Thesis (PhD)--Montana State University--Bozeman, 2009. / Typescript. Chairperson, Graduate Committee: Sarah L. Codd. Includes bibliographical references (leaves 141-154).

The primary aim of this thesis is to investigate and quantify the self-diffusion processes of gaseous molecules adsorbed in industrially relevant microporous zeolite materials using Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). The main body of this work involves the use of weakly adsorbing hydrocarbon gases (CH4, C2H6 and C3H¬8) adsorbed in a large pore β-zeolite structure. This thesis describes the development of a solely PFG NMR based technique for measuring the molecular displacements of these species at varying length-scales. This enabled the characterisation of self-diffusion regimes across zeolite beds and within individual zeolite crystallites. The characterisation of self-diffusion processes within single zeolite crystallites was critical with respect to accounting for quantitative discrepancies reported in the literature between PFG NMR and alternative measurement techniques. This approach also revealed that the transitions in the Gaussian probability distributions of the molecular displacements in the aforementioned self-diffusion regimes could be recorded by varying the experimental time-scale for observing molecular motion. This technique was extended to characterise the self-diffusion processes of the aforementioned hydrocarbons in small (≤ 1 μm) and large (≥ 15 μm) zeolite crystallites to investigate the dependence of this technique on zeolite geometry. It was found that the self-diffusion coefficients within single crystallites were in good agreement with one another, despite their differing crystallite geometries. This technique was subsequently used to study the self-diffusion behaviour of two-component hydrocarbon gaseous mixtures with differing sorption properties co-adsorbed in β-zeolite. Excellent chemical shift resolution was obtained for chemically similar species using NMR spectroscopy, relaxometry and diffusometry without the use of Magic Angle Spinning (MAS). This connoted that conventional PFG NMR is capable of precisely characterising individual species in real world multi-component systems. This thesis also describes the self-diffusion of ammonia in small pore chabazite structures, which are typically used in Selective Catalytic Reduction (SCR) processes. It was found that the self-diffusion coefficient of this strongly adsorbing species increased with molecular loading up to a certain point. This peculiar behaviour implied a strong concentration and inter-molecular dependence within the zeolite structure. Lastly, the techniques which were developed at high magnetic field strengths (300 MHz) were transferred to a lower field strength (43 MHz) benchtop spectrometer at the Johnson Matthey Technology Centre (JMTC). This describes the first characterisation of mass transport behaviour of weakly interacting sorbates in zeolites using a portable spectrometer. This presents an excellent opportunity for future off-line molecular displacement measurements to be made for complex and real-world systems in a matter of minutes.

The workshop program will focus on adsorption measurement techniques and methodologies for the assessment of adsorption properties and textural/structural characterization of novel nanoporous materials including zeolites, carbons, MOFs as well as materials consisting of hierarchically structured pore networks. A major point will be the correlation of textural properties, adsorption behavior, catalytic reaction pathways as well as transport properties with applications in gas and energy storage, separations and catalysis. Within this framework, the workshop will offer a platform for scientific discussions and for a knowledge transfer between various scientific areas where diffusion and transport properties of porous materials are of importance.

With reference to these advantages, the poster goes the other way round and identifies a couple of similarities where, on looking at molecular diffusion in nanoporous materials, one is able to recognize features of spreading, which may occur in quite different fields of research. The examples presented include (i) considering molecular uptake and release with nanoporous particles as a model for, respectively, occupation of a habitat by a new species and, vice versa, for the loss of a species in this habitat [2], (ii) the effect of additional highways on overall mass transfer [3,4], (iii) transport impediment (and enhancement!) by diffusant interference [5], (iv) invader-induced changes in the host system [2] and (v) host-induced changes of the invaders [6].

Successful design and application of nanoporous materials are essentially dependent on the molecular diffusion. Two mechanisms, i.e. surface barriers and intracrystalline diffusion, may dominate the mass transport. In the previous studies, these two mechanisms are difficult to determine with certainty by dual resistance model [1] (DRM). Here, we derive an expression of uptake rate relying solely on surface permeability, which provides a method to directly quantify the surface barriers. Subsequently, the effects of surface barriers and intracrystalline diffusion could be identified separately.

Magnesium (Mg) is a light-weight metal that has extraordinary physical and chemical properties for many potential applications in automobile, military, and electronics. Aluminum alloys, because of its light-weight, high strength and corrosion resistance have a wide range of commercial applications. Given these two, sometime competing, alloy systems, there are now many applications where the metallurgical compatibility of Mg- and Al-alloys are required for engineering applications. One such case is the development of diffusion barrier for U-Mo metallic fuel in Al-alloy cladding, where Mg, with its complete immiscibility with U and Mo is being considered as the diffusion barrier. While negligible diffusional interaction between Mg and U-Mo alloys have been reported, diffusional interaction between the Mg and Al-alloy cladding has not been investigated. In this study, solid-to-solid diffusion couples were assembled using discs of pure Mg (99.999 %) and AA6061 Al-alloy. After preparation, Mg was diffusion bonded to AA6061 in sealed quartz capsule at 300°, 350°, and 400°C for 720, 360, and 240 hours, respectively. Scanning electron microscopy was used to inspect the interdiffusion zone, while phase identification was performed using X-ray energy dispersive spectroscopy. One specific phase that exists in the binary Mg-Al system, labeled “ε” was observed and characterized by transmission electron microscopy. From the preceding data, the growth rates as well as interdiffusion coefficients of the intermetallic phases were extracted and compared to previous investigations using pure Mg and Al.

The use of interference microscopy has enabled the direct observation of transient concentration profiles generated by intracrystalline transport diffusion in nanoporous materials. The thus accessible intracrystalline concentration profiles contain a wealth of information which cannot be deduced by any macroscopic method. In this paper, we illustrate five different ways for determining the concentration-dependent diffusivity in one-dimensional systems and two for the surface permeability. These methods are discussed by application to concentration profiles evolving during the uptake of methanol by the zeolite ferrierite and of methanol by the metal organic framework (MOF) manganese(II) formate. We show that the diffusivity can be calculated most precisely by means of Fick’s 1st law. As the circumstances permit, Boltzmann’s integration method also yields very precise results. Furthermore, we present a simple procedure that enables the estimation of the influence of the surface barrier on the overall

Within this general context, this talk will consider the use of novel nanoporous materials as the basis for adsorption based separations [3] that will range from concentrated mixtures to direct capture of carbon dioxide from air. An overview of different classes of materials will show how these can be tailored to such a wide range of conditions. The sheer scale of the task leads to having to optimize systems and speed up processes, which in turn brings in diffusion limitations.

Gegenstand der Arbeit ist die PFG NMR (nuclear magnetic resonance with pulsed field gradients), wobei speziell die apparativen und experimentellen Bedingungen untersucht werden, welche sich durch die Verwendung ultra-hoher gepulster magnetischer Feldgradienten von bis zu 35T/m ergeben. Motiv für die Arbeit ist die Untersuchung von Diffusionserscheinungen in mikroporösen Wirtssystemen mit inneren magnetischen Feldgradienten oder/und kurzen T2-Relaxationzeiten. Nach Zusammenstellung der notwendigen Werkzeuge zur mathematischen Beschreibung von PFG NMR-Experimenten werden die aus der Literatur bekannten Impulssequenzen kritisch untersucht und durch eigene Weiterentwicklungen ergänzt. Für wichtige PFG NMR-Impulssequenzen wird eine verallgemeinerte Schreibweise vorgestellt und auf beliebige Formen der gepulsten magnetischen Feldgradienten ausgedehnt. Weiterhin werden Störeinflüsse auf das PFG NMR-Experiment untersucht und zunächst in allgemeiner Form Möglichkeiten zu deren Beseitigung bzw. Unterdrückung dargestellt. Die so gewonnenen Erkenntnisse fanden konkrete Anwendung bei der Konzeption und dem Bau des PFG NMR-Spektrometers Fegris 400 NT. Dieses Gerät wird, soweit es den Gegenstand der Arbeit berührt, ebenfalls beschrieben und in der Anlage dokumentiert. Abschließend sind einige Untersuchungen, die mit dem Fegris 400 NT durchgeführt wurden und in der dargestellten Form erst mit diesem Gerät möglich waren, kurz skizziert, wobei für weitergehende Informationen auf die entsprechenden Veröffentlichungen verwiesen wird.

Nous modélisons la diffusion des atomes interstitiels (C et O) dans des solutions solides (Fe-Cr et Nb-V) et comparons nos résultats aux données expérimentales disponibles dans la littérature. Un ensemble d’énergies de liaisons entre interstitiels et solutés substitutionnels, et de barrières de migration des interstitiels, ont d’abord été calculés en utilisant la théorie de la fonctionnelle de la densité. Des modèles d’interactions de paires ont ensuite été ajustés sur ces données pour calculer les barrières de migration dans n’importe quel environnement chimique local. Ces modèles de paires sont enfin intégrés dans des simulations Monte Carlo cinétiques, afin de modéliser des expériences de diffusion de traceur et de frottement interne. Dans les alliages Fe-Cr-C, les simulations prévoient la formation d’un pic de Snoek unique, dans tout le domaine de composition entre le fer pur et le chrome pur. La barrière de migration moyenne du carbone, donnée par la température de ce pic, augmente progressivement avec la teneur en chrome, l’augmentation étant très faible en dessous de 6% de Cr. Dans les alliages riches en Cr, la barrière de migration moyenne obtenue lors d’une simulation de diffusion de traceur est plus grande que celle obtenue lors d’une simulation de frottement interne. Nous en concluons que la barrière mesurée lors d’une expérience de diffusion de traceur est fortement affectée par le piégeage du carbone dans des environnements riches en fer, qui limite la diffusion à grande distance ; alors que la barrière mesurée par friction interne, qui ne nécessite qu’une diffusion à courte distance, est principalement contrôlée par les barrières de migration des configurations les plus probables. Dans les alliages Nb-V-O dilués, les simulations font apparaitre un pic de Snoek à haute température lorsque la concentration en oxygène est plus faible que celle en vanadium. Quand la concentration en oxygène devient plus importante, un deuxième pic apparait à plus basse température, tandis que le premier pic se déplace vers des températures plus petites. Nous en concluons que le pic à haute température correspond à des paires V-O, et que celui à basse température correspond à la diffusion de l’oxygène dans le niobium pur. Les simulations sont utilisées pour tester le modèle de Koiwa, dans la limite de l’alliage ternaire infiniment dilué. Les deux approches sont en bon accord et nous montrons que la position du pic à haute température n’est pas reliée à une fréquence de saut unique, mais à une fonction complexe de plusieurs fréquences de sauts. Nous présentons enfin les résultats d’une étude préliminaire sur l’effet du carbone sur les cinétiques de séparation de phases dans les alliages fer-chrome irradiés. Nous montrons que la forte attraction entre atomes de carbone et défauts d’irradiation (auto-interstitiels et surtout lacunes) peut dans certaines conditions limiter l’accélération de la précipitation du chrome habituellement provoquée par l’irradiation. / The diffusion of interstitial atoms (C and O) in bcc solid solutions (Fe-Cr and Nb-V) is modelled and compared to experimental data. A set of binding energies and migration barriers for the direct interstitial diffusion mechanism in different local chemical environments are first calculated using Density Functional Theory. Two different pair interaction models are developed in order to reproduce these data and predict the migration barriers in all possible environments. The diffusion models are then implemented in a kinetic Monte Carlo method to simulate tracer diffusion experiments, using a standard procedure, and internal friction experiments, using a novel method. In the Fe-Cr-C systems our internal friction simulations show a unique Snoek peak in the whole concentration range, between pure iron and pure chromium. The average migration enthalpy for C diffusion in Fe-Cr alloys is found to increase progressively with the Cr concentration, with a small rate below 6 %Cr. In Cr-rich alloys, the effective migration barrier for C diffusion is found to be larger in tracer diffusion than in the internal friction simulations. We conclude that the effective migration barrier extracted from tracer diffusion is closely related to trapping effects of C atoms in Fe-rich local environments, whereas the migration barrier associated with internal friction is mainly controlled by the spectrum of migration barriers of the most frequent configurations, as it is clearly shown in the Cr-rich domain. In the dilute Nb-V-O alloys, we find a high temperature Snoek peak when the concentration of oxygen is lower than the vanadium content. But when the oxygen concentration is higher, we see the appearance of a second peak but at a lower temperature and a shift of the first peak to lower temperatures. We conclude that the high temperature peaks correspond to the oxygen-vanadium pairs, and the low temperature peak corresponds to the oxygen Snoek peak in pure Nb. We also use our model in order to validate the Koiwa model in infinitely dilute ternary alloys. Both approaches are in good agreement and we observe that the high temperature peak cannot be directly related to a single jump frequency but to a complex function of them. We also show preliminary results on the effect of C in the precipitation of the Fe-Cr phase separation under irradiation. We observee that a strong attraction between carbon atoms and point defects (vacancies and self-interstitials) might be able to slow down the acceleration of the α’ precipitation.