Maria Letizia Terranova

Mechanical characterization of polymeric thin films by atomic force microscopy based techniques

Polymeric thin films have been awakening continuous and growing interest for application in nanotechnology. For such applications, the assessment of their (nano)mechanical properties is a key issue, since they may dramatically vary between the bulk and the thin film state, even for the same polymer. Therefore, techniques are required for the in situ characterization of mechanical properties of thin films that must be nondestructive or only minimally destructive. Also, they must also be able to probe nanometer-thick ultrathin films and layers and capable of imaging the mechanical properties of the sample with nanometer lateral resolution, since, for instance, at these scales blends or copolymers are not uniform, their phases being separated. Atomic force microscopy (AFM) has been proposed as a tool for the development of a number of techniques that match such requirements. In this review, we describe the state of the art of the main AFM-based methods for qualitative and quantitative single-point measurements and imaging of mechanical properties of polymeric thin films, illustrating their specific merits and limitations.

Local indentation modulus characterization of diamondlike carbon films by atomic force acoustic microscopy two contact resonance frequencies imaging technique

Two contact resonance frequencies atomic force acoustic microscopy imaging technique has been used to evaluate local indentation modulus of a diamondlike carbon film deposited on a molybdenum foil by laser ablation from glassy carbon target. Acoustic images were obtained by measuring both first and second contact resonance frequency at each point of the scanned area, and then numerically evaluating local contact stiffness and reconstructing an indentation modulus bidimensional pattern. The wide difference of the indentation modulus values allows to detect the presence of residual glassy carbon agglomerates in the diamondlike carbon film.

Effect of tip geometry on local indentation modulus measurement via atomic force acoustic microscopy technique

Atomic force acoustic microscopy (AFAM) is a dynamical AFM-based technique very promising for nondestructive analysis of local elastic properties of materials. AFAM technique represents a powerful investigation tool in order to retrieve quantitative evaluations of the mechanical parameters, even at nanoscale. The quantitative determination of elastic properties by AFAM technique is strongly influenced by a number of experimental parameters that, at present, are not fully under control. One of such issues is that the quantitative evaluation require the knowledge of the tip geometry effectively contacting the surface during the measurements. We present and discuss an experimental approach able to determine, at first, tip geometry from contact stiffness measurements and, on the basis of the achieved information, to measure sample indentation modulus. The reliability and the accuracy of the technique has been successfully tested on samples (Si, GaAs, and InP) with very well known structural and morphological ...

Carbon nanotubes and nanowires grown from spherical carbon nano-particles

Abstract In this Letter, we report a new method for the fabrication of carbon nanotubes (CNT) and nanowires where amorphous hydrogenated carbon nano-particles were used as precursor, without metal catalyst addition. In particular, depending on the process parameters, we obtained single walled nanotubes (SWNTs) with mean diameter 1.2 nm and carbon nanowires with mean diameter 250 nm. A discussion on the possible growth mechanism is also reported.

Self-assembled carbon nanotubes grown without catalyst from nanosized carbon particles adsorbed on silicon

Carbon nanotubes films have been prepared by low-velocity spraying of carbon nanosized particles on heated Si substrate. Studies reveal that by properly choosing the deposition temperature, well-aligned carbon nanotubes are self-assembled from the particles without a catalyst. Raman scattering and reflection high-energy electron diffraction show that the tubes are bundles of single-wall nanotubes.

Laser‐induced structural modifications of glassy carbon surfaces

Structural modifications induced by pulsed laser irradiations in the surface layers of glassy carbon have been monitored by reflection high energy electron diffraction, Raman spectroscopy, and electron energy loss spectroscopy. The glassy carbon samples were irradiated by 30 superimposed laser pulses (λ=6.943 nm). The energy density (100–500 mJ/cm2 per pulse) delivered to the material and the repetition rate of the laser (0.05 Hz) have been chosen so that the temperature increase of the irradiated surface layers was below the melting point of the glassy carbon. The combined use of the analysis techniques indicated that the beginning of the solid state processes, leading to microstructural modifications of the surface layers, occurs at energy density of 300 mJ/cm2. An increase of the average crystalline size of graphitic clusters occurs upon radiation performed at fluences of 300 and 400 mJ/cm2, whereas at higher energy density the material undergoes complete amorphization. The analysis of chemical state ...

X-ray absorption and photoelectron spectroscopy studies on graphite and single-walled carbon nanotubes: Oxygen effect

We have investigated the electronic states of highly oriented pyrolitic graphite and single-walled carbon nanotubes using x-ray absorption spectroscopy (XAS) before and after annealing treatment in ultrahigh vacuum, and observed that the small peak between pi(*) and sigma(*) features, which has been previously assigned to free-electron-like interlayer states, disappears after in situ annealing treatment, suggesting that the signal may be assigned to a surface contamination, especially oxygen contamination introduced by chemical processing or gas adsorption. Additional experiments by photoelectron spectroscopy as well as XAS methods, performed after aging in air, fully support this interpretation. (c) 2005 American Institute of Physics.

Residual stress in polycrystalline diamond/Ti6Al4V systems

Abstract Polycrystalline diamond coatings were deposited on Ti6Al4V alloy by HF-CVD, at fixed temperature (650 C) for different deposition times. During the process, thick titanium carbide layers were formed at the metal/diamond interface. X-ray diffraction (XRD) methods were used to assess coating quality, phase composition, texture, and residual macrostress of the diamond/TiC/Ti system. For a better evaluation of the residual stress present in each phase, three independent measurements were performed with synchrotron radiation (SR-XRD). The measured residual strain could be interpreted in terms of a simple axially uniform residual stress model: σ11 = σ22, σ33 = 0, σij = 0 (i ≠ j). Irrespective of film thickness, the residual stress was very intense, compressive both in the diamond layer (approx. −6.5 GPa) and in TiC (approx. −1.4 GPa), and tensile in Ti6Al4V (approx. 70 MPa). The high residual strain in the diamond layer affected the results of texture measurements using the traditional pole figure method; more reliable results were obtained by measuring the integrated intensity, rather than peak maximum intensity, as a function of tilting angles.

Experimental evidence of different crystalline forms in chemical vapor deposited diamond films

Diamond films have been obtained on Ta polycrystalline substrates from mixtures of methane and hydrogen by the hot‐filament chemical vapor deposition technique. The structural characteristics of the polycrystalline deposits have been investigated by reflection high energy electron diffraction (RHEED), while the surface morphologies have been observed by scanning electron microscopy or carbon replica transmission electron microscopy. For one of the films, the formation of thermal spikes during the deposition process yielded a structure giving a RHEED pattern with d spacings and intensities not corresponding to the already identified carbon and diamond phases. On the base of the RHEED pattern the observed phase has been identified as a face‐centered‐cubic lattice, belonging to the space group F43m and ascribed to a so‐called X‐diamond polytype.

Nanodiamonds coupled with plant bioactive metabolites: A nanotech approach for cancer therapy

Nanodiamond application in biotechnological and medical fields is nowadays in continuous progress. In fact, biocompatibility, reduced dimensions and high surface chemical interaction are specific features that make nanodiamonds perfect intracellular carriers of bioactive compounds. By confocal microscopy, we confirmed that nanodiamonds were able to penetrate in cell cytoplasm but we also demonstrated how they remained embedded in nuclear membrane just exposing some little portions into nuclear area, definitively clarifying this topic. In this work, for the first time, nanodiamonds were conjugated with plant secondary metabolites, ciproten and quercetin. Moreover, since drug-loading on nanoparticles was strongly conditioned by their chemical surface, different types of nanodiamonds (oxidized, wet chemical reduced and plasma reduced) were synthesized in this work and then functionalized with plant compounds. We found that ciproten and quercetin antiproliferative effects, on human (HeLa) and murine (B16F10) tumor cells, were improved after nanodiamond conjugation. Moreover, plant molecules highly reduced their in vitro pro-oxidant, cytotoxic and pro-apoptotic activity when associated with nanodiamond. We are led to suppose that natural drug-nanodiamond adducts would act at cellular level by different molecular mechanisms with respect to plant metabolite pure forms. Finally, our results showed that chemical and structural modifications of nanodiamond surfaces influenced the bioactivity of transported drugs. According to all these evidences, this work can be considered as a promotional research to favor the use of bioactive plant molecules associated with nanodiamonds for therapeutic purposes.