Evolution of load transfer between hydroxyapatite and collagen during creep deformation of bone.

While the matrix/reinforcement load-transfer occurring at the micro- and nanoscale in nonbiological composites subjected to creep deformation is well understood, this topic has been little studied in biological composites such as bone. Here, for the first time in bone, the mechanisms of time-dependent load transfer occurring at the nanoscale between the collagen phase and the hydroxyapatite (HAP) platelets are studied. Bovine cortical bone samples are subjected to synchrotron X-ray diffraction to measure in situ the evolution of elastic strains in the crystalline HAP phase and the evolution of viscoelastic strains accumulating in the mineralized collagen fibrils under creep conditions at body temperature. For a constant compressive stress, both types of strains increase linearly with time. This suggests that bone, as it deforms macroscopically, is behaving as a traditional composite, shedding load from the more compliant, viscoelastic collagen matrix to the reinforcing elastic HAP platelets. This behavior is modeled by finite-element simulation carried out at the fibrillar level.

Internal strain gradients quantified in bone under load using high-energy X-ray scattering.

High-energy synchrotron X-ray scattering (>60 keV) allows noninvasive quantification of internal strains within bone. In this proof-of-principle study, wide angle X-ray scattering maps internal strain vs position in cortical bone (murine tibia, bovine femur) under compression, specifically using the response of the mineral phase of carbonated hydroxyapatite. The technique relies on the response of the carbonated hydroxyapatite unit cells and their Debye cones (from nanocrystals correctly oriented for diffraction) to applied stress. Unstressed, the Debye cones produce circular rings on the two-dimensional X-ray detector while applied stress deforms the rings to ellipses centered on the transmitted beam. Ring ellipticity is then converted to strain via standard methods. Strain is measured repeatedly, at each specimen location for each applied stress. Experimental strains from wide angle X-ray scattering and an attached strain gage show bending of the rat tibia and agree qualitatively with results of a simplified finite element model. At their greatest, the apatite-derived strains approach 2500 µÎµ on one side of the tibia and are near zero on the other. Strains maps around a hole in the femoral bone block demonstrate the effect of the stress concentrator as loading increased and agree qualitatively with the finite element model. Experimentally, residual strains of approximately 2000 µÎµ are present initially, and strain rises to approximately 4500 µÎµ at 95 MPa applied stress (about 1000 µÎµ above the strain in the surrounding material). The experimental data suggest uneven loading which is reproduced qualitatively with finite element modeling.

Functionalized graphene sheets for polymer nanocomposites.

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.

Mimicking mussel adhesion to improve interfacial properties in composites.

The macroscale properties of polymer-matrix composites depend immensely on the quality of the interaction between the reinforcement phase and the bulk polymer. This work presents a method to improve the interfacial adhesion between metal-oxides and a polymer matrix by performing surface-initiated polymerization (SIP) by way of a biomimetic initiator. The initiator was modeled after 3,4-dihydroxy-L-phenylalanine (dopa), an amino acid that is highly concentrated in mussel foot adhesive proteins. Mechanical pull out tests of NiTi and Ti-6Al-4V wires from poly (methyl methacrylate) (PMMA) were performed to directly test the interfacial adhesion. These tests demonstrated improvements in maximum interfacial shear stress of 116% for SIP-modified NiTi wires and 60% for SIP-modified Ti-6Al-4V wires over unmodified specimens. Polymer chain growth from the metal oxides was validated using x-ray photoemission spectroscopy (XPS), ellipsometry, scanning electron microscopy (SEM), and contact angle analysis.