Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

Rates of hydrogen/deuterium (H/D) exchange determined by H-1 NMR spectroscopy are utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation of the integral areas of H-1 NMR resonances to the first order decay function permitted the determination of HID exchange rate constants (k) and their precise half-lives (t(1/2)) with high degree of reproducibility. The comparative study also permitted the unambiguous determination of relative strength of hydrogen bonds and the contribution from electronic effects on the HID exchange rate. (C) 2015 Elsevier B.V. All rights reserved.

Microstructural evolution and strength variability in microwires

Tensile experiments on cold-drawn Ni microwires with diameters from similar to 115 to 50 gm revealed high strengths, with significant strength variability for finer wires with diameters less than similar to 50 gm. The wires showed pronounced necking at fracture. The coarser wires with diameters > 50 mu m exhibited conventional ductile cup-cone fracture, with dimples in the central zone and peripheral shear lips, whereas finer wires failed by shear with knife or chisel-edge fractures. Shear bands were observed in all samples. Further, through- section microscopy of selected fractured samples revealed that the shear bands did not go across the enitre specimen for the coarser wires. The shear bands led to grain fragmention, with a reduction in grain aspect ratio as well as rotations away from the initial < 111 > orientations. The strength data were analysed based on a Weibull approach. The data could be rationalized in terms of failure from volume defects in coarser wires, with a high Weibull modulus, and from surface defects in finer wires, with a low Weibull modulus and greater variability. (C) 2015 Elsevier B.V. All rights reserved.

Strength reliability and in vitro degradation of three-dimensional powder printed strontium-substituted magnesium phosphate scaffolds

Strontium ions (Sr2+) are known to prevent osteoporosis and also encourage bone formation. Such twin requirements have motivated researchers to develop Sr-substituted biomaterials for orthopaedic applications. The present study demonstrates a new concept of developing Sr-substituted Mg-3(PO4)(2) - based biodegradable scaffolds. In particular, this work reports the fabrication, mechanical properties with an emphasis on strength reliability as well as in vitro degradation of highly biodegradable strontium-incorporated magnesium phosphate cements. These implantable scaffolds were fabricated using three-dimensional powder printing, followed by high temperature sintering and/or chemical conversion, a technique adaptable to develop patient-specific implants. A moderate combination of strength properties of 36.7 MPa (compression), 242 MPa (bending) and 10.7 MPa (tension) were measured. A reasonably modest Weibull modulus of up to 8.8 was recorded after uniaxial compression or diametral tensile tests on 3D printed scaffolds. A comparison among scaffolds with varying compositions or among sintered or chemically hardened scaffolds reveals that the strength reliability is not compromised in Sr-substituted scaffolds compared to baseline Mg-3(PO4)(2). The micro-computed tomography analysis reveals the presence of highly interconnected porous architecture in three-dimension with lognormal pore size distribution having median in the range of 17.74-26.29 mu m for the investigated scaffolds. The results of extensive in vitro ion release study revealed passive degradation with a reduced Mg2+ release and slow but sustained release of Sr2+ from strontium-substituted magnesium phosphate scaffolds. Taken together, the present study unequivocally illustrates that the newly designed Sr-substituted magnesium phosphate scaffolds with good strength reliability could be used for biomedical applications requiring consistent Sr2+-release, while the scaffold degrades in physiological medium. Statement of significance The study investigates the additive manufacturing of scaffolds based on different strontium-substituted magnesium phosphate bone cements by means of three-dimensional powder printing technique (3DPP). Magnesium phosphates were chosen due to their higher biodegradability compared to calcium phosphates, which is due to both a higher solubility as well as the absence of phase changes (to low soluble hydroxyapatite) in vivo. Since strontium ions are known to promote bone formation by stimulating osteoblast growth, we aimed to establish such a highly degradable magnesium phosphate ceramic with an enhanced bioactivity for new bone ingrowth. After post-processing, mechanical strengths of up to 36.7 MPa (compression), 24.2 MPa (bending) and 10.7 MPa (tension) could be achieved. Simultaneously, the failure reliability of those bioceramic implant materials, measured by Weibull modulus calculations, were in the range of 4.3-8.8. Passive dissolution studies in vitro proved an ion release of Mg2+ and PO43- as well as Sr2+, which is fundamental for in vivo degradation and a bone growth promoting effect. In our opinion, this work broadens the range of bioceramic bone replacement materials suitable for additive manufacturing processing. The high biodegradability of MPC ceramics together with the anticipated promoting effect on osseointegration opens up the way for a patient-specific treatment with the prospect of a fast and complete healing of bone fractures. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Transient Ventilation Dynamics Following a Change in Strength of a Point Source of Heat

We investigate the transient ventilation flow within a confined ventilated space, with high- and low-level openings, when the strength of a low-level point source of heat is changed instantaneously. The steady-flow regime in the space involves a turbulent buoyant plume, which rises from the point source to a well-mixed warm upper layer. The steady-state height of the interface between this layer and the lower layer of exterior fluid is independent of the heat flux, but the upper layer becomes progressively warmer with heat flux. New analogue laboratory experiments of the transient adjustment between steady states identify that if the heat flux is increased, the continuing plume propagates to the top of the room forming a new, warmer layer. This layer gradually deepens, and as the turbulent plume entrains fluid from the original warm layer, the original layer is gradually depleted and disappears, and a new steady state is established. In contrast, if the source buoyancy flux is decreased, the continuing plume is cooler than the original plume, so that on reaching the interface it is of intermediate density between the original warm layer and the external fluid. The plume supplies a new intermediate layer, which gradually deepens with the continuing flow. In turn, the original upper layer becomes depleted, both as a result of being vented through the upper opening of the space, but also due to some penetrative entrainment of this layer by the plume, as the plume overshoots the interface before falling back to supply the new intermediate layer. We develop quantitative models which are in good accord with our experimental data, by combining classical plume theory with models of the penetrative entrainment for the case of a decrease in heating. Typically, we find that the effect of penetrative entrainment on the density of the intruding layer is relatively weak, provided the change in source strength is sufficiently large. However, penetrative entrainment measurably increases the rate at which the depth of the draining layer decreases. We conclude with a discussion of the importance of these results for the control of naturally ventilated spaces.

Dissimilar autogenous full penetration welding of superalloy K418 and 42CrMo steel by a high power CWNd : YAG laser

Experiments of autogenous laser full penetration welding between dissimilar cast Ni-based superalloy K418 and alloy steel 42CrMo flat plates with 3.5 mm thickness were conducted using a 3 kW continuous wave (CW) Nd:YAG laser. The influences of laser welding velocity, flow rate of side-blow shielding gas, defocusing distance were investigated. Microstructure of the welded seam was characterized by optical microscopy (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD) and energy dispersive spectrometer (EDS). Mechanical properties of the welded seam were evaluated by microhardness and tensile strength testing. Results show that high quality full penetration laser-welded joint can be obtained by optimizing the welding velocity, flow rate of shielding gas and defocusing distance. The laser-welded seam have non-equilibrium solidified microstructures consisting of gamma-FeCr0.29Ni0.16C0.06 austenite solid solution dendrites as the dominant and very small amount of super-fine dispersed Ni3Al gamma' phase and Laves particles as well as MC needle-like carbides distributed in the interdendritic regions. Although the microhardness of the laser-welded seam was lower than that of the base metal, the strength of the joint was equal to that of the base metal and the fracture mechanism showed fine ductility. (c) 2007 Elsevier B.V. All rights reserved.

Fatigue crack-growth from a circular notch under high-levels of biaxial stress

A series of experiments have been conducted on cruciform specimens to investigate fatigue crack growth from circular notches under high levels of biaxial stress. Two stress levels (Δσ₁= 380 and 560 MPa) and five stress biaxialities (λ=+1.0, +0.5, 0, −0.5 and −1.0; where λ=σ₂/σ₁ were adopted in the fatigue tests in type 316 stainless steel having a monotonic yield strength of 243 MPa. The results reveal that fatigue crack growth rates are markedly influenced by both the stress amplitude and the stress biaxiality. A modified model has been developed to describe fatigue crack growth under high levels of biaxial stress.

Mechanical properties and constitutive relationships of 30CrMnSiA steel heated at high rate

In this paper, the mechanical behavior of 30CrMnSiA steel after heating at a high rate are investigated experimentally and theoretically, including a detailed discussion of the effects of strain rate and temperature. Two constitutive models are presented to describe the mechanical response of this material after heating at a high rate, and verified by experimental results. (C) 2007 Elsevier B.V. All rights reserved.

Mechanisms of thermal shock failure for ultra-high temperature ceramic

The materials considered in our analysis were ZrB2 ceramic matrix composites. Effect of two different additives (graphite and AlN) on thermal shock stability for the materials was measured by water quench test. It showed that it may provide more stable thermal shock properties with additives of graphite. It was explained by different thermal properties and crack resistance of the two materials in detail. Surface oxidation was one of main reasons for strength degradation of ceramic with additives of graphite after quenched in water, and surface crack was one of main reasons for strength degradation of ceramic with additives of AlN after quenched in water. It was presented that it was a potential method for improving thermal shock stability of ZrB2 ceramic matrix composites by introducing proper quantities of graphite.

High-efficiency volume hologram recording with a pulsed signal beam

We present an efficient photorefractive volume hologram recording technique with a pulsed signal beam and continuous reference-beam illumination. The grating envelope can be simply controlled by manipulation of the duty cycle of the signal beam. Thus, for any grating coupling strength and different initial reference-signal intensity ratios, the diffraction efficiency can be maximized with this technique and can be greatly increased in comparison with that of the conventional recording technique. (C) 1998 Optical Society of America.

Magnetic alignment of high-aspect ratio microwires into vertical arrays

Fundamental studies of magnetic alignment of highly anisotropic mesostructures can enable the clean-room-free fabrication of flexible, array-based solar and electronic devices, in which preferential orientation of nano- or microwire-type objects is desired. In this study, ensembles of 100 micron long Si microwires with ferromagnetic Ni and Co coatings are oriented vertically in the presence of magnetic fields. The degree of vertical alignment and threshold field strength depend on geometric factors, such as microwire length and ferromagnetic coating thickness, as well as interfacial interactions, which are modulated by varying solvent and substrate surface chemistry. Microwire ensembles with vertical alignment over 97% within 10 degrees of normal, as measured by X-ray diffraction, are achieved over square cm scale areas and set into flexible polymer films. A force balance model has been developed as a predictive tool for magnetic alignment, incorporating magnetic torque and empirically derived surface adhesion parameters. As supported by these calculations, microwires are shown to detach from the surface and align vertically in the presence of magnetic fields on the order of 100 gauss. Microwires aligned in this manner are set into a polydimethylsiloxane film where they retain their vertical alignment after the field has been removed and can subsequently be used as a flexible solar absorber layer. Finally, these microwires arrays can be protected for use in electrochemical cells by the conformal deposition of a graphene layer.

Understanding planet formation through high precision photometry and spectroscopy

From studies of protoplanetary disks to extrasolar planets and planetary debris, we aim to understand the full evolution of a planetary system. Observational constraints from ground- and space-based instrumentation allows us to measure the properties of objects near and far and are central to developing this understanding. We present here three observational campaigns that, when combined with theoretical models, reveal characteristics of different stages and remnants of planet formation. The Kuiper Belt provides evidence of chemical and dynamical activity that reveals clues to its primordial environment and subsequent evolution. Large samples of this population can only be assembled at optical wavelengths, with thermal measurements at infrared and sub-mm wavelengths currently available for only the largest and closest bodies. We measure the size and shape of one particular object precisely here, in hopes of better understanding its unique dynamical history and layered composition.

Molecular organic chemistry is one of the most fundamental and widespread facets of the universe, and plays a key role in planet formation. A host of carbon-containing molecules vibrationally emit in the near-infrared when excited by warm gas, T~1000 K. The NIRSPEC instrument at the W.M. Keck Observatory is uniquely configured to study large ranges of this wavelength region at high spectral resolution. Using this facility we present studies of warm CO gas in protoplanetary disks, with a new code for precise excitation modeling. A parameterized suite of models demonstrates the abilities of the code and matches observational constraints such as line strength and shape. We use the models to probe various disk parameters as well, which are easily extensible to others with known disk emission spectra such as water, carbon dioxide, acetylene, and hydrogen cyanide.

Lastly, the existence of molecules in extrasolar planets can also be studied with NIRSPEC and reveals a great deal about the evolution of the protoplanetary gas. The species we observe in protoplanetary disks are also often present in exoplanet atmospheres, and are abundant in Earth's atmosphere as well. Thus, a sophisticated telluric removal code is necessary to analyze these high dynamic range, high-resolution spectra. We present observations of a hot Jupiter, revealing water in its atmosphere and demonstrating a new technique for exoplanet mass determination and atmospheric characterization. We will also be applying this atmospheric removal code to the aforementioned disk observations, to improve our data analysis and probe less abundant species. Guiding models using observations is the only way to develop an accurate understanding of the timescales and processes involved. The futures of the modeling and of the observations are bright, and the end goal of realizing a unified model of planet formation will require both theory and data, from a diverse collection of sources.

High-strain composites and dual-matrix composite structures

Most space applications require deployable structures due to the limiting size of current launch vehicles. Specifically, payloads in nanosatellites such as CubeSats require very high compaction ratios due to the very limited space available in this typo of platform. Strain-energy-storing deployable structures can be suitable for these applications, but the curvature to which these structures can be folded is limited to the elastic range. Thanks to fiber microbuckling, high-strain composite materials can be folded into much higher curvatures without showing significant damage, which makes them suitable for very high compaction deployable structure applications. However, in applications that require carrying loads in compression, fiber microbuckling also dominates the strength of the material. A good understanding of the strength in compression of high-strain composites is then needed to determine how suitable they are for this type of application.

The goal of this thesis is to investigate, experimentally and numerically, the microbuckling in compression of high-strain composites. Particularly, the behavior in compression of unidirectional carbon fiber reinforced silicone rods (CFRS) is studied. Experimental testing of the compression failure of CFRS rods showed a higher strength in compression than the strength estimated by analytical models, which is unusual in standard polymer composites. This effect, first discovered in the present research, was attributed to the variation in random carbon fiber angles respect to the nominal direction. This is an important effect, as it implies that microbuckling strength might be increased by controlling the fiber angles. With a higher microbuckling strength, high-strain materials could carry loads in compression without reaching microbuckling and therefore be suitable for several space applications.

A finite element model was developed to predict the homogenized stiffness of the CFRS, and the homogenization results were used in another finite element model that simulated a homogenized rod under axial compression. A statistical representation of the fiber angles was implemented in the model. The presence of fiber angles increased the longitudinal shear stiffness of the material, resulting in a higher strength in compression. The simulations showed a large increase of the strength in compression for lower values of the standard deviation of the fiber angle, and a slight decrease of strength in compression for lower values of the mean fiber angle. The strength observed in the experiments was achieved with the minimum local angle standard deviation observed in the CFRS rods, whereas the shear stiffness measured in torsion tests was achieved with the overall fiber angle distribution observed in the CFRS rods.

High strain composites exhibit good bending capabilities, but they tend to be soft out-of-plane. To achieve a higher out-of-plane stiffness, the concept of dual-matrix composites is introduced. Dual-matrix composites are foldable composites which are soft in the crease regions and stiff elsewhere. Previous attempts to fabricate continuous dual-matrix fiber composite shells had limited performance due to excessive resin flow and matrix mixing. An alternative method, presented in this thesis uses UV-cure silicone and fiberglass to avoid these problems. Preliminary experiments on the effect of folding on the out-of-plane stiffness are presented. An application to a conical log-periodic antenna for CubeSats is proposed, using origami-inspired stowing schemes, that allow a conical dual-matrix composite shell to reach very high compaction ratios.

Strength, Deformation and Fracture in Metallic Nanostructures

An understanding of the mechanics of nanoscale metals and semiconductors is necessary for the safe and prolonged operation of nanostructured devices from transistors to nanowire- based solar cells to miniaturized electrodes. This is a fascinating but challenging pursuit because mechanical properties that are size-invariant in conventional materials, such as strength, ductility and fracture behavior, can depend critically on sample size when materials are reduced to sub- micron dimensions. In this thesis, the effect of nanoscale sample size, microstructure and structural geometry on mechanical strength, deformation and fracture are explored for several classes of solid materials. Nanocrystalline platinum nano-cylinders with diameters of 60 nm to 1 μm and 12 nm sized grains are fabricated and tested in compression. We find that nano-sized metals containing few grains weaken as sample diameter is reduced relative to grain size due to a change from deformation governed by internal grains to surface grain governed deformation. Fracture at the nanoscale is explored by performing in-situ SEM tension tests on nanocrystalline platinum and amorphous, metallic glass nano-cylinders containing purposely introduced structural flaws. It is found that failure location, mechanism and strength are determined by the stress concentration with the highest local stress whether this is at the structural flaw or a microstructural feature. Principles of nano-mechanics are used to design and test mechanically robust hierarchical nanostructures with structural and electrochemical applications. 2-photon lithography and electroplating are used to fabricate 3D solid Cu octet meso-lattices with micron- scale features that exhibit strength higher than that of bulk Cu. An in-situ SEM lithiation stage is developed and used to simultaneously examine morphological and electrochemical changes in Si-coated Cu meso-lattices that are of interest as high energy capacity electrodes for Li-ion batteries.

Small scale turbulence in high Karlovitz number premixed flames

The purpose of this thesis is to characterize the behavior of the smallest turbulent scales in high Karlovitz number (Ka) premixed flames. These scales are particularly important in the two-way coupling between turbulence and chemistry and better understanding of these scales will support future modeling efforts using large eddy simulations (LES). The smallest turbulent scales are studied by considering the vorticity vector, ω, and its transport equation.

Due to the complexity of turbulent combustion introduced by the wide range of length and time scales, the two-dimensional vortex-flame interaction is first studied as a simplified test case. Numerical and analytical techniques are used to discern the dominate transport terms and their effects on vorticity based on the initial size and strength of the vortex. This description of the effects of the flame on a vortex provides a foundation for investigating vorticity in turbulent combustion.

Subsequently, enstrophy, ω² = ω • ω, and its transport equation are investigated in premixed turbulent combustion. For this purpose, a series of direct numerical simulations (DNS) of premixed n-heptane/air flames are performed, the conditions of which span a wide range of unburnt Karlovitz numbers and turbulent Reynolds numbers. Theoretical scaling analysis along with the DNS results support that, at high Karlovitz number, enstrophy transport is controlled by the viscous dissipation and vortex stretching/production terms. As a result, vorticity scales throughout the flame with the inverse of the Kolmogorov time scale, τ_η, just as in homogeneous isotropic turbulence. As τ_η is only a function of the viscosity and dissipation rate, this supports the validity of Kolmogorov’s first similarity hypothesis for sufficiently high Ka numbers (Ka ≳ 100). These conclusions are in contrast to low Karlovitz number behavior, where dilatation and baroclinic torque have a significant impact on vorticity within the flame. Results are unaffected by the transport model, chemical model, turbulent Reynolds number, and lastly the physical configuration.

Next, the isotropy of vorticity is assessed. It is found that given a sufficiently large value of the Karlovitz number (Ka ≳ 100) the vorticity is isotropic. At lower Karlovitz numbers, anisotropy develops due to the effects of the flame on the vortex stretching/production term. In this case, the local dynamics of vorticity in the strain-rate tensor, S, eigenframe are altered by the flame. At sufficiently high Karlovitz numbers, the dynamics of vorticity in this eigenframe resemble that of homogeneous isotropic turbulence.

Combined, the results of this thesis support that both the magnitude and orientation of vorticity resemble the behavior of homogeneous isotropic turbulence, given a sufficiently high Karlovitz number (Ka ≳ 100). This supports the validity of Kolmogorov’s first similarity hypothesis and the hypothesis of local isotropy under these condition. However, dramatically different behavior is found at lower Karlovitz numbers. These conclusions provides/suggests directions for modeling high Karlovitz number premixed flames using LES. With more accurate models, the design of aircraft combustors and other combustion based devices may better mitigate the detrimental effects of combustion, from reducing CO₂ and soot production to increasing engine efficiency.

Effects of Spring Temperatures on the Strength of Selection on Timing of Reproduction in a Long-Distance Migratory Bird

Climate change has differentially affected the timing of seasonal events for interacting trophic levels, and this has often led to increased selection on seasonal timing. Yet, the environmental variables driving this selection have rarely been identified, limiting our ability to predict future ecological impacts of climate change. Using a dataset spanning 31 years from a natural population of pied flycatchers (Ficedula hypoleuca), we show that directional selection on timing of reproduction intensified in the first two decades (1980-2000) but weakened during the last decade (2001-2010). Against expectation, this pattern could not be explained by the temporal variation in the phenological mismatch with food abundance. We therefore explored an alternative hypothesis that selection on timing was affected by conditions individuals experience when arriving in spring at the breeding grounds: arriving early in cold conditions may reduce survival. First, we show that in female recruits, spring arrival date in the first breeding year correlates positively with hatch date; hence, early-hatched individuals experience colder conditions at arrival than late-hatched individuals. Second, we show that when temperatures at arrival in the recruitment year were high, early-hatched young had a higher recruitment probability than when temperatures were low. We interpret this as a potential cost of arriving early in colder years, and climate warming may have reduced this cost. We thus show that higher temperatures in the arrival year of recruits were associated with stronger selection for early reproduction in the years these birds were born. As arrival temperatures in the beginning of the study increased, but recently declined again, directional selection on timing of reproduction showed a nonlinear change. We demonstrate that environmental conditions with a lag of up to two years can alter selection on phenological traits in natural populations, something that has important implications for our understanding of how climate can alter patterns of selection in natural populations.