Hydrogenated amorphous carbon as protective coating for a forming tool

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Understanding growth mechanisms and tribocorrosion behaviour of porous TiO2 anodic films containing calcium, phosphorous and magnesium

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influence of Crystal Quality on the Excitation and Propagation of Surface and Bulk Acoustic Waves in Polycrystalline AlN Films

We investigate the excitation and propagation of acoustic waves in polycrystalline aluminum nitride films along the directions parallel and normal to the c-axis. Longitudinal and transverse propagations are assessed through the frequency response of surface acoustic wave and bulk acoustic wave devices fabricated on films of different crystal qualities. The crystalline properties significantly affect the electromechanical coupling factors and acoustic properties of the piezoelectric layers. The presence of misoriented grains produces an overall decrease of the piezoelectric activity, degrading more severely the excitation and propagation of waves traveling transversally to the c-axis. It is suggested that the presence of such crystalline defects in c-axis-oriented films reduces the mechanical coherence between grains and hinders the transverse deformation of the film when the electric field is applied parallel to the surface.

TiN-based coatings on fuel cladding tubes for advanced nuclear reactors

Titanium nitride (TiN) thin films are coated on HT-9 and MA957 fuel cladding tubes and bars to explore their mechanical strength, thermal stability, diffusion barrier properties, and thermal conductivity properties. The ultimate goal is to implement TiN as an effective diffusion barrier to prevent the inter-diffusion between the nuclear fuel and the cladding material, and thus lead to a longer lifetime of the cladding tubes. Mechanical tests including hardness and scratch tests for the samples before and after thermal cycle tests show that the films have a high hardness of 28GPa and excellent adhesion properties despite the thermal treatment. Thermal conductivity measurements demonstrate that the thin TiN films have very minimal impact on the overall thermal conductivity of the MA957 and HT-9 substrates, i.e., the thermal conductivity of the uncoated HT-9 and MA957 substrates was 26.25 and 28.44 W m-1 K-1, and that of the coated ones was 26.21 and 28.38W m-1 K-1, respectively. A preliminary Ce diffusion test on the couple of Ce/TiN/HT-9 suggests that TiN has excellent material compatibility and good diffusion barrier properties.

Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Low-frequency noise and static analysis of the impact of the TiN metal gate thicknesses on n- and p-channel MuGFETs

The impact of the titanium nitride (TIN) gate electrode thickness has been investigated in n and p channel SOI multiple gate field effect transistors (MuGFETs) through low frequency noise charge pumping and static measurements as well as capacitance-voltage curves The results suggest that a thicker TIN metal gate electrode gives rise to a higher EOT a lower mobility and a higher interface trap density The devices have also been studied for different back gate biases where the GIFBE onset occurs at lower front-gate voltage for thinner TIN metal gate thickness and at higher V(GF) In addition it is demonstrated that post deposition nitridation of the MOCVD HfSiO gate dielectric exhibits an unexpected trend with TIN gate electrode thickness where a continuous variation of EOT and an increase on the degradation of the interface quality are observed (C) 2010 Elsevier Ltd All rights reserved

Safety and outcome of coronary interventions with special reference to anticoagulation and stent type

University of Turku, Faculty of Medicine, Department of Cardiology and Cardiovascular Medicine, Doctoral Programme of Clinical Investigation, Heart Center, Turku University Hospital, Turku, Finland Division of Internal Medicine, Department of Cardiology, Seinäjoki Central Hospital, Seinäjoki, Finland Heart Center, Satakunta Central Hospital, Pori, Finland Annales Universitatis Turkuensis Painosalama Oy, Turku, Finland 2015 Antithrombotic therapy during and after coronary procedures always entails the challenging establishment of a balance between bleeding and thrombotic complications. It has been generally recommended to patients on long-term warfarin therapy to discontinue warfarin a few days prior to elective coronary angiography or intervention to prevent bleeding complications. Bridging therapy with heparin is recommended for patients at an increased risk of thromboembolism who require the interruption of anticoagulation for elective surgery or an invasive procedure. In study I, consecutive patients on warfarin therapy referred for diagnostic coronary angiography were compared to control patients with a similar disease presentation without warfarin. The strategy of performing coronary angiography during uninterrupted therapeutic warfarin anticoagulation appeared to be a relatively safe alternative to bridging therapy, if the international normalized ratio level was not on a supratherapeutic level. In-stent restenosis remains an important reason for failure of long-term success after a percutaneous coronary intervention (PCI). Drug-eluting stents (DES) reduce the problem of restenosis inherent to bare metal stents (BMS). However, a longer delay in arterial healing may extend the risk of stent thrombosis (ST) far beyond 30 days after the DES implantation. Early discontinuation of antiplatelet therapy has been the most important predisposing factor for ST. In study II, patients on long-term oral anticoagulant (OAC) underwent DES or BMS stenting with a median of 3.5 years’follow-up. The selective use of DESs with a short triple therapy seemed to be safe in OAC patients, since late STs were rare even without long clopidogrel treatment. Major bleeding and cardiac events were common in this patient group irrespective of stent type. In order to help to predict the bleeding risk in patients on OAC, several different bleeding risk scorings have been developed. Risk scoring systems have also been used also in the setting of patients undergoing a PCI. In study III, the predictive value of an outpatient bleeding risk index (OBRI) to identify patients at high risk of bleeding was analysed. The bleeding risk seemed not to modify periprocedural or long-term treatment choices in patients on OAC after a percutaneous coronary intervention. Patients with a high OBRI often had major bleeding episodes, and the OBRI may be suitable for risk evaluation in this patient group. Optical coherence tomography (OCT) is a novel technology for imaging intravascular coronary arteries. OCT is a light-based imaging modality that enables a 12–18 µm tissue axial resolution to visualize plaques in the vessel, possible dissections and thrombi as well as, stent strut appositions and coverage, and to measure the vessel lumen and lesions. In study IV, 30 days after titanium-nitride-oxide (TITANOX)-coated stent implantation, the binary stent strut coverage was satisfactory and the prevalence of malapposed struts was low as evaluated by OCT. Long-term clinical events in patients treated with (TITANOX)-coated bio-active stents (BAS) and paclitaxel-eluting stents (PES) in routine clinical practice were examined in study V. At the 3-year follow-up, BAS resulted in better long-term outcome when compared with PES with an infrequent need for target vessel revascularization. Keywords: anticoagulation, restenosis, thrombosis, bleeding, optical coherence tomography, titanium

Vascular Healing after Coronary Stenting Evaluated by Optical Coherence Tomography

Optical coherence tomography (OCT) is a novel intracoronary imaging application for the assessment of native lesions and coronary stents. The purpose of this thesis was to evaluate the safety and feasibility of frequency-domain OCT (FD-OCT) based on experiences of the Satakunta Central Hospital (I). Early vascular healing was evaluated after implantation of endothelial progenitor cell capturing (II) and bio-active titanium-nitride-oxide coated stents (III) in two studies, each with 20 patients. Vascular healing was also compared after implantation of bio-active and everolimus-eluting stents on 28 patients after 9-month follow-up (IV). Long-term vascular healing of bio-active and paclitaxel-eluting stents was assessed in the last study with 18 patients (V). The results indicate that FD-OCT is safe and feasible (I). Both bio-active and endothelial progenitor cell capturing stents showed near-complete endothelialisation after one-month follow-up, which is desirable when prolonged dual anti-platelet therapy needs to be avoided after stenting (II and III). Endothelialisation of bio-active stents showed a predictable pattern at mid-term and long-term follow up (IV and V). Endothelialisation of everolimus-eluting stents was not complete at 9 months follow-up, which may suggest that interruption of dual antiplatelet therapy at this time point may not be safe (IV). Finally, delayed vascular healing may be present in patients treated with paclitaxel-eluting stents as long as 4 years from implantation, which reinforces the previously raised concerns on the long-term safety of this device (V).

Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

Preload Evaluation of Different Screws in External Hexagon Joint

Purpose: This study compared the maintenance of tightening torque in different retention screw types of implant-supported crowns.Materials and Methods: Twelve metallic crowns in UCLA abutments cast with cobalt-chromium alloy were attached to external hexagon osseointegrated implants with different retention screws: group A: titanium alloy retention screw; group B: gold alloy retention screw with gold coating; group C: titanium alloy retention screw with diamond-like carbon film coating; and group D: titanium alloy retention screw with aluminum titanium nitride coating. Three detorque measurements were obtained after torque insertion in each replica. Data were evaluated by analysis of variance (ANOVA), Tukey's test (P < 0.05), and t test (P < 0.05).Results: Detorque value reduced in all groups (P < 0.05). Group A retained the highest percentage of torque in comparison with the other groups (P < 0.05). Groups B and D retained the lowest percentage of torque without statistically significant difference between them (P < 0.05).Conclusions: All screw types exhibited reduction in the detorque value. The titanium screw maintained the highest percentage of torque whereas the gold-coated screw and the titanium screw with aluminum titanium nitride coating retained the lowest percentage. (Implant Dent 2012;21:46-50)

Turning of compacted graphite iron using commercial tiN coated Si 3N4 under dry machining conditions

Due to their high hardness and wear resistance Si3N4 based ceramics are one of the most suitable cutting tool materials for machining hardened materials. Therefore, their high degree of brittleness usually leads to inconsistent results and sudden catastrophic failures. Improvement of the functional properties these tools and reduction of the ecological threats may be accomplished by employing the technology of putting down hard coatings on tools in the state-of-the-art PVD processes, mostly by improvement of the tribological contact conditions in the cutting zone and by eliminating the cutting fluids. However in this paper was used a Si3N4 based cutting tool commercial with a layer TiN coating. In this investigation, the performance of TiN coating was assessed on turning used to machine an automotive grade compacted graphite iron. As part of the study were used to characterise the performance of cutting tool, flank wear, temperature and roughness. The results showed that the layer TiN coating failed to dry compacted graphite iron under aggressive machining conditions. However, using the measurement of flank wear technique, the average tool life of was increased by VC=160 m/min.The latter was also observed using a toolmakers microscope and scanning electron microscopy (SEM).

Redes neurais: aplicação no monitoramento da vida de ferramentas de corte

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Relação desgaste-acabamento superficial em ferramentas de metal duro com revestimento triplo no torneamento de aços

Pós-graduação em Engenharia Mecânica - FEG

Torque Stability of Different Abutment Screws Submitted to Mechanical Cycling

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)