Shefford P. Baker

Effects of tissue age on bone tissue material composition and nanomechanical properties in the rat cortex.

Although osteoporosis is known to alter bone tissue composition, the effects of such compositional changes on tissue material properties have not yet been examined. The natural gradient in tissue mineral content arising from skeletal appositional growth provides a basic model for investigation of relationships between tissue composition and mechanical properties. The purpose of this study was to examine the effects of tissue age on bone tissue composition and nanomechanical properties. The nanomechanical properties and composition of regions of differing tissue age were characterized in the femoral cortices of growing rats using nanoindentation and Raman spectroscopy. In addition, spatial maps of the properties of periosteal tissue were examined to investigate in detail the spatial gradients in the properties of newly formed tissue. Newly formed tissue (0-4 days) was 84% less stiff and had 79% lower mineral:matrix ratio than older intracortical (15-70 days) tissue. Tissue modulus, hardness, mineral:matrix ratio, and carbonate:phosphate ratio increased sharply with distance from the periosteum and attained the properties of intracortical tissue within 4 days of formation. The mineral: matrix ratio explained 54% and 62% of the variation in tissue indentation modulus and hardness, respectively. Our data demonstrate significant variations in tissue mechanical properties with tissue age and relate mechanical properties to composition at the microscale.

Contribution of Mineral to Bone Structural Behavior and Tissue Mechanical Properties

Bone geometry and tissue material properties jointly govern whole-bone structural behavior. While the role of geometry in structural behavior is well characterized, the contribution of the tissue material properties is less clear, partially due to the multiple tissue constituents and hierarchical levels at which these properties can be characterized. Our objective was to elucidate the contribution of the mineral phase to bone mechanical properties across multiple length scales, from the tissue material level to the structural level. Vitamin D and calcium deficiency in 6-week-old male rats was employed as a model of reduced mineral content with minimal collagen changes. The structural properties of the humeri were measured in three-point bending and related to the mineral content and geometry from microcomputed tomography. Whole-cortex and local bone tissue properties were examined with infrared (IR) spectroscopy, Raman spectroscopy, and nanoindentation to understand the role of altered mineral content on the constituent material behavior. Structural stiffness (−47%) and strength (−50%) were reduced in vitamin D-deficient (−D) humeri relative to controls. Moment of inertia (−38%), tissue mineral density (TMD, −9%), periosteal mineralization (−28%), and IR mineral:matrix ratio (−19%) were reduced in −D cortices. Thus, both decreased tissue mineral content and changes in cortical geometry contributed to impaired skeletal load-bearing function. In fact, 97% of the variability in humeral strength was explained by moment of inertia, TMD, and IR mineral:matrix ratio. The strong relationships between structural properties and cortical material composition demonstrate a critical role of the microscale material behavior in skeletal load-bearing performance.

Dislocation interactions in thin FCC metal films

Abstract High strength, high hardening rates, and strong Bauschinger-like effects in thin films have been attributed to constraints on dislocation motion and dislocation interactions. To understand these phenomena, dislocation interactions in (1 1 1) and (0 0 1) oriented single crystal FCC films were studied using dislocation dynamics simulations. Interactions on intersecting glide planes resulted in junction formation, annihilation, or attractive non-junction-forming configurations, while dislocations on parallel glide planes formed dipoles. The configurations adopted by interacting dislocations, and thus the strengths of the interactions, were found to be sensitive to the applied strain, film thickness, crystallographic orientation, and boundary conditions. Different interactions thus dominate film behavior in different ranges of film thickness and applied strain. Interactions are stronger on unloading than on loading. Interactions involving three or more dislocations are found to be different from pairwise interactions. The results suggest that simple analytical calculations are unlikely to describe film phenomena but that full 3-D simulations can be used to understand many features of thin film mechanical behavior.

Microstructure and nanomechanical properties in osteons relate to tissue and animal age

Material property changes in bone tissue with ageing are a crucial missing component in our ability to understand and predict age-related fracture. Cortical bone osteons contain a natural gradient in tissue age, providing an ideal location to examine these effects. This study utilized osteons from baboons aged 0-32 years (n=12 females), representing the baboon lifespan, to examine effects of tissue and animal age on mechanical properties and composition of the material. Tissue mechanical properties (indentation modulus and hardness), composition (mineral-to-matrix ratio, carbonate substitution, and crystallinity), and aligned collagen content (aligned collagen peak height ratio) were sampled along three radial lines in three osteons per sample by nanoindentation, Raman spectroscopy, and second harmonic generation microscopy, respectively. Indentation modulus, hardness, mineral-to-matrix ratio, carbonate substitution, and aligned collagen peak height ratio followed biphasic relationships with animal age, increasing sharply during rapid growth before leveling off at sexual maturity. Mineral-to-matrix ratio and carbonate substitution increased 12% and 6.7%, respectively, per year across young animals during growth, corresponding with a nearly 7% increase in stiffness and hardness. Carbonate substitution and aligned collagen peak height ratio both increased with tissue age, increasing 6-12% across the osteon radii. Indentation modulus most strongly correlated with mineral-to-matrix ratio, which explained 78% of the variation in indentation modulus. Overall, the measured compositional and mechanical parameters were the lowest in tissue of the youngest animals. These results demonstrate that composition and mechanical function are closely related and influenced by tissue and animal age.

Bauschinger effect and anomalous thermomechanical deformation induced by oxygen in passivated thin Cu films on substrates

Annealed thin metal films on Si substrates often show early yielding behavior, similar to the well-known Bauschinger effect in bulk metals, during thermomechanical cycling. Small amounts of oxygen added to a Cu film dramatically enhance early yielding, and lead to extensive plastic deformation at zero stress and increasing stress with temperature during heating. These anomalous plastic deformation effects were explored using tests in which the stresses in the films were measured during thermal cycles with varying temperature endpoints. Anomalous behavior is attributed to a mechanism whereby reversible plastic strain is enhanced by recovery of misfit dislocation line length, which is apparently prevented by strain hardening in films showing normal thermoelastic behavior. The mechanism can account for a variety of thermomechanical behaviors including stress asymmetry and memory effects in thin films.

Between nanoindentation and scanning force microscopy: measuring mechanical properties in the nanometer regime

Abstract Interest in the properties of materials in small dimensions has led to the parallel development of nanoindentation and scanning force microscopy (SFM). Nanoindentation has extended indentation testing into the submicrometer regime via the development of suitable equipment and means of interpreting indentation load-displacement data which obviate the need to image such microscopic indentations. SFM, on the other hand, has been developed primarily as an imaging tool which depends on tip-surface interaction forces. Both of these methods depend on very low load mechanical contacts and can, in principle, be used to examine mechanical properties on a very fine, near atomic, dimensional scale. Indeed, efforts have been made to apply the technique of nanoindentation at ever smaller loads, while SFM-based techniques have been developed which enable one to assess mechanical properties. Nonetheless, approximately three orders of magnitude separate the commonly-used load ranges of these methods, and it is precisely in this load gap that one might like to work in order to investigate mechanical properties in the 1–10 nm regime. A review of recent work in this area is presented along with results obtained using SFM-based nanoindentation techniques on surfaces and thin coatings. Methods for interpreting the results of such experiments are evaluated, and some prospects for the future are outlined.

Tuning hardness in calcite by incorporation of amino acids

Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit-mineral single crystals containing embedded macromolecules-remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

Extrinsic scaling effects on the dielectric response of ferroelectric thin films

Scaling effects in polycrystalline ferroelectric thin films were investigated by preparing barium titanate in a manner that maintained constant composition and film thickness while allowing systematically increased grain size and crystalline coherence. The average grain dimensions ranged from 60to110nm, and temperature dependence of permittivity analysis revealed diffuse phase transitions in all cases. Maximum permittivity values ranged from 380 to 2040 for the smallest to largest sizes, respectively. Dielectric hysteresis is evident at room temperature for all materials, indicating stability of the ferroelectric phase. Comparison of permittivity values at high electric fields indicates that the intrinsic dielectric response is identical and microstructural artifacts likely have a minimal influence on film properties across the sample series. Permittivity values, however, are substantially smaller than those reported for bulk material with similar grain dimensions. X-ray line broadening measurements were ...

Variations in nanomechanical properties and tissue composition within trabeculae from an ovine model of osteoporosis and treatment.

Osteoporosis and treatment may affect both composition and nanomechanical properties and their spatial distributions within the individual trabeculae of cancellous bone at length scales that cannot be captured by bulk measurements. This study utilized 25 mature adult ewes divided into 5 treatment groups. Four treatment groups were given a dietary model for human high-turnover osteoporosis, and two of these were treated with antiresorptive drugs, either zoledronate (ZOL) or raloxifene (RAL), to examine their effects on bulk tissue properties and nanoscale tissue composition and mechanical properties within trabeculae. Treatment effects were most pronounced at the nanoscale, where RAL increased indentation modulus and hardness throughout trabeculae by 10% relative to the osteoporosis model. In comparison, ZOL increased these properties exclusively at the surfaces of trabeculae (indentation modulus +12%, hardness +16%). Nanomechanical alterations correlated with changes in tissue mineralization, carbonate substitution, crystallinity, and aligned collagen. Despite only minimal changes in bulk tissue tBMD, the nanomechanical improvements within trabeculae with both treatments greatly improved the predicted theoretical bending stiffness of individual trabeculae when idealized as cylindrical struts. Hence, small tissue-level alterations in critical locations for resisting trabecular failure could account for some of the discrepancy between the large reductions in fracture risk and the only modest changes in BMD with antiresorptive treatments.

Plastic deformation and strength of materials in small dimensions

Materials with characteristic crystallite dimensions in the nanometer regime are expected to have interesting and useful mechanical properties (high strength and ductility). However, understanding of these properties has been obscured by variations in the density and possibly the composition of the tested samples. An overview of recent progress in understanding plastic deformation and strength in nanocrystalline metals in bulk and thin film form is presented. Deviations from classical scaling laws are discussed from a mechanistic point of view.