Membrane Computing:Traces, Neural Inspired Models, ControlsAutor: Armand-Mihai IonescuDirectores: Dr. Victor Mitrana (URV)Dr. Takashi Yokomori (Universidad Waseda, Japón)Resumen Castellano:El presente trabajo está dedicado a una área muy activa del cálculo natural (que intenta descubrir la odalidad en la cual la naturaleza calcula, especialmente al nivel biológico), es decir el cálculo con membranas, y más preciso, a los modelos de membranas inspirados de la funcionalidad biológica de la neurona.La disertación contribuye al área de cálculo con membranas en tres direcciones principales. Primero, introducimos una nueva manera de definir el resultado de una computación siguiendo los rastros de un objeto especificado dentro de una estructura celular o de una estructura neuronal. A continuación, nos acercamos al ámbito de la biología del cerebro, con el objetivo de obtener varias maneras de controlar la computación por medio de procesos que inhiben/de-inhiben. Tercero, introducimos e investigamos en detallo - aunque en una fase preliminar porque muchos aspectos tienen que ser clarificados - una clase de sistemas inspirados de la manera en la cual las neuronas cooperan por medio de spikes, pulsos eléctricos de formas idénticas.English summary:The present work is dedicated to a very active branch of natural computing (which tries to discover the way nature computes, especially at a biological level), namely membrane computing, more precisely, to those models of membrane systems mainly inspired from the functioning of the neural cell.The present dissertation contributes to membrane computing in three main directions. First, we introduce a new way of defining the result of a computation by means of following the traces of a specified object within a cell structure or a neural structure. Then, we get closer to the biology of the brain, considering various ways to control the computation by means of inhibiting/de-inhibiting processes. Third, we introduce and investigate in a great - though preliminary, as many issues remain to be clarified - detail a class of P systems inspired from the way neurons cooperate by means of spikes, electrical pulses of identical shapes.

Les industries chimiques sont aujourd'hui sujettes à des réglementations environnementales très strictes quant à leur production de déchets. La récupération des cations comme le Zn²⁺ en solution acide est une préoccupation actuelle. Il existe une multitude de techniques de séparation comme l'électrodialyse qui utilisent des membranes échangeuses de cations. Il est possible par modification chimique de la membrane d'augmenter sa sélectivité et de contribuer au blocage des cations bivalents métalliques. Dans le domaine de l'énergie, les piles à combustible au méthanol direct (DMFCs) sont vouées à une utilisation considérable pour les appareils électroniques et pour le remplacement futur des moteurs à combustion interne conventionnels. Un facteur limitant pour leur commercialisation à grande échelle est la diffusion du méthanol du compartiment anodique au compartiment cathodique de la pile. Ce projet comporte deux volets: i) la modification chimique par différentes amines de la membrane de Nafion® par la formation d'un pont sulfonamide via les groupements sulfonates de la membrane, et ii) la caractérisation de ces membranes concernant leurs propriétés susceptibles d'influencer leurs performances dans les deux contextes mentionnés ci-dessus. Ces modifications chimiques sont effectuées afin d'augmenter les facteurs de performance et d'efficacité de la membrane pour les processus de séparation (électrodialyse) et de conversion d'énergie chimique en énergie électrique (DMFCs). Les objectifs principaux sont d'améliorer la sélectivité de la membrane, de diminuer sa perméabilité au méthanol tout en conservant une conductivité ionique satisfaisante, d'étudier les propriétés physico-chimiques de ces membranes modifiées (épaisseur, hydratation, stabilité et capacité d'échange ionique) et de confirmer la formation d'un pont sulfonamide entre un groupement sulfonate et l'amine greffée. Ce travail montre que les modifications chimiques avec l'acide sulfanilique permettent d'obtenir des taux de fuite en méthanol plus faibles d'un facteur de dix face au Nafion® non-modifié, tandis que la conductivité ionique diminue d'un facteur de 2. Cette membrane démontre un facteur de performance de 5.3 comparativement à un facteur de 1 pour le Nafion® non-modifié. L'analyse XPS confirme la formation d'un pont sulfonamide. Avec la N,N-diméthyléthylènediamine, le taux de fuite en méthanol diminue de façon plus importante, mais la conductivité ionique est insatisfaisante pour une future utilisation pour des piles à combustible. En électrodialyse, seules les modifications chimiques de la membrane de Nafion® ayant été effectuées dans le toluène et utilisant la N,N-diméthyléthylènediamine présentent une augmentation de la sélectivité du transport des protons par rapport aux ions métalliques bivalents, Zn²⁺. Cependant la résistance ionique de la membrane augmente également de façon importante ce qui se traduit par une différence de potentiel observée au cours de l'électrodialyse plus élevée. En effet, plus la résistance ionique de la membrane est élevée, plus le transport de charge (ou la conductivité) s'effectue difficilement. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Nafion®, Électrodialyse, Pile à combustible au méthanol direct, Membrane échangeuse de cations.

Electrostatic self-assembly is a simple, yet versatile and environmentally friendly technique. This technique has been widely used in different areas and recently it has also been used to make nano-structured separating layers for composite polyelectrolyte pervaporation membranes. Non-porous substrates are usually employed for electrostatic self-assembly depositions, but porous substrates have to be used for membrane applications because the composite membranes fabricated with non-porous substrates will have low permeation fluxes. When porous substrates were used to make composite membranes for pervaporation, it was reported that 60 double-layers were needed to get a membrane with suitable separation performance. The deposition of each double-layer needed about one hour, and the fabrication of reported self-assembled membranes with porous substrates was time-consuming and, from an industrial point of view, not practical. <br /><br /> The aim of this work was to make self-assembled composite membranes in a more practical way. The methodology used here is to find appropriate materials and suitable preparation conditions to make self-assembled composite membranes that have less than 10 self-assembled double layers but still have good performance for the dehydration of isopropyl alcohol (IPA)/ water mixtures by pervaporation. <br /><br /> A hydrolyzed polyacrylonitrile (PAN) ultrafiltration membrane is a permanently charged porous material. In this work, this porous material was, for the first time, used as a substrate for the fabrication of a composite self-assembled membrane. It was found that the hydrolyzed porous PAN membranes were good substrates for making self-assembled membranes for pervaporation. <br /><br /> In order to reduce the number of the depositions required for making composite membranes with suitable separation performance, a new deposition technique, concentration-changing deposition technique, has been developed. To obtain more extended conformations of polyelectrolytes to prevent them from going into the pores on a porous substrate, dilute deposition solutions were used for the first several depositions. After these first depositions, the pore size of the porous substrate had been reduced and more concentrated solutions (but still dilute solutions) could be used for the subsequent depositions. By using more concentrated deposition solutions, the number of the polyelectrolyte coils adsorbed by the charged substrate was increased and the thickness of each deposited layer was increased. In this way, the total number of deposition layers needed for a good membrane would be decreased. It has been proved in this work that the number of deposition layers in a composite membrane can be reduced by using the concentration-changing deposition technique. <br /><br /> By selecting appropriate materials and by selecting proper preparation conditions, composite polyelectrolyte membranes with less than 10 self-assembled double layers have been successfully fabricated. The obtained membranes had good performance for the dehydration of IPA/water mixtures by pervaporation. The lowest number of double layers in a composite membrane was 2 and this composite membrane had both a high flux and a high selectivity. It was also found that using polyelectrolytes with high molecular weights and a porous substrate with fine pores were the prerequisites for making composite polyelectrolyte membranes with less than 10 self-assembled double layers, while using a polyelectrolyte pair with high charge densities was the prerequisite for making composite membranes with a high selectivity. The successful fabrication of polyelectrolyte membranes with less than 10 double layers makes self-assembled membranes more practical because self-assembled composite membranes can be easily fabricated. <br /><br /> The data reproducibility and the stability of self-assembled composite membranes with less than 10 double layers have been discussed in this work. Random defects in the self-assembled separating layer and low repeatability of thickness in the first several deposition layers are believed to be the major reasons for the relatively low data reproducibility of single composite membranes, while the conformation change of adsorbed polyelectrolytes is one of the reasons for the flux reduction of composite membranes with less than 10 self-assembled double layers. Though the flux reproducibility of single membranes is barely acceptable (relative error about 25%), the average fluxes of several membranes made under the same conditions show good reproducibility. All composite membranes with less than 10 self-assembled double layers, from a structure point of view, were stable because the fluxes of polyelectrolyte membranes didn?t increase as time passed. <br /><br /> The separation performance of the self-assembled composite membranes developed in this work is not as good as it was originally expected, but it is still better than that of commercial poly(vinyl alcohol) (PVA) membranes for the dehydration of IPA/water mixtures, which indicates that new self-assembled composite membranes could be used for practical dehydration of IPA. The flux of the self-assembled composite membrane with 2 double layers was two times higher than that of reported self-assembled membrane in the literature when an IPA/water feed mixture with 10. 0 wt% of water was used at 60&deg;C. The composite membrane with 2 self-assembled double layers is a high performance membrane for IPA dehydration. <br /><br /> The formation of a single self-assembled layer on a non-porous substrate has been studied, but nothing has been reported about the formation of a self-assembled multilayer on a porous substrate. Based on the separation performance of different self-assembled composite membranes made from different materials and at different fabrication conditions, a two-stage process is proposed to explain the formation of a self-assembled multilayer on a porous substrate. Polyelectrolyte molecules, in the first stage, will deposit on the non-porous portion of the surface of a porous substrate while polyelectrolyte molecules will go into and fill the pores on the surface of a porous substrate to change a porous substrate into a "non-porous" substrate. In the second stage, polyelectrolyte molecules will deposit on a "non-porous substrate" to form a multilayer. This process can also be used to explain the formation of a multilayer on a non-porous substrate.

Membrane extraction with a sorbent interface (MESI) is a sample preparation technique with a rugged and simple design allowing for solvent-free, on-line performance. When coupled to gas chromatography (GC), MESI is an extremely promising tool for the analysis of volatile organic compounds (VOCs), as it is selective and sensitive for detecting trace levels of analytes. A new calibration method to be used with the MESI technique is presented herein. The aim of this project was to characterize and quantify the biomarker ethylene in human breath and plant emissions. The MESI-GC system was optimized, and an external calibration curve for ethylene standard was obtained. Qualitative measures were obtained from emissions of the higher plant Arabidopsis thaliana. The dominant calibration method was validated by examining changes in mass transfer trends when flow and temperature conditions were altered. Finally, the dominant calibration method was used to quantify ethylene in real human breath samples from non-smoking and smoking volunteers. Results were consistent with those reported in literature. These findings suggest that the dominant calibration technique is a useful tool for monitoring ethylene in human breath and Arabidopsis.

Waste activated sludge (WAS) is one of the largest by-products of biological wastewater treatment. Anaerobic digestion of WAS is beneficial for several reasons. In an ever increasingly energy conscientious world the production of renewable energy resources is becoming more important, and thus the production of methane has been seen as a valuable product. To achieve efficient conversion of organic matter to methane, the biomass in the digester must be provided optimal operating conditions, as well as adequate retention times, that will allow for substrate metabolism and prevent bacteria washout. Two approaches have been taken in this research to achieve improved biodegradation. Initially microwave pretreatment was employed to improve the biodegradability of the sludge, then the addition of a submerged hollow fibre membrane separation unit was used to allow for a longer SRT while maintaining the hydraulic residence time (HRT). The impact of microwave pretreatment on WAS characteristics was assessed for both the low temperature operations and the high temperature operations. An increase due to pretreatment on the filtered to total COD ratio when comparing the feed to the microwaved feed was established to be 200 % for low temperature operations and 254 % for high temperature operations. For the low temperature operations, CODT destruction, VS destruction, and organic nitrogen destruction were all higher for the test digester than the control digester indicating that the microwaving of the WAS increased the biodegradation in the anaerobic digester. For the high temperature operation, CODT destruction and organic nitrogen destruction were improved with microwave application, however VS destruction did not support this. The measured biogas data indicated that microwaving did influence the volume of biogas produced during anaerobic digestion of WAS for both the low and high temperature operations, and hence the VS destruction data for the high temperature operations was determined to be incorrect. For the membrane operations both the CODT and the VS destruction calculations indicated that at the same SRT the test digester was capable of more biodegradation than the control digester. The control digester organic nitrogen reduction was calculated to be higher than for the test digester, suggesting that the control digester removed more organic nitrogen than the test digester, however, these results were likely due to the lower HRT of the test digester compared to those of the control digester. A greater volume of biogas was produced by the test digester than the control digester; however, the composition of the gas from both digesters was similar, although the percentage of methane produced by the test digester was higher than that produced by the control digester. The higher destruction by the test digester indicated that the presence of the membrane unit and the decoupling of the HRT and SRT improved the biodegradation capability of the digesters. The results of the membrane performance study indicated that for a hollow fibre anaerobic membrane bioreactor, stable operations could be achieved with a total solids concentration of 2.01 %+/-0.34, an HRT of 15 days and an SRT of 30 days. With a constant flux of 14 L/m2-h +/-0.68 the average TMP was 0.079 kPa/min+/-0.08. No cleaning was required to achieve this, however the operations consisted of 20 minutes of permeation followed by 5 hours and 40 minutes of relaxation. The critical flux was determined to be in the range of 18 to 22 L/m2-h.

Electrostatic self-assembly is a simple, yet versatile and environmentally friendly technique. This technique has been widely used in different areas and recently it has also been used to make nano-structured separating layers for composite polyelectrolyte pervaporation membranes. Non-porous substrates are usually employed for electrostatic self-assembly depositions, but porous substrates have to be used for membrane applications because the composite membranes fabricated with non-porous substrates will have low permeation fluxes. When porous substrates were used to make composite membranes for pervaporation, it was reported that 60 double-layers were needed to get a membrane with suitable separation performance. The deposition of each double-layer needed about one hour, and the fabrication of reported self-assembled membranes with porous substrates was time-consuming and, from an industrial point of view, not practical. <br /><br /> The aim of this work was to make self-assembled composite membranes in a more practical way. The methodology used here is to find appropriate materials and suitable preparation conditions to make self-assembled composite membranes that have less than 10 self-assembled double layers but still have good performance for the dehydration of isopropyl alcohol (IPA)/ water mixtures by pervaporation. <br /><br /> A hydrolyzed polyacrylonitrile (PAN) ultrafiltration membrane is a permanently charged porous material. In this work, this porous material was, for the first time, used as a substrate for the fabrication of a composite self-assembled membrane. It was found that the hydrolyzed porous PAN membranes were good substrates for making self-assembled membranes for pervaporation. <br /><br /> In order to reduce the number of the depositions required for making composite membranes with suitable separation performance, a new deposition technique, concentration-changing deposition technique, has been developed. To obtain more extended conformations of polyelectrolytes to prevent them from going into the pores on a porous substrate, dilute deposition solutions were used for the first several depositions. After these first depositions, the pore size of the porous substrate had been reduced and more concentrated solutions (but still dilute solutions) could be used for the subsequent depositions. By using more concentrated deposition solutions, the number of the polyelectrolyte coils adsorbed by the charged substrate was increased and the thickness of each deposited layer was increased. In this way, the total number of deposition layers needed for a good membrane would be decreased. It has been proved in this work that the number of deposition layers in a composite membrane can be reduced by using the concentration-changing deposition technique. <br /><br /> By selecting appropriate materials and by selecting proper preparation conditions, composite polyelectrolyte membranes with less than 10 self-assembled double layers have been successfully fabricated. The obtained membranes had good performance for the dehydration of IPA/water mixtures by pervaporation. The lowest number of double layers in a composite membrane was 2 and this composite membrane had both a high flux and a high selectivity. It was also found that using polyelectrolytes with high molecular weights and a porous substrate with fine pores were the prerequisites for making composite polyelectrolyte membranes with less than 10 self-assembled double layers, while using a polyelectrolyte pair with high charge densities was the prerequisite for making composite membranes with a high selectivity. The successful fabrication of polyelectrolyte membranes with less than 10 double layers makes self-assembled membranes more practical because self-assembled composite membranes can be easily fabricated. <br /><br /> The data reproducibility and the stability of self-assembled composite membranes with less than 10 double layers have been discussed in this work. Random defects in the self-assembled separating layer and low repeatability of thickness in the first several deposition layers are believed to be the major reasons for the relatively low data reproducibility of single composite membranes, while the conformation change of adsorbed polyelectrolytes is one of the reasons for the flux reduction of composite membranes with less than 10 self-assembled double layers. Though the flux reproducibility of single membranes is barely acceptable (relative error about 25%), the average fluxes of several membranes made under the same conditions show good reproducibility. All composite membranes with less than 10 self-assembled double layers, from a structure point of view, were stable because the fluxes of polyelectrolyte membranes didn?t increase as time passed. <br /><br /> The separation performance of the self-assembled composite membranes developed in this work is not as good as it was originally expected, but it is still better than that of commercial poly(vinyl alcohol) (PVA) membranes for the dehydration of IPA/water mixtures, which indicates that new self-assembled composite membranes could be used for practical dehydration of IPA. The flux of the self-assembled composite membrane with 2 double layers was two times higher than that of reported self-assembled membrane in the literature when an IPA/water feed mixture with 10. 0 wt% of water was used at 60&deg;C. The composite membrane with 2 self-assembled double layers is a high performance membrane for IPA dehydration. <br /><br /> The formation of a single self-assembled layer on a non-porous substrate has been studied, but nothing has been reported about the formation of a self-assembled multilayer on a porous substrate. Based on the separation performance of different self-assembled composite membranes made from different materials and at different fabrication conditions, a two-stage process is proposed to explain the formation of a self-assembled multilayer on a porous substrate. Polyelectrolyte molecules, in the first stage, will deposit on the non-porous portion of the surface of a porous substrate while polyelectrolyte molecules will go into and fill the pores on the surface of a porous substrate to change a porous substrate into a "non-porous" substrate. In the second stage, polyelectrolyte molecules will deposit on a "non-porous substrate" to form a multilayer. This process can also be used to explain the formation of a multilayer on a non-porous substrate.

Membrane extraction with a sorbent interface (MESI) is a sample preparation technique with a rugged and simple design allowing for solvent-free, on-line performance. When coupled to gas chromatography (GC), MESI is an extremely promising tool for the analysis of volatile organic compounds (VOCs), as it is selective and sensitive for detecting trace levels of analytes. A new calibration method to be used with the MESI technique is presented herein. The aim of this project was to characterize and quantify the biomarker ethylene in human breath and plant emissions. The MESI-GC system was optimized, and an external calibration curve for ethylene standard was obtained. Qualitative measures were obtained from emissions of the higher plant Arabidopsis thaliana. The dominant calibration method was validated by examining changes in mass transfer trends when flow and temperature conditions were altered. Finally, the dominant calibration method was used to quantify ethylene in real human breath samples from non-smoking and smoking volunteers. Results were consistent with those reported in literature. These findings suggest that the dominant calibration technique is a useful tool for monitoring ethylene in human breath and Arabidopsis.

Waste activated sludge (WAS) is one of the largest by-products of biological wastewater treatment. Anaerobic digestion of WAS is beneficial for several reasons. In an ever increasingly energy conscientious world the production of renewable energy resources is becoming more important, and thus the production of methane has been seen as a valuable product. To achieve efficient conversion of organic matter to methane, the biomass in the digester must be provided optimal operating conditions, as well as adequate retention times, that will allow for substrate metabolism and prevent bacteria washout. Two approaches have been taken in this research to achieve improved biodegradation. Initially microwave pretreatment was employed to improve the biodegradability of the sludge, then the addition of a submerged hollow fibre membrane separation unit was used to allow for a longer SRT while maintaining the hydraulic residence time (HRT). The impact of microwave pretreatment on WAS characteristics was assessed for both the low temperature operations and the high temperature operations. An increase due to pretreatment on the filtered to total COD ratio when comparing the feed to the microwaved feed was established to be 200 % for low temperature operations and 254 % for high temperature operations. For the low temperature operations, CODT destruction, VS destruction, and organic nitrogen destruction were all higher for the test digester than the control digester indicating that the microwaving of the WAS increased the biodegradation in the anaerobic digester. For the high temperature operation, CODT destruction and organic nitrogen destruction were improved with microwave application, however VS destruction did not support this. The measured biogas data indicated that microwaving did influence the volume of biogas produced during anaerobic digestion of WAS for both the low and high temperature operations, and hence the VS destruction data for the high temperature operations was determined to be incorrect. For the membrane operations both the CODT and the VS destruction calculations indicated that at the same SRT the test digester was capable of more biodegradation than the control digester. The control digester organic nitrogen reduction was calculated to be higher than for the test digester, suggesting that the control digester removed more organic nitrogen than the test digester, however, these results were likely due to the lower HRT of the test digester compared to those of the control digester. A greater volume of biogas was produced by the test digester than the control digester; however, the composition of the gas from both digesters was similar, although the percentage of methane produced by the test digester was higher than that produced by the control digester. The higher destruction by the test digester indicated that the presence of the membrane unit and the decoupling of the HRT and SRT improved the biodegradation capability of the digesters. The results of the membrane performance study indicated that for a hollow fibre anaerobic membrane bioreactor, stable operations could be achieved with a total solids concentration of 2.01 %+/-0.34, an HRT of 15 days and an SRT of 30 days. With a constant flux of 14 L/m2-h +/-0.68 the average TMP was 0.079 kPa/min+/-0.08. No cleaning was required to achieve this, however the operations consisted of 20 minutes of permeation followed by 5 hours and 40 minutes of relaxation. The critical flux was determined to be in the range of 18 to 22 L/m2-h.

The dynamical characteristics and the structure of lithium in Nafion were investigated by solid state magic angel spinning nuclear magnetic resonance(MAS NMR). Variable temperature, longitudinal NMR relaxation time(T1), self-diffusion coefficients and rotational activation energy of various concentrations were determined. The distribution of the 7Li MAS NMR spectra of Nafion/Li represent the pore size, and T1 of Nafion/Li is slower than the bulk lithium solution, it implied the lithium were crowed in the pore(exchanged with the proton). Rotational activation energy illustrated the block level of lithium in different pores of Nafion. In the longitudinal NMR relaxation rate of various concentrations, instead, the type of bonding between lithium and water were different. The variable temperature experiments of 7Li MAS NMR spectra also illustrated the temperature about 60~66¢J result in the change of microstructure of Nafion.

In this thesis, the treatments of MEA and the special structures within carbon fiber bunch unipolar plates on the performance of PEMFC are studied. At first, the factors affecting on the water content within MEA will be studied. A passive HFC stack usually exposes in the ambient no matter that it works or not. However, the ambient is far from saturated. The water within MEA will vaporize continuously. Especially, if the stack is shutdown for a long period, there is no water generation in the cathode and then the membrane will be short in water. If it occurs, the conductivity of H+ will decrease greatly, and the electrode of MEA is also possible to separate from its membrane. This separation will make the performance of the stack an unrecovered decay. On the other hand, in order to improve the performance of a air-breathing HFC, the inner structure within cathode carbon fiber bunch unipolar plates is modified. The structure of the unipolar plates is modified in the following three aspects: 1. Increasing soft end height of carbon fiber bunch, 2. Increasing the number of silver-coated wires in carbon fiber bunch, 3. Cutting several serrated slots on the soft end of carbon fiber bunch. In the MEA treatment, firstly, a MEA is boiled in 80oC, 0.5M H2SO4 solution and then boiled in 80oC DI water for an hour, respectively. When the single-cell HFC operates in hydrogen inlet pressure 0.1 bar, air-breathing, and room temperature, experimental results display that the power density of this HFC with the aforementioned treatments and the special structure of unipolar plates can reach a value about 185mW/cm2. This value is about 130% higher than that of the untreated MEA and about 50% higher than that of the treatment of MEA only immersed in DI water. In addition, the comparison of the performance of HFC between with carbon fiber bunch unipolar plates and with graphite unipolar plates are also studied. The experimental result displays that the performance of HFC with the carbon fiber bunch unipolar plates is superior to that with graphite unipolar plates, especially the fuel cell operating under low gas inlet pressure.