Thermal Conductivity Enhancement in Ion-Irradiated Hydrogenated Amorphous Carbon Films.

Amorphous solids are traditionally assumed to set the lower bound to the vibrational thermal conductivity of a material due to the high degree of structural disorder. Here, were demonstrate the ability to increase the thermal conductivity of amorphous solids through ion irradiation, in turn, altering the bonding network configuration. We report on the thermal conductivity of hydrogenated amorphous carbon implanted with C+ ions spanning fluences of 3 × 1014-8.6 × 1014 cm-2 and energies of 10-20 keV. Time-domain thermoreflectance measurements of the films' thermal conductivities reveal significant enhancement, up to a factor of 3, depending upon the preirradiation composition. Films with higher initial hydrogen content provide the greatest increase, which is complemented by an increased stiffening and densification from the irradiation process. This enhancement in vibrational transport is unique when contrasted to crystalline materials, for which ion implantation is known to produce structural degradation and significantly reduced thermal conductivities.

Interfacial Defect Vibrations Enhance Thermal Transport in Amorphous Multilayers with Ultrahigh Thermal Boundary Conductance.

The role of interfacial nonidealities and disorder on thermal transport across interfaces is traditionally assumed to add resistance to heat transfer, decreasing the thermal boundary conductance (TBC). However, recent computational studies have suggested that interfacial defects can enhance this thermal boundary conductance through the emergence of unique vibrational modes intrinsic to the material interface and defect atoms, a finding that contradicts traditional theory and conventional understanding. By manipulating the local heat flux of atomic vibrations that comprise these interfacial modes, in principle, the TBC can be increased. In this work, experimental evidence is provided that interfacial defects can enhance the TBC across interfaces through the emergence of unique high-frequency vibrational modes that arise from atomic mass defects at the interface with relatively small masses. Ultrahigh TBC is demonstrated at amorphous SiOC:H/SiC:H interfaces, approaching 1 GW m-2 K-1 and are further increased through the introduction of nitrogen defects. The fact that disordered interfaces can exhibit such high conductances, which can be further increased with additional defects, offers a unique direction to manipulate heat transfer across materials with high densities of interfaces by controlling and enhancing interfacial thermal transport.

Role of Hydrogen and Nitrogen on the Surface Chemical Structure of Bioactive Amorphous Silicon Oxynitride Films.

Silicon oxynitride (Si-O-N) is a new biomaterial in which its O/N ratio is tunable for variable Si release and its subsequent endocytotic incorporation into native hydroxyapatite for enhanced bone healing. However, the effect of nitrogen and hydrogen bonding on the formation and structure of hydroxyapatite is unclear. This study aims to uncover the roles of H and N in tuning Si-O-N surface bioactivity for hydroxyapatite formation. Conformal Si-O-N films were fabricated by plasma-enhanced chemical vapor deposition (PECVD) onto Ti/Si substrates. Fourier transform infrared spectroscopy (FTIR) and Rutherford backscattering spectrometry (RBS) analysis indicated increased Si-H and N-H bonding with increased N content. Surface energy decreased with increased N content. X-ray absorbance near edge structure (XANES) analysis showed tetrahedral coordination in O-rich films and trigonal coordination in N-rich films. O-rich films exhibited a 1:1 ratio of 2p3/2 to 2p1/2 electron absorbance, while this ratio was 1.73:1 for N-rich films. Both Si and N had a reduced partial charge for both O- and N-rich films, whereas O maintained its partial charge for either film. O-rich films were found to exhibit random bonding SizOxNy, while N-rich films exhibited random mixing: [Si-Si]-[Si-O]-[Si-N]. Thus, hydrogen bonding limits random nitrogen bonding in Si-O-N films via surface Si-H and N-H bonding. Moreover, increased nitrogen content reduces the partial charge of constituent elements and changes the bonding structure from random bonding to random mixing.

Ion depletion near a solution surface: is image-charge repulsion sufficient?

Grazing-incidence Rutherford backscattering and angle-resolved x-ray photoelectron spectrometry are used to determine the ion-concentration profiles near the surface of a solution consisting of a salt (TEABr) in a weakly polar organic liquid (polyethylene glycol) with atomic-layer depth resolution. The predictions of a model, in which ions in solution are repelled from the surface due to a screened Coulomb interaction with their image charge, are in good agreement with measured ion profiles. This contrasts with the behavior of salts in aqueous and highly polar organic solutions.

Increased osteoblast adhesion on titanium-coated hydroxylapatite that forms CaTiO3.

CaTiO(3) is a strong candidate to form at the interface between hydroxylapatite (HA) and titanium implants during many coating procedures. However, few studies have compared the cytocompatibility properties of CaTiO(3) to HA pertinent for bone-cell function. For this reason, the objective of the present in vitro study was to determine the ability of bone-forming cells (osteoblasts) to adhere on titanium coated with HA that resulted in the formation of CaTiO(3). To accomplish the formation of CaTiO(3), titanium was coated on HA discs and annealed either under air or a N(2)+H(2) environment. Materials were characterized by X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), and atomic force microscopy (AFM). These characterization techniques demonstrated the formation of a nanometer rough CaTiO(3) layer as a consequence of interactions between HA and titanium during coating conditions. Results from cytocompatibility tests revealed increased osteoblast adhesion on materials that contained CaTiO(3) compared to both pure HA and uncoated titanium. The greatest osteoblast adhesion was observed on titanium-coated HA annealed under air conditions. Because adhesion is a crucial prerequisite to subsequent functions of osteoblasts (such as the deposition of calcium containing mineral), the present in vitro results imply that orthopedic coatings that form CaTiO(3) could increase osseointegration with juxtaposed bone needed for increased implant efficacy.

Hydroxylapatite and titanium: interfacial reactions.

The chemical reactions between hydroxylapatite (HA) and titanium were studied in three different kinds of experiments to increase understanding of how to bond HA to titanium for implant materials. HA powder was bonded to a titanium rod with hot isostatic pressing. Interdiffusion of the HA elements and titanium was found in concentration profiles measured in the electron microprobe. Titanium was vapor-deposited on sintered HA discs and heated in air; perovskite (CaTiO(3)) was found on the HA surface with Rutherford backscattering and X-ray diffraction measurements. Powder composites of HA and titanium and TiO(2) were sintered at 1100 degrees C; again, perovskite was a reaction product, as well as beta-Ca(3)(PO(4))(2), from decomposition of the HA. These results demonstrate chemical reactions and interdiffusion between HA and TiO(2) during sintering, resulting in chemical bonding between HA and titanium. Thus, cracks and weakness at HA-titanium interfaces probably result from mismatch between the coefficients of thermal expansion of these materials. HA composites with other ceramics and different alloys should lead to better thermal matching and better bonding at the interface.

Rutherford backscattering to study the near-surface region of volatile liquids and solids.

Here we describe the use of Rutherford backscattering spectrometry (RBS) to measure quantitative in situ elemental profiles with high depth resolution, online and nondestructively, in volatile substances (liquid and frozen acids, ice). Samples for analysis are held in a chamber with controlled temperature and partial pressures designed to match conditions for aerosols in Earth's atmosphere. This technique is demonstrated in studies of water solubility in sulfuric acid, hydrochloric acid (HCl) on ice surfaces, the formation of a HCl-hexahydrate surface layer on evaporating HCl-doped ice, and the diffusion of water through this layer.