Interactions between organic polymers and cement hydration products

Organic substances, particularly polymers, are finding increasing use in modifying the properties of cements and concrete. Although a significant amount of research has been conducted into the modification of the mechanical properties of cements by polymers, little is known about the nature of the interface and interactions taking place between the two phases. This thesis addresses the problem of elucidating such interactions. Relevant literature is reviewed, covering the general use of polymers with cements, the chemistry of cements and polymers, adhesion and known interactions between polymers and both cements and related minerals. Although several polymer systems were studied, two in particular were selected, as being well characterized. These were: - 1) polymethyl methacrylate (PMMA), the polymer derived from methyl methacrylate (MMA), and 2) an amine-cured epoxy resin system. By this approach, a methodology was developed for the examination of other polymer/cement interactions. Experiments were conducted in five main areas:- 1) polymer-cement adhesion and the feasibility of revealing interfacial regions mechanically, 2) chemical reactions between polymers and cements, 3) characterization of cement adhesion surfaces, 4) interactions affecting overall polymerisation rates, and 5) studies of polymer impregnated cements. The following conclusions were reached:- 1) The PMMA/cement interface contains calcium methacrylate as an interfacial reaction product, water being a reactant. Calcium methacrylate is detrimental to the properties of PMMA/cement composites, being highly water-soluble. 2) The pore surface of cement accelerates the polymerisation of MMA, leading to an increased molecular weight compared to polymerisation of pure MMA, minerals in hydrated cement powders having the opposite effect. 3) The investigation of reaction products presents a number of experimental problems, selection of appropriate techniques depending upon the system studied. For the two systems examined in detail, ion chromatography proved particularly useful; DTA, IRS and XPS indicated reactions, though the data was hard to interpret; XRD proving inconclusive. 4) It is impractical to reveal interfacial regions mechanically, but may be accomplished by chemical means.

SQUID magnetometry as a tool for following a clock reaction in solution

SQUID magnetometry, normally used to characterise the properties of solids, was used to follow a clock reaction in solution, namely the auto-catalytic oxidation of [Co(ii)EDTA] by HO, in real time and it was shown that, in combination with other methods (e.g., magnetic resonance proton relaxation studies and UV-vis absorption analysis), SQUID magnetometry can be a powerful method in elucidating and interpreting the time-profile of chemical reactions so as long as reactants, intermediates and products have suitably large differences in their respective magnetic susceptibilities. © 2009 The Royal Society of Chemistry.

Increase of the photosensitivity of undoped poly(methylmethacrylate) under UV radiation at 325 nm

In this paper we report, for the first time to our knowledge, an increase of the photosensitivity of a microstructured polymer optical fibre (mPOF) made of undoped PMMA due to applied strain during the fabrication of the gratings. In the work, fibre Bragg gratings (FBGs) have been fabricated in undoped PMMA mPOFs with a hexagonal structure of three rings in the inner cladding. Two sets of FBGs were inscribed at two different resonant wavelengths (827 nm and 1562 nm) at different strains using an UV He-Cd laser at 325 nm focused by a lens and scanned over the fibre. We observed an increase of the reflection of the fibre Bragg gratings when the fabrication strain is higher. The photosensitivity mechanism is discussed in the paper along with the chemical reactions that could underlie the mechanism. Furthermore, the resolution limit of the material was investigated. © 2014 Copyright SPIE.

Branching Stochastic Processes: History, Theory, Applications

Косто В. Митов - Разклоняващите се стохастични процеси са модели на популационната динамика на обекти, които имат случайно време на живот и произвеждат потомци в съответствие с дадени вероятностни закони. Типични примери са ядрените реакции, клетъчната пролиферация, биологичното размножаване, някои химични реакции, икономически и финансови явления. В този обзор сме се опитали да представим съвсем накратко някои от най-важните моменти и факти от историята, теорията и приложенията на разклоняващите се процеси.

Activated escape from polarization pulling in fibre Raman amplifiers

Fluctuation-induced escape (FIE) from a metastable state with probability controlled by external force is a process inherent in many physical phenomena such as diffusion in crystals, protein folding, activated chemical reactions etc. [1-3]. In this work we present a novel example of FIE problem, considering a very practical nonlinear system recently emerged in the area of fibre telecommunications. Unlike the standard FIE problems where noise is time-dependent, in fibre Raman amplifier (FRA) the role of noise is played by frozen fluctuations of parameters (random birefringence) along the fibre span which result from the breaking of cylindrical symmetry during the fibre drawing [4-6]. The role of periodic forcing in this problem is played by the periodic fibre spinning, leading to key model that is formally similar to the time-domain equations for periodically forced escape [1-3]. © 2011 IEEE.

Theoretical study of chloroperoxidase catalyzed chlorination of beta-cyclopentanedione and role of water in the chlorination mechanism

Chloroperoxidase (CPO) is a potential biocatalyst for use in asymmetric synthesis. The mechanisms of CPO catalysis are therefore of interest. The halogenation reaction, one of several chemical reactions that CPO catalyzes, is not fully understood and is the subject of this dissertation. The mechanism by which CPO catalyzes halogenation is disputed. It has been postulated that halogenation of substrates occurs at the active site. Alternatively, it has been proposed that hypochlorous acid, produced at the active site via oxidation of chloride, is released prior to reaction, so that halogenation occurs in solution. The free-solution mechanism is supported by the observation that halogenation of most substrates often occurs non-stereospecifically. On the other hand, the enzyme-bound mechanism is supported by the observation that some large substrates undergo halogenation stereospecifically. The major purpose of this research is to compare chlorination of the substrate β-cyclopentanedione in the two environments. One study was of the reaction with limited hydration because such a level of hydration is typical of the active site. For this work, a purely quantum mechanical approach was used. To model the aqueous environment, the limited hydration environment approach is not appropriate. Instead, reaction precursor conformations were obtained from a solvated molecular dynamics simulation, and reaction of potentially reactive molecular encounters was modeled with a hybrid quantum mechanical/molecular mechanical approach. Extensive work developing parameters for small molecules was pre-requisite for the molecular dynamics simulation. It is observed that a limited and optimized (active-site-like) hydration environment leads to a lower energetic barrier than the fully solvated model representative of the aqueous environment at room temperature, suggesting that the stable water network near the active site is likely to facilitate the chlorination mechanism. The influence of the solvent environment on the reaction barrier is critical. It is observed that stabilization of the catalytic water by other solvent molecules lowers the barrier for keto-enol tautomerization. Placement of water molecules is more important than the number of water molecules in such studies. The fully-solvated model demonstrates that reaction proceeds when the instantaneous dynamical water environment is close to optimal for stabilizing the transition state.

Mangrove tannins in aquatic ecosystems: Their fate and possible influence on dissolved organic carbon and nitrogen cycling

We describe the fate of mangrove leaf tannins in aquatic ecosystems and their possible influence on dissolved organic nitrogen (DON) cycling. Tannins were extracted and purified from senescent yellow leaves of the red mangrove (Rhizophora mangle) and used for a series of model experiments to investigate their physical and chemical reactivity in natural environments. Physical processes investigated included aggregation, adsorption to organic matter-rich sediments, and co-aggregation with DON in natural waters. Chemical reactions included structural change, which was determined by excitation–emission matrix fluorescence spectra, and the release of proteins from tannin–protein complexes under solar-simulated light exposure. A large portion of tannins can be physically eliminated from aquatic environments by precipitation in saline water and also by binding to sediments. A portion of DON in natural water can coprecipitate with tannins, indicating that mangrove swamps can influence DON cycling in estuarine environments. The chemical reactivity of tannins in natural waters was also very high, with a half-life of less than 1 d. Proteins were released gradually from tannin–protein complexes incubated under light conditions but not under dark conditions, indicating a potentially buffering role of tannin– protein complexes on DON recycling in mangrove estuaries. Although tannins are not detected at a significant level in natural waters, they play an important ecological role by preserving nitrogen and buffering its cycling in estuarine ecosystems through the prevention of rapid DON export/loss from mangrove fringe areas and/or from rapid microbial mineralization.

Development of an enhanced hydro-geochemical model to address mercury-speciation fate and transport in aquatic environments

An awareness of mercury (Hg) contamination in various aquatic environments around the world has increased over the past decade, mostly due to its ability to concentrate in the biota. Because the presence and distribution of Hg in aquatic systems depend on many factors (e.g., pe, pH, salinity, temperature, organic and inorganic ligands, sorbents, etc.), it is crucial to understand its fate and transport in the presence of complexing constituents and natural sorbents, under those different factors. An improved understanding of the subject will support the selection of monitoring, remediation, and restoration technologies. The coupling of equilibrium chemical reactions with transport processes in the model PHREEQC offers an advantage in simulating and predicting the fate and transport of aqueous chemical species of interest. Thus, a great variety of reactive transport problems could be addressed in aquatic systems with boundary conditions of specific interest. Nevertheless, PHREEQC lacks a comprehensive thermodynamic database for Hg. Therefore, in order to use PHREEQC to address the fate and transport of Hg in aquatic environments, it is necessary to expand its thermodynamic database, confirm it and then evaluate it in applications where potential exists for its calibration and continued validation. The objectives of this study were twofold: 1) to develop, expand, and confirm the Hg database of the hydrogeochemical PHREEQC to enhance its capability to simulate the fate of Hg species in the presence of complexing constituents and natural sorbents under different conditions of pH, redox, salinity and temperature; and 2) to apply and evaluate the new database in flow and transport scenarios, at two field test beds: Oak Ridge Reservation, Oak Ridge, TN and Everglades National Park, FL, where Hg is present and is of much concern. Overall, this research enhanced the capability of the PHREEQC model to simulate the coupling of the Hg reactions in transport conditions. It also demonstrated its usefulness when applied to field situations.

Dificuldades de aprendizagem do conteúdo de soluções: proposta de ensino contextualizada

The study of solutions is considered very important to chemist’s education because most of the chemical reactions occur in aqueous medium, being also required to understand other subject such as chemical changes, electrochemical and chemical balance. Nevertheless, it is noticed that many students indicate learning difficulties related to the content of solutions, how to pass among the macro-submicroscopic knowledge levels, and how to solve quantitative problems that demanding the establishment of a stoichiometric ratios. This thesis defended considers the use of contextualized teaching strategies about some subject associated to the study of solution, can foster student learning through reflection and understanding of their own difficulties, besides to provide motivation and active participation. The target group is formed by students of the undergraduate distance education with major in chemistry education of the Universidade Federal do Rio Grande do Norte (UFRN), and they were chosen because this education system is expanding and its learning difficulties publications number is reduced as well. Thus, the first methodological stage was to identify the student’s main learning difficulties associated to the study of solutions through literature sources. Next, using an adapted script of the Plano Nacional do Livro Didático para o Ensino Médio (PNLEM, Textbook National Plan for High School), the approach of the content of solutions printed in educational materials used by the target group was analyzed. Afterward, a teaching unit was planned in the last methodological stage and, finally, a new teaching unite was given with a sequence of contextualized activities such as video presentation, dialogued lecture, questionnaires application, exercises, and an experiment, where the target group’s main difficulties related to learning of solution were identified. The participants of the teaching unit activities had some learning difficulties in understand concepts of compound, ion, charge, entropy and solubility, as well as to identify the ion charge, interpret statements, decode tables, use the chemical language, perform mathematical calculations and use concentration units, similar results raised in the literature sources. In order to work on these difficulties, these students were encouraged to expose, question and test their ideas about the phenomenon under study, allowing learn from their mistakes and reflect on the organization strategy of scientific explanatory models they use. Therefore, activities and information about learning difficulties presented in this thesis need to be critical reflection object, because it can help both students in the process of acquiring knowledge about the content of solutions and professors in the planning of their lessons.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

A compreensão de reação química como um sistema complexo a partir da discussão dos erros e dificuldades de aprendizagem de estudantes do ensino médio

The study of chemical reactions is among the most important contents to the understanding of Chemistry discipline in basic education. However, there are still few studies about chemical reactions as a complex system because, generally, this content is presented in textbooks, taught and even researched in a fragmented form. The thesis here presented aims to investigate, identify and characterize the mistakes and learning difficulties of the students about chemical reactions as a complex system, using for that purpose the analysis of the answers of 126 exams of candidates for the bachelor’s degree in Chemistry Teaching on the entrance exam for the Federal University of Rio Grande do Norte (UFRN). The mistakes and learning difficulties about the parameters ΔG°, Kp, Ea and of the calculation of the amount of substance in a chemical reaction have been identified, as well as the levels of development of the ability to interpret the chemical reaction as a system. The main theoretical source of this study is structured based on the mistakes and learning difficulties (NÚÑEZ, RAMALHO, 2012), of the chemical reactions as complex systems (NÚÑEZ, 1994; RESHETOVA, 1988; SANDERSON, 1968). As methodology, it was prioritized the analysis of the answers to the exams and the interview with the teachers. The results showed typical mistakes in the study of this subject, especially low levels and skill development. No student was able to integrate the different aspects in the systemic understanding of the chemical reaction. From the interviews with Chemistry teachers from High School, it was determined the reasons the teachers assign to those mistakes and learning difficulties. The interviews revealed that the teachers do not work in the perspective of integration of the contents which leads the students to present difficulties and make mistakes related to the content previously mentioned. The study presents a proposal for the organization of the contents of Chemistry discipline for High School as a possibility of a dialectic systemic integration of contents, understanding that this systematic vision, leads to important contributions to the development of the theoretical thinking of the students. We can mention as one of the conclusions of this study, the fact that the non-systemic organization of contents do not favor this kind of thinking in students.

Influência do tempo de adição do policarboxilato em pastas de cimento Portland para cimentação de poços petrolíferos

Cement pastes used in cementing oil wells operations are prepared according to the specific characteristics of each well. The physical properties requested for each folder formulation depend on the temperature and pressure of the well to be cemented. The rheological properties of the pulp are important control parameter for efficiency in transportation and positioning the folder during the cementing operation. One of the main types of additive used for the adjustment of rheological properties of cement pastes is the dispersant additive. This work aims to study the influence of variation of the time of addition of the polycarboxylate (0, 5, 10 and 15 minutes) in cement pastes, considering the initial periods of hydration of cement particles as fundamental point for better performance dispersant additive. Pastes were prepared with a density set at 15.6 lb/gal (1.87 g/cm3) and polycarboxylate concentrations ranging from 0.01 gpc to 0.05 gpc circulation temperature (BHCT) of 51°C and static temperature (BHST) of 76 C. The pastes were characterized from a rheological measurements, volume filtered, thickening time and resistance to compression formulations. Also were carried out tests Diffraction X-ray (XRD) and Scanning Electron Microscopy (MEV). The results showed that the addition of policaboxilato after 15 minutes decreased by 70% the values of rheological parameters. According to results of DRX and MEV, the addition of dispersant after 15 minutes did not affect the chemical reactions and subsequent formation of cement hydration products. A study of the economic feasibility to realize the financial benefits of the technique, which can be seen only with the use of the technique in this work to reduce the cost of production of cement paste was carried out, can get up to $ 1015.00 for each folder 100 barrels produced with said formulations.

Influência do tempo de adição do policarboxilato em pastas de cimento Portland para cimentação de poços petrolíferos

Cement pastes used in cementing oil wells operations are prepared according to the specific characteristics of each well. The physical properties requested for each folder formulation depend on the temperature and pressure of the well to be cemented. The rheological properties of the pulp are important control parameter for efficiency in transportation and positioning the folder during the cementing operation. One of the main types of additive used for the adjustment of rheological properties of cement pastes is the dispersant additive. This work aims to study the influence of variation of the time of addition of the polycarboxylate (0, 5, 10 and 15 minutes) in cement pastes, considering the initial periods of hydration of cement particles as fundamental point for better performance dispersant additive. Pastes were prepared with a density set at 15.6 lb/gal (1.87 g/cm3) and polycarboxylate concentrations ranging from 0.01 gpc to 0.05 gpc circulation temperature (BHCT) of 51°C and static temperature (BHST) of 76 C. The pastes were characterized from a rheological measurements, volume filtered, thickening time and resistance to compression formulations. Also were carried out tests Diffraction X-ray (XRD) and Scanning Electron Microscopy (MEV). The results showed that the addition of policaboxilato after 15 minutes decreased by 70% the values of rheological parameters. According to results of DRX and MEV, the addition of dispersant after 15 minutes did not affect the chemical reactions and subsequent formation of cement hydration products. A study of the economic feasibility to realize the financial benefits of the technique, which can be seen only with the use of the technique in this work to reduce the cost of production of cement paste was carried out, can get up to $ 1015.00 for each folder 100 barrels produced with said formulations.

Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively. Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.