Kenneth S. Vecchio

Quasi-static and dynamic mechanical response of Haliotis Rufescens (Abalone) shells

Abstract Quasi-static and dynamic compression and three-point bending tests have been carried out on Haliotis rufescens (abalone) shells. The mechanical response of the abalone shell is correlated with its microstructure and damage mechanisms. The mechanical response is found to vary significantly from specimen to specimen and requires the application of Weibull statistics in order to be quantitatively evaluated. The abalone shell exhibited orientation dependence of strength, as well as significant strain-rate sensitivity; the failure strength at loading rates between 10×103 and 25×103 GPa/s was approx. 50% higher than the quasi-static strength. The compressive strength when loaded perpendicular to the shell surface was approx. 50% higher than parallel to the shell surface. The compressive strength of abalone is 1.5–3 times the tensile strength (as determined from flexural tests), in contrast with monolithic ceramics, for which the compressive strength is typically an order-of-magnitude greater than the tensile strength. Quasi-static compressive failure occurred gradually, in a mode sometimes described as “graceful failure”. The shear strength of the organic/ceramic interfaces was determined to be approx. 30 MPa by means of a shear test. Considerable inelastic deformation of the organic layers (up to a shear strain of 0.4) preceded failure. Crack deflection, delocalization of damage, plastic microbuckling (kinking), and viscoplastic deformation of the organic layers are the most important mechanisms contributing to the unique mechanical properties of this shell. The plastic microbuckling is analysed in terms of the equations proposed by Argon (Treatise of Materials Science and Technology. Academic Press, New York, 1972, p. 79) and Budiansky (Comput. Struct. 1983, 16, 3).

DYNAMIC RECRYSTALLIZATION IN HIGH-STRAIN, HIGH-STRAIN-RATE PLASTIC DEFORMATION OF COPPER

When copper is deformed to high plastic strain (y ~ 34) at high strain rates (~ ~ I04 s -1) a microstructure with grain sizes of ~0.1 am can be produced. It is proposed that this microstructure develops by dynamic recrystallization, which is enabled by the adiabatic temperature rise. By shock-load- ing the material, and thereby increasing its flow stress, the propensity for dynamic recrystallization can be enhanced. The grain size-flow stress relationship observed after cessation of plastic deformation is consistent with the general formulation proposed by Derby (Acta metall, mater. 39, 955 (1991)). The temperatures reached by the specimens during dynamic deformation are calculated from a constitutive equation and are found to be, for the shock-loaded material, in the 500-800 K range; these temperatures are consistent with static annealing experiments on shock-loaded specimens, that show the onset of static recrystallization at 523 K. A possible recrystallization mechanism is described and its effect on the mechanical response of copper is discussed.

Evolution of iridium-based molecular catalysts during water oxidation with ceric ammonium nitrate.

Organometallic iridium complexes have been reported as water oxidation catalysts (WOCs) in the presence of ceric ammonium nitrate (CAN). One challenge for all WOCs regardless of the metal used is stability. Here we provide evidence for extensive modification of many Ir-based WOCs even after exposure to only 5 or 15 equiv of Ce(IV) (whereas typically 100-10000 equiv are employed during WOC testing). We also show formation of Ir-rich nanoparticles (likely IrO(x)) even in the first 20 min of reaction, associated with a Ce matrix. A combination of UV-vis and NMR spectroscopy, scanning transmission electron microscopy, and powder X-ray diffraction is used. Even simple IrCl(3) is an excellent catalyst. Our results point to the pitfalls of studying Ir WOCs using CAN.

Recrystallization kinetics within adiabatic shear bands

Abstract Small recrystallized grains (0.1-0.2 μm diameter) are observed to form in adiabatic shear bands of shock-prestrained copper. However, the mechanism for recrystallization under the high strain, high-strain-rate conditions within shear bands is somewhat unclear. The kinetics of two classical mechanisms for recrystallization, high angle boundary migration and subgrain coalescence, are compared with the time-temperature profile determined for these adiabatic shear bands. It was found that the kinetics of the existing models are inadequate to explain the observed grain sizes, with the kinetics being several orders of magnitude slower than the deformation, time and/or the cooling time of the shear bands. Tests conducted at liquid nitrogen temperature also demonstrated that temperature did not play a major role in dynamic recrystallization under these circumstances. A dynamic recrystallization model is suggested in which mechanically-driven subgrain rotations assist the mechanism for recrystallization. This approach may enable dynamic recrystallization to proceed at very high strain rates, with only limited thermal assistance.

Resistance-curve and fracture behavior of Ti–Al3Ti metallic–intermetallic laminate (MIL) composites

The R-curve and fracture toughness behavior of single-edge notch beams of Ti–Al3Ti metallic–intermetallic laminate (MIL) composites has been investigated. Composites with 14, 20, and 35% volume fraction Ti, with a corresponding intermetallic layer thickness of ~540, ~440, and ~300 microns, respectively, were tested in crack arrester and crack divider orientations. In the arrester orientation, the R-curve could not be determined for the two highest Ti volume fraction compositions as the main crack could not be grown through the test samples. In the divider orientation, R-curves were determined for all three Ti volume fractions tested. The laminate composites were found to exhibit more than an order of magnitude improvement in fracture toughness over monolithic Al3Ti. Crack bridging and crack deflection by the Ti layers were primarily responsible for the large-scale bridging conditions leading to the R-curve behavior and enhanced fracture toughness. Estimates of steady-state toughness under small-scale bridging conditions were in close agreement with experimental results.

Microstructural evolution in adiabatic shear bands in Ta and Ta-W alloys

Abstract Microstructural evolution of adiabatic shear bands originated due to high strain, high strain rate deformation in Ta and Ta–W alloys has been examined. Tests were performed using a specially designed stepped specimen in a Hopkinson bar. Upon completion of the deformation, the region is cooled to below one half of the temperature achieved during adiabatic heating in less than one millisecond. Microstructural characterization of the shear bands was performed using optical microscopy as well as scanning and transmission electron microscopy. No evidence of recrystallization within the shear bands could be found. This is in contradiction with several recent reports, which claim that recrystallization may take place at these stringent time and temperature conditions. These studies, however, do not take into account the kinetics of boundary refinement processes, which are a distinctive characteristic of a recrystallized microstructure. It will be shown that the absence of recrystallization in Ta and Ta–W adiabatic shear bands can be predicted by a progressive subgrain misorientation (PriSM) recrystallization model, applied successfully in previous studies to predict the microstructure evolution in copper adiabatic shear bands.

Calcium phosphate-bearing matrices induce osteogenic differentiation of stem cells through adenosine signaling

Significance A mechanistic understanding of how calcium phosphate (CaP) minerals contribute to osteogenic commitment of stem cells and bone tissue formation is a necessary requirement for developing efficient CaP-based synthetic matrices to treat bone defects. This study unravels a previously unknown mechanism, phosphate-ATP-adenosine metabolic signaling, by which the CaP-rich mineral environment in bone tissues promotes osteogenic differentiation of human mesenchymal stem cells. In addition to a mechanical perspective on how biomaterials can influence stem cell differentiation through metabolic pathways, this discovery opens up new avenues for treating critical bone defects and bone metabolic disorders. Synthetic matrices emulating the physicochemical properties of tissue-specific ECMs are being developed at a rapid pace to regulate stem cell fate. Biomaterials containing calcium phosphate (CaP) moieties have been shown to support osteogenic differentiation of stem and progenitor cells and bone tissue formation. By using a mineralized synthetic matrix mimicking a CaP-rich bone microenvironment, we examine a molecular mechanism through which CaP minerals induce osteogenesis of human mesenchymal stem cells with an emphasis on phosphate metabolism. Our studies show that extracellular phosphate uptake through solute carrier family 20 (phosphate transporter), member 1 (SLC20a1) supports osteogenic differentiation of human mesenchymal stem cells via adenosine, an ATP metabolite, which acts as an autocrine/paracrine signaling molecule through A2b adenosine receptor. Perturbation of SLC20a1 abrogates osteogenic differentiation by decreasing intramitochondrial phosphate and ATP synthesis. Collectively, this study offers the demonstration of a previously unknown mechanism for the beneficial role of CaP biomaterials in bone repair and the role of phosphate ions in bone physiology and regeneration. These findings also begin to shed light on the role of ATP metabolism in bone homeostasis, which may be exploited to treat bone metabolic diseases.

Quasi-static and dynamic mechanical response of Strombus gigas (conch) shells

Abstract Quasi-static and dynamic compression and three-point bending tests have been carried out on Strombus gigas (conch) shells. The mechanical response is correlated with its microstructure and damage mechanisms. The mechanical response is found to vary significantly from specimen to specimen and requires the application of Weibull statistics in order to be quantitatively evaluated. The conch exhibited orientation dependence of strength as well as significant strain-rate sensitivity; the failure strength at loading rates between 10×103 and 25×103 GPa s−1 was approximately 50% higher than the quasi-static strength. Quasi-static compressive failure occurred gradually, in a mode sometimes described as ‘graceful failure’. Crack deflection, delocalization of damage, and viscoplastic deformation of the organic layers are the most important mechanisms contributing to the unique mechanical properties of these shells.

Stimuli-responsive liposome fusion mediated by gold nanoparticles.

We report a new approach to controlling the fusion activity of liposomes by adsorbing carboxyl-modified gold nanoparticles to the outer surface of phospholipid liposomes. The bound gold nanoparticles can effectively prevent liposomes from fusing with one another at neutral pH value, while at acidic environments (e.g., pH < 5), the gold particle stabilizers will detach from the liposomes, with liposome fusion activity resuming. The binding of carboxyl-modified gold nanoparticles to cationic phospholipid liposomes at neutral pH and detaching at acidic pH values are evaluated and confirmed by dynamic light scattering, electron microscopy, fluorescence and UV-vis absorption experiments. The relative fusion efficiency of gold-nanoparticle-stabilized cationic liposomes with anionic liposomes is approximately 25% at pH = 7 in contrast to approximately 80% at pH = 4. Since liposomes have been extensively used as drug nanocarriers and the infectious lesions on human skin are typically acidic with a pH < 5, these acid-responsive liposomes with tunable fusion ability hold great promise for dermal drug delivery to treat a variety of skin diseases such as acne vulgaris and staph infections.

Mechanical behavior of ultralong multiwalled carbon nanotube mats

Carbon nanotubes (CNTs) have been a subject of great interest partially due to their potential for exceptional material properties. Improvements in synthesis methods have facilitated the production of ultralong CNT mats, with lengths in the millimeter range. The increased length of these ultralong mats has, in return, opened the way to greater flexibility to probe their mechanical response. In this work, mats of dense, well-aligned, multiwalled carbon nanotubes were grown with a vapor-phase chemical vapor deposition technique using ferrocene and benzene as reactants, and subsequently tested in both tension and compression using two methods, in a thermomechanical analyzer and in situ inside a scanning electron microscope. In compression, measured stiffness was very low, due to buckling of the nanotubes. In tension, the nanotube mats behaved considerably stiffer; however, they were still more compliant than expected for nanotubes (∼1TPa). Analysis of both the growth method used and the nanotube mat fracture...