Outside-the-(cavity-prep)-box thinking.

Direct placement restorative materials must interface with tooth structures that are often compromised by caries or trauma. The material must seal the interface while providing sufficient strength and wear resistance to assure function of the tooth for, ideally, the lifetime of the patient. Needed are direct restorative materials that are less technique-sensitive than current resin-based composite systems while having improved properties. The ideal material could be successfully used in areas of the world with limited infrastructure. Advances in our understanding of the interface between the restoration adhesive system and the stages of carious dentin can be used to promote remineralization. Application of fracture mechanics to adhesion at the tooth-restoration interface can provide insights for improvement. Research in polymer systems suggests alternatives to current composite resin matrix systems to overcome technique sensitivity, while advances in nano- and mesoparticle reinforcement and alignment in composite systems can increase material strength, toughness, and wear resistance, foreshadowing dental application.

Passivation oxide controlled selective carbon nanotube growth on metal substrates.

Vertically aligned arrays of multi-wall carbon nanotubes (MWNT) are grown on Inconel 600, a nickel-based super-alloy. Using x-ray photoelectron spectroscopy (XPS) and chemical vapor deposition (CVD) growth of the MWNTs it is shown that a stable oxidation barrier is required for the stabilization of iron on the substrate and subsequent nanotube growth. This evidence for passivation oxide supported growth of MWNTs was then used to grow MWNTs on patterned oxidized substrates in a selective growth furnace. The unique advantage of this patterned growth on Inconel 600 is found to be the chromia passivation layer's electrical conductivity (measured value of 1.08 micro Omega m), creating the opportunity for low resistivity electrodes made from nanotubes. Inconel substrates with 100 microm long aligned MWNTs are demonstrated to exhibit an average resistance value of 2 Omega.

Time and temperature dependence of multi-walled carbon nanotube growth on Inconel 600.

The growth kinetics of vertically aligned multi-walled carbon nanotubes (MWNTs) on conductive substrates is investigated by synthesizing MWNTs at different growth temperatures and measuring ex situ the length of the nanotubes as a function of growth duration. A typical 'root growth' mechanism (saturation of MWNT lengths with increasing growth duration) was observed. The value of the activation energy (E(a)≈136 ± 5 kJ mol(-1)) of the MWNT growth reaction is suggestive of carbon diffusion through the bulk of the iron catalyst particle versus diffusion on its surface. These findings will help in optimizing MWNT growth on conductive substrates for various applications.

Anisotropic thermal diffusivity characterization of aligned carbon nanotube-polymer composites.

The anisotropic thermal diffusivity of aligned carbon nanotube-polymer composites was determined using a photothermoelectric technique. The composites were obtained by infiltrating poly-dimethyl siloxane (PDMS) in aligned multiwall CNT arrays grown by chemical vapor deposition on silicon substrates. The thermal diffusivities are insensitive to temperature in the range of 180 K-300 K. The thermal diffusivity values across the alignment direction are approximately 2-4 times smaller than along the alignment direction and larger than effective media theory predictions using reported values for the thermal diffusivity of millimeter thick aligned multiwall carbon nanotube arrays. The effective room temperature thermal conductivity of the composite along the carbon nanotube alignment direction is at least 6X larger than the thermal conductivity of the polymer matrix and is in good agreement with the effective media predictions. This work indicates that infiltration of long and aligned carbon nanotube arrays is currently the most efficient method to obtain high thermal conductivity polymer composites.

Dynamics and internal stress at the nanoscale related to unique thermomechanical behavior in polymer nanocomposites.

A small amount of alumina nanoparticles in polymethylmethacrylate causes a sharp depression of the glass transition temperature (Tg) accompanied by a toughening of the composite. We investigated this phenomenon using multispeckle x-ray photon correlation spectroscopy. Measurements reveal a dynamic structure factor that has the form exp[-(t/taua)beta], with beta greater than 1. We show for the first time that beta(T) tracks the internal stress at the polymer-particle interface. The internal stress, which we propose arises due to the entropic penalty that the polymer faces in the presence of the nanoparticles, engenders temporally heterogeneous dynamics. In the jammed glassy state, we show that the dominant fast relaxation mode--taumax--aided by a weak dewetting interface relieves the stress and follows the variations in Tg.

Mechanisms of enhanced osteoblast adhesion on nanophase alumina involve vitronectin.

The role, including concentration, conformation, and bioactivity, of adsorbed vitronectin in enhancing osteoblast adhesion on nanophase alumina was investigated in the present study. Vitronectin adsorbed in a competitive environment in the highest concentration on nanophase alumina compared to conventional alumina. Enhanced adsorption of vitronectin on nanophase alumina was possibly due to decreased adsorption of apolipoprotein A-I and/or increased adsorption of calcium on nanophase alumina. In a novel manner, the present study utilized surface-enhanced Raman scattering (SERS) to determine the conformation of vitronectin adsorbed on nanophase alumina. These results provided the first evidence of increased unfolding of vitronectin adsorbed on nanophase alumina. Increased adsorption of calcium on nanophase alumina may affect the conformation of adsorbed vitronectin specifically to promote unfolding of the macromolecule to expose cell-adhesive epitopes recognized by specific cell-membrane receptors. Results of the present study also provided evidence of dose-dependent inhibition of osteoblast adhesion on nanophase alumina pretreated with vitronectin following preincubation (and thus blocking respective cell-membrane receptors) with either Arginine-Glycine-Aspartic Acid-Serine (RGDS) or Lysine-Arginine-Serine-Arginine (KRSR). These events, namely, enhanced vitronectin adsorption, comformation, and bioactivity, may explain the increased osteoblast adhesion on nanophase alumina.