The structure and dynamics of the smectic-A liquid crystal 8CB (4 cyano-4 octylbiphenyl) when sheared and confined to mesoscale gaps (with crossed cylindrical geometry and mica confining surfaces) were studied using a Surface Forces Apparatus (SFA). Triangular shear patterns with frequencies of 0.01, 0.1, 1.0 and 10 Hz, and amplitudes of 62.5 nm, 625 nm and 6.25 m were applied to samples at gap sizes of 0.5 and 5.0 m. The study was performed at room temperature (20.5C) and at two higher temperatures (22C and 27C). In order to minimize the thermal fluctuations within the test chamber and hence to allow for the rapid re-initialization of test runs, the SFA was modified to allow for quick, precise and remote control of the confining surfaces. The procedure maximized the number of tests that could be undertaken with a single pair of surfaces so that a single gap geometry could be maintained for the duration of the test run. In order to run the SFA remotely, scripts written with a commercial software package, LabVIEW, were used to control of the SFA components, its FECO-monitoring camera and all its peripheral electronic equipment as well. Samples were agitated to disrupt any shear-induced liquid crystal domain alignment from previous testing following each shear test, and methodologies were developed to ascertain the extent of confinement quickly and remotely following agitation. Separate methods were developed for gap sizes at each extreme of the mesoscale regime, where the transition from bulklike structure and dynamics to nano-confinement occurs (between 1 and 10 microns for smectic-A 8CB). The results revealed that the greater amplitude-gap aspect ratio and surface-to-domain contact associated with smaller gaps facilitated reorientation of the domains in the shear direction. Evidence was also presented of domains at the higher end or outside of the mesoscale regime that, while straining and accreting, were unable to reorient and thereby led to an overall increase of viscoelastic response. The effective viscosity was found to obey a simple power law with respect to shear rate, , and the flow behaviour indices, n, slightly in excess of unity indicate shear thickening occurs with large enough shear amplitude, and that the viscosity reached a plateau near unity over shear rates of 0.005 to 500 s-1 within the mesoscale regime. Different K and n values were observed depending on the shear amplitude used. Unlike bulk smectic 8CB, whose domains do not align well in the shear direction with large shear-strain amplitude, at mesoscale levels of confinement large amplitude shearing (up to 12.5 shear strain amplitude) was found to be very effective at aligning domains. In general domain reorientation is found to be much more rapid within the mesoscale regime than has been reported in bulk. Aggressive shearing was found to result in a complete drop in viscoelastic response within seconds, while gentler shearing is found to produce a very gradual increase that persists for more than six hours, with individual shear periods exhibiting frequent and significant deviations from the expected smooth shear path that may be a product of discrete domain reorientations. From these findings, certain traits of the smectic 8CB domain structures under mesoscale confinement were deduced, including how they respond to shear depending on the level of confinement, and how their reorientation due to shear varies not only with shear rate but also independently with shear amplitude. An equation describing the viscosity change as a function of both shear rate and shear amplitude is proposed. The shear amplitude dependence introduces the notion of shearing beyond the proposed smectic 8CB “viscoelastic limit”, which was shown to exhibit behaviour in accordance with Large Amplitude Oscillatory Shear (LAOS) techniques developed for Fourier Transform rheology. The findings provided an understanding of the behavioural changes that occur as one reduces the level of confinement of smectic materials from bulk to nanoconfinement.

The structure and dynamics of the smectic-A liquid crystal 8CB (4 cyano-4 octylbiphenyl) when sheared and confined to mesoscale gaps (with crossed cylindrical geometry and mica confining surfaces) were studied using a Surface Forces Apparatus (SFA). Triangular shear patterns with frequencies of 0.01, 0.1, 1.0 and 10 Hz, and amplitudes of 62.5 nm, 625 nm and 6.25 m were applied to samples at gap sizes of 0.5 and 5.0 m. The study was performed at room temperature (20.5C) and at two higher temperatures (22C and 27C). In order to minimize the thermal fluctuations within the test chamber and hence to allow for the rapid re-initialization of test runs, the SFA was modified to allow for quick, precise and remote control of the confining surfaces. The procedure maximized the number of tests that could be undertaken with a single pair of surfaces so that a single gap geometry could be maintained for the duration of the test run. In order to run the SFA remotely, scripts written with a commercial software package, LabVIEW, were used to control of the SFA components, its FECO-monitoring camera and all its peripheral electronic equipment as well. Samples were agitated to disrupt any shear-induced liquid crystal domain alignment from previous testing following each shear test, and methodologies were developed to ascertain the extent of confinement quickly and remotely following agitation. Separate methods were developed for gap sizes at each extreme of the mesoscale regime, where the transition from bulklike structure and dynamics to nano-confinement occurs (between 1 and 10 microns for smectic-A 8CB). The results revealed that the greater amplitude-gap aspect ratio and surface-to-domain contact associated with smaller gaps facilitated reorientation of the domains in the shear direction. Evidence was also presented of domains at the higher end or outside of the mesoscale regime that, while straining and accreting, were unable to reorient and thereby led to an overall increase of viscoelastic response. The effective viscosity was found to obey a simple power law with respect to shear rate, , and the flow behaviour indices, n, slightly in excess of unity indicate shear thickening occurs with large enough shear amplitude, and that the viscosity reached a plateau near unity over shear rates of 0.005 to 500 s-1 within the mesoscale regime. Different K and n values were observed depending on the shear amplitude used. Unlike bulk smectic 8CB, whose domains do not align well in the shear direction with large shear-strain amplitude, at mesoscale levels of confinement large amplitude shearing (up to 12.5 shear strain amplitude) was found to be very effective at aligning domains. In general domain reorientation is found to be much more rapid within the mesoscale regime than has been reported in bulk. Aggressive shearing was found to result in a complete drop in viscoelastic response within seconds, while gentler shearing is found to produce a very gradual increase that persists for more than six hours, with individual shear periods exhibiting frequent and significant deviations from the expected smooth shear path that may be a product of discrete domain reorientations. From these findings, certain traits of the smectic 8CB domain structures under mesoscale confinement were deduced, including how they respond to shear depending on the level of confinement, and how their reorientation due to shear varies not only with shear rate but also independently with shear amplitude. An equation describing the viscosity change as a function of both shear rate and shear amplitude is proposed. The shear amplitude dependence introduces the notion of shearing beyond the proposed smectic 8CB “viscoelastic limit”, which was shown to exhibit behaviour in accordance with Large Amplitude Oscillatory Shear (LAOS) techniques developed for Fourier Transform rheology. The findings provided an understanding of the behavioural changes that occur as one reduces the level of confinement of smectic materials from bulk to nanoconfinement.

In dieser Dissertation wird das viskoplastische Schubverhalten eines magnetorheologischen Fluids (MRF) modelliert. Mithilfe eines phänomenologischen Modellierungsansatzes auf Basis nichtlinearer rheologischer Elemente können die gemessenen Fließkurven sowie Speicher- und Verlustmoduli abgebildet werden. Ein MRF ist ein Material mit fest-flüssig Übergang. Es besitzt von einem Magnetfeld abhängige Materialeigenschaften. Um diese beschreiben zu können, wird zunächst eine phänomenologische Stoffklassifizierung eingeführt. Auf deren Grundlage teilen sich Stoffe allgemein in Flüssigkeiten, Festkörper und Materialien mit fest-flüssig Übergang auf. Zur Beschreibung des Materialverhaltens von MRF werden drei viskoplastische Modelle formuliert und gegenübergestellt. Zur Identifikation der Materialparameter wird eine Identifikationsstrategie auf der Grundlage charakteristischer Punkte entwickelt. Charakteristische Punkte sind exklusive Punkte von Materialfunktionen, die analytisch beschrieben und ohne Weiteres experimentell ermittelt werden können. Analytische Ausdrücke für charakteristische Punkte der Speicher- und Verlustmoduli werden über das Analogieprinzip unter Verwendung von Lissajous Diagrammen abgeleitet. Infolgedessen können die Materialparameter durch das Auswerten algebraischer Zusammenhänge identifiziert werden, ohne nichtlineare Optimierungsverfahren anwenden zu müssen. Hierbei stellt die Fließspannung einen signifikanten Materialparameter dar. Deswegen werden die Standardverfahren zur Bestimmung der Fließspannung auf rheologische Modelle angewendet und bewertet.

No description available.

Short Large-Amplitude Magnetic Structures (SLAMS) have been observedby spacecraft near Earth’s quasi-parallel bow shock. They arecharacterized by a short and sudden increase of the magnetic field,usually by a factor of 2 or more. SLAMS studies have previously beenlimited to small sample sizes because SLAMS were identified throughmanual inspection of the spacecraft data. This makes it difficult to drawgeneral conclusions and the subjective element complicates collaborationbetween researchers. A solution is presented in this thesis; anautomatic SLAMS detection algorithm. We investigate several movingwindowmethods and measure their performance on a set of manuallyidentified SLAMS. The best algorithm is then used to identify 98406SLAMS in data from the Magnetospheric Multiscale (MMS) mission. Ofthose, 66210 SLAMS were detected when the Fast Plasma Investigation(FPI) instrument was active. Additionally, we are interested in knowingwhether a detected SLAMS is located in the foreshock or magnetosheath.Therefore, we implement a Gaussian mixture model classifier,based on hierarchical clustering of the FPI data, that can separatebetween the four distinct regions of the magnetosphere that MMSencounters; magnetosphere, magnetosheath, solar wind and (ion) foreshock.The identified SLAMS are compiled into a database which holdstheir start and stop dates, positional coordinates, B-field informationand information from the magnetospheric classifier to allow for easyfiltering to a specific SLAMS population. To showcase the potentialof the database we use it to perform preliminary statistical analysison how the properties of SLAMS are affected by its spatial and/ormagnetospheric location. The database and Matlab implementationare available on github: https://github.com/cfognom/MMS_SLAMS_detection_and_magnetospheric_classification. / Korta magnetiska strukturer med hög amplitud (SLAMS) har observeratsav satelliter nära jordens kvasi-parallella bogchock. En kortoch plötslig höjning av magnetfältsstyrkan är ett typiskt drag förSLAMS, vanligtvis med en faktor 2 eller mer. Forskning om SLAMShar tidigare varit begränsad till mindre fallstudier eftersom SLAMSidentifierats genom manuell inspektion av satellitdata. Detta gör detsvårt att dra generella slutsatser och det subjektiva elementet försvårarsamarbetet mellan forskare. En lösning till detta problem presenteras idenna avhandling; en automatisk identifieringsalgoritm för SLAMS. Viundersöker flera metoder och mäter deras prestanda på en uppsättningmanuellt identifierade SLAMS. Den bästa algoritmen används sedan föratt identifiera 98406 SLAMS i data från MMS-uppdraget. Av dessa upptäcktes66210 SLAMS när FPI-instrumentet var aktivt. Vi är dessutomintresserade av att veta om en upptäckt SLAMS finns i förshocken ellermagnetoskiktet. Därför implementerar vi en Gaussisk klassificeraresom bygger på hierarkisk klustring av FPI-data. Den kan separerade fyra distinkta regionerna av magnetosfären som MMS observerar;magnetosfär, magnetoskikt, solvind och (jon) förchock. De identifieradeSLAMS:en sammanställs till en databas som innehåller deras start- ochstoppdatum, positionskoordinater, B-fältsinformation och informationfrån magnetosfärsklassificeraren för att möjliggöra enkel filtrering tillen specifik SLAMS-population. För att visa potentialen av databasenutför vi en preliminär statistisk undersökning av hur egenskapernaav SLAMS påverkas av deras rumsliga och/eller magnetosfäriska position.Databasen och Matlab-implementationen är tillgängliga på Github:https://github.com/cfognom/MMS_SLAMS_detection_and_magnetospheric_classification.

Polymerní nanokompozity (PNCs) mají slibnou budoucnost jako lehké funkční materiály zpracovatelné aditivními výrobními technologiemi. Jejich rychlému rozšíření však brání silná závislost jejich užitných vlastností na prostorovém uspořádání nanočástic (NP). Schopnost řídit disperzi nanočástic je tak klíčovým předpokladem pro jejich uplatnění ve funkčních kompozitech. Tato práce zkoumá přípravu polymerních nanokompozitů v modelové sklotvorné polymerní matrici roztokovou metodou, technikou schopnou vytvářet prostorové uspořádání nanočástic řízené strukturními a kinetickými parametry přípravného procesu. Prezentované výsledky popisují rozdíly mezi změnami rheologického chování roztoku polystyrenu při oscilačním smyku s vysokou amplitudou (LAOS) vyvolanými nanočásticemi. Výsledky vedou k závěru, že vysoce-afinní OP-POSS nanočástice při nízkých koncentracích dobře interagují s PS a tvoří tuhé agregáty, zatímco nízko-afinní OM-POSS nanočástice za těchto podmínek neovlivňují deformační chování polymerních řetězců. Dále byla pozornost zaměřena na vliv použitého rozpouštědla na uspořádání nanočástic v SiO2/PMMA a SiO2/PS nanokompozitech, který je v literatuře prezentován jako parametr řídící prostorové uspořádání nanočástic v pevném stavu. Důraz byl kladen na kvalitativní rozdíly mezi „špatně dispergovanými“ shluky nanočástic, které byly na základě rheologie a strukturální analýzy (TEM, USAXS) identifikovány jako polymerními řetězci vázané nanočásticové klastry a dva typy agregátů, jeden termodynamického a druhý kinetického původu. Jednotlivé druhy agregátů se vyznačují odlišnými kinetikami vzniku a rozdílnými vlastnostmi jak mezi sebou, tak v porovnání s dispergovanými nanočásticemi. Pozorované typy disperze nanočástic byly kvantitativně posouzeny podle svých rheologických vlastností během roztokové přípravy, podle kterých byla vyhodnocena míra adsorpce polymeru na povrch nanočástic a atrakce ve vypuzeném objemu. Výsledky byly porovnány s teorií PRISM. Důležitost uspořádání nanočástic byla demonstrována na porovnání teplot skelných přechodů různých struktur při stejném chemickém složení.