Energy dependence of methyl-radical adsorption on diamond (001)-(2×1) surface

The deposition of hyperthermal CH3 on diamond (001)-(2×1) surface at room temperature has been studied by means of molecular dynamics simulation using the many-body hydrocarbon potential. The energy threshold effect has been observed. That is, with fixed collision geometry, chemisorption can occur only when the incident energy of CH3 is above a critical value (Eth). Increasing the incident energy, dissociation of hydrogen atoms from the incident molecule was observed. The chemisorption probability of CH3 as a function of its incident energy was calculated and compared with that of C2H2. We found that below 10 eV, the chemisorption probability of C2H2 is much lower than that of CH3 on the same surface. The interesting thing is that it is even lower than that of CH3 on a hydrogen covered surface at the same impact energy. It indicates that the reactive CH3 molecule is the more important species than C2H2 in diamond synthesis at low energy, which is in good agreement with the experimental observation.

Sensitive methods for studying the environmental performance of protective coatings

The safe working lifetime of a structure in a corrosive or other harsh environment is frequently not limited by the material itself but rather by the integrity of the coating material. Advanced surface coatings are usually crosslinked organic polymers such as epoxies and polyurethanes which must not shrink, crack or degrade when exposed to environmental extremes. While standard test methods for environmental durability of coatings have been devised, the tests are structured more towards determining the end of life rather than in anticipation of degradation. We have been developing prognostic tools to anticipate coating failure by using a fundamental understanding of their degradation behaviour which, depending on the polymer structure, is mediated through hydrolytic or oxidation processes. Fourier transform infrared spectroscopy (FTIR) is a widely-used laboratory technique for the analysis of polymer degradation and with the development of portable FTIR spectrometers, new opportunities have arisen to measure polymer degradation non-destructively in the field. For IR reflectance sampling, both diffuse (scattered) and specular (direct) reflections can occur. The complexity in these spectra has provided interesting opportunities to study surface chemical and physical changes during paint curing, service abrasion and weathering, but has often required the use of advanced statistical analysis methods such as chemometrics to discern these changes. Results from our studies using this and related techniques and the technical challenges that have arisen will be presented.

Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip-based nanospray mass spectrometry

RATIONALE: Polymer-based surface coatings in outdoor applications experience accelerated degradation due to exposure to solar radiation, oxygen and atmospheric pollutants. These deleterious agents cause undesirable changes to the aesthetic and mechanical properties of the polymer, reducing its lifetime. The use of antioxidants such as hindered amine light stabilisers (HALS) retards these degradative processes; however, mechanisms for HALS action and polymer degradation are poorly understood. METHODS: Detection of the HALS TINUVINW123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) and the polymer degradation products directly from a polyester-based coil coating was achieved by liquid extraction surface analysis (LESA) coupled to a triple quadrupole QTRAPW 5500 mass spectrometer. The detection of TINUVINW123 and melamine was confirmed by the characteristic fragmentation pattern observed in LESA-MS/MS spectra that was identical to that reported for authentic samples. RESULTS: Analysis of an unstabilised coil coating by LESA-MS after exposure to 4 years of outdoor field testing revealed the presence of melamine (1,3,5-triazine-2,4,6-triamine) as a polymer degradation product at elevated levels. Changes to the physical appearance of the coil coating, including powder-like deposits on the coating's surface, were observed to coincide with melamine deposits and are indicative of the phenomenon known as polymer ' blooming'. CONCLUSIONS: For the first time, in situ detection of analytes from a thermoset polymer coating was accomplished without any sample preparation, providing advantages over traditional extraction-analysis approaches and some contemporary ambient MS methods. Detection of HALS and polymer degradation products such as melamine provides insight into the mechanisms by which degradation occurs and suggests LESA-MS is a powerful new tool for polymer analysis. Copyright (C) 2012 John Wiley & Sons, Ltd.

Plasma polymerization of 1,1,1-trichloroethane yields a coating with robust antibacterial surface properties

Novel, highly chlorinated surface coatings were produced via a one-step plasma polymerization (pp) of 1,1,1-trichloroethane (TCE), exhibiting excellent antimicrobial properties against the vigorously biofilm-forming bacterium Staphylococcus epidermidis.

Autocatalytic duplex Ni-P/Ni-W-P coatings on AZ31B magnesium alloy

Autocatalytic duplex Ni-P/Ni-W-P coatings were deposited on AZ31B magnesium alloy using stabilizer free nickel carbonate bath. Some of the coated specimens were passivated in chromate solution with and without heat treatment. Plain Ni-P coatings were also prepared for comparison. Coatings were characterized for their surface morphology, composition and corrosion resistance. Energy dispersive analysis of X-ray (EDX) showed that the phosphorous content in the Ni-P coating is 6 wt.% and for Ni-W-P it reduced to 3 wt.% due to the codeposition of tungsten in the Ni-P coating. Marginal increase in P and W contents was observed on passivated coupons along with Cr (0.18 wt.%) and O (2.8 wt.%) contents. Field emission scanning electron microscopy (FESEM) examination of these coating surfaces exhibited the nodular morphology. Chromate passivated surfaces showed the presence of uniformly distributed bright Ni particles along with nodules. Potenfiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies were carried out in deaerated 0.15 M NaCI solution to find out the corrosion resistance of the coatings. Among the coatings developed, duplex-heat treated-passivated (duplex-HIP) coatings showed lower corrosion current density (i(corr)) and higher polarization resistance (R-p) indicating the improved corrosion resistance. The charge transfer resistance (R-ct) value obtained for the duplex-HIP was about 170 times higher compared to that for Ni P coating. (c) 2013 Elsevier B.V. All rights reserved.

The influence of current density on the morphology and corrosion properties of MAO coatings on AZ31B magnesium alloy

Micro-arc oxidation (MAO) coatings were prepared on AZ31B magnesium alloy using alkaline silicate electrolyte at different current densities (0.026, 0.046 and 0.067 A/cm(2)). Field Emission Scanning Electron Microscopy (FESEM) analysis of the coating revealed an irregular porous structure with cracked morphology. Compositional analysis carried out for MAO coating showed the presence of almost an equal amount of Mg and 0 (34 wt.%) apart from other elements such as F, Si and AI. The cross-sectional FESEM images clearly portrayed that the MAO coating was dense along with the presence of very few fine pores. The surface roughness (R-a) of the coatings increased with an increase in the current density. Potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies were carried out for both the bare and MAO coated AZ31B Mg alloy in 3.5% NaCl solution. The corrosion potential (E-corr) and corrosion current density (i(corr)) values obtained for the bare substrate were -1.49 V and 46 mu A/cm(2), respectively. The coating prepared at 0.046 A/cm(2) exhibited the lowest i(corr) value of 7.79 x 10(-10) A/cm(2) and highest polarization resistance (41.6 M Omega cm(2)) attesting to the better corrosion resistance of the coating compared to other samples. EIS results also indicated almost similar corrosion behavior for the MAO coatings. Mott-Schottky analysis showed n-type and p-type semiconductor behavior for the oxide layer present on the bare magnesium alloy and MAO coatings respectively. (C) 2016 Published by Elsevier B.V.

Effect of current density on the microstructure and corrosion properties of plasma electrolytic oxidation (PEO) coatings on AM50 Mg alloy produced in an electrolyte containing clay additives

Plasma electrolytic oxidation coatings were produced on AM50 Mg alloy in alkaline phosphate based electrolyte with montmorillonite clay additives employing current densities of 30, 60, and 120 mA/cm(2). The effect of current density on the microstructure and corrosion properties of the coating was investigated. The clay additives got melted and reactively incorporated into the coating forming an amorphous phase, at all the current densities. However, the coating was predominantly amorphous only at 30 mA/cm(2) and with increasing current density, increasing fractions of crystalline phases were formed. Higher current densities resulted in increased thickness of the coating, but reduced the compactness of the coatings. Electrochemical impedance spectroscopy tests in 0.5 wt.% (0.08 M) and 3.5 wt.% (0.6 M) NaCl solution revealed that the coatings processed at 30 mA/cm(2) exhibited a relatively better initial corrosion resistance owing to its relatively defect-free barrier layer and compactness of the coating. However, the presence of amorphous phases in significant amounts and lack of MgO in the coating resulted in increased rate of dissolution of the coatings and degradation of corrosion resistance. Coatings produced at higher current densities exhibited initial inferior corrosion resistance due to a more defective barrier layer and increased porosity in pore band and outer porous layer. However, the increased amount of crystalline phases and an increased amount of MgO, which resisted dissolution, counterbalanced the negative effects of defective barrier and increased porosity resulting in a relatively lower rate of the degradation of the corrosion resistance. Thus, the corrosion resistance of all the coatings continuously decreased with time and became similar after prolonged immersion in NaCl solution. Increasing current density, therefore, did not prove to be beneficial for the improvement of the corrosion performance of the PEO coatings. (C) 2016 Elsevier B.V. All rights reserved.

In Situ Synthesis Of Nanocrystalline Intermetallic Layer During Surface Plastic Deformation Of Zirconium

By means of a surface plastic deformation method a nanocrystalline (NC) intermetallic compound was in situ synthesized on the surface layer of bulk zirconium (Zr). Hardened steel shots (composition: 1.0C, 1.5Cr, base Fe in wt.%) were used to conduct repetitive and multidirectional peening on the surface layer of Zr. The microstructure evolution of the surface layer was investigated by X-ray diffraction and scanning and transmission electron microscopy observations. The NC intermetallic layer of about 25 gm thick was observed and confirmed by concentration profiles of Zr, Fe and Cr, and was found to consist of the Fe100-xCrx compound with an average grain size of 22 nm. The NC surface layer exhibited an extremely high average hardness of 10.2 GPa. The Zr base immediately next to the compound/Zr interface has a grain size of similar to 250 nm, and a hardness of similar to 3.4 GPa. The Fe100-xCrx layer was found to securely adhere to the Zr base. (c) 2007 Elsevier B.V All rights reserved.

Growth Mechanism And Corrosion Behavior Of Ceramic Coatings On Aluminum Produced By Autocontrol Ac Pulse Peo

Ceramic coatings are produced on aluminum alloy by autocontrol AC pulse Plasma Electrolytic Oxidation (PEO) with stabilized average current. Transient signal gathering system is used to study the current, voltage, and the transient wave during the PEO process. SEM, OM, XRD and EDS are used to study the coatings evolution of morphologies, composition and structure. TEM is used to study the micro profile of the outer looser layer and inner compact layer. Polarization test is used to study the corrosion property of PEO coatings in NaCl solution. According to the test results, AC pulse PEO process can be divided into four stages with different aspects of discharge phenomena, voltage and current. The growth mechanism of AC PEO coating is characterized as anodic reaction and discharge sintering effect. PEO coating can increase the corrosion resistance of aluminum alloy by one order or two; however, too long process time is not necessarily needed to increase the corrosion resistance. In condition of this paper, PEO coating at 60 min is the most protective coating for aluminum alloy substrate. (C) 2008 Elsevier B.V. All fights reserved.

Interface Fracture Property Of Peo Ceramic Coatings On Aluminum Alloy

This paper combines the four-point bending test, SEM and finite element method to study the interface fracture property of PEO coatings on aluminum alloy. The interface failure mode of the coating on the compression side is revealed. The ceramic coating crack firstly along the 45 degrees to the interface, then the micro crack in the coating deduces the interface crack. The plastic deformation observed by SEM shows excellent adhesion property between the coating and substrate. The plastic deformation in the substrate is due to the interfacial crack extension, so the interface crack mode of PEO coatings is ductile crack. The results of FEM show that the compression strength is about 600 MPa. (C) 2008 Elsevier B.V. All rights reserved.

On The Thermally Induced Cracking Of A Segmented Coating Deposited On The Outer Surface Of A Hollow Cylinder

In this work, the thermally induced cracking behavior of a segmented coating has been investigated. The geometry under consideration is a hollow cylinder with a segmented coating deposited onto its outer surface. The segmentation cracks are modeled as a periodic array of axial edge cracks. The finite element method is utilized to obtain the solution of the multiple crack problem and the Thermal Stress Intensity Factors (TSIFs) are calculated. Based on dimensional analysis, the main parameters affecting TSIFs are identified. It has been found that the TSIF is a monotonically increasing function of segmentation crack spacing. This result confirms that a segmented coating exhibits much higher thermal shock resistance than an intact counterpart, if only the segmentation crack spacing is narrow enough. The dependence of TSIF on some other parameters, such as normalized time, segmentation crack depth, convection severity as well as material constants, has also been discussed. (C) 2008 Elsevier B.V. All rights reserved.

Thermal analysis of microstructural evolution of Al2O3 surface modified layers

Solidification behavior and microstructural evolution of surface modified layers in plasma cladding technique are studied via numerical simulations. Both the coupling effect of temperature and solid volume fraction are considered in the proposed thermal analytical model, by which the transient temperature distributions are calculated and the shape of melting pool is determined. Furthermore, we perform microscopic thermal analysis on the nucleation and growth behaviors of ceramic hardening phases and dendrites, as well as the kinetics of related two-phase flow systems. By comparing with experimental observations, the evolution mechanisms of the morphology of Al2O3 ceramic hardening layer are explained. Based on the above results, a relationship among the scanning velocity of plasma stream, dendritic growth rate and the advancing speed of solid/liquid interface is found, and an energy criterion is proposed for predicting the pushing/engulfing transition of ceramic particles by grain growth fronts. (C) 2009 Elsevier B.V. All rights reserved.

Sputtering induced by highly charged Pb-208(q+) bombardment on Al surface

Highly charged ions (HCls) carrying high Coulomb potential energy (E-p) could cause great changes in the physical and chemical properties of material surface when they bombard on the solid surface. In our work, the secondary ion yield dependence on highly charged Pbq+ (q = 4-36) bombardment on Al surface has been investigated. Aluminum films (99.99%) covered with a natural oxide film was chosen as our target and the kinetic energy (E-k) was varied between 80 keV and 400 keV. The yield with different incident angles could be described well by the equation developed by us. The equation consists of two parts due to the kinetic sputtering and potential sputtering. The physical interpretations of the coefficients in the said equation are discussed. Also the results on the kinetic sputtering produced by the nuclear energy loss on target Surface are presented.