Hundertneunundzwanzig Xe NMR for investigations of complex and dynamic systems

In this work, the remarkable versatility and usefulness of applications of Xe-129 NMR experiments is further extended. The application of Xe-129 NMR spectroscopy to very different system is studied, including dynamic and static, solid and liquid, porous and non-porous systems. Using the large non-equilibrium polarization created by hyperpolarization of Xe-129, time-resolved NMR measurements can be used for the online-monitoring of dynamic systems. In the first part of this work, several improvements for medical applications of hyperpolarized Xe-129 are achieved and their feasibility shown experimentally. A large gain in speed and reproducibility of the accumulation process of Xe-129 as ice and an enhancement of the usable polarization in any experiment requiring prior accumulation are achieved. An enhancement of the longitudinal relaxation time of Xe-129 is realized by admixture of a buffer gas during the storage of hyperpolarized Xe-129. Pursuing the efforts of simplifying the accumulation process and enhancing the storage time of hyperpolarized Xe-129 will allow for a wider use of the hyperpolarized gas in (medical) MRI experiments. Concerning the use of hyperpolarized Xe-129 in MRI, the influence of the diffusion coefficient of the gas on parameters of the image contrast is experimentally demonstrated here by admixture of a buffer gas and thus changing the diffusion coefficient. In the second part of this work, a polymer system with unique features is probed by Xe-129 NMR spectroscopy, proving the method to be a valuable tool for the characterization of the anisotropic properties of semicrystalline, syndiotactic polystyrene films. The polymer films contain hollow cavities or channels with sizes in the sub-nanometer range, allowing for adsorption of Xe-129 and subsequent NMR measurements. Despite the use of a ’real-world’ system, the transfer of the anisotropic properties from the material to adsorbed Xe-129 atoms is shown, which was previously only known for fully crystalline materials. The anisotropic behavior towards atomar guests inside the polymer films is proven here for the first time for one of the phases. For the polymer phase containing nanochannels, the dominance of interactions between Xe-129 atoms in the channels compared to interactions between Xe atoms and the channel walls are proven by measurements of a powder sample of the polymer material and experiments including the rotation of the films in the external magnetic field as well as temperature-dependent measurements. The characterization of ’real-world’ systems showing very high degrees of anisotropy by Xe-129 are deemed to be very valuable in future applications. In the last part of this work, a new method for the online monitoring of chemical reactions has been proposed and its feasibility and validity are experimentally proven. The chemical shift dependence of dissolved Xe-129 on the composition of a reaction mixture is used for the online monitoring of free-radical miniemulsion polymerization reactions. Xe-129 NMR spectroscopy provides an excellent method for the online monitoring of polymerization reactions, due to the simplicity of the Xe-129 NMR spectra and the simple relationship between the Xe-129 chemical shift and the reaction conversion. The results of the time-resolved Xe-129 NMR measurements are compared to those from calorimetric measurements, showing a good qualitative agreement. The applicability of the new method to reactions other than polymerization reactions is investigated by the online monitoring of an enzymatic reaction in a miniemulsion. The successful combination of the large sensitivity of Xe-129, the NMR signal enhancements due to hyperpolarization, and the solubility of Xe-129 gives access to the large new field of investigations of chemical reaction kinetics in dynamic and complex systems like miniemulsions.

Dynamic wetting of complex liquids

A simple dependency between contact angle θ and velocity or surface tension has been predicted for the wetting and dewetting behavior of simple liquids. According to the hydrodynamic theory, this dependency was described by Cox and Voinov as θ ∼ Ca^(1/3) (Ca: Capillary number). For more complex liquids like surfactant solutions, this prediction is not directly given.rnHere I present a rotating drum setup for studying wetting/dewetting processes of surfactant solutions on the basis of velocity-dependent contact angle measurements. With this new setup I showed that surfactant solutions do not follow the predicted Cox-Voinov relation, but showed a stronger contact angle dependency on surface tension. All surfactants independent of their charge showed this difference from the prediction so that electrostatic interactions as a reason could be excluded. Instead, I propose the formation of a surface tension gradient close to the three-phase contact line as the main reason for the strong contact angle decrease with increasing surfactant concentration. Surface tension gradients are not only formed locally close to the three-phase contact line, but also globally along the air-liquid interface due to the continuous creation/destruction of the interface by the drum moving out of/into the liquid. By systematically hindering the equilibration routes of the global gradient along the interface and/or through the bulk, I was able to show that the setup geometry is also important for the wetting/dewetting of surfactant solutions. Further, surface properties like roughness or chemical homogeneity of the wetted/dewetted substrate influence the wetting/dewetting behavior of the liquid, i. e. the three-phase contact line is differently pinned on rough/smooth or homogeneous/inhomogeneous surfaces. Altogether I showed that the wetting/dewetting of surfactant solutions did not depend on the surfactant type (anionic, cationic, or non-ionic) but on the surfactant concentration and strength, the setup geometry, and the surface properties.rnSurfactants do not only influence the wetting/dewetting behavior of liquids, but also the impact behavior of drops on free-standing films or solutions. In a further part of this work, I dealt with the stability of the air cushion between drop and film/solution. To allow coalescence between drop and substrate, the air cushion has to vanish. In the presence of surfactants, the vanishing of the air is slowed down due to a change in the boundary condition from slip to no-slip, i. e. coalescence is suppressed or slowed down in the presence of surfactant.

Closed-loop investigation of the dynamical properties of cardiomyocyte electrophysiology by means of Dynamic clamp and Mathematical modelling

The research field of my PhD concerns mathematical modeling and numerical simulation, applied to the cardiac electrophysiology analysis at a single cell level. This is possible thanks to the development of mathematical descriptions of single cellular components, ionic channels, pumps, exchangers and subcellular compartments. Due to the difficulties of vivo experiments on human cells, most of the measurements are acquired in vitro using animal models (e.g. guinea pig, dog, rabbit). Moreover, to study the cardiac action potential and all its features, it is necessary to acquire more specific knowledge about single ionic currents that contribute to the cardiac activity. Electrophysiological models of the heart have become very accurate in recent years giving rise to extremely complicated systems of differential equations. Although describing the behavior of cardiac cells quite well, the models are computationally demanding for numerical simulations and are very difficult to analyze from a mathematical (dynamical-systems) viewpoint. Simplified mathematical models that capture the underlying dynamics to a certain extent are therefore frequently used. The results presented in this thesis have confirmed that a close integration of computational modeling and experimental recordings in real myocytes, as performed by dynamic clamp, is a useful tool in enhancing our understanding of various components of normal cardiac electrophysiology, but also arrhythmogenic mechanisms in a pathological condition, especially when fully integrated with experimental data.

Dynamic development of hydrofractures

Natürliche hydraulische Bruchbildung ist in allen Bereichen der Erdkruste ein wichtiger und stark verbreiteter Prozess. Sie beeinflusst die effektive Permeabilität und Fluidtransport auf mehreren Größenordnungen, indem sie hydraulische Konnektivität bewirkt. Der Prozess der Bruchbildung ist sowohl sehr dynamisch als auch hoch komplex. Die Dynamik stammt von der starken Wechselwirkung tektonischer und hydraulischer Prozesse, während sich die Komplexität aus der potentiellen Abhängigkeit der poroelastischen Eigenschaften von Fluiddruck und Bruchbildung ergibt. Die Bildung hydraulischer Brüche besteht aus drei Phasen: 1) Nukleation, 2) zeitabhängiges quasi-statisches Wachstum so lange der Fluiddruck die Zugfestigkeit des Gesteins übersteigt, und 3) in heterogenen Gesteinen der Einfluss von Lagen unterschiedlicher mechanischer oder sedimentärer Eigenschaften auf die Bruchausbreitung. Auch die mechanische Heterogenität, die durch präexistierende Brüche und Gesteinsdeformation erzeugt wird, hat großen Einfluß auf den Wachstumsverlauf. Die Richtung der Bruchausbreitung wird entweder durch die Verbindung von Diskontinuitäten mit geringer Zugfestigkeit im Bereich vor der Bruchfront bestimmt, oder die Bruchausbreitung kann enden, wenn der Bruch auf Diskontinuitäten mit hoher Festigkeit trifft. Durch diese Wechselwirkungen entsteht ein Kluftnetzwerk mit komplexer Geometrie, das die lokale Deformationsgeschichte und die Dynamik der unterliegenden physikalischen Prozesse reflektiert. rnrnNatürliche hydraulische Bruchbildung hat wesentliche Implikationen für akademische und kommerzielle Fragestellungen in verschiedenen Feldern der Geowissenschaften. Seit den 50er Jahren wird hydraulisches Fracturing eingesetzt, um die Permeabilität von Gas und Öllagerstätten zu erhöhen. Geländebeobachtungen, Isotopenstudien, Laborexperimente und numerische Analysen bestätigen die entscheidende Rolle des Fluiddruckgefälles in Verbindung mit poroelastischen Effekten für den lokalen Spannungszustand und für die Bedingungen, unter denen sich hydraulische Brüche bilden und ausbreiten. Die meisten numerischen hydromechanischen Modelle nehmen für die Kopplung zwischen Fluid und propagierenden Brüchen vordefinierte Bruchgeometrien mit konstantem Fluiddruck an, um das Problem rechnerisch eingrenzen zu können. Da natürliche Gesteine kaum so einfach strukturiert sind, sind diese Modelle generell nicht sonderlich effektiv in der Analyse dieses komplexen Prozesses. Insbesondere unterschätzen sie die Rückkopplung von poroelastischen Effekten und gekoppelte Fluid-Festgestein Prozesse, d.h. die Entwicklung des Porendrucks in Abhängigkeit vom Gesteinsversagen und umgekehrt.rnrnIn dieser Arbeit wird ein zweidimensionales gekoppeltes poro-elasto-plastisches Computer-Model für die qualitative und zum Teil auch quantitativ Analyse der Rolle lokalisierter oder homogen verteilter Fluiddrücke auf die dynamische Ausbreitung von hydraulischen Brüchen und die zeitgleiche Evolution der effektiven Permeabilität entwickelt. Das Programm ist rechnerisch effizient, indem es die Fluiddynamik mittels einer Druckdiffusions-Gleichung nach Darcy ohne redundante Komponenten beschreibt. Es berücksichtigt auch die Biot-Kompressibilität poröser Gesteine, die implementiert wurde um die Kontrollparameter in der Mechanik hydraulischer Bruchbildung in verschiedenen geologischen Szenarien mit homogenen und heterogenen Sedimentären Abfolgen zu bestimmen. Als Resultat ergibt sich, dass der Fluiddruck-Gradient in geschlossenen Systemen lokal zu Störungen des homogenen Spannungsfeldes führen. Abhängig von den Randbedingungen können sich diese Störungen eine Neuausrichtung der Bruchausbreitung zur Folge haben kann. Durch den Effekt auf den lokalen Spannungszustand können hohe Druckgradienten auch schichtparallele Bruchbildung oder Schlupf in nicht-entwässerten heterogenen Medien erzeugen. Ein Beispiel von besonderer Bedeutung ist die Evolution von Akkretionskeilen, wo die große Dynamik der tektonischen Aktivität zusammen mit extremen Porendrücken lokal starke Störungen des Spannungsfeldes erzeugt, die eine hoch-komplexe strukturelle Entwicklung inklusive vertikaler und horizontaler hydraulischer Bruch-Netzwerke bewirkt. Die Transport-Eigenschaften der Gesteine werden stark durch die Dynamik in der Entwicklung lokaler Permeabilitäten durch Dehnungsbrüche und Störungen bestimmt. Möglicherweise besteht ein enger Zusammenhang zwischen der Bildung von Grabenstrukturen und großmaßstäblicher Fluid-Migration. rnrnDie Konsistenz zwischen den Resultaten der Simulationen und vorhergehender experimenteller Untersuchungen deutet darauf hin, dass das beschriebene numerische Verfahren zur qualitativen Analyse hydraulischer Brüche gut geeignet ist. Das Schema hat auch Nachteile wenn es um die quantitative Analyse des Fluidflusses durch induzierte Bruchflächen in deformierten Gesteinen geht. Es empfiehlt sich zudem, das vorgestellte numerische Schema um die Kopplung mit thermo-chemischen Prozessen zu erweitern, um dynamische Probleme im Zusammenhang mit dem Wachstum von Kluftfüllungen in hydraulischen Brüchen zu untersuchen.

Topological mass of magnetic Skyrmions probed by ultrafast dynamic imaging

In dieser Arbeit untersuchen wir mittels zeitaufgelöster Abbildungen die Gigahertz-Dynamik von magnetischen Skyrmionen, um die Bewegungsgleichungen für diese Quasiteilchen zu bestimmen. Um dieses Ziel zu erreichen haben wir zunächst ein CoB/Pt Schichtsystem entwickelt, das starke senkrechte magnetische Anisotropie mit einer besonders geringen Rauigkeit der Energielandschaft verbindet. Diese Eigenschaften sind für das repetitive dynamische Abbildungsverfahren unerlässlich. In einem zweiten Schritt haben wir das Probendesign optimiert und so weiterentwickelt, dass eine Beobachtung der Skyrmionenbewegung mit einer Auflösung von besser als 3 nm möglich wurde. Aufgrund dieser Verbesserungen ist es uns gelungen, die Trajektorie eines Skyrmionen aufzuzeichnen. Diese Bewegung ist eine Superposition von zwei Drehbewegungen, einer im Uhrzeigersinn und einer gegen läufigen. Aus der Existenz dieser zwei Moden lässt sich schließen, dass Skyrmionen träge Quasiteilchen sind, und aus den Frequenzen können wir einen Wert für die träge Masse ableiten. Es stellt sich heraus, dass die Masse von Skyrmion fünfmal größer ist als von existierenden Theorien vorhergesagt. Die Masse wird folglich durch einen neuartigen Mechanismus bestimmt, der sich aus der räumlichen Beschränkung der Skyrmionen ergibt, welche sich direkt aus der Topologie bleitenrnlässt.

The dynamics of ultra-thin polymer films in different confinements studied by resonance enhanced dynamic light scattering

Die Kontroverse über den Glasübergang im Nanometerbereich, z. B. die Glas¬über¬gangs-temperatur Tg von dünnen Polymerfilmen, ist nicht vollständig abgeschlossen. Das dynamische Verhalten auf der Nanoskala ist stark von den einschränkenden Bedingungen abhängig, die auf die Probe wirken. Dünne Polymerfilme sind ideale Systeme um die Dynamik von Polymerketten unter der Einwirkung von Randbedingungen zu untersuchen, wie ich sie in dieser Arbeit variiert habe, um Einblick in dieses Problem zu erhalten.rnrnResonanzverstärkte dynamische Lichtstreuung ist eine Methode, frei von z.B. Fluoreszenzmarkern, die genutzt werden kann um in dünnen Polymerfilmen dynamische Phänomene

Synthesis and dynamic study of atropisomeric compounds containing boron-carbon bond

In this thesis we studied the stereodynamic behavior of 1,2-azaborines variously substituted on boron (7a, 7b, 13). Depending on the hindrance of the asymmetric aryl substituent the resulting conformations could be stereolabile or configurationally stable. Through dynamic NMR and lineshape simulation, the energy rotational barriers of the different conformers are obtained. When the barrier is higher than 22-23 kcal/mol stable atropisomers that are fisically separable could be obtained (case of compound 13) and the free activation energy barrier is determinable by kinetic analysis. Absolute configuration of two atropisomers were assigned by comparison between computational calculations and experimental ECD. Isosteric compound 21 is then synthesized in order to compare the rotational barrier around B-Caryl with the one around Cnaphth-Caryl bond.

The influence of infill walls on seismic behavior of a historical building in Shanghai

Seismic assessment and seismic strengthening are the key issues need to be figured out during the process of protection and reusing of historical buildings. In this thesis the seismic behaviors of the hinged steel structure, a typical structure of historical buildings, i.e. hinged steel frames in Shanghai, China, were studied based on experimental investigations and theoretic analysis. How the non-structural members worked with the steel frames was analyzed thoroughly. Firstly, two 1/4 scale hinged steel frames were constructed based on the structural system of Bund 18, a historical building in Shanghai: M1 model without infill walls, M2 model with infill walls, and tested under the horizontal cyclic loads to investigate their seismic behavior. The Shaking Table Test and its results indicated that the seismic behavior of the hinged steel frames could be improved significantly with the help of non-structural members, i.e., surrounding elements outside the hinged steel frames and infilled walls. To specify, the columns are covered with bricks, they consist of I shape formed steel sections and steel plates, which are clenched together. The steel beams are connected to the steel column by steel angle, thus the structure should be considered as a hinged frame. And the infilled wall acted as a compression diagonal strut to withstand the horizontal load, therefore, the seismic capacity and stiffness of the hinged steel frames with infilled walls could be estimated by using the equivalent compression diagonal strut model. A SAP model has been constructed with the objective to perform a dynamic nonlinear analysis. The obtained results were compared with the results obtained from Shaking Table Test. The Test Results have validated that the influence of infill walls on seismic behavior can be estimated by using the equivalent diagonal strut model.

Dynamic computer simulations of electrophoresis: a versatile research and teaching tool

Software is available, which simulates all basic electrophoretic systems, including moving boundary electrophoresis, zone electrophoresis, ITP, IEF and EKC, and their combinations under almost exactly the same conditions used in the laboratory. These dynamic models are based upon equations derived from the transport concepts such as electromigration, diffusion, electroosmosis and imposed hydrodynamic buffer flow that are applied to user-specified initial distributions of analytes and electrolytes. They are able to predict the evolution of electrolyte systems together with associated properties such as pH and conductivity profiles and are as such the most versatile tool to explore the fundamentals of electrokinetic separations and analyses. In addition to revealing the detailed mechanisms of fundamental phenomena that occur in electrophoretic separations, dynamic simulations are useful for educational purposes. This review includes a list of current high-resolution simulators, information on how a simulation is performed, simulation examples for zone electrophoresis, ITP, IEF and EKC and a comprehensive discussion of the applications and achievements.

Intraoperative determination of the load-displacement behavior of scoliotic spinal motion segments: preliminary clinical results

Introduction: Spinal fusion is a widely and successfully performed strategy for the treatment of spinal deformities and degenerative diseases. The general approach has been to stabilize the spine with implants so that a solid bony fusion between the vertebrae can develop. However, new implant designs have emerged that aim at preservation or restoration of the motion of the spinal segment. In addition to static, load sharing principles, these designs also require a profound knowledge of kinematic and dynamic properties to properly characterise the in vivo performance of the implants. Methods: To address this, an apparatus was developed that enables the intraoperative determination of the load–displacement behavior of spinal motion segments. The apparatus consists of a sensor-equipped distractor to measure the applied force between the transverse processes, and an optoelectronic camera to track the motion of vertebrae and the distractor. In this intraoperative trial, measurements from two patients with adolescent idiopathic scoliosis with right thoracic curves were made at four motion segments each. Results: At a lateral bending moment of 5 N m, the mean flexibility of all eight motion segments was 0.18 ± 0.08°/N m on the convex side and 0.24 ± 0.11°/N m on the concave side. Discussion: The results agree with published data obtained from cadaver studies with and without axial preload. Intraoperatively acquired data with this method may serve as an input for mathematical models and contribute to the development of new implants and treatment strategies.

The new insight into dynamic crossover in glass forming liquids from the apparent enthalpy analysis

One of the most intriguing phenomena in glass forming systems is the dynamic crossover (T(B)), occurring well above the glass temperature (T(g)). So far, it was estimated mainly from the linearized derivative analysis of the primary relaxation time τ(T) or viscosity η(T) experimental data, originally proposed by Stickel et al. [J. Chem. Phys. 104, 2043 (1996); J. Chem. Phys. 107, 1086 (1997)]. However, this formal procedure is based on the general validity of the Vogel-Fulcher-Tammann equation, which has been strongly questioned recently [T. Hecksher et al. Nature Phys. 4, 737 (2008); P. Lunkenheimer et al. Phys. Rev. E 81, 051504 (2010); J. C. Martinez-Garcia et al. J. Chem. Phys. 134, 024512 (2011)]. We present a qualitatively new way to identify the dynamic crossover based on the apparent enthalpy space (H(a)(') = dlnτ/d(1/T)) analysis via a new plot lnH(a)(') vs. 1∕T supported by the Savitzky-Golay filtering procedure for getting an insight into the noise-distorted high order derivatives. It is shown that depending on the ratio between the "virtual" fragility in the high temperature dynamic domain (m(high)) and the "real" fragility at T(g) (the low temperature dynamic domain, m = m(low)) glass formers can be splitted into two groups related to f < 1 and f > 1, (f = m(high)∕m(low)). The link of this phenomenon to the ratio between the apparent enthalpy and activation energy as well as the behavior of the configurational entropy is indicated.

Dynamic changes of cardiac conduction during rapid pacing

Slow conduction and unidirectional conduction block (UCB) are key mechanisms of reentry. Following abrupt changes in heart rate, dynamic changes of conduction velocity (CV) and structurally determined UCB may critically influence arrhythmogenesis. Using patterned cultures of neonatal rat ventricular myocytes grown on microelectrode arrays, we investigated the dynamics of CV in linear strands and the behavior of UCB in tissue expansions following an abrupt decrease in pacing cycle length (CL). Ionic mechanisms underlying rate-dependent conduction changes were investigated using the Pandit-Clark-Giles-Demir model. In linear strands, CV gradually decreased upon a reduction of CL from 500 ms to 230-300 ms. In contrast, at very short CLs (110-220 ms), CV first decreased before increasing again. The simulations suggested that the initial conduction slowing resulted from gradually increasing action potential duration (APD), decreasing diastolic intervals, and increasing postrepolarization refractoriness, which impaired Na(+) current (I(Na)) recovery. Only at very short CLs did APD subsequently shorten again due to increasing Na(+)/K(+) pump current secondary to intracellular Na(+) accumulation, which caused recovery of CV. Across tissue expansions, the degree of UCB gradually increased at CLs of 250-390 ms, whereas at CLs of 180-240 ms, it first increased and subsequently decreased. In the simulations, reduction of inward currents caused by increasing intracellular Na(+) and Ca(2+) concentrations contributed to UCB progression, which was reversed by increasing Na(+)/K(+) pump activity. In conclusion, CV and UCB follow intricate dynamics upon an abrupt decrease in CL that are determined by the interplay among I(Na) recovery, postrepolarization refractoriness, APD changes, ion accumulation, and Na(+)/K(+) pump function.

Monte Carlo simulation of a dynamic MLC: implementation and applications

PURPOSE: Study of behavior and influence of a multileaf collimator (MLC) on dose calculation, verification, and portal energy spectra in the case of intensity-modulated fields obtained with a step-and-shoot or a dynamic technique. METHODS: The 80-leaf MLC for the Varian Clinac 2300 C/D was implemented in a previously developed Monte Carlo (MC) based multiple source model (MSM) for a 6 MV photon beam. Using this model and the MC program GEANT, dose distributions, energy fluence maps and energy spectra at different portal planes were calculated for three different MLC applications. RESULTS: The comparison of MC-calculated dose distributions in the phantom and portal plane, with those measured with films showed an agreement within 3% and 1.5 mm for all cases studied. The deviations mainly occur in the extremes of the intensity modulation. The MC method allows to investigate, among other aspects, dose components, energy fluence maps, tongue-and-groove effects and energy spectra at portal planes. CONCLUSION: The MSM together with the implementation of the MLC is appropriate for a number of investigations in intensity-modulated radiation therapy (IMRT).

Shear band evolution in Zr/Hf-based bulk metallic glasses under static and dynamic indentations

Bulk metallic glasses (BMGs) exhibit superior mechanical properties as compared with other conventional materials and have been proposed for numerous engineering and technological applications. Zr/Hf-based BMGs or tungsten reinforced BMG composites are considered as a potential replacement for depleted uranium armor-piercing projectiles because of their ability to form localized shear bands during impact, which has been known to be the dominant plastic deformation mechanism in BMGs. However, in conventional tensile, compressive and bending tests, limited ductility has been observed because of fracture initiation immediately following the shear band formation. To fully investigate shear band characteristics, indentation tests that can confine the deformation in a limited region have been pursued. In this thesis, a detailed investigation of thermal stability and mechanical deformation behavior of Zr/Hf-based BMGs is conducted. First, systematic studies had been implemented to understand the influence of relative compositions of Zr and Hf on thermal stability and mechanical property evolution. Second, shear band evolution under indentations were investigated experimentally and theoretically. Three kinds of indentation studies were conducted on BMGs in the current study. (a) Nano-indentation to determine the mechanical properties as a function of Hf/Zr content. (b) Static Vickers indentation on bonded split specimens to investigate the shear band evolution characteristics beneath the indention. (c) Dynamic Vickers indentation on bonded split specimens to investigate the influence of strain rate. It was found in the present work that gradually replacing Zr by Hf remarkably increases the density and improves the mechanical properties. However, a slight decrease in glass forming ability with increasing Hf content has also been identified through thermodynamic analysis although all the materials in the current study were still found to be amorphous. Many indentation studies have revealed only a few shear bands surrounding the indent on the top surface of the specimen. This small number of shear bands cannot account for the large plastic deformation beneath the indentations. Therefore, a bonded interface technique has been used to observe the slip-steps due to shear band evolution. Vickers indentations were performed along the interface of the bonded split specimen at increasing loads. At small indentation loads, the plastic deformation was primarily accommodated by semi-circular primary shear bands surrounding the indentation. At higher loads, secondary and tertiary shear bands were formed inside this plastic zone. A modified expanding cavity model was then used to predict the plastic zone size characterized by the shear bands and to identify the stress components responsible for the evolution of the various types of shear bands. The applicability of various hardness—yield-strength ( H −σγ ) relationships currently available in the literature for bulk metallic glasses (BMGs) is also investigated. Experimental data generated on ZrHf-based BMGs in the current study and those available elsewhere on other BMG compositions were used to validate the models. A modified expanding-cavity model, employed in earlier work, was extended to propose a new H −σγ relationship. Unlike previous models, the proposed model takes into account not only the indenter geometry and the material properties, but also the pressure sensitivity index of the BMGs. The influence of various model parameters is systematically analyzed. It is shown that there is a good correlation between the model predictions and the experimental data for a wide range of BMG compositions. Under dynamic Vickers indentation, a decrease in indentation hardness at high loading rate was observed compared to static indentation hardness. It was observed that at equivalent loads, dynamic indentations produced more severe deformation features on the loading surface than static indentations. Different from static indentation, two sets of widely spaced semi-circular shear bands with two different curvatures were observed. The observed shear band pattern and the strain rate softening in indentation hardness were rationalized based on the variations in the normal stress on the slip plane, the strain rate of shear and the temperature rise associated with the indentation deformation. Finally, a coupled thermo-mechanical model is proposed that utilizes a momentum diffusion mechanism for the growth and evolution of the final spacing of shear bands. The influence of strain rate, confinement pressure and critical shear displacement on the shear band spacing, temperature rise within the shear band, and the associated variation in flow stress have been captured and analyzed. Consistent with the known pressure sensitive behavior of BMGs, the current model clearly captures the influence of the normal stress in the formation of shear bands. The normal stress not only reduces the time to reach critical shear displacement but also causes a significant temperature rise during the shear band formation. Based on this observation, the variation of shear band spacing in a typical dynamic indentation test has been rationalized. The temperature rise within a shear band can be in excess of 2000K at high strain rate and high confinement pressure conditions. The associated drop in viscosity and flow stress may explain the observed decrease in fracture strength and indentation hardness. The above investigations provide valuable insight into the deformation behavior of BMGs under static and dynamic loading conditions. The shear band patterns observed in the above indentation studies can be helpful to understand and model the deformation features under complex loading scenarios such as the interaction of a penetrator with armor. Future work encompasses (1) extending and modifying the coupled thermo-mechanical model to account for the temperature rise in quasistatic deformation; and (2) expanding this model to account for the microstructural variation-crystallization and free volume migration associated with the deformation.