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Influence of defects and geometry in welded jointsNerman, Peter January 2005 (has links)
No description available.
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Control of weldability : Research leading to the development of two new quenched and tempered tool steelsHansson, Per January 2004 (has links)
<p>The understanding of the hardenability is important in steel development with respect to weldability of steels as well as to the design of quenched and tempered steels.The common way to judge if steel is suitability to welding is the use of a carbon equivalent, which reflects the alloy content to the hardenability of the heat affected zone (HAZ). Most common of these equivalent is the IIW carbon equivalent wich has been in use for decades.</p><p>However, this is an empirical equivalent, developed for CMn steels, and it doesn't say anything about the mechanical properties obtained in the HAZ. As a guideline a maximum HAZ hardness of 350 HV is normally put to avoid cold cracking in the HAZ. Numerous carbon equivalents have been published during the years, but few have been accepted and used. A drawnback of all these equivalents is that they have been evaluated for a set of chemical compositions which may be quite narrow, or that they have been evaluated on steels produced having other cleanliness, residual element levels etc. as is common in modern steelmarketing. </p><p>The hardenability of steel designated to quenching and tempering is normally evaluated using either Jominy testing or using a calculation using the Grossmann formalism. As the hardenability described in the carbon equivalents used in welding and the hardenability of quenched and tempered steels using the Grossmann formalism are two different descriptions of the same phenomenon the aim of this thesis is to link these two formalisms together and use the knowledge from the HAZ hardenability to design quenched and tempered steels. The goal is to produce such steel grades having a much better weldability as compared with standard grades available at the market. </p><p>In this work the hardenability in the heat affected zone (HAZ) in weldments in high strength low alloyed steels (HSLA steels) having a yield strength of 350 MPa. This part microalloying elements on the phase transformations which take place during cooling from the peak temperature of the welding cycle. These results have been linked to the mechanical properties of the HAZs. </p><p>In the second part of this thesis the development of tool steel grades with respect to optimise both hardenability with respect to; </p><p>- matrix hardenability (i.e the Grossmann approach) </p><p>- an enhanced weldability of such new steels due to a lower alloying content than is usual in such grades</p>
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Investigation of nickel phospor coat : -As corrosion protection inside water heatersWikstrand, Björn January 2009 (has links)
This thesis explores the possibility of alternatives to copper lining inside the water heater tank in water heaters. The need for an alternative is based on the increasing copper prices the recent years. The aim of this thesis is to compare three different materials, stainless steel, copper and a nickel coated plain carbon steel. This comparison is based on a basic corrosion test and a literature survey to render a merit value for each environment/metal interface. The testing solution consists of 100ppm Cl - concentration the specimens are tested in three different pH levels and at three different temperatures. The specimens have their weight measured before and after the test. The 15μm thick nickel coating was performed by Ferroprodukter AB, composing of 9% P and 91% Ni. The copper and stainless steel specimens are both from Thermia’s actual water heater tank. The copper lining is made of pure copper and the stainless steel hull is made of ferritic stainless steel. The results from the corrosion test are measured in weight change by modulus, |Δw|/w, for the comparison of the three materials. It was found that stainless steel was the worst material, performing better at higher temperatures and higher pH , but overall performance is far from copper and nickel’s corrosion properties. The nickel coating and copper specimen showed comparable results and perform more or less equally well. Regarding identification of corrosion mechanics, it may consist of either pitting and general corrosion damage or a mixture of both. To avoid the fact that weight change may be both negative and positive, the solution to this was to incorporate a merit value based on the absolute value of the weight change, divided by the initial weight of the specimen. In conclusion, stainless steel total weight change by modulus accumulates to 16.072g, nickel coated specimen accumulates a weight change by modulus equal to 8.544g, important note: two of the nickel coated specimen account for ~72.4% of the total weight change by modulus which then accumulates to 2.36g. Copper’s total weight change by modulus was 2.937g thus the lowest. However, disregarding from the 90캜 regime; stainless steel scores 13.496g, copper 2.151g, and nickel 1.095g.
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Organic Bioelectronics : Electrochemical Devices using Conjugated PolymersIsaksson, Joakim January 2007 (has links)
Since the Nobel Prize awarded discovery that some polymers or “plastics” can be made electronically conducting, the scientific field of organic electronics has arisen. The use of conducting polymers in electronic devices is appealing, because the materials can be processed from a liquid phase, much like ordinary non-conducting plastics. This gives the opportunity to utilize printing technologies and manufacture electronics roll-to-roll on flexible substrates, ultimately at very low costs. Even more intriguing are the possibilities to achieve completely novel functionalities in combination with the inherent compatibility of these materials with biological species. Therefore, organic electronics can be merged with biology and medicine to create organic bioelectronics, i.e. organic electronic devices that interact with biological samples directly or are used for biological applications. This thesis aims at giving a background to the field of organic bioelectronics and focuses on how electrochemical devices may be utilized. An organic electronic wettability switch that can be used for lab-on-a-chip applications and control of cell growth as well as an electrochemical ion pump for cell communication and drug delivery are introduced. Furthermore, the underlying electrochemical structures that are the basis for the above mentioned devices, electrochemical display pixels etc. are discussed in detail. In summary, the work contributes to the understanding of electrochemical polymer electronics and, by presenting new bioelectronic inventions, builds a foundation for future projects and discoveries.
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Porphyrins based detection of NH3 and CO, using field effect grid gate devicesSánchez Reátegui, Rafael January 2010 (has links)
<p>Porphyrins consist of twenty-atom rings containing four nitrogen atoms and can be used as sensor to detect odours and gases.</p><p>This thesis investigates whether or not porphyrins can be used as functional materials on grid gate devices. Drops of PVC embedded porphyrins were deposited on the surface of a grid gate which is a Metal Oxide Semiconductor (MOS) capacitor. In order to detect the gas sensing properties of the porphyrins a light addressable method called Scanning Light Pulse Technique (SLPT) has been used.</p><p>Drops of porphyrins were deposited with a stretched capillary tube (1 mm diameter).</p><p>The MOS capacitor has been exposed to nitrogen atmosphere as reference environment, while the target gases were carbon monoxide (100 ppm) and ammonia (500 ppm).</p><p>The result from the eight porphyrins is that one of them [Pt(II) TPP] has a response for both gases, ammonia induces a change in both the work function and surface resistance, while the carbon monoxide induces only a change in the surface resistance.</p>
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Rheology and Reactivity of Cementitious Binders with PlasticizersVikan, Hedda Vestøl January 2005 (has links)
<p>The rheological behaviour of cementitious pastes has been studied by various means. Six different cements have been studied in main parts of the work and all of them have been characterized according to the Rietveld method in order to determine the exact content of minerals. Easily soluble alkalis were measured by plasma-emission- spectroscopy of the fluid filtered from paste. Three types of plasticizers namely naphthalene sulfonate formaldehyde condensate (SNF), lignosulphonate and polyacrylate grafted with polyether (PA) have been used throughout the work. The influence of the plasticizer type on the rheological properties of the cementitious pastes, their adsorption characteristics and their effects on heat of hydration of the pastes has been studied. Limestone has been used as a nonreactive model material for cement in some parts of the work. </p><p>All rheological measurements were performed with a parallel plate rheometer. Rather than describing the shear stress-shear rate flow curve with the usual Bingham model resulting in plastic viscosity and yield stress, the area under the curve (Pa/s) was used as a measure of “flow resistance”. </p><p><b>The effect of silica fume and limestone on the rheology of cementitious pastes</b> </p><p>The rheological behaviour of cementitious pastes, with the cement being increasingly replaced by densified and untreated silica fume (SF) or limestone was studied. Three plasticizers were investigated namely two types of polyacrylate (PA1 and PA2) and SNF. PA2 proved to be the most efficient plasticizer of the three while PA1 and SNF provided comparable results. </p><p>The flow resistance was found to increase with increasing silica fume replacement when SNF and polyacryalte (PA1) were added as plasticizers which was explained by ionization of the silica fume surface and possible bridging with polyvalent cations like calcium. The flow resistance decreased, however, with increasing silica fume replacement when the second and more efficient type of polyacrylate (PA2) was utilized which was believed to occur since the cement pastes were better dispersed by PA2 than SNF and PA1. The silica fume particles could thus pack between the cement grains and displace water. An alternative explanation for reduced flow resistance with increasing silica fume replacement could be a ball-bearing effect of silica spheres. </p><p>There was found a trend of <i>increasing</i> gel strength with increasing silica fume replacement of cement even though the pastes seemed to be dispersed by PA2. Cement pastes with densified SF developed lower gel strengths than pastes with untreated SF. This phenomenon was attributed to more grain shaped agglomerates with lower outer surface in densified SF compared to dendritic agglomerated in untreated SF. Decreasing gel strength was found for pastes with increasing limestone filler replacement. Thus silica fume may be advantageous as stabilizing agent for self-compacting concrete preventing segregation upon standing due to a more rapid gel formation. </p><p><b>Effect of cement characteristics on flow resistance</b> </p><p>Rheological experiments were performed on pastes prepared from 4 cements originating from the same clinker, but ground to different finenesses (Blaine). The results showed that the flow resistance increased exponentially with increasing Blaine number. No correlations between single cement characteristics such as Blaine, content of C<sub>3</sub>A, cubic C<sub>3</sub>A (cC<sub>3</sub>A) and C<sub>3</sub>S with the flow resistance were however found when cements from different clinkers were used. This finding indicates that cement should not be treated as a univariable material. However, the combined cement characteristic (Blaine•{d•cC<sub>3</sub>A+[1-d]•C<sub>3</sub>S}) was found to correlate with flow resistance, where the factor d represents relative reactivity of C<sub>3</sub>A and C<sub>3</sub>S. The flow resistance was found to be either a linear or exponential function of the combined cement characteristic depending on plasticizer type and dosage. Correlations were found for a mix of pure cement and cement with fly ash, limestone filler (4%), as well as pastes with constant silica fume dosage when the minerals were determined by XRD. </p><p><b>Influence of cement and plasticizer type on the heat of hydration</b> </p><p>The initial heat of hydration peak was measured for the 6 main cements with 0.32% SNF, lignosulphonate and PA2 by cement weight. Correlations were attempted between the maximum heat of hydration rates of the initial peaks with various cement characteristics. The maximum heat of hydration rate seemed to correlate with the product of the cement fineness and C<sub>3</sub>A content regardless of plasticizer type. The fly ash cement had to be left out of the correlation plots due to its low initial heat of hydration. </p><p>The second, third and fourth hydration peaks were measured on the cement pastes with 0-0.8% SNF, lignosulphonate and PA2 by weight of cement. Lignosulphonate was found to be the strongest retarder while SNF had the least effect on the setting time of the three plasticizers. No correlations could be found between the setting times and cement characteristics such as cement fineness, aluminate and alkali contents for un-plasticized pastes probably because the setting times might have been too close to each other to be able to obtain accurate values. Correlations between setting time and cement characteristics were however found for pastes with plasticizers. The setting times did not correlate with the cement fineness (Blaine) as a single parameter. The product of cement Blaine and C<sub>3</sub>A content, however, resulted in a correlation. Furthermore the setting time correlated with the cubic modification of C<sub>3</sub>A. It may seem that the setting times depend more on the cubic modification of C<sub>3</sub>A than the sum of orthorhombic and cubic aluminate. This finding indicates that the cubic aluminate modification is more reactive than the orthorhombic. The setting time decreased with increasing content of easily soluble K-ions in the cements probably due to the formation of syngenite, K<sub>2</sub>SO<sub>4</sub>·CaSO<sub>4</sub>·H<sub>2</sub>O, which removes some sulphate from solution that would otherwise retard C<sub>3</sub>A hydration. A similar correlation was not found between the setting time and the sodium equivalent.</p><p><b>Cement interactions with plasticizers </b></p><p>Three plasticizers were studied namely SNF, lignosulphonate and polyacrylate (PA2). PA2 was the most efficient plasticizer of the three tested even thought it was found to adsorb to a lesser extent on cement than SNF and lignosulphonate. SNF and lignosulphonate brought about comparable results. </p><p>PA2 was observed to induce flow gain within the 2 hours of rheological measurements which might be caused by the polymer expanding in the water phase and thus improve the dispersion of the paste. Furthermore the grafted side chains of the polymer are considered to be long enough to provide steric dispersion even thought the backbone might be embedded in the hydration products. Cement pastes with SNF and lignosulphonate exhibited flow loss as a function of time which indicates that the plasticizer molecules were consumed by the hydration products. </p><p>The concentrations of superplasticizer in the pore water were not found to change markedly in the time range 20-95 min after water addition, indicating that most of the plasticizer molecules were consumed (i.e. adsorbed or intercalated in surface hydration products) within the first 20 minutes after water addition. </p><p>The adsorption characteristics were found to depend on the plasticizer type. The adsorption curves of SNF and lignosulphonate reached a plateau at saturation characterizing high-affinity adsorption or increased continuously as a sign of low affinity adsorption. The adsorbed amounts of polyacrylate decreased, however, after saturation had been reached which might indicate that surplus molecules in the water phase compress the ionic double layer or that adsorbed molecules expand and hinder molecules in the water phase to attach at the surface (i.e. osmosis). </p><p>The plasticizer saturation dosages were found to depend on cement surface area (Blaine), amount of cubic C<sub>3</sub>A and easily soluble sulphates. The saturation dosage of lignosulphonate seemed to have a dependency on the amount of soluble alkali that was somewhat stronger than observed for pastes with SNF. This difference might be caused by lignosulphonate forming complexes with solvated ions in a higher degree than SNF. Moreover alkali sulphates are furthermore often added to commercial SNF based products as the one used in this work. The best correlation, overall, was found for the product of cubic C<sub>3</sub>A and Blaine which is logical since high surface and cubic aluminate contents accounts for high cement reactivity and since the plasticizers are known to coordinate with calcium sites. Correlations were also found between saturation dosage with the product of Na<sub>eqv </sub>and Blaine as well as the product of Na<sub>eqv</sub> and cubic C<sub>3</sub>A. The investigations seemed to indicate that the plasticizer saturation concentration increase with increasing alkali content. These findings, however, are rather unclear. According to literature an increased concentration of alkali sulphate in solution results in both an increased hydration rate (which would lead to a higher plasticizer intercalation) and a reduced plasticizer adsorption (due to SO<sub>4</sub><sup>2-</sup> - superplasticizer competition). The easily soluble sulphates might, of course, entail the opposing effects of Blaine and C<sub>3</sub>A in a way that smoothen the correlation plots of the plasticizer saturation dosage with the cement characteristics.</p><p><b>Effect of temperature on rheology and plasticizer adsorption</b> </p><p>Flow resistance and adsorbed amounts of SNF, lignosulphonate and PA2 were measured at temperatures ranging from 11 to 40<sup>o</sup>C. Limestone was used as a nonreactive model material for cement. The adsorbed amounts of SNF and lignosulphonate on limestone were found to decrease after reaching a maximum which occurred at approximately 25<sup>o</sup>C. Decreased amounts of adsorbed plasticizer with increasing temperature might be explained by increased kinetic energy to the molecules or by an entropy effect. The adsorption of PA2 on limestone seemed to be independent of paste temperature in the range of 16-34<sup>o</sup>C which might be caused by low reduction of entropy at adsorption due to its short backbone and long, grafted side chains. The flow resistance of the limestone pastes generally increased with increasing temperature which may be caused by reduced amounts of adsorbed plasticizer and/or dehydration of the paste during the rheological measurements. </p><p>Two types of cements were used to study adsorption and flow resistance with increasing temperature namely CEM I 42.5 RR and CEM I 52.5 R-LA. Amounts of plasticizer adsorbed and intercalated (consumed) by cement reached a plateau or even decreased with increasing temperature in the case of SNF and lignosulphonate. This finding might be caused by two opposing effects namely: increased number of adsorption sites due to increased hydration rate with increasing temperature and reduced adsorption due to increased kinetic energy and/or reduced entropy of the plasticizer. Amounts of PA2 consumed by cement increased linearly with increasing temperature as might be explained by the experiments with limestone where the adsorbed amounts of PA2 seemed to be independent of temperature. Increased consumption of plasticizer by the cements with rising temperature is thus probably governed by the increased number of adsorption cites due to increased hydration rate. The flow resistance of CEM I 52.5 R-LA cement increased exponentially with increasing temperature as a function of temperature most likely because of the increased hydration rate. The pastes of CEM I 42.5 RR cement were generally highly viscous and probably agglomerated. The flow resistance reached a plateau value with increasing temperature in this case.</p>
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Determination of Oxygen Transport Coefficients in Perovskites and Perovskite related Materials with mixed ConductivityWatterud, Geir January 2005 (has links)
<p>Perovskites and perovskite related materials are materials that are candidates for applications such as oxygen permeable membranes, cathodes for SOFC and high-temperature oxygen sensors. This arises from the potential high ionic conductivity and the chemical stability even at low partial pressures of oxygen. From an application point of view, it is important to have knowledge about the oxygen transport properties in these materials. Oxygen transport in mixed conducting oxides involves two inherently different processes; oxygen exchange between bulk gas and surface and solid state diffusion. The objective of this work has been to obtain fundamental understanding of these transport properties in mixed ionic and electronic conductors. For that purpose two materials systems with significant differences in electronic conductivty and oxygen vacancy concentration were chosen as objectives for the investigation, viz.: Sr-substituted LaCoO<sub>3</sub> and Al-substituted SrTiO<sub>3</sub>.</p><p>All transport properties (diffusion and surface exchange) have been assessed by electrical conductivity relaxation, and the work also evaluate the pros and cons using this specific method to obtain transport data for the materials in question.</p><p>In the first two papers (Paper 1 and Paper 2) transport properties are derived for La<sub>1-x</sub>Sr<sub>x</sub>CoO<sub>3-δ</sub> (x=0 (LC), 0.2 (LSC-02) and 0.5 (LSC-05)). In Paper 1 “chemical transport coefficients”, D<sub>chem</sub> and k<sub>chem</sub>, are reported. More fundamental transport coefficients, such as oxygen component diffusion coefficient (D<sub>O</sub>) and vacancy diffusion coefficients (D<sub>V</sub>), are also deduced and discussed. Activation energies for D<sub>O</sub> and D<sub>V</sub>, were determined. The activation energies for D<sub>O</sub> varies from 279 kJ/mol for LC to 174-222 kJ/mol for LSC-02 and 90-105 kJ/mol for LSC-05, decreasing with increasing Srcontent. The activation energies for the vacancy diffusion coefficient, DV, are smaller than for the component diffusion coefficients and typical values are 77 kJ/mol for LC, 85 kJ/mol for LSC-02 and 75 kJ/mol for LSC-05, that is, almost independent of Sr-content. The enthalpies of vacancy formation decreases with increasing Sr content. The values are 206 kJ/mol for LC, 75 kJ/mol for LSC-02 and 15 kJ/mol for LSC-05, which agrees well with values reported in the literature. However, the vacancy diffusion coefficient showed an unexpected increase at high concentrations of oxygen vacancies, corresponding to δ=0.27-0.30. The phenomena with a PO<sub>2</sub> dependent D<sub>V</sub> is discussed.</p><p>In Paper 2, the oxygen surface exchange coefficient, k<sub>0</sub>, is derived from “chemical values” reported in Paper 1, and used as a basis to deduce probable reaction mechanisms associated with surface exchange. The temperature dependency plots showed that for the composition with x = 0.5, the k0 made a shift in activation energy from ~120 kJ/mol to ~15 kJ/mol above 950 °C. It is suggested that this significant shift in activation energy might be due to an oxygen adsorption/desorption mechanism on the surface becoming rate controlling at high temperatures. The composition with x=0.2 did not show this shift in activation energy. Relations between possible rate controlling reactions and reaction rates (k<sub>0</sub>) were established, and formed the basis for discussions on probable rate controlling processes. There are reasons to assume that for oxidation prosesses a rate controlling reaction involving a direct “installation” of an oxygen molecule into two vacancies is dominating, while a dissociation of an oxygen molecule generally gives a better description for a reduction process.</p><p>In Paper 3 the oxygen transport properties in SrTi<sub>1-x</sub>Al<sub>x</sub>O<sub>3</sub> (x=0 (ST), 0.02 (STA-02) and 0.05 (STA-05)) were determined in O2/N2 mixtures. In this contribution the electrical conductivity is also presented in a large P<sub>O2</sub>- interval (O<sub>2</sub>/N<sub>2</sub>- and CO/CO<sub>2</sub>-mixtures). Electrical conductivity for pure SrTiO<sub>3</sub> (ST) in terms of P<sub>O2</sub> applied well with defect chemistry reported in the literature. For the two Al-substituted compositions the electrical conductivity followed predicted behaviour at high and low P<sub>O2</sub>’s. However, in the medium P<sub>O2</sub> range we were not able to describe the conductivity behaviour in terms of classical defect chemistry. Reasons for the discrepancy is discussed.</p><p>D<sub>chem</sub> for ST and STA-02 are reported and are, along with their corresponding activation energies, 187 and 104-180 kJ/mol, respectively, in good accordance with values from literature. Furthermore, values for the component diffusion coefficient, D<sub>O</sub>, and the vacancy diffusion coefficient, D<sub>V</sub>, are reported for ST at 950 °C, the only composition where oxygen vacancy concentrations are available in the literature. Values for kchem in STA-02 and STA-05 are also reported, and show pronounced P<sub>O2</sub> dependencies. For STA-05 the activation energy for k<sub>chem</sub> is found to vary between 90 and 105 kJ/mol. Due to a high uncertainty, activation energies are not reported for STA-02.</p><p>Reported D<sub>chem</sub> and k<sub>chem</sub> values for related materials in literature indicate increasing numeric values with decreasing concentration of oxygen vacancies. It is reasoned that this is due to an ever increasing thermodynamic factor with decreasing population of vacancies. The implications for the component diffusion coefficient is discussed.</p><p>In Paper 4 the oxygen transport properties in SrTiO<sub>3</sub> pure and with Al were investigated in mixtures of CO/CO<sub>2</sub>. D<sub>chem</sub> are reported for ST and STA-02 while k<sub>chem</sub> are reported for ST, STA-02 and STA-05. The D<sub>chem</sub> showed a P<sub>O2</sub>-dependency, which can be explained by the variation in the thermodynamic factor. The introduction of Al in the sample increases the value of D<sub>chem,</sub> probably due to the introduction of more oxygen vacancies. STA-02 showed a discrete increase in D<sub>chem</sub> in the CO-rich atmospheres, this may be due to phase transition or phase separation at P<sub>O2 </sub>~10<sup>-17</sup> atm. The k<sub>chem </sub>showed a maximum at P<sub>CO</sub>/P<sub>CO2</sub> = 1 for STA-02 and STA-05. This behaviour corresponds well with a rate controlling reaction involving a charged and adsorbed CO<sub>2</sub> molecule. The same maximum is also reported in the literature for BaTiO<sub>3</sub> wihtout and with 1.8 % Al and for La<sub>0.9</sub>Sr<sub>0.1</sub>FeO<sub>3</sub>.</p><p>This work has examined chemical diffusion and surface exchange coefficients with electrical conductivity relaxation in two material systems with distinct differences in electrical conductivity and oxygen vacancy concentrations. The main focus has been to elucidate properties of the transport coefficients based on own measurements, but also include transport coefficients from other material systems from literature as references. The vacancy diffusion coefficients have been examined, showing that they increase with increasing concentration of oxygen vacancies in materials where the concentration of vacancies is high. No obvious reason for this behaviour has been found, however, it may be related to a change in activation energy. It is rather well established in the literature that for materials where the concentration of vacancies may be characterized as dilute, we should expect a D<sub>V</sub> independent of the population of vacancies. Finally, based on own results and data reported in the literature it appears that with respect to the oxygen surface flux the oxygen vacancy concentration seems to be the property of most importance. That is, for oxidation processes the oxygen exchange flux will increase with vacancy population.</p>
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Investigation of nickel phospor coat : -As corrosion protection inside water heatersWikstrand, Björn January 2009 (has links)
<p><p>This thesis explores the possibility of alternatives to copper lining inside the water heater</p><p>tank in water heaters. The need for an alternative is based on the increasing copper prices the</p><p>recent years. The aim of this thesis is to compare three different materials, stainless steel,</p><p>copper and a nickel coated plain carbon steel. This comparison is based on a basic corrosion</p><p>test and a literature survey to render a merit value for each environment/metal interface. The</p><p>testing solution consists of 100ppm Cl</p><p>- concentration the specimens are tested in three<p>different pH levels and at three different temperatures. The specimens have their weight</p><p>measured before and after the test.</p><p>The 15μm thick nickel coating was performed by Ferroprodukter AB, composing of 9% P</p><p>and 91% Ni. The copper and stainless steel specimens are both from Thermia’s actual water</p><p>heater tank. The copper lining is made of pure copper and the stainless steel hull is made of</p><p>ferritic stainless steel.</p><p>The results from the corrosion test are measured in weight change by modulus, |Δw|/w, for</p><p>the comparison of the three materials. It was found that stainless steel was the worst</p><p>material, performing better at higher temperatures and higher pH , but overall performance is</p><p>far from copper and nickel’s corrosion properties. The nickel coating and copper specimen</p><p>showed comparable results and perform more or less equally well. Regarding identification</p><p>of corrosion mechanics, it may consist of either pitting and general corrosion damage or a</p><p>mixture of both. To avoid the fact that weight change may be both negative and positive, the</p><p>solution to this was to incorporate a merit value based on the absolute value of the weight</p><p>change, divided by the initial weight of the specimen.</p><p>In conclusion, stainless steel total weight change by modulus accumulates to 16.072g, nickel</p><p>coated specimen accumulates a weight change by modulus equal to 8.544g, important note:</p><p>two of the nickel coated specimen account for ~72.4% of the total weight change by modulus</p><p>which then accumulates to 2.36g. Copper’s total weight change by modulus was 2.937g thus</p><p>the lowest. However, disregarding from the 90캜 regime; stainless steel scores 13.496g,</p><p>copper 2.151g, and nickel 1.095g.</p></p></p>
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Water-Induced Charge Transport in Microcrystalline Cellulose / Vatteninducerad laddningstransport i mikrokristallin cellulosaNilsson, Martin January 2006 (has links)
<p>Microcrystalline cellulose (MCC) is the most frequently used excipient for direct compaction of tablets within the pharmaceutical industry. It has earlier been indicated that the interactions between the hydration shell – surrounding the drug molecules in an MCC tablet – and the cellulose regulate the speed of the drug release process. These interactions, and the charge transport governed by moisture, are therefore important to analyze and understand to be able to tailor make new functional drug delivery systems.</p><p>In this thesis the physical parameters affecting the water-induced ionic transport have been studied with impedance spectroscopy, transient current measurements, nitrogen adsorption and scanning electron microscopy. Dielectric relaxation processes, pertaining to other processes, have also been assessed and analysed, and a generalized regular singular point model has been shown to be able to describe all features of the dielectric spectrum.</p><p>It has been shown that the ionic charge transport mechanism in humid MCC most likely is governed by two parallel processes: One involving water constituent ions diffusing between adjacent lowest energy sites (free OH- groups) in disordered regions of the cellulose and the other caused by impurity ions, such as Na<sup>+</sup>, and protons or H<sub>3</sub>O<sup>+</sup> ions, jumping between neighboring cellulose OH<sup>-</sup> groups to which primary water molecules are attached. At relative humidities of ~ 37 % (representing monolayer coverage) and higher, the latter process is totally dominating the charge transport.</p><p>At a given moisture content, there are two parameters determining the magnitude of the water-induced ionic conductivity in MCC: The connectedness of the interparticulate bonds and the connectedness of pores with a diameter in the 5-20 nm size range. </p><p>The presented findings emphasize the importance of analysing and being able to control the nanostructure of a pharmaceutical cellulose-based system in order to tailor the drug transport properties. The presented results should also be significant for other areas where cellulose-water interactions are of key issue; such as for paper and sanitary product research and for food industries using cellulose-based gels.</p>
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Rheology and Reactivity of Cementitious Binders with PlasticizersVikan, Hedda Vestøl January 2005 (has links)
The rheological behaviour of cementitious pastes has been studied by various means. Six different cements have been studied in main parts of the work and all of them have been characterized according to the Rietveld method in order to determine the exact content of minerals. Easily soluble alkalis were measured by plasma-emission- spectroscopy of the fluid filtered from paste. Three types of plasticizers namely naphthalene sulfonate formaldehyde condensate (SNF), lignosulphonate and polyacrylate grafted with polyether (PA) have been used throughout the work. The influence of the plasticizer type on the rheological properties of the cementitious pastes, their adsorption characteristics and their effects on heat of hydration of the pastes has been studied. Limestone has been used as a nonreactive model material for cement in some parts of the work. All rheological measurements were performed with a parallel plate rheometer. Rather than describing the shear stress-shear rate flow curve with the usual Bingham model resulting in plastic viscosity and yield stress, the area under the curve (Pa/s) was used as a measure of “flow resistance”. <b>The effect of silica fume and limestone on the rheology of cementitious pastes</b> The rheological behaviour of cementitious pastes, with the cement being increasingly replaced by densified and untreated silica fume (SF) or limestone was studied. Three plasticizers were investigated namely two types of polyacrylate (PA1 and PA2) and SNF. PA2 proved to be the most efficient plasticizer of the three while PA1 and SNF provided comparable results. The flow resistance was found to increase with increasing silica fume replacement when SNF and polyacryalte (PA1) were added as plasticizers which was explained by ionization of the silica fume surface and possible bridging with polyvalent cations like calcium. The flow resistance decreased, however, with increasing silica fume replacement when the second and more efficient type of polyacrylate (PA2) was utilized which was believed to occur since the cement pastes were better dispersed by PA2 than SNF and PA1. The silica fume particles could thus pack between the cement grains and displace water. An alternative explanation for reduced flow resistance with increasing silica fume replacement could be a ball-bearing effect of silica spheres. There was found a trend of increasing gel strength with increasing silica fume replacement of cement even though the pastes seemed to be dispersed by PA2. Cement pastes with densified SF developed lower gel strengths than pastes with untreated SF. This phenomenon was attributed to more grain shaped agglomerates with lower outer surface in densified SF compared to dendritic agglomerated in untreated SF. Decreasing gel strength was found for pastes with increasing limestone filler replacement. Thus silica fume may be advantageous as stabilizing agent for self-compacting concrete preventing segregation upon standing due to a more rapid gel formation. <b>Effect of cement characteristics on flow resistance</b> Rheological experiments were performed on pastes prepared from 4 cements originating from the same clinker, but ground to different finenesses (Blaine). The results showed that the flow resistance increased exponentially with increasing Blaine number. No correlations between single cement characteristics such as Blaine, content of C3A, cubic C3A (cC3A) and C3S with the flow resistance were however found when cements from different clinkers were used. This finding indicates that cement should not be treated as a univariable material. However, the combined cement characteristic (Blaine•{d•cC3A+[1-d]•C3S}) was found to correlate with flow resistance, where the factor d represents relative reactivity of C3A and C3S. The flow resistance was found to be either a linear or exponential function of the combined cement characteristic depending on plasticizer type and dosage. Correlations were found for a mix of pure cement and cement with fly ash, limestone filler (4%), as well as pastes with constant silica fume dosage when the minerals were determined by XRD. <b>Influence of cement and plasticizer type on the heat of hydration</b> The initial heat of hydration peak was measured for the 6 main cements with 0.32% SNF, lignosulphonate and PA2 by cement weight. Correlations were attempted between the maximum heat of hydration rates of the initial peaks with various cement characteristics. The maximum heat of hydration rate seemed to correlate with the product of the cement fineness and C3A content regardless of plasticizer type. The fly ash cement had to be left out of the correlation plots due to its low initial heat of hydration. The second, third and fourth hydration peaks were measured on the cement pastes with 0-0.8% SNF, lignosulphonate and PA2 by weight of cement. Lignosulphonate was found to be the strongest retarder while SNF had the least effect on the setting time of the three plasticizers. No correlations could be found between the setting times and cement characteristics such as cement fineness, aluminate and alkali contents for un-plasticized pastes probably because the setting times might have been too close to each other to be able to obtain accurate values. Correlations between setting time and cement characteristics were however found for pastes with plasticizers. The setting times did not correlate with the cement fineness (Blaine) as a single parameter. The product of cement Blaine and C3A content, however, resulted in a correlation. Furthermore the setting time correlated with the cubic modification of C3A. It may seem that the setting times depend more on the cubic modification of C3A than the sum of orthorhombic and cubic aluminate. This finding indicates that the cubic aluminate modification is more reactive than the orthorhombic. The setting time decreased with increasing content of easily soluble K-ions in the cements probably due to the formation of syngenite, K2SO4·CaSO4·H2O, which removes some sulphate from solution that would otherwise retard C3A hydration. A similar correlation was not found between the setting time and the sodium equivalent. <b>Cement interactions with plasticizers </b> Three plasticizers were studied namely SNF, lignosulphonate and polyacrylate (PA2). PA2 was the most efficient plasticizer of the three tested even thought it was found to adsorb to a lesser extent on cement than SNF and lignosulphonate. SNF and lignosulphonate brought about comparable results. PA2 was observed to induce flow gain within the 2 hours of rheological measurements which might be caused by the polymer expanding in the water phase and thus improve the dispersion of the paste. Furthermore the grafted side chains of the polymer are considered to be long enough to provide steric dispersion even thought the backbone might be embedded in the hydration products. Cement pastes with SNF and lignosulphonate exhibited flow loss as a function of time which indicates that the plasticizer molecules were consumed by the hydration products. The concentrations of superplasticizer in the pore water were not found to change markedly in the time range 20-95 min after water addition, indicating that most of the plasticizer molecules were consumed (i.e. adsorbed or intercalated in surface hydration products) within the first 20 minutes after water addition. The adsorption characteristics were found to depend on the plasticizer type. The adsorption curves of SNF and lignosulphonate reached a plateau at saturation characterizing high-affinity adsorption or increased continuously as a sign of low affinity adsorption. The adsorbed amounts of polyacrylate decreased, however, after saturation had been reached which might indicate that surplus molecules in the water phase compress the ionic double layer or that adsorbed molecules expand and hinder molecules in the water phase to attach at the surface (i.e. osmosis). The plasticizer saturation dosages were found to depend on cement surface area (Blaine), amount of cubic C3A and easily soluble sulphates. The saturation dosage of lignosulphonate seemed to have a dependency on the amount of soluble alkali that was somewhat stronger than observed for pastes with SNF. This difference might be caused by lignosulphonate forming complexes with solvated ions in a higher degree than SNF. Moreover alkali sulphates are furthermore often added to commercial SNF based products as the one used in this work. The best correlation, overall, was found for the product of cubic C3A and Blaine which is logical since high surface and cubic aluminate contents accounts for high cement reactivity and since the plasticizers are known to coordinate with calcium sites. Correlations were also found between saturation dosage with the product of Naeqv and Blaine as well as the product of Naeqv and cubic C3A. The investigations seemed to indicate that the plasticizer saturation concentration increase with increasing alkali content. These findings, however, are rather unclear. According to literature an increased concentration of alkali sulphate in solution results in both an increased hydration rate (which would lead to a higher plasticizer intercalation) and a reduced plasticizer adsorption (due to SO42- - superplasticizer competition). The easily soluble sulphates might, of course, entail the opposing effects of Blaine and C3A in a way that smoothen the correlation plots of the plasticizer saturation dosage with the cement characteristics. <b>Effect of temperature on rheology and plasticizer adsorption</b> Flow resistance and adsorbed amounts of SNF, lignosulphonate and PA2 were measured at temperatures ranging from 11 to 40oC. Limestone was used as a nonreactive model material for cement. The adsorbed amounts of SNF and lignosulphonate on limestone were found to decrease after reaching a maximum which occurred at approximately 25oC. Decreased amounts of adsorbed plasticizer with increasing temperature might be explained by increased kinetic energy to the molecules or by an entropy effect. The adsorption of PA2 on limestone seemed to be independent of paste temperature in the range of 16-34oC which might be caused by low reduction of entropy at adsorption due to its short backbone and long, grafted side chains. The flow resistance of the limestone pastes generally increased with increasing temperature which may be caused by reduced amounts of adsorbed plasticizer and/or dehydration of the paste during the rheological measurements. Two types of cements were used to study adsorption and flow resistance with increasing temperature namely CEM I 42.5 RR and CEM I 52.5 R-LA. Amounts of plasticizer adsorbed and intercalated (consumed) by cement reached a plateau or even decreased with increasing temperature in the case of SNF and lignosulphonate. This finding might be caused by two opposing effects namely: increased number of adsorption sites due to increased hydration rate with increasing temperature and reduced adsorption due to increased kinetic energy and/or reduced entropy of the plasticizer. Amounts of PA2 consumed by cement increased linearly with increasing temperature as might be explained by the experiments with limestone where the adsorbed amounts of PA2 seemed to be independent of temperature. Increased consumption of plasticizer by the cements with rising temperature is thus probably governed by the increased number of adsorption cites due to increased hydration rate. The flow resistance of CEM I 52.5 R-LA cement increased exponentially with increasing temperature as a function of temperature most likely because of the increased hydration rate. The pastes of CEM I 42.5 RR cement were generally highly viscous and probably agglomerated. The flow resistance reached a plateau value with increasing temperature in this case.
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