I. Jiménez

Core-level photoabsorption study of defects and metastable bonding configurations in boron nitride

A comprehensive study of different local bonding environments in boron nitride -bulk and thin filmshas been performed by core level photoabsorption. Several new features not present in crystalline reference samples are found in the absorption spectra of the thin films. These are identified as nitrogen vacancies in the hexagonal bonding of BN, nitrogen interstitials, boron clustering, sp -like metastable phases and sp phases. Quantitative information on the concentration and distribution of point defects is easily extracted from the photoabsorption data and is discussed with regard to formation of riew phases, the B :N ratio in the films, and compared with a random model of defect formation. Information on the stability of the new bonding environments is gained by annealing the thin films. Modification of the orientation of the sp hexagonal planes is attained by ion bombardment and annealing, and is monitored by angle resolved photoabsorption.

Novel Melt-Processable Poly(ether ether ketone)(PEEK)/Inorganic Fullerene-like WS2 Nanoparticles for Critical Applications

The combination of high-performance thermoplastic poly(ether ether ketone) (PEEK) with inorganic fullerene-like tungsten disulfide (IF-WS(2)) nanoparticles offers an attractive way to combine the merits of organic and inorganic materials into novel polymer nanocomposite materials. Here, we report the processing of novel PEEK/IF-WS(2) nanocomposites, which overcome the nanoparticle agglomerate formation and provide PEEK-particle interactions. The IF-WS(2) nanoparticles do not require exfoliation or modification, making it possible to obtain stronger, lighter materials without the complexity and processing cost associated with these treatments. The nanocomposites were fabricated by melt blending, after a predispersion step based on ball milling and mechanical treatments in organic solvent, which leads to the dispersion of individually IF-WS(2) nanoparticles in the PEEK matrix as confirmed by scanning electron microscopy. In order to determine the performance of the PEEK/IF-WS(2) nanocomposites for potential critical applications, particularly for the aircraft industry, we have extensively investigated these materials with a wide range of structural, thermal, and mechanical techniques using time-resolved synchrotron X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, dynamic-mechanical analysis, and tensile and impact tests as well as thermal measurements. Modulus, tensile strengh, thermal stability, and thermal conductivity of PEEK exhibited remarkable improvement with the addition of IF-WS(2).

Bonding and hardness in nonhydrogenated carbon films with moderate sp3 content

Amorphous carbon films with an sp3 content up to 25% and a negligible amount of hydrogen have been grown by evaporation of graphite with concurrent Ar+ ion bombardment. The sp3 content is maximized for Ar+ energies between 200 and 300 eV following a subplantation mechanism. Higher ion energies deteriorate the film due to sputtering and heating processes. The hardness of the films increases in the optimal assisting range from 8 to 18 GPa, and is explained by crosslinking of graphitic planes through sp3 connecting sites.

Use of Inorganic Fullerene-like WS2 to Produce New High-Performance Polyphenylene Sulfide Nanocomposites: Role of the Nanoparticle Concentration

The use of tungsten disulfide (WS2) nanoparticles offers the opportunity to produce novel and advanced polymer-based nanocomposite materials via melt blending. The developed materials, based on the high-performance engineering thermoplastic polyphenylene sulfide (PPS), display a unique nanostructure on variation of the nanoparticle concentration, as confirmed by time-resolved synchrotron X-ray diffraction. The cold-crystallization kinetics and morphology of PPS chains under confined conditions in the nanocomposite, as determined by differential scanning calorimetry (DSC) and atomic force microscopy (AFM), also manifest a dependence on the IF-WS2 concentration which are unexpected for polymer nanocomposites. The addition of IF-WS2 with concentrations greater than or equal to 0.5 wt % of IF-WS2 remarkably improves the mechanical performance of PPS with an increase in the storage modulus of 40-75%.

Hydrogen quantification in hydrogenated amorphous carbon films by infrared, Raman, and x-ray absorption near edge spectroscopies

In this study, we have employed infrared (IR) absorption spectroscopy, visible Raman spectroscopy, and x-ray absorption near edge structure (XANES) to quantify the hydrogen (H) content in hydrogenated amorphous carbon (a-C:H) films. a-C:H films with a hydrogen content varying from 29 to 47 at. % have been synthesized by electron cyclotron resonance chemical vapor deposition at low substrate temperatures (<120 °C) applying a wide range of bias voltage, Vb, (−300 V<Vb<+100 V). With the application of high negative Vb, the a-C:H films undergo a dehydrogenation process accompanied by a sharp structural modification from polymer- to fullerenelike films. The trend in the H content derived from elastic recoil detection analysis (ERDA) is quantitatively reproduced from the intensity of the C–H bands and states in the IR and XANES spectra, respectively, as well as from the photoluminescence (PL) background drop in the Raman spectra. Using the H contents obtained by ERDA as reference data, semiquantitative expressi...

Identification of ternary boron–carbon–nitrogen hexagonal phases by x-ray absorption spectroscopy

Boron carbon nitride (BCN) films have been grown by B4C evaporation with concurrent N2+ ion assistance, and have been characterized by x-ray absorption near edge (XANES) spectroscopy. Upon the nitrogen insertion, the film structure evolves from BxC-like to h-BN-like. The hexagonal structure corresponds to a true ternary BCN compound that can be understood as h-BN with carbon incorporated in substitutional sites. The C(1s)XANES presents π* states characteristic of the BCN arrangement. The basal planes of the h-BCN phase are oriented perpendicular to the substrate, as derived from the angle dependence of the XANES signal.

Bonding modifications in carbon nitride films induced by thermal annealing: An x-ray absorption near edge study

The thermal stability of nonstoichiometric carbon nitride films has been studied by x-ray absorption near edge spectroscopy. Amorphous carbon nitride thin films were annealed in vacuum up to 1150 °C revealing the presence of nitrogen in different bonding configurations. Annealing to 450 °C results in the loss of ∼50% of the nitrogen. The remaining nitrogen is bonded to carbon within a graphitic framework and it evolves into a more stable configuration with increasing temperature without significant N loss up to 820 °C. Beyond this temperature, nitrogen loss occurs without important structural changes.

X-Ray Absorption Studies of Cubic Boron carbon nitrogen Films Grown by Ion Beam Assisted Evaporation

Abstract We have synthesised boron carbon nitride (BCN) thin films with tetrahedral structure by evaporation of B 4 C and concurrent ion bombardment. The film structure and composition are characterised by infrared and X-ray absorption near edge (XANES) spectroscopies. The addition of Ar to the N 2 assisting gas is necessary to reach a momentum transfer above the threshold to promote tetrahedral bonding. Under these conditions, c-BCN compounds are achieved, but the carbon content is limited to ∼5 at.%. This phase grows on the top of a ∼50-nm h-BCN layer oriented perpendicular to the substrate. The hexagonal BCN phase permits the accommodation of a carbon content between 10 and 15 at.%. The percentage of cubic and hexagonal phases is controlled by the temperature and ion assisting parameters. There is a narrow window for promoting the cubic structure with values similar to those reported for c-BN.

Unique isothermal crystallization behavior of novel polyphenylene sulfide/inorganic fullerene-like WS2 nanocomposites.

The isothermal crystallization of polyphenylene sulfide (PPS) nanocomposites with inorganic fullerene-like tungsten disulfide nanoparticles (IF-WS2) has been studied from a thermal and morphological point of view, using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), polarized optical microscopy (POM) and time-resolved synchrotron X-ray diffraction. All the analyses revealed that the incorporation of the IF-WS2 altered significantly the crystallization behavior of PPS, in a way strongly dependent with the nanocomposite composition. The addition of IF-WS2 in 0.1 wt % proportion retarded the crystallization of PPS by increasing its fold surface free energy in a 10%. However, addition of the nanoparticles in excess of 1 wt % results in a promotion of the crystallization rate with reduction of the fold surface free energy to half the value of pure PPS.

Transition from amorphous boron carbide to hexagonal boron carbon nitride thin films induced by nitrogen ion assistance

Boron carbon nitride films (BCN) were grown by B4C evaporation under concurrent N2 ion beam assistance. The films were characterized by x-ray absorption near-edge spectroscopy, infrared and Raman spectroscopies, and high-resolution transmission electron microscopy. The bonding structure and film composition correlate with the momentum transfer per incoming atom during deposition. As the momentum transfer is increased, the film structure evolves from an amorphous boron carbide network towards a hexagonal ternary compound (h–BCN) with standing basal planes. The growth of h–BCN takes place for momentum transfer in the window between 80 and 250 (eV×amu)1/2. The characteristic vibrational features of the h–BCN compounds have also been studied. Finally, the solubility limit of carbon in the hexagonal BN structure, under the working conditions of this article, is found to be ∼15 at. %.