Nanoporous (NP) metals are a unique class of materials that are characterized by extremely high surface-to-volume ratios and possess such desirable properties of metals as high electrical conductivity, catalytic activity, and mechanical strength. At the same time, understanding of their physical properties is often lacking, especially for hierarchical NP metals where individual struts and joints that make up open cell 3D network are nanocrystalline. The aim of this work is to employ a dedicated experimental campaign to understand the structure property relation of nanostructured nanoporous metals. Towards this goal, NP Pt and NP Cu have been synthesized for a range of strut sizes and their mechanical properties have been investigated via ex-situ and in-situ nanoindentation experiments. Both NP Pt and NP Cu exhibit relatively high hardness in the range of 0.2 to 1.3 GPa. The relative role of material effects arising from small dimensions of the struts/joints and the geometrical features of NP metals are discussed. Selected applications of the systems synthesized during this work in electrochemistry and catalysis are demonstrated. In the examined applications the NP metals exhibited catalytic activity comparable to or significantly exceeding the best available alternative systems, while offering superior stability.

No description available.

Studying physical properties of nanoscale materials has gained a significant attention owing to their applications in the fields such as electronics, medicine, pharmaceutical industry, and materials science. However, owing to size constraints, number of techniques that measures physical properties of materials at nanoscale with a high accuracy and sensitivity is limited. In this context, development of atomic force microscopy (AFM) based techniques to measure physical properties of nanomaterials has led to significant advancements across the disciplines including chemistry, engineering, biology, material science and physics. AFM has recently been utilized in the quantification of physical-chemical properties such as electrical, mechanical, magnetic, electrochemical, binding interaction and morphology, which are enormously important in establishing structure-property relationship. The overarching objective of the investigations discussed here is to gain quantitative insights into the factors that control electrical and mechanical properties of nano-dimensional organic materials and thereby, potentially, establishing reliable structure-property relationships particularly for organic molecular solids which has not been explored enough. Such understanding is important in developing novel materials with controllable properties for molecular level device fabrication, material science applications and pharmaceutical materials with desirable mechanical stability. First, we have studied electrical properties of novel silver based organic complex in which, the directionality of coordination bonding in the context of crystal engineering has been used to achieve materials with structurally and electrically favorable arrangement of molecules for an enhanced electrical conductivity. This system have exhibited an exceptionally high conductivity compared to other silver based organic complexes available in literature. Further, an enhancement in conductivity was also observed herein, upon photodimerization and the development of such materials are important in nanoelecrtonics. Next, mechanical properties of a wide variety of nanocrystals is discussed here. In particular, an inverse correlation between the Young’s modulus and atomic/molecular polarizability has been demonstrated for members of a series of macro- and nano-dimensional organic cocrystals composed of either resorcinol (res) or 4,6-di-X-res (X = Cl, Br, I) (as the template) and trans-1,2-bis(4-pyridyl)ethylene (4,4’-bpe) where cocrystals with highly-polarizable atoms result in softer solids. Moreover, similar correlation has been observed with a series of salicylic acid based cocrystals wherein, the cocrystal former was systematically modified. In order to understand the effect of preparation method towards the mechanical properties of nanocrystalline materials, herein we have studied mechanical properties of single component and two component nanocrystals. Similar mechanical properties have been observed with crystals despite their preparation methods. Furthermore, size dependent mechanical properties of active pharmaceutical ingredient, aspirin, has also been studied here. According to results reduction in size (from millimetre to nanometer) results in crystals that are approximately four fold softer. Overall, work discussed here highlights the versatility of AFM as a reliable technique in the electrical, mechanical, and dimensional characterization of nanoscale materials with a high precision and thereby, gaining further understanding on factors that controls these processes at nanoscale.

Zinc oxide is a very versatile material that can be used in many microsystems and MEMS applications. ZnO thin film has been utilized in a wide variety of MEMS devices because of its unique piezoelectric, optical, and electrical properties. In particular, piezoelectric property of ZnO can be used in numerous applications from resonators and filters to mass sensors and micro-actuators (e.g., micro-valve and micro-pump). Because of its versatility, this research was focused on analyzing some key properties of ZnO thin film achieved by two different deposition techniques, Pulsed Laser Deposition (PLD) and Sputtering. Multiple experiments were conducted in order to identify the best conditions for the growth of ZnO thin film. Under the optimum conditions, the ZnO thin films will provide the best piezoelectric performance in devices such as microcantilevers. In order to find the best deposition conditions in both PLD and Sputtering multiple depositions have been done and then analyzed using the XRD, AFM, FTIR, nanoindenter, and ellipsometer. For the PLD the best conditions were found to be at 200°C with a partial pressure of O2 of 100 millitorr. For the sputtering system the best film formed when the substrate temperature was kept at 400°C along with RF power of 250 Watts, and a flow rate of 25% O2 and 75% Ar. Both experiments were similar in the fact that both a certain amount of O2 in the chamber and an elevated temperature are needed to facilitate the formation of ZnO crystal structure.

Nanocrystalline materials with grain size less than 100 nm have been receiving much attention because of their unparallel properties compared with their microcrystalline counterparts. Because of its high hardness, nanocrystalline nickel has been used for MEMS. Long term thermomechnical properties and deformation mechanism at both ambient and elevated temperatures need to be evaluated which is vital for reliability of its applications as structural material. In this thesis, nanoindentation creep of nanocrystalline nickel with an as-deposited grain size of 14 nm was characterized at elevated temperatures. The nanoindentation creep rate was observed to scale with temperature and applied load (or stress), and could be expressed by an empirical power-law equation for describing conventional crystalline solids. Creep activation energy was found to be close to that for grain boundary self-diffusion in nickel. The activation volume was also evaluated using a stress relaxation technique. The creep results were compared with those for fine-grained nickel in the literature. Possible mechanisms were discussed in light of the creep rate and temperature ranges. To provide a direct comparison, uniaxial creep tests were conducted on nanocrystalline nickel with an as-deposited grain size of 14 nm at 398 K. It was found that stress exponents under the two test conditions are almost the same, indicating a similar creep mechanism. However, the strain rate measured by nanoindentation creep was about 100 times faster than that by uniaxial creep. The rate difference was discussed in terms of stress states and the appropriate selection of Tabor factor. To further explore the time-dependent plastic behavior, multiple unload-reload tests were conducted on electrodeposited nanocrystalline nickel in both compression and tension. A hysteresis was observed during each unload-reload cycle, indicating irreversible energy dissipation. The dissipated energy was evaluated and the energy dissipation rate was found to increase with the flow stress to the third power and sensitive to the stress state (tension or compression). A mechanistic model based on grain boundary sliding was proposed to describe the unload-reload behavior. Experimental results were found to be in good agreement with the model predictions, suggesting the observed hysteresis was indeed caused by grain boundary sliding.

In the past two decades depth-sensing indentation has becomea widely used technique to measure the mechanical properties ofmaterials. This technique is particularly suitable for thecharacterisation of materials at sub-micro or nano scale thoughthere is a tendency to extend its application to the micro ormacro scale. The load-penetration depth curve of depth-sensingindentation is a characteristic of a material and can be usedfor analysing various mechanical properties in addition tohardness. This thesis deals with the mechanicalcharacterisation of bulk materials, thin films and coatings,gradient materials, and composites using depth-sensingindentation. Finite element method has been resorted to as atool to understand the indentation behaviour of materials. The piling-up or sinking-in behaviour of materials plays animportant role in the accurate determination of materialsproperties using depth-sensing indentation. Finite elementsimulations show that the piling-up or sinking-in behaviour isdetermined by the material parameters, namelyE/σyratio and strain hardening exponent orexperimental parameterhe/hmaxratio, and the contact friction. Anempirical model has been proposed to relate the contact area ofindentation to theE/σyratio and thehe/hmaxratio and used to predict thepiling-up orsinking-in of materials. The existence of friction is found toenhance the sinking-in tendency of materials. A generalrelationship between the hardness and the indentationrepresentative stress valid for both soft and hard materialshas been obtained. A possible method to estimate the plasticproperties of bulk materials has been suggested. Measuring the coating-only properties requires theindentation to be done within a critical penetration depthbeyond which substrate effect comes in. The ratio of thecritical penetration depth to the coating thickness determinedby nanoindentation is independent of coating thickness andabout 0.2 for gold / nickel, 0.4 for aluminium / BK7 glass, and0.2 for diamond-like-carbon / M2 steel and alumina / nickel.Finite element simulations show that this ratio is dependent onthe combination of the coating and the substrate and moresensitive to differences in the elastic properties than in theplastic properties of the coating/substrate system. Thedeformation behaviour of coatings, such as, piling-up of thesoft coatings and cracking of the hard coatings, has also beeninvestigated using atomic force microscope. The constraint factors, 2.24 for WC phase and 2.7 for WC-Cocemented carbides, are determined through nanoindentation andfinite element simulations. A modified hardness model of WC-Cocemented carbides has been proposed, which gives a betterestimation than the Lee and Gurland hardness model. Finiteelement method has also been used to investigate theindentation behaviour of WC-Co gradient coatings. Keywords:depth-sensing indentation, nanoindentation,finite element method, atomic force microscope, mechanicalproperties, hardness, deformation, dislocations, cracks,piling-up, sinking-in, indentation size effect, thin coatings,composite, gradient materials, WC-Co, diamond-like-carbon,alumina, gold, aluminium, nickel, BK7 glass, M2 steel.

This thesis addresses normal axisymmetric contact of dissimilar elastic solids at finite interfacial friction. It is shown that in the case of smooth and convex but otherwise arbitrary contact profiles and monotonically increasing loading a single stick-slip contour evolves being independent of loading and profile geometry. This allows developing an incremental procedure based on a reduced problem corresponding to frictional rigid flat punch indentation of an elastic half-space. The reduced problem, being independent of loading and contact region, was solved by a finite element method based on a stationary contact contour and characterized by high accuracy. Subsequently, a tailored cumulative superposition procedure was developed to resolve the original problem to determine global and local field values for two practically important geometries: flat and conical profiles with rounded edges and apices. Results are given for relations between force, depth and contact contours together with surface stress distributions and maximum von Mises effective stress, in particular to predict initiation of fracture and plastic flow. It is also observed that the presence of friction radically reduces the magnitude of the maximum surface tensile stress, thus retarding brittle fracture initiation. Hertzian fracture through indentation of flat float glass specimens by steel balls has been examined experimentally for a full load cycle. It has been observed that if the specimen survived during loading to a maximum level it frequently failed at decreasing load. It has been proposed by Johnson et al. (1973) that the underlying physical cause of Hertzian fracture initiation during load removal is that at unloading frictional tractions reverse their sign over part of the contact region. Guided by these considerations a robust computational procedure has been developed to determine global and local field values in particular at unloading at finite friction. In contrast to the situation at monotonically increasing loading, at unloading invariance properties are lost and stick-slip regions proved to be severely history dependent and in particular with an opposed frictional shear stress at the contact boundary region. This causes an increase of the maximum tensile stress at the contour under progressive unloading. It is shown that the experimental observations concerning Hertzian fracture initiation at unloading are at least in qualitative correlation with the effect friction has on the maximum surface tensile stress. A contact cycle between two dissimilar elastic bodies at finite Coulomb friction has been further investigated analytically and numerically for a wider range of material parameters and contact geometries. With the issue of Hertzian fracture initiation in mind, results concerning the influence of the friction coefficient and compliance parameters on the absolute maximum surface tensile stress during a frictional contact cycle are reported along with the magnitudes of the relative increase of maximum tensile stresses at unloading. Based on a critical stress fracture criterion it is discussed how the predicted increases will influence the critical loads required for crack initiation. Fracture loads are measured with steel and tungsten carbide spherical indenters in contact with float glass specimens at monotonically increasing loading and during a load cycle. Computational predictions concerning the fracture loads are given based on Hertz and frictional contact theories combined with a critical stress fracture criterion. The computational results obtained for frictional contact are shown to be in better agreement with experimental findings as compared to the predictions based on the Hertz theory. The remaining quantitative discrepancy was attributed to the well-known fact that a Hertzian macro-crack initiates from pre-existing defects on the specimen’s surface. In order to account for the influence of the random distribution of these defects on the fracture loads at monotonic loading, Weibull statistics was introduced. The predicted critical loads corresponding to 50% failure probability were found to be in close agreement with experimentally observed ones. / QC 20100729

In this Thesis Ti-Al-C thin films deposited by cathodic arc at 700, 800 and 900 °C were investigated with respect to composition, structure and mechanical properties. The highest growth temperature resulted in close to single crystalline Ti2AlC MAX phase.   A high oxygen incorporation of 7-12 at.% was detected in all the films, likely originating from residual gas and the Al2O3 substrate. It was evident that the characteristic nanolaminated MAX phase structure was retained upon deflection from the ideal MAX phase stoichiometry.   Hardness and elastic modulus of the sample grown at 900 °C were 16 and 259 GPa, respectively, as determined by nanoindentation using a Berkovich tip. Nanoindentation measurements with a cube corner tip were also performed on all three samples in order to extract elastic moduli.   Analysis of loading-unloading curves and SPM images revealed no relation between pop-in events and pile-ups around the residual imprints, indicating that other mechanisms than formation of kink bands may be responsible for formation of pile-ups. This was also confirmed by cross-sectional TEM investigation of an indent: Ti2AlC MAX phase deformed without kinking and delamination, as opposed to the observations in single crystalline Ti3SiC2 films. Several possible reasons for the different deformation mechanism observed are discussed.    These results are of importance for the fundamental understanding of the origin of material characteristics, and serve as an initial study initiating further investigations of the influence of defects on MAX phase properties.

Mechanical characterization of four polymer nanocomposite systems and two pure polymer reference systems was performed. Alumina (Al2O3) and magnetite (Fe3O4) nanoparticles were embedded in poly(methyl methacrylate) (PMMA) and polystyrene (PS) matrices. Mechanical testing techniques utilized include tensile testing, dynamic mechanical analysis (DMA), and nanoindentation. Consistent results from the three techniques proved that these nanocomposite systems exhibit worse mechanical properties than their respective pure polymer systems. The interphase, an interfacial area between the nanoparticle filler and the polymer matrix, was investigated using two approaches to explain the mechanical testing results. The first approach utilized data from thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM) to predict the structure and density of the interphase for the four nanocomposite systems. The second approach analyzed the bonding between the polymer and the nanoparticle surfaces using Fourier Transform Infrared Spectroscopy (FT-IR) to calculate the density of the interphase for the two PMMA-based nanocomposite systems. Results from the two approaches were compared to previous studies. The results indicate that Al2O3 nanoparticles are more reactive with the polymer matrix than are Fe3O4 nanoparticles, but neither have strong interaction with the polymer matrix. The poor interaction leads to low density interphase which results in the poor mechanical properties.

Since the first discovery of amorphous alloys in 1960, researchers have explored many unique mechanical, magnetic, and optical characteristics of such materials for potential applications. Up to now, well-developed processes, such as rapid quenching, sputtering, evaporation, pulse laser deposition, etc, have been applied for different applications in micro-electro-mechanical systems (MEMS). Due to the lack of ordered structure, amorphous alloys can bear a high stress in the elastic region. Their plastic deformation stability is also of interest and has been widely studied. The shear-band characteristic, a kind of inhomogeneous deformation mechanism, dominates the deformation after yielding at room temperature. While a shear band nucleate, its propagation usually cannot be arrested or stopped. In other words, the occurrence of matured shear bands needs to be prevented. There are two major approaches in this aspect. The first is to increase the material yield strength so as to delay the shear band nucleation. Another is to incorporate intrinsic or extrinsic particles so as to absorb the kinetic energy of shear bands in the amorphous matrix. In this study, we utilize three strategies to control the propagation of shear bands in thin film metallic glasses (TFMGs): sub-Tg annealing, the addition of strong element in solute form, and the introduction of strong nanocrystalline layers. For sub-Tg annealing, the base alloy system is Zr69Cu31, with a base film hardness of 5.1 GPa measured by nanoindentation. After annealing, the hardness exhibits ~30% increase. Without the occurrence of the phase transformation, as confirmed by X-ray diffraction, the possible reaction during sub-Tg annealing is attributed to structural relaxation, not crystallization. The full width at half maximum of the X-ray peak exhibits a decreasing trend in the using X-ray and transmission electron microscopy diffraction, meaning the excess free volumes forming during vapor-to-solid deposition process would be annihilated by localized atomic re-arrangement. Moreover, the formation of medium-ordering-range clusters was confirmed utilizing high-resolution transmission electronic microscopy. The denser amorphous structure leads to the increment of hardness. For the addition of Ta in Zr55Cu31Ti14, sputtering provides a wide glass forming range with solubility of Ta approaching ~75 at%. With increasing Ta content, the elastic modulus and hardness increase slowly. A steep rise occurs at ~50 at% of Ta. Up to 75 at% of Ta, the elastic modulus and hardness approaches 140 GPa and 10.0 GPa, respectively (100% increment). Up to now, Ta-rich TFMGs exhibit the highest elastic modulus and hardness among all amorphous alloys fabricated using vapor deposition techniques. The irregular increase is attributed to the formation of Ta-Ta bonding. A large quantity of Ta bonds would lead to the formation of Ta-rich nanoclusters, drastically decreasing the strain rate while shear band propagates under nanoindentation and microcompression tests. The introduction of nanocrystalline Ta layers can not only effectively enhance the yield strength but also serve as the absorber for the kinetic energy of shear bands, revealing ductility in the microcompression test.