There are many different methods available for the solution of the heat equation and the choice of which to use is dependent upon the nature of the problem and the specific regions of the domain where the temperature is required. In the case of melting or freezing problems it is usual for the position of the boundary, at which change of physical state (phase change) occurs, to be of greater interest than the temperature at particular points. Again there are several solution methods enabling the tracking of the moving interface between the physical states of the material. For this work we begin with the isotherm migration method, which first appeared in the 1970s but is less frequently cited now. We first solve problems in one dimension with no phase change using the isotherm migration method, which is in itself new work, since all references we have found allude to it as a tool for the solution of phase change problems. We test the method using a variety of examples to explore the difficulties and challenges it produces, and we find it to be robust and tolerant of errors. We then combine it with the Laplace transform method, a well-established technique for solving ordinary and partial differential equations, in which the number of independent variables is reduced by one. The solution is then transformed back into the time domain using a suitable numerical process. The Laplace transform isotherm migration method is a new process, not mentioned previously to our knowledge, and it produces results which are comparable with the isotherm migration method. The new process is applied to one-dimensional phase change problems,where we find that due to the mathematics at the phase change boundary, we are required to make a modification to the usual manner of operating the Laplace transform. This is novel as far as we are aware. Our method is applied to a variety of problems and produces satisfactory results. We then move on to a two-dimensional setting where we find the situation to be much more complex and challenging, as it requires interpolation and curve-fitting processes. Finally we examine the possiblity of speeding up the calculation time using the Laplace transform isotherm migration method by setting problems in a parallel environment and using an MPI platform. This has not been previously attempted and we are able to show a measure of success in our objective.

No description available.

Novel amphiphilic graft copolymers with a backbone of poly(norbornene) (PNB) with poly(ethylene oxide) (PEO) grafts have been synthesised by a combination of ring opening metathesis and anionic polymerisation methods. The polymer has been prepared with hydrogenous and deuterated grafts and with grafts of different degrees of polymerisation. These graft copolymers spread at the air-water and air-PEO solution interface forming thin films and their organisation and dynamic behaviour is discussed. Monolayer behaviour was characterised from surface pressure isotherms and it was demonstrated that the shape of the isotherm is dependent on graft length and on the concentration of PEO in the subphase. Using neutron reflectometry the organisation of such spread films at the air-water interface have been obtained over a range of surface concentrations for each length of PEO graft. Data were analysed by both exact calculation methods and the partial kinematic approximation and the models adopted were verified by applying the model independent Bayesian analysis. All yield the same description i.e. the hydrophobic backbone remains at the uppermost surface while the PEO grafts penetrate the subphase. The PEO layer increases in thickness with increased surface concentration and graft length. In each case the rate of increase with surface concentration was initially rapid but above a critical concentration, a slower rate was observed. In this latter regime the variation of the tethered layer height scales with surface density (ơ) and degree of polymerisation of the graft (N) as, r(_s) = N(^1.06)ơ(^0.33),which agrees well with scaling and self consistent field theory of polymer brushes. The dynamic behaviour of each copolymer film spread on water has been studied using surface quasi-elastic light scattering. A resonance between the capillary and dilational waves is observed at identical surface concentrations for each copolymer film. The viscoelastic behaviour of the dilational mode is reminiscent of Kramers-Kronig relations. The phenomenon of resistive mode mixing was observed in frequency dependency studies.

A biomassa residual proveniente de atividades agrícolas tem sido avaliada como biossorvente de metais e compostos orgânicos devido às propriedades adsortivas, ao baixo custo, abundância e ser uma fonte renovável. Neste trabalho apresenta-se a eficiência das fibras de coco como biossorvente na remoção de íons de U, Th, Pb, Zn e Ni de meio aquoso. A fibra de coco é um sub-produto do coco, uma fonte natural renovável. O estudo foi realizado por ensaio em batelada. Estudaram-se a influência do pH 1 a 8, a dosagem das fibras de coco e o tempo de equilíbrio. Verificou-se que a adsorção aumenta com o aumento do pH e da dose. Os modelos de Langmuir e Freundlich foram aplicados para descrever a isoterma de equilíbrio de adsorção. A cinética do processo foi analisada a partir dos modelos de pseudo- primeira e pseudo-segunda ordem. Calculou-se a energia livre de Gibbs. No intervalo de concentração de 100 mg.L-1 a 500 mg.L-1, o processo de adsorção foi melhor descrito pela equação de Langmuir para os íons Pb2+ e Zn2+ e Freundlich para os íons UO2 2+, Th4+ e Ni2+. A cinética foi melhor representada pelo modelo de pseudo-segunda ordem. O processo de biossorção para remoção dos íons das soluções foi considerado espontâneo. Os resultados são promissores indicando perspectivas de aplicação das fibras de coco como biossorvente de íons de U, Th, Pb, Zn e Ni em processos de tratamento de águas residuárias. / The residual biomass from agricultural activities has been evaluated as biosorbent for metals and organic composts from aqueous solutions, because of its adsorptive properties, low cost, abundance and to be a renewable resource. In this work, the efficiency of coir pith as biosorbent for the removal of U, Th, Pb, Zn e Ni ions from the aqueous solutions is presented. The coir pith is a by-product of the harvest of the coconut, a renewable natural source. The study was conducted by batch method. The influence of pH from 1 to 8, the dosage of the coir pith and the equilibrium time were studied. The adsorption of metal ions increased with the increase of pH and the dose. The Langmuir and Freundlich models were applied to describe the adsorption equilibrium isotherm. The kinetic process was studied using the pseudo-first order and pseudo-second order models. The Gibbs free energy was calculated. In the concentration range of 100 mg.L-1 500 mg.L-1, the adsorption process was described better by the Langmuir equation for Pb2+ and Zn2+ ions and the Freundlich equation for UO2 2+, Th4+ and Ni2+ ions, and represented by the pseudo-second order model. The biosorption process for removal of metal ions from the solutions was considered spontaneous. The results were promising, showing perspectives of application of coir pith as biosorbent of U, Th, Pb, Zn and Ni ions in wastewater treatment processes.

A biomassa residual proveniente de atividades agrícolas tem sido avaliada como biossorvente de metais e compostos orgânicos devido às propriedades adsortivas, ao baixo custo, abundância e ser uma fonte renovável. Neste trabalho apresenta-se a eficiência das fibras de coco como biossorvente na remoção de íons de U, Th, Pb, Zn e Ni de meio aquoso. A fibra de coco é um sub-produto do coco, uma fonte natural renovável. O estudo foi realizado por ensaio em batelada. Estudaram-se a influência do pH 1 a 8, a dosagem das fibras de coco e o tempo de equilíbrio. Verificou-se que a adsorção aumenta com o aumento do pH e da dose. Os modelos de Langmuir e Freundlich foram aplicados para descrever a isoterma de equilíbrio de adsorção. A cinética do processo foi analisada a partir dos modelos de pseudo- primeira e pseudo-segunda ordem. Calculou-se a energia livre de Gibbs. No intervalo de concentração de 100 mg.L-1 a 500 mg.L-1, o processo de adsorção foi melhor descrito pela equação de Langmuir para os íons Pb2+ e Zn2+ e Freundlich para os íons UO2 2+, Th4+ e Ni2+. A cinética foi melhor representada pelo modelo de pseudo-segunda ordem. O processo de biossorção para remoção dos íons das soluções foi considerado espontâneo. Os resultados são promissores indicando perspectivas de aplicação das fibras de coco como biossorvente de íons de U, Th, Pb, Zn e Ni em processos de tratamento de águas residuárias. / The residual biomass from agricultural activities has been evaluated as biosorbent for metals and organic composts from aqueous solutions, because of its adsorptive properties, low cost, abundance and to be a renewable resource. In this work, the efficiency of coir pith as biosorbent for the removal of U, Th, Pb, Zn e Ni ions from the aqueous solutions is presented. The coir pith is a by-product of the harvest of the coconut, a renewable natural source. The study was conducted by batch method. The influence of pH from 1 to 8, the dosage of the coir pith and the equilibrium time were studied. The adsorption of metal ions increased with the increase of pH and the dose. The Langmuir and Freundlich models were applied to describe the adsorption equilibrium isotherm. The kinetic process was studied using the pseudo-first order and pseudo-second order models. The Gibbs free energy was calculated. In the concentration range of 100 mg.L-1 500 mg.L-1, the adsorption process was described better by the Langmuir equation for Pb2+ and Zn2+ ions and the Freundlich equation for UO2 2+, Th4+ and Ni2+ ions, and represented by the pseudo-second order model. The biosorption process for removal of metal ions from the solutions was considered spontaneous. The results were promising, showing perspectives of application of coir pith as biosorbent of U, Th, Pb, Zn and Ni ions in wastewater treatment processes.

This thesis is an experimental investigation on the binding of self-assembling peptides to oligodeoxynucleotides (ODNs) and the characterization of the resulting peptide-ODN complexes/aggregates, the first key step in the development of a peptide-based gene delivery system. Effects of pH, charge distribution along the peptide backbone, and oligonucleotide sequences on the peptide-ODN binding were investigated by a series of physicochemical methods. UV-Vis absorption and fluorescence anisotropy experiments demonstrate that aggregates are formed after mixing the peptide and ODN in aqueous solution. The aggregates in solution can be centrifuged out. Based on this property, the fraction of ODNs incorporated in the peptide-ODN aggregates can be obtained by comparing the UV-Vis absorption of the solution before and after centrifugation. Binding isotherms are generated by a binding density function analysis of the UV absorbance results. The binding parameters are extracted from the analysis of the binding isotherms based on the McGhee and von Hippel model. Equilibrium binding parameter studies show that the binding of two self-assembling peptides, EAK16-II and EAK 16-IV, to model single and double-stranded ODNs at pH 4 is stronger than at pH 7, and that no binding occurs at pH 11. These results demonstrate that electrostatic interactions play an important role in the EAK-ODN binding because EAKs are more positively charged at low pH. EAKs bind more strongly to dG16 than to the other ODN sequences dC16 and dGC16. This demonstrates that the hydrogen bond might be involved because they promote the binding of the lysine residues of the peptide to dG16 to a greater extent than to dC16. The charge distribution along the peptides is found to have an effect on the binding. EAK16-IV, whose positively charged residues are clustered at one end of the peptide, binds to the ODNs more strongly than EAK16-II, whose positively charged residues are distributed throughout the peptide chain, at the same pH. The binding process of EAKs to the ODNs was investigated by fluorescence anisotropy and static light scattering experiments. The results show that individual EAK and ODN molecules complex first, followed by the aggregation of these complexes into large aggregates. The nature of the resulting peptide-ODN complexes/aggregates is examined by UV-Vis absorption, fluorescence anisotropy, and PAGE experiments. The results demonstrate that free EAK, free ODNs, and small EAK-ODN complexes, which can not be centrifuged out, exist in the supernatant, and that large aggregates are collected in the pellets after centrifugation of the solution. The size of the resulting EAK-ODN complexes/aggregates measured by AFM and DLS is around a few hundreds of nanometers at low EAK concentrations. The accessibility of the ODNs to the quencher in the solution is reduced by 40 % and 60 % after binding to EAK16-II and EAK16-IV, respectively, as determined by fluorescence quenching experiments on EAK-ODN mixture solutions. An ODN protection from Exonuclease 1 degradation is provided by the EAK16-II or EAK16-IV matrix when they are mixed with the ODNs at pH 4. However, the ODNs are protected to a much lower degree when the EAK-ODN aggregates are prepared at pH 7. The EAK-ODN aggregates prepared at pH 7 are found to dissociate more easily than those prepared at pH 4 when they are incubated with exonuclease I solution at pH 9.5. These results suggest that the ODN protection afforded by the EAK-ODN aggregates is correlated with their structural stability after being incubated with the nuclease solution. The stability of the EAK-ODN aggregates after dilution is determined by UV-Vis absorption. No detectable dissociation of the aggregates is observed over 20 hrs after a 5- and 10-fold dilution of the solution in the same buffer used for their preparation. The EAK-ODN aggregates remain stable after the solutions are centrifuged, and re-dissolved in fresh buffer solutions. The ability of an EAK matix to protect ODNs from nuclease degradation together with its biocompatibility and low-toxicity suggests that EAK self-assembling peptides could be used as carriers for gene delivery.

Chromatography is a widely used separation technique including many different modes, for example supercritical fluid chromatography (SFC) which uses a supercritical fluid as mobile phase. A supercritical fluid is achieved when a substance is subjected to a temperature and pressure above the critical point and the boundary between the liquid phase and gas phase is erased. The interest for SFC has increased in recent years, mainly for separation of chiral molecules in the pharmaceutical industry. What makes SFC interesting is that it is a quick, cost-efficient and green method. This is in part due to less organic solvent used in the mobile phase in SFC compared with liquid chromatography and that the carbon dioxide that represents the major part of the mobile phase is a by-product from other processes. In SFC modifiers, often small alcohols, are added to carbon dioxide based mobile phase in order to increase the solubility of polar compounds. In this study the adsorption of methanol to two different stationary phases; Kromasil-Diol and chiral Lux Cellulose-4 were studied. Adsorption is a phenomenon where surface interactions crate a higher density of molecules at the surface than in the bulk. The aim of this work has been to study the adsorption of modifier (methanol) to the stationary phase both to determine the extent of adsorption and the kinetics for system equilibration. These findings were then put into perspective of normal use of SFC for separation of molecules. There are a number of techniques for measuring adsorption; in this study the tracer pulse method is used. This is a pulse method where a concentration plateau is created and an isotope labelled molecule is injected. This was performed in the mobile phase composition from pure carbon dioxide to pure methanol. In addition to the tracer pulse experiments the isotope effect, the eluent flow, equilibration times for the column and retention times for a set of analytes were measured. For the Diol column no large isotope effect was observed, the method was also proved to be highly reproducible since several runs gave consistent results. Calculations based on the experimental data showed that a 6.3 Å thick layer was built up at a methanol fraction of 13% (v/v), corresponding to a monolayer. Changes of the methanol fraction below the saturation level has has greater effect on the retention factor for the analytes than at higher methanol fractions, when the monolayer was saturated. The conclusion of this is that SFC is more stable in the area where the layer has been built up. A preliminary study has been made for the chiral Lux Cellulose-4 column which was not as conclusive as for the Kromasil-Diol column. This type of column needs further studies to confirm the deviating observations and to investigate the cause for these.

Mercury is a serious hazard to humans, mammals and fish, which when emitted into the atmosphere reaches back to the earth. Coal-fired plants in the U.S. emit mercury upon the burning of coal in the particulate, oxidized and elemental state. Of these, elemental mercury is the most difficult to capture. U.S. coal-fired plants emit approximately 48 tons of mercury per year. Based on the U.S. EPA Clean Air Mercury Rule, these emissions need to be capped by 90%. This project deals with the Development of Bamboo Derived Sorbents for the capture of elemental mercury in gas phase. Raw bamboo is used to process sorbents using carbonization, activation and acidulation techniques. These sorbents are tested in a Batch Test, which includes a mercury permeation assembly, sampling bags, and uses nitrogen as a carrier gas. Many tests are conducted on sorbent samples with varying masses, samples with the presence or absence of skin material found on the bamboo stem along with various treatments, and varying initial concentrations of mercury. Other studies conducted also include Three-Point Bending tests for structural integrity, Surface Area Measurements, and Scanning Electron Microscopy for microstructure studies. Results and analyses of these sorbents depict successful capture of mercury in nitrogen atmosphere. Treatments such as carbon dioxide activation and hydrochloric acid functionalization are very effective in enhancing mercury adsorption. This project acts as a stepping stone for the development of bamboo derived material. Major recommendations include the optimization of the sorbents for adsorption properties, and the scaling up of experiments. Eventually, a bamboo derived sorbent could be applied in coal-fired plants on a large scale for the capture of mercury.

This study presents the synthesis of polymers of intrinsic microporosity and the investigation of their microporosity using gas sorption and adsorption of liquids and vapours. Microporous polymeric materials PIM-1, TAPIM-1, PIM-2 and PIM-7 were synthesised using step-growth polymerisation. The microporosity of these materials was studied using gas sorption and adsorption of molecules in the liquid phase. A procedure to validate gas sorption methods was undertaken before being used to characterise microporous materials. The sorption methodology was validated using standard reference materials (SRMs) and collaborative testing, and the PSD evaluation was validated using a well defined crystalline material. Different approaches to obtaining pore size distribution (PSD) data were dealt with. Gas sorption methods that use CO2 at 273 K and at 303 K, N2 at 77 K, H2 at77 K, and Xe (298 K) to determine PSD were compared. The Horvath-Kawazoe(HK) model was presented as the preferred model and the N2, CO2 and H2 sorption data were treated under this approach. CO2 PSD data at 273 K and at303 K was compared against N2 PSD data and a novel complementary relationship established. PIM-1 samples in film form and powder form were used to investigate the effect of sample form on the sorption properties of the material. PIM-1, PIM-2, TAPIM-1, ethano-anthracene PIM-1 copolymers, and triptycene based PIMs were used to investigate the influence of polymer structure on gas sorption properties. The free volume properties of a PIM-1 ethano-anthracene copolymer (PIM-CO1-40), was compared against PIM-1. A number of independent techniques, namely N2 sorption, Xe sorption, Positron annihilation lifetime spectroscopy (PALS), and 129Xe NMR were used to probe the free volume. The time dependence of free volume and its bearing on diffusivity of PIM-1 membranes was investigated. Water, chloroform and simple alcohols were used to investigate adsorption in the liquid and vapour phases. Interaction with PIM-1 the aromatic ether linkage and the nitrile group produced frequency shifts in ATR-FT-IR spectra. These frequency shifts were used to compare relative strengths of the hydrogen bonds.

Metal - metal and to an extent metal - insulator contact or triboelectric charging are well known phenomena with good theoretical understanding of the charge exchange mechanism. However, insulator – insulator charging is not as well understood. Theoretical and experimental research has been performed that shows that the surface charge on an insulator after triboelectric charging with another insulator is rapidly dissipated with lowered atmospheric pressure. This pressure discharge is consistent with surface ions being evaporated off the surface once their vapor pressure falls below the saturation vapor pressure. A two-phase equilibrium model based on an ideal gas of singly charged ions in equilibrium with a submonolayer adsorbed film was developed to describe the pressure dependence of the surface charge on an insulator. The resulting charge density equation is an electrostatic version of the Langmuir isotherm for adsorbed surface particles, which describes well the experimental observations.