvida para contaminar provetes de betão com iões sulfato obtém bons resultados ao fim de, apenas, 48h de contaminação.

An elegant way to increase acidity in SAPOs: use of methylamine as co-template during synthesis

SAPO-34 and SAPO-11 with an increased number of acid sites were synthesized by adding methylamine (MA) as co-template to tetraethylammonium hydroxide (TEAOH) or dipropylamine (DPA) respectively used as true templates.

Argamassas e betões geopoliméricos: estado da arte e potencial de industrialização em Portugal

Dissertação para obtenção do grau de Mestre em Engenharia Civil

Eletrólise da água para produção de gás de síntese

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica Ramo de Processos Químicos

Syngas production by water electrolysis: preliminary tests on methane production

Master Thesis to obtain the Master degree in Chemical Engineering - Branch Chemical Processes

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Studies of nucleophilic attack on tris (pentafluorophenyl) phosphine and its oxides

The reaction of tris(pentafluorophenyl)phosphine [5] with the nucleophiles dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPA), diethyl formamide (DEF), hexaethylphosphoric triamide (HEPA), hydrazine, N,N-dimethyl hydrazine (in presence and/or absence of KF), phenylhydrazine, ammonium hydroxide, formamide, aniline, sodium hydrogen sulfide, and hexaethylphosphorous triamide was investigated. The reaction of [5] with DMF and HMPA gave the same product, namely tris-[4-(N,N-dimethylamino)-2,3,5,6-tetrafluorophenyl]phosphine [12] but in higher yield in the case of HMPA. Compound (5] also reacted with DEF to give tris[4-(N,N-diethylamino)-2,3,5,6-tetrafluorophenyl] phosphine [14]. When [51 was treated with HEPA, it gave a mixture of bis(pentafluorophe~yl)-(N,N-diethylamino-tetrafluorophenyl)phosphine, pentafluorophenyl-bis-(N,N-diethylamino-tetrafluorophenyl)phosphine and tris (N,N-diethylamino-tetrafluorophenyl)phosphine. Treatment of [5] with aqueeus hydrazine solution in excess ethanol gave tris(4-hydrazo-2,3,4,6-tetrafluorophenyl)phosphine [1s1 in high yield while reaction with aqueous hydrazine led to C-P cleavage and production of tetrafluorophenyl hydrazine. With N,N-dimethyl hydrazine, [5] gave tris(4-N,N-dimethylhydrazine-2,3,5,6-tetrafluorophenyl) phosphine {20j. The latter could be obtained in higher yield and shorter reaction time, by the addition of KF. The reaction of compound {51 with phenylhydrazine in THF gave bis(pentafluorophe~yl)-4-S-phenylhydrazino- 2,3,5,6-tetrafluorophenyl phosphine [22] in low yield. Reaction of [5] with ammonium hydroxide in THF at high pressure in the presence of KF gave tris-~4-amino-2,3,5,6-tetrafluorophenyl)phosphine [25]. Similarly, formamide led to a mixture of (C6F4NHZ)3P, (C6F4NHZ)ZPC6FS, (C6F4NHZ)ZPC6F4NHCHO, and C6F4NHZP(C6Fs)(C6F4NHCHO). When [5] was treated with aniline, a mixture of mono-, di-, and tri-substituted products was obtained. Sodium hydrogen sulfide in ethylene glycol/ pyridine led to C-P cleavage and the isolation of pentafluorobenzene and tetrafluorothiophenol. Reaction of [5] and its oxide [35] with different alkoxides in the corresponding alcohols led mainly to C-P bond cleavage products, with the exception of one case where sodium methoxide was used in ether, and which led to tris-(4-methoxy-2,3,9,6-tetrafluorophenyl)phosphine [37]. On the basis of various spectroscopic data, it was concluded that the para position in compound [5] was generally the favoured site of attack.

The chemistry of heterocyclic methine bases and of their acyl and thioacyl derivatives

The work described in this thesis has been dtvided into six sections . The first section involves the reaction of 3,5-diphenyl-2-methyl-l,3,4-oxadiazolium perchlorate with acetic and benzoic anhydrides. The second section deals with the preparation and reactions of 1,3,4-thia diazolium salts. Some monomeric 1,3,4-thiadiazoline methine bases have also been prepared by reacting 1,3,4-thia d iaz ol ium s al t s with concen trated ammonium hydroxide solution. Variable temperature p.m.r. of 2-(3-acetylacetonylidene)-3,5-diphenyl-A4 -1,3,4-thiadiazoline has also been described. The third section deals with prepar a tion and reactions of some compounds in benzoxazole series. The fourth section deals with the prep a ration and reactions of N-alkyl-2-methylbenzothi azolium salts with base , a nd with some a cetylating and thioacetylating agents. Treatment of 2,3-dimethylbenzothiazolium iodide and of 3-ethyl-2-methylbenzothia zolium iodide with base wa s found to give the corresponding dimeric methine b a ses and evidence supporting their structure is also given. Thiol acetic acid was found to exchange 0 for S in its reactions with 2-acetonylidene-3-methylbenzothiazoline and 2-acetophenonylidene-3-methylbenzothi a zoline. (ii) In th e fifth section, the r eactions of 2,3-dimethylbenzselenazolium iodide with a variety of ac e tylating and thioacetylating agents has been described. The treatment of 2,3-dimethylbenzselenazolium iodide with base was found to give rise to a dimeric methine base and evidence supporting its structure is also given. The reactions of this dimeric methine b a se with benzoic anhydride and phenylisothiocyanate have also been described. The sixth section deals with the preparation and reactions of l-alkyl-2-methylquinolinium salts. Treatment of 1,2-dimethylquinolinium iodide and l-ethyl-2-methylquinolinium iodide was found to give the corresponding monomeric methine bases and evidence supporting their structure is also given. The E-type geometry of the olefinic bond in 2-acetonylidene-l-methylquinoline has been established on the basis of an N.O.E. experiment.

(A) BODIPY as a versatile fluorophore (B) Synthesis of PNAs via Staudinger reaction

(A) In recent years, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophores have attracted considerable interest due to their unique photochemical properties. However detailed studies on the stability of BODIPY and analogues under acidic and basic conditions have been lacking. Thus the stability of a series of BODIPY analogues in acidic (di- and trichloroacetic acid) and basic (aqueous ammonium hydroxide) conditions was investigated using 11B NMR spectroscopy. Among the analogues tested, 4,4-diphenyl BODIPY was the most stable under the conditions used in the experiments. It was found that reaction of 4,4-dimethoxy BODIPY with dichloroacetic acid gave mixed anhydride 4,4-bis(dichloroacetoxy) BODIPY in good yields. Treatment of the latter mixed anhydride with alcohols such as methanol and ethanol in the presence of a base afforded corresponding borate esters, whereas treatment with 1,2-diols such as ethylene glycol and catechol in the presence of a base gave corresponding cyclic borate esters. Furthermore treatment of 4,4-difluoro-8-methyl-BODIPY with secondary amines in dihalomethane resulted in carbon–carbon bond formation at the meso-methyl position of BODIPY via Mannich-type reactions. The resulting modified BODIPY fluorophores possess high fluorescent quantum yields. Five BODIPY analogues bearing potential ion-binding moieties were synthesized via this Mannich-type reaction. Among these, the BODIPY bearing an aza-18-crown-5 tether was found to be selective towards copper (II) ion, resulting in a large blue shift in absorption and sharp fluorescent quenching, whereas aza-15-crown-4 analogue was selected towards fluoride ion, leading to effective florescent quenching and blue shift. (B) Peptide nucleic acids (PNA), as mimics of natural nucleic acids, have been widely applied in molecular biology and biotechnology. Currently, the preparation of PNA oligomers is commonly achieved by a coupling reaction between carboxyl and amino groups in the presence of an activator. In this thesis attempts were made towards the synthesis of PNA through the Staudinger ligation reactions between C-terminal diphenylphosphinomethanethiol thioesters and N-terminal α-azido PNA building blocks.

A DFT Guided/Experimental Approach to Asymmetric Allylation and Phase-Transfer Catalysis

The Dudding group is interested in the application of Density Functional Theory (DFT) in developing asymmetric methodologies, and thus the focus of this dissertation will be on the integration of these approaches. Several interrelated subsets of computer aided design and implementation in catalysis have been addressed during the course of these studies. The first of the aims rested upon the advancement of methodologies for the synthesis of biological active C(1)-chiral 3-methylene-indan-1-ols, which in practice lead to the use of a sequential asymmetric Yamamoto-Sakurai-Hosomi allylation/Mizoroki Heck reaction sequence. An important aspect of this work was the utilization of ortho-substituted arylaldehyde reagents which are known to be a problematic class of substrates for existing asymmetric allylation approaches. The second phase of my research program lead to the further development of asymmetric allylation methods using o-arylaldehyde substrates for synthesis of chiral C(3)-substituted phthalides. Apart from the de novo design of these chemistries in silico, which notably utilized water-tolerant, inexpensive, and relatively environmental benign indium metal, this work represented the first computational study of a stereoselective indium-mediated process. Following from these discoveries was the advent of a related, yet catalytic, Ag(I)-catalyzed approach for preparing C(3)-substituted phthalides that from a practical standpoint was complementary in many ways. Not only did this new methodology build upon my earlier work with the integrated (experimental/computational) use of the Ag(I)-catalyzed asymmetric methods in synthesis, it provided fundamental insight arrived at through DFT calculations, regarding the Yamamoto-Sakurai-Hosomi allylation. The development of ligands for unprecedented asymmetric Lewis base catalysis, especially asymmetric allylations using silver and indium metals, followed as a natural extension from these earlier discoveries. To this end, forthcoming as well was the advancement of a family of disubstituted (N-cyclopropenium guanidine/N-imidazoliumyl substituted cyclopropenylimine) nitrogen adducts that has provided fundamental insight into chemical bonding and offered an unprecedented class of phase transfer catalysts (PTC) having far-reaching potential. Salient features of these disubstituted nitrogen species is unprecedented finding of a cyclopropenium based C-H•••πaryl interaction, as well, the presence of a highly dissociated anion projected them to serve as a catalyst promoting fluorination reactions. Attracted by the timely development of these disubstituted nitrogen adducts my last studies as a PhD scholar has addressed the utility of one of the synthesized disubstituted nitrogen adducts as a valuable catalyst for benzylation of the Schiff base N-diphenyl methylene glycine ethyl ester. Additionally, the catalyst was applied for benzylic fluorination, emerging from this exploration was successful fluorination of benzyl bromide and its derivatives in high yields. A notable feature of this protocol is column-free purification of the product and recovery of the catalyst to use in a further reaction sequence.