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A variety of liquid crystalline (LC) materials have been examined as potential membrane separation materials. The order present in the LC phases has measurable effects on solute sorption, diffusivity, permeability, and selectivity, and can thus be used to tune the transport and separation of different species. The current work has focused on polymer dispersed liquid crystal (PDLC), linear butadiene diol based side chain liquid crystalline polymer (LCP), and linear and crosslinked acrylate based LCP membranes. The focus was primarily on the separation of propylene and propane, a separation of significant industrial interest that is not easily achieved with current membrane technology. Polysulfone (Psf) and 4-cyano-4'-octylbiphenyl (8CB) were used to fabricate polymer dispersed liquid crystal (PDLC) membranes. Permeation properties for propane and propylene through polysulfone membranes with increasing LC concentrations were measured at temperatures above and below the glass transition temperature and in several LC phases. The plasticization of PSf by 8CB increased permeability and selectivity with increasing temperatures below the Tg, and membranes with higher LC concentrations exhibited a higher mixed gas permeability and selectivity for propylene. Permeability selectivity decreased across the smectic to nematic phase transition. Overall, selectivities were low, and membrane stability was a significant problem, especially at higher pressures. Thus, several LCP systems were studies as candidates for membrane gas separations. A side chain liquid crystalline poly(butadiene)diol with cyanobiphenyl mesogens was impregnated in a porous PTFE support for gas transport studies. Single gas sorption for propane and propylene in the LCP were investigated in the smectic A mesophase. Gas transport in the glassy state showed separation dominated by differences in gas diffusivity. Permeabilities and selectivities for propylene/propane in the liquid crystal mesophase increased with increasing temperature due to an increase in the segmental motional of the mesogenic units which facilitated solubility of propylene over propane. In addition, an increase solubility differences between propane and propylene were observed with an increase in feed pressure. Mixed gas permeability measurements resulted in an increase in selectivity both below and above the glass transition temperature due to competitive sorption of the two gases. The thermal behavior of liquid crystalline poly(butadiene)diols (PBDs) containing methoxy- or butoxy-substituted azobenzene side chains was studied. A strong dependence of the viscous and dynamic moduli of the polymer with respect to frequency and degree of modification was observed, but the results suggested that prolonged membrane stability for linear poly(butadiene)diol LCPs would be difficult to achieve. As a result, a new class of cross-linkable acrylate based side-chain LCPs was developed. A mesogenic cyanobiphenyl based acrylate monomer, in combination with a non-mesogenic comonomers and a cross-linking agent, was used was used to fabricate stable cross-linked LCP films for membrane separation applications using an in situ free radical polymerization technique with UV initiation. To our knowledge, this is the first reported example of a crosslinked LCP membrane. Increasing the cross-linker content resulted in a decrease in mesogen order. At temperatures in the LC mesophase permeability selectivity for propylene over propane was derived from both solubility and diffusivity selectivity and was higher for the membrane with lower crosslinker content. An increase in the temperature causes a decrease in molecular ordering and consequently decreased permeability selectivity. At temperatures approaching the nematic/isotropic transition and above, the membrane with higher crosslinker content exhibited higher propylene selectivity. Mixed gas studies of propylene/propane resulted in higher selectivities compared to the single gas runs due to the decrease of propane permeability by the presence of propylene. / Ph. D.

In the post-operational phase of a Low/Intermediate-Low radioactive waste repository, gas will be generated in the caverns due to anaerobic corrosion of metals, and also chemical and microbial degradation of organic substances. Previous investigations on gas migration have indicated that discrete water conducting features (e.g. shear zones) are mainly responsible for gas transport from the caverns through the geosphere. Two phase flow processes occur in these water conducting features; the continuity and spatial distribution of pore spaces, the pore size distribution and the interfacial forces of the three phases gas-water-rock have a significant influence on gas transport.The main difficulties to be resolved when simulating two-phase flow processes in fractured rock are:- The description of the internal heterogeneity of the individual water conducting features. The influence of channelling along preferential flow paths is even more important than for single phase fluid flow, because gas transport takes place more or less exclusively along the most transmissive channels. - The determination of effective mass exchange coefficients of the relevant components of the system. Mass exchange may occur between three phases (gas-water-rock). It depends on the spatial distribution of water and gas along the water conducting features (i.e. specific surface of contact areas between phases), and on the solubility and diffusivity of the different components, but also on a couple of state variables of liquid phase (initial content of dissolve/free gas, initial pressure).The work presented in this thesis aims to improve the understanding of the physics of single and multiphase transport phenomena, to be able to develop a quantitative description of gas transport in shear zones to overcome in a satisfactory way the problems described above.

This study is part of the Diavik Waste-Rock Pile Project taking place at the Diavik Diamond Mine in the Northwest Territories, Canada. The project involves the construction of three 15m-scale low sulfide test waste-rock piles and monitoring of fluid flow, geochemical reactions, heat and gas transport within the waste-rock piles and characterization of the physical properties of the waste-rock piles. The focus of this thesis is characterizing grain-size distribution of the waste-rock and quantifying gas transport in the test waste-rock piles. Grain size of waste rock ranges from millimeters to meters. Sieve analysis typically only provides information of grain size <0.1 m at a single location. A computer program was developed using digital image-processing techniques to obtain a spatial grain-size distribution from photographs of tip faces of the test waste-rock piles acquired in the field. The program characterizes grain size >0.1 m and employs a region-growing algorithm for segmentation of waste-rock grains with pre- and post-processing techniques to improve the accuracy of segmentation. The program was applied to photographs of six different tip faces of the test waste-rock piles. For grain size <0.1 m, data from sieve analyses were attached to the grain-size curves generated from image grain-size analyses to obtain a full spectrum grain-size analyses ranging from boulders to fines. The results show that fine fractions are retained at the top of the tip faces and grain size increases non-linearly from top to bottom of a waste-rock pile. Calculations show that although the greatest mass is associated with the medium and coarse fractions, the greatest surface area is associated with the fine fractions. The results are consistent with field observation that the initial solute concentrations are greatest at the top of the pile and saturated hydraulic conductivity are lower at the top of the pile than in the pile interior. Statistical moments show that the test waste-rock piles have mean grain size of granules and are very poorly sorted, coarse skewed and leptokurtic. Permeability is calculated using empirical formulae and good agreement is obtained between calculated values and field measurements. The heterogeneity of grain size obtained from this study can provide a basis for future modeling efforts. Gas transport analysis focused on 1) substantiating the relationship between wind flow external to the waste-rock pile and gas pressures within the pile, 2) determining the gas flow regime in the pile, and 3) quantifying the temporal variation in wind speed and direction and determining the relevant time scales. Differential gas pressures were measured in 2008 at 49 locations within one of the three test waste-rock piles and 14 locations on the surface of the pile at one-minute intervals. Wind speed and direction were measured at 10-min intervals. Correlations between wind vectors and pressure measurements show that the wind influences pressure fluctuations in the test pile. The strength of the correlation is roughly inversely proportional to the distance between measurement ports and the atmospheric boundary. The linear relationship between internal pressure measurements and surface pressure measurements demonstrate that gas flow is Darcian within the test waste-rock pile. Spectral analysis of wind data and a one-dimensional analytical solution to the flow equations show that the persistence of wind in a certain direction has most pronounced effects on transient gas flow within the pile. The penetration depth of wind-induced gas pressure wave is a function of the periodicity of the wind and permeability of the waste-rock pile.

Both novel membrane materials with better separation characteristics and a better fundamental understanding of membrane transport stability are needed to improve the competitiveness of commercial membrane separations. In this work, the effect of a novel moiety, hexafluoroalcohol, on the gas transport properties of an aromatic polyimide membrane are evaluated. The hexafluoroalcohol group increases the membrane’s fractional free volume, which increases the membrane’s permeability to all gases. Additionally, the HFA-containing polyimide shows resistance to plasticization by carbon dioxide. However, ideal selectivity for several gas pairs is unchanged by the inclusion of hexafluoroalcohol and the increase in the polymer’s fractional free volume. This lack of selectivity loss with increasing free volume is attributed to hydrogen bonding between the hexafluoroalcohol and imide groups, which reduces chain mobility. The ethanol dehydration characteristics of a so-called “TR” polymer are also evaluated in this work. TR polymers are heterocyclic, aromatic polymers synthesized by a solid-state, high temperature condensation from ortho-functional polyimides. Pervaporation studies on a representative TR polymer film demonstrate that the material has separation properties that exceed those of a commercial ethanol dehydration membrane. The transport properties of the TR film, combined with high thermal and chemical stability characteristic of these materials, make TR polymers promising materials for high-temperature, high-water content ethanol dehydration. Finally, the physical aging and plasticization of cellulose triacetate, the dominant natural gas purification membrane, is presented. Although this material has been used industrially for over 30 years, the physical aging and plasticization of the material, particularly in sub-micron films, has never been studied. Although cellulose triacetate does show physical aging behavior, as observed by permeability decreases over time, cellulose triacetate thin films do not show accelerated aging. Furthermore, the plasticization of thin cellulose triacetate films is reduced, rather than increased as seen in other polymers. The unusual transport stability of thin cellulose triacetate films may be due to their complex, semi-crystalline morphology, which, due to the thermal instability of the material, may not be thermally controlled. / text

This study is part of the Diavik Waste-Rock Pile Project taking place at the Diavik Diamond Mine in the Northwest Territories, Canada. The project involves the construction of three 15m-scale low sulfide test waste-rock piles and monitoring of fluid flow, geochemical reactions, heat and gas transport within the waste-rock piles and characterization of the physical properties of the waste-rock piles. The focus of this thesis is characterizing grain-size distribution of the waste-rock and quantifying gas transport in the test waste-rock piles. Grain size of waste rock ranges from millimeters to meters. Sieve analysis typically only provides information of grain size <0.1 m at a single location. A computer program was developed using digital image-processing techniques to obtain a spatial grain-size distribution from photographs of tip faces of the test waste-rock piles acquired in the field. The program characterizes grain size >0.1 m and employs a region-growing algorithm for segmentation of waste-rock grains with pre- and post-processing techniques to improve the accuracy of segmentation. The program was applied to photographs of six different tip faces of the test waste-rock piles. For grain size <0.1 m, data from sieve analyses were attached to the grain-size curves generated from image grain-size analyses to obtain a full spectrum grain-size analyses ranging from boulders to fines. The results show that fine fractions are retained at the top of the tip faces and grain size increases non-linearly from top to bottom of a waste-rock pile. Calculations show that although the greatest mass is associated with the medium and coarse fractions, the greatest surface area is associated with the fine fractions. The results are consistent with field observation that the initial solute concentrations are greatest at the top of the pile and saturated hydraulic conductivity are lower at the top of the pile than in the pile interior. Statistical moments show that the test waste-rock piles have mean grain size of granules and are very poorly sorted, coarse skewed and leptokurtic. Permeability is calculated using empirical formulae and good agreement is obtained between calculated values and field measurements. The heterogeneity of grain size obtained from this study can provide a basis for future modeling efforts. Gas transport analysis focused on 1) substantiating the relationship between wind flow external to the waste-rock pile and gas pressures within the pile, 2) determining the gas flow regime in the pile, and 3) quantifying the temporal variation in wind speed and direction and determining the relevant time scales. Differential gas pressures were measured in 2008 at 49 locations within one of the three test waste-rock piles and 14 locations on the surface of the pile at one-minute intervals. Wind speed and direction were measured at 10-min intervals. Correlations between wind vectors and pressure measurements show that the wind influences pressure fluctuations in the test pile. The strength of the correlation is roughly inversely proportional to the distance between measurement ports and the atmospheric boundary. The linear relationship between internal pressure measurements and surface pressure measurements demonstrate that gas flow is Darcian within the test waste-rock pile. Spectral analysis of wind data and a one-dimensional analytical solution to the flow equations show that the persistence of wind in a certain direction has most pronounced effects on transient gas flow within the pile. The penetration depth of wind-induced gas pressure wave is a function of the periodicity of the wind and permeability of the waste-rock pile.

abstract: Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications. In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance. An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å). / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2018

The objective of this research work was to understand the molecular mechanism of gas transport through amorphous glassy polymers. Especially, emphasis was placed on determining whether or not gas transport in amorphous glassy polymers is directly correlated with the free volume content. Free volume arguments are indeed commonly used to explain the gas transport process. The gas transport properties of bisphenol-A polycarbonate films were examined as a function of the cooling rate, physical aging, and orientation. Such conditions affect the free volume content and its size and shape distribution. Results obtained from permeation experiments were accompanied with dynamic mechanical and density measurements. The experimental results suggest that the diffusion coefficient of small gas molecules in glassy polycarbonate is influenced by the local dynamics or mobility of the polymer chains rather than by the overall free volume content. Indeed, the diffusion coefficient of nitrogen for instance was reduced in fast-cooled samples, despite of the fact that those samples possessed a greater overall free volume content. Fast cooling rates may generate highly restricted conformations which hinder local motions, and therefore tend to increase the activation energy of diffusion. As expected, the greater the free volume content, the greater was the solubility coefficient. The increase in the polymer relaxation times with aging time is believed to restrict the local chain motions, leading to enhanced activation energies of diffusion, and therefore to reduced diffusion coefficients. The change in the solubility coefficients with physical aging revealed that the aging process might not affect all the cavity sizes in polycarbonate equally. According to free volume arguments, one would anticipate that the physical aging of fast-cooled samples (which possess more free volume) should be enhanced compared to that of slowly-cooled samples. Quite interestingly, the decrease in the diffusion coefficient with aging was found to occur much slower in fast-cooled samples, despite of the higher initial free volume content. In contrast, properties directly related to the free volume content, such as density or isothermal DMTA measurements actually showed a greater aging rate in the sample containing the greatest amount of free volume. Slow-cooled samples that are in a low energy conformational state may loose their internal degrees of freedom more rapidly, due to the closer interchain packing and the possibly restricted segmental motions. Studies dealing with orientation and gas transport were complicated by several factors. For instance the fact that the permeation experiments were performed perpendicularly to the orientation of the chains and not along the orientation axis limited the sensitivity of the gas transport properties to orientation. This work points out that dynamic rather than static models should be developed to predict the gas transport phenomenon. / Ph. D.

La thèse discute des conséquences des changements majeurs du modèle de la demande de gaz décrits précédemment. L´exigence de flexibilité à court terme a été l´une des principales caractéristiques de la demande de gaz pour la production d´électricité. Ainsi, la capacité de l´industrie du gaz à fournir des services flexibles à court terme a été valorisée par le biais du marché de l´électricité. Cela signifie une augmentation de la valeur économique des services permettant d´adopter une position attentiste vis-à-vis de la consommation avant toute prise de décision. Différents secteurs de l´industrie du gaz ont été affectés par les variations de la demande, c´est le cas de la production des champs de gaz, du stockage et des mécanismes d´importation du gaz qui ont été incités à la flexibilité. L´introduction des outils de flexibilité, qu’impliquent les variations de la demande, dépend directement des services de réseau. Par conséquent la concrétisation de la valeur économique de la flexibilité de l´industrie gazière dépend des services de réseau.Le réseau de transports de gaz est un élément-clé de l´industrie gazière portant sur deux types de flexibilités physiques: la mobilité et l´aptitude au stockage. Les propriétés physiques du gaz naturel permettent la flexibilité par la gestion des différentiels de pression. Les différentiels de pression contrôlent les mouvements de gaz. Le réseau est de loin le principal mécanisme de transport de gaz et donc un élément majeur de la filière du gaz permettant le commerce de cette matière première. Cependant, le réseau peut aussi être l´une des parties les plus couteuses de l´industrie gazière et, une fois les investissements réalisés ils ne sont ni remboursables, ni récupérables par un autre moyen car ils n'ont pas d’autres utilisations, ce sont les coûts irrécupérables. Malgré cela, la spécificité de le utilisation des actifs des réseaux évolue au cours du développement du réseau.L´intervention des réseaux de transport dans la prestation de services de flexibilité du gaz est une condition obligatoire de la flexibilité du système gazier. Premièrement parce que les services de réseau sont complémentaires de tout autre instrument de flexibilité tels que le stockage souterrain, les infrastructures GNL et le commerce de gaz. Deuxièmement, parce que les services du réseau de transport gazier, tel le que stock en conduite, peuvent également être compétitifs vis à vis d´autres instruments de flexibilité dégroupé.Par conséquent, la régulation du réseau doit prendre en compte l´impact à court et à long terme des règles d´incitation. Compte tenu du fait que le développement du réseau dépend des exigences de flux prévisibles, des variations importantes de la demande de gaz et les changements de flux qui en découlent auront un impact sur l´activité d´exploitation des réseaux gaziers. D´un côté le développement du réseau dépend de la prévision des besoins de flux, et de l´autre, la flexibilité des infrastructures du réseau conditionne nécessairement celle de l´utilisation. Par conséquent, les variations de la demande, responsable de l´accroissement des exigences de flexibilité ainsi que des variations des flux de gaz qui en découlent doivent avoir un impact sur l´exploitation du réseau de gaz et sur l´incitation aux investissements d’infrastructure. / This thesis discusses the consequences of the major changes in gas demand patterns. The requirement of short term flexibility has been one of the main features of electricity generation gas demand. As consequence, the capacity of gas industry to provide short term flexibility services has been valorized through electricity market. It means an increasing economic value to services allowing waiting and seeing before consumption decision. Different parts of the gas industry was impacted by the changes on demand, for instance gas fields productions, storage and gas importation mechanisms were incited to offer flexible provisions. The introduction of tools to provide flexibility required by demand depends on network services. It means the realization of the flexibility value of gas industry depends on gas network services. The gas transport network is the key part of gas industry, and it may provide two kinds of gas physical flexibility: mobility and storability. The physical properties of natural gas allow flexibility by means of pressure differential management. The change on pressures may compress natural gas and the pressures differences drive gas motions. The network has been, by far, the main mechanism to carry gas, thus an essential part of the gas industry chain to allow commodity trade. Network, however, may be one of the most expensive parts of gas industry, and, after the investment done, it becomes sunk costs. But the specificity of networks assets changes in the course of network development. The use of transport network in the provision of gas flexibility services is a necessary condition to provide flexibility in the gas system. First, because network services are complementary of any other flexibility tool, as underground storage, LNG infrastructures and gas trade. Second, because gas transport network services, as line-pack storage, may also be competitive to the others unbundled flexibility tools. Therefore, network regulation needs to take into account the short and the long term impact of the rules incentives. Given that network development depends on expected flow requirements, strong change on gas demand and the consequent changes on gas flows must impact gas network operation. On the one hand, network development depends on expected flow requirements, and on the other, provisions of flexibility depend necessarily on the flexible use of network infrastructures. Hence, changes on gas demand increasing flexibility requirements and the consequent changes on gas flow must impact gas network operation and must impact the incentive on infrastructures investment.

<p>The aim of the study was to investigate if methane emission in a constructed wetland changed in a diurnal pattern correlating to temperature, humidity or light conditions. The gas measurements were carried out with a static chamber technique. The wetland (in Nykvarn outside of Linköping, Sweden) takes care of wastewater to reduce the nitrogen loads. Measurements were carried out at three different occasions in the summer of 1998 on two sites in the wetland. One site was close to the inflow, inhabited by Lemnaceae, and another site was located further downstream inhabited by the emergent macrophyte Typha latifolia. The results showed a variation, but no discernible diurnal pattern. The Typha site had a methane emission rate of 166 mg CH₄ m-2d-1 and the Lemnaceae site had an methane emission rate of 712 mg CH₄ m-2d-1. In all experiments at the Typha site, the highest methane emission rate was obtained at sunrise.</p>