Bond-Breaking Efficiency of High-Energy Ions in Ultrathin Polymer Films.

Thin films of poly(methyl methacrylate) and poly(vinyl chloride) of different thickness are used to investigate the effect of spatial confinement on the efficiency of bond breaking induced by 2 MeV H^{+} and 2.1 GeV Bi ions. Effective cross sections for oxygen and chlorine loss are extracted for films down to a thickness of about 5 nm and are compared to theoretical estimations based on radial energy density profiles simulated with geant-dna. The cross sections are to a large extent thickness independent, indicating that bond breaking is dominated by short-range processes. This is in contrast to the strongly reduced efficiencies found recently for cratering induced by high-energy ions in similar ultrathin polymer films [Phys. Rev. Lett. 114, 118302 (2015)PRLTAO0031-900710.1103/PhysRevLett.114.118302].

Controlled Distribution and Clustering of Silver in Ag-DLC Nanocomposite Coatings Using a Hybrid Plasma Approach.

Incorporation of selected metallic elements into diamond-like carbon (DLC) has emerged as an innovative approach to add unique functional properties to DLC coatings, thus opening up a range of new potential applications in fields as diverse as sensors, tribology, and biomaterials. However, deposition by plasma techniques of metal-containing DLC coatings with well-defined structural properties and metal distribution is currently hindered by the limited understanding of their growth mechanisms. We report here a silver-incorporated diamond-like carbon coating (Ag-DLC) prepared in a hybrid plasma reactor which allowed independent control of the metal content and the carbon film structure and morphology. Morphological and chemical analyses of Ag-DLC films were performed by atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. The vertical distribution of silver from the surface toward the coating bulk was found to be highly inhomogeneous due to top surface segregation and clustering of silver nanoparticles. Two plasma parameters, the sputtered Ag flux and ion energy, were shown to influence the spatial distribution of silver particles. On the basis of these findings, a mechanism for Ag-DLC growth by plasma was proposed.

Controlled modification of mono- and bilayer graphene in O2, H2 and CF4 plasmas.

In this work, covalent modification of mono- and bilayer graphene is achieved using tetrafluoromethane (CF4), oxygen and hydrogen RF plasma. Controlled modification of graphene is usually difficult to achieve, in particular with oxygen plasma, which is rather aggressive and usually leads to etching of graphene. Here we use x-ray photoelectron spectroscopy and Raman spectroscopy to show that mild plasma conditions and fine tuning of the number of functional groups can be obtained in all plasmas by varying parameters such as exposure time and sample position inside the chamber. We found that even for the usual harsh oxygen treatment the defect density could be lowered, down to one defect for 3.5 × 104 carbon atoms. Furthermore, we show that CF4 plasma leads to functionalization without etching and that graphene becomes an insulator at saturation coverage. In addition, the reactivity of mono- and bilayer graphene was studied revealing faster modification of monolayer in oxygen and CF4 plasma, in agreement with previous works. In contrast, similar modification rates were observed for both mono- and bilayer during hydrogenation. We attribute this discrepancy to the presence of more energetic species in the hydrogen plasma such as positive ions that could play a role in the functionalization process.

Carbon nanotubes decorated with gold, platinum and rhodium clusters by injection of colloidal solutions into the post-discharge of an RF atmospheric plasma.

In this paper, we present a new, simple, robust and efficient technique to decorate multi-wall carbon nanotubes (MWCNT) with metal nanoparticles. As case studies, Au, Pt and Rh nanoparticles are grafted onto MWCNTs by spraying a colloidal solution into the post-discharge of an atmospheric argon or argon/oxygen RF plasma. The method that we introduce here is different from those usually described in the literature, since the treatment is operated at atmospheric pressure, allowing the realization in only one step of the surface activation and the deposition processes. We demonstrate experimentally that the addition of oxygen gas in the plasma increases significantly the amount of grafted metal nanoparticles. Moreover, TEM pictures clearly show that the grafted nanoparticles are well controlled in size.

Carbon nanotubes randomly decorated with gold clusters: from nano2hybrid atomic structures to gas sensing prototypes.

Carbon nanotube surfaces, activated and randomly decorated with metal nanoclusters, have been studied in uniquely combined theoretical and experimental approaches as prototypes for molecular recognition. The key concept is to shape metallic clusters that donate or accept a fractional charge upon adsorption of a target molecule, and modify the electron transport in the nanotube. The present work focuses on a simple system, carbon nanotubes with gold clusters. The nature of the gold-nanotube interaction is studied using first-principles techniques. The numerical simulations predict the binding and diffusion energies of gold atoms at the tube surface, including realistic atomic models for defects potentially present at the nanotube surface. The atomic structure of the gold nanoclusters and their effect on the intrinsic electronic quantum transport properties of the nanotube are also predicted. Experimentally, multi-wall CNTs are decorated with gold clusters using (1) vacuum evaporation, after activation with an RF oxygen plasma and (2) colloid solution injected into an RF atmospheric plasma; the hybrid systems are accurately characterized using XPS and TEM techniques. The response of gas sensors based on these nano(2)hybrids is quantified for the detection of toxic species like NO(2), CO, C(2)H(5)OH and C(2)H(4).

Electronic structure of Pd nanoparticles on carbon nanotubes.

The effect of the oxygen plasma treatment on the electronic states of multi-wall carbon nanotubes (MWCNTs) is analyzed by X-ray photoemission measurements (XPS) and UPS, both using synchrotron radiation. It is found that the plasma treatment effectively grafts oxygen at the CNT-surface. Thereafter, the interaction between evaporated Pd and pristine or oxygen plasma-treated MWCNTs is investigated. Pd is found to nucleate at defective sites, whether initially present or introduced by oxygen plasma treatment. The plasma treatment induced a uniform dispersion of Pd clusters at the CNT-surface. The absence of additional features in the Pd 3d and C 1s core levels spectra testifies that no Pd-C bond is formed. The shift of the Pd 3d core level towards high-binding energy for the smallest clusters is attributed to the Coulomb energy of the charged final state.

Carbon nanotube-TiO(2) hybrid films for detecting traces of O(2).

Hybrid titania films have been prepared using an adapted sol-gel method for obtaining well-dispersed hydrogen plasma-treated multiwall carbon nanotubes in either pure titania or Nb-doped titania. The drop-coating method has been used to fabricate resistive oxygen sensors based on titania or on titania and carbon nanotube hybrids. Morphology and composition studies have revealed that the dispersion of low amounts of carbon nanotubes within the titania matrix does not significantly alter its crystallization behaviour. The gas sensitivity studies performed on the different samples have shown that the hybrid layers based on titania and carbon nanotubes possess an unprecedented responsiveness towards oxygen (i.e. more than four times higher than that shown by optimized Nb-doped TiO(2) films). Furthermore, hybrid sensors containing carbon nanotubes respond at significantly lower operating temperatures than their non-hybrid counterparts. These new hybrid sensors show a strong potential for monitoring traces of oxygen (i.e. ≤10 ppm) in a flow of CO(2), which is of interest for the beverage industry.

Morphology of polystyrene films deposited by RF plasma.

A new plasma reactor, set up with a large planar inductively coupled source, is used for the first time to deposit a polymer coating (pPS) from a styrene monomer. This work is devoted to the relationship between external plasma parameters and substrate topography, and pPS coating morphology, which is investigated by scanning electron microscopy and atomic force microscopy. Stainless steel, gold and glass surfaces are used as substrates. It is clearly demonstrated that the film morphology can be controlled by adjustment of RF input power, pressure. The analysis performed further reveals that the pPS film's characteristics strongly depend on the substrate topography and its electrical potential during the discharge. Finally, the plasma duration also strongly influences the morphology of the films. The morphologies obtained include smooth films without any specific feature, worm-like structures, particles (nanometer- and micrometer-sized) associated along preferential directions and randomly distributed particles (micrometer-sized). The intrinsic topography of the substrate influences the film structure in the case of thin films (thickness lower than about 100 nm). Polymerization is suggested to take place at the surface in contact with the discharge rather than in the gas phase. Nucleation and growth start preferentially on substrate defects such as polishing scratches.

Metal-assisted secondary ion mass spectrometry using atomic (Ga+, In+) and fullerene projectiles.

The advantages and drawbacks of using either monatomic or buckminsterfullerene primary ions for metal-assisted secondary ion mass spectrometry (MetA-SIMS) are investigated using a series of organic samples including additive molecules, polyolefins, and small peptides. Gold deposition is mostly performed by sputter-coating, and in some cases, the results are compared to those of thermal evaporation (already used in a previous article: Delcorte, A.; Médard, N.; Bertrand, P. Anal. Chem. 2002, 74, 4955). The microstructure of the gold-covered sample surfaces is assessed by scanning and transmission electron microscopies. The merits of the different sets of experimental conditions are established via the analysis of fragment and parent-like ion yields. For most of the analyzed samples, the highest yields of fragment and parent-like ions are already reached with the sole use of C60+ projectiles. Metallization of the sample does not lead to a significant additional enhancement. For polyethylene and polypropylene, however, gold metallization associated with Ga+/In+ projectiles appears to be the only way to observe large cationized, sample-specific chain segments (m/z approximately 1000-2000). A detailed study of the polypropylene mass spectra as a function of gold coverage shows that the dynamics of yield enhancement by metal nanoparticles is strongly dependent on the choice of the projectile, e.g., a pronounced increase with Ga+ and a slow decay with C60+. The cases of Irganox 1010, a polymer antioxidant, and leucine enkephalin, a small peptide, allow us to investigate the specific influence of the experimental conditions on the emission of parent(like) ions such as M+, (M + Na)+, and (M + Au)+. The results show a dependence on both the type of sample and the considered secondary ion. Using theoretical and experimental arguments, the discussion identifies some of the mechanisms underlying the general trends observed in the results. Guidelines concerning the choice of the experimental conditions for MetA-SIMS are provided.

Increase of enamel fluoride retention by low fluence argon laser beam: a 6-month follow-up study in vivo.

BACKGROUND AND OBJECTIVES: The aim of this 6-month in vivo study was to investigate if argon laser irradiation of enamel can increase the retention of fluoride. STUDY DESIGN/MATERIALS AND METHODS: Ninety-eight teeth in 12 patients were randomly divided into three groups: (1) EF group: 40 teeth were only treated with fluoride gel (applied for 5 minutes followed by a 1 minute rinsing with distilled water). (2) EFL group: 40 teeth were treated the same way as in the EF group but they were lased after fluoridation. (3) E group: 18 teeth were kept without any treatment as a control group. In order to quantify the fluoride content in the enamel samples, the teeth were analyzed by proton beam delivered by a tandem accelerator (PIgE, particle induced gamma-ray emission). A low energy density of argon laser beam was used: 10.74 J/cm2 (11 mm of beam diameter, irradiation time of 30 seconds, and an output power of 340 mW in continuous mode). RESULTS: The results after 6 months showed that the lased enamel still retained 52.55+/-8.47 ppm or 14.12% of fluoride after the fluoridation process, whereas the unlased enamel retained only 12.18+/-6.82 ppm or 3.27% of fluoride. The untreated and control enamel (E group: unlased and without fluoride treatment) had 1.16+/-4.27 ppm value of fluoride. The statistical test (ANOVA tests at 95% level) showed that the difference is significant between the fluoride retention in the group EFL and the group EF 6 months after fluoridation. CONCLUSIONS: The use of argon laser at low energy density (10.74 J/cm2) significantly increased the fluoride retention in lased enamel that had approximately 400 times more fluoride than the unlased enamel. We consider this procedure as an alternative clinical procedure to increase the fluoride content of enamel surface.

Increase of enamel fluoride retention by low fluence argon laser in vivo.

BACKGROUND AND OBJECTIVES: The aim of this in vivo study was to investigate if argon laser irradiation of enamel can increase the retention of fluoride. STUDY DESIGN/MATERIALS AND METHODS: Ninety-eight teeth in 12 patients were randomly divided into three groups: (1) EF group: 40 teeth were only treated by fluoride gel (application for 5 minutes followed by 1 minute rinsing with distilled water). (2) EFL group: 40 teeth were treated the same way as in the EF group but they were lased after fluoridation. (3) E group of 18 teeth were kept without any treatment and considered as reference. In order to quantify the fluoride content in the enamel samples, the teeth were analyzed by proton beam delivered by a tandem accelerator (PIgammaE, particle induced gamma-ray emission). The fluoride content of enamel surface is not homogeneous. Therefore, it is necessary to analyze the same enamel area after each treatment. Each tooth was maintained in a fixed tooth holder which was designed to analyze the tooth enamel surface at the same place (1 mm(2) and around 20 mum in depth) after various treatments. A low energy density of argon laser beam was used: 10.74 J/cm(2), 30 seconds of irradiation time and 340 m W of output power. RESULTS: The results after 7 days showed that the lased enamel still retained 157.4 +/- 23.371 ppm or 42.29% of fluoride after fluoridation process whereas the unlased enamel retained 45.59 +/- 9.377 ppm or 12.25% of fluoride. CONCLUSIONS: We concluded that the use of argon laser at low energy density (10.74 J/cm(2)) significantly increases the fluoride retention in lased enamel which had approximately three times more fluoride than the unlased enamel.

Analysis of titanium dental implants after failure of osseointegration: combined histological, electron microscopy, and X-ray photoelectron spectroscopy approach.

A multitechnique approach has been used to characterize the surface of nonosseointegrated titanium implants and the surrounding biological tissues. Five pure titanium dental implants were used as reference, and 25 removed implants were studied. Surface and in-depth chemical compositions of the implants (from a total of 16 patients) were investigated by X-ray photoelectron spectroscopy (XPS). Histological slides of the surrounding tissues were examined by light microscopy, XPS, and electron microprobe analysis. None of the failed implants presented the regular surface composition and depth profile of the TiO2 overlayer; foreign elements (Ca, Na, P, Si, Cl, Zn, Pb, and Al) were observed on some implants. Fibrosis, lymphocytic and plasmocytic infiltrates, and granulomatous lesions were detected in the surrounding tissues. XPS and electron microprobe analysis indicated the presence of Zn, Fe, Sn, and Ti in the tissues. As a possible scenario for implant failure, we propose and discuss a oxidoreduction mechanism, leading to a partial dissolution or the complete dissociation of the protective titanium dioxide overlayer and to ion diffusion through the surrounding tissues.

An XPS and SEM evaluation of six chemical and physical techniques for cleaning of contaminated titanium implants.

The purpose of the present study was to analyse clinically failed and retrieved implants prior to and after cleaning by means of scanning electron microscopy (SEM) and X-ray induced photoelectron spectroscopy (XPS) as compared to unused controls. Six different chemical and physical techniques for cleaning of contaminated titanium implants were evaluated: 1) rinsing in absolute ethanol for 10 min, 2) cleaning in ultrasonic baths containing trichloroethylene (TRI) and absolute ethanol, 10 min in each solution, 3) abrasive cleaning for 30 s, 4) cleaning in supersaturated citric acid for 30 s, 5) cleaning with continuous CO2-laser in dry conditions at 5 W for 10 s, 6) cleaning with continuous CO2-laser in wet conditions (saline) at 5 W for 10 s. SEM of failed implants showed the presence of contaminants of varying sizes and XPS showed almost no titanium but high carbon signals. XPS of unused titanium implants showed lower levels of titanium as previously reported, probably due to contamination of carbon which increased with time in room air. Cleaning of used implants in citric acid followed by rinsing with deionized water for 5 min followed by cleaning in ultrasonic baths with TRI and absolute ethanol gave the best results with regard to macroscopical appearance and surface composition. However, as compared to the unused implants the results from an element composition point of view were still unsatisfactory. It is concluded that further development and testing of techniques for cleaning of organically contaminated titanium is needed.

Amination of polystyrene microwells: application to the covalent grafting of DNA probes for hybridization assays.

Amine functionalization of polystyrene microwells for covalent binding of DNA is described. Polystyrene support was first carboxylated by permanganate oxidation in diluted sulfuric acid. These functions were activated with water-soluble carbodiimide and grafted with N-methyl-1,3-propane diamine to introduce a free secondary amino group on the support. The samples were characterized by X-ray photoelectron spectroscopy and radiochemical assay. The conditions for covalent linkage of secondary amine on polystyrene microwells were optimized. Functionalized supports were used for covalent binding of a DNA capture probe for the detection of human cytomegalovirus in a sandwich hybridization assay. Sensitivity of the assay compared very well with a commercially available surface, Covalink-NH, microwell plate obtained by electromagnetic irradiation.

Surface study of biomaterials by electron induced vibrational spectroscopy.

Besides the identification of elements and chemical groups on a material surface, the determination of its structure, or of the relative orientation of different chemical groups, is probably of utmost importance for biomaterials and their modified surfaces. 'Electron induced vibrational spectroscopy' is a new technique, as far as applications to biomaterials are concerned, and is capable of recording well-resolved vibrational bands from the extreme surface. Basics and the potentials of the technique are presented here for nonspecialists, with illustrations from model polymers, Langmuir-Blodgett films, carbon materials, and ceramics.

Surface studies on titanium IMZ implants.

The aim of this study was to investigate the surface feature of the IMZ implant. Eight non-implanted new samples and four implanted samples removed one year after insertion were prepared. The 8 non-implanted samples were divided into two groups. The first group was sterilized and the second group was manipulated by bare hands. The implanted samples underwent a careful procedure to recover the metal surface. Then, both the non-implanted new samples and implanted samples were subjected to X-ray electron spectroscopy (XPS) and Rutherford back-scattering spectroscopy (KBS) analyses. Subsequently, all the samples were subjected to scanning electron microscopic (SEM) examination, and surface roughness and profilometric measurements. The SEM photomicrograph showed a rough surface composed of fused granular metal separated by gaps. Sometimes the presence of isolated well-shaped granules of 0.8-1.8 microns in diameter was observed. This structure was related to the manufacturing process of the IMZ implant. The implanted surfaces showed no intergranular gaps and appeared less rough (average roughness: Ra = 1.91 +/- 0.1 microns) compared with the new non-implanted surfaces (Ra = 4.93 +/- 0.3). XPS analysis at a maximum resolution depth of 1.5 nm revealed TiO2, C, O compounds on sterilized non-implanted surfaces. The hand-handled non-implanted surfaces on the contrary did not show TiO2 due to contamination. The elements Ca, C, O and N were found on the one-year implanted IMZ surfaces; TiO2, however, was absent. RBS analysis at a maximum resolution depth of 1000 nm, indicated a decrease of the total thickness of TiO2 after one year of IMZ implantation. The TiO2 thickness was 0.5-0.7 microns for the non-implanted new IMZ surfaces and 0.03-0.2 microns for implanted IMZ surfaces.

Brushite in the pulp of primary molars.

This study was undertaken to investigate the mineral phase of spherulitic calcifications discovered in the pulpous mesenchyme of human primary molars by microradiography. Analytical scanning electron microscopy and x-ray diffraction disclosed that well-crystallized brushite is the major compound of the spherulites. The mechanism leading to the crystallization of brushite is far from well understood. Histologically, on decalcified sections, inflammatory cells and capillaries can be seen trapped in the spherulites. In the light of these findings, it could be suggested that metabolic conditions may promote the crystallization of brushite in the pulp of primary molars.