Surface Characterization Studies of Thiols as a Blocking Mechanism for Specific Adsorption for Application of Charge Selective Membrane Transport

Author(s):  
Damena D. Agonafer ◽  
Edward Chainani ◽  
Muhammed E. Oruc ◽  
Ki Sung Lee ◽  
Mark A. Shannon

This paper proposes the use of electrochemical impedance spectroscopy (EIS) to measure characteristics of gold (Au)-coated membranes and their inherent limitations. In this work, the fabrication of a membrane permeate flow cell is described with the aim of subsequently studying the transport of ions through conductive polycarbonate track etched membrane (PCTE) by interrogating the system using EIS and CV measurements. In particular, we would like to ascertain the voltage range that can be applied to the Au-coated membrane without getting a considerable faradaic activity; the difference between platinum and Au electrode; the effects of different electrolyte concentrations and various applied DC potentials. We extend our previous work done [1] by studying the differences of using a hrydroxyl and methyl terminated self assembled monolayer (SAM). We also extend the quality of the monolayer with respect to the amount of time in which the monolayer is grown. Finally, finding the voltage in which a ‘defect free’ monolayer transforms from insulative to ‘leaky’ behavior extends a detailed analysis of the critical voltage of an alkane thiol.

Author(s):  
Damena D. Agonafer ◽  
Edward Chainani ◽  
Muhammed E. Oruc ◽  
Ki Sung Lee ◽  
Mark A. Shannon

The electrochemical interfacial properties of a well-ordered self-assembled monolayer (SAM) of 1-undecanethiol (UDT) on evaporated gold surface have been investigated by electrochemical impedance spectroscopy (EIS) in electrolytes without a redox couple. Using a constant-phase element (CPE) series resistance model, prolonged incubation times (up to 120 h) show decreasing monolayer capacitance approaching the theoretical value for 1-undecanethiol. Using the CPE exponent α as a measure of ideality, it was found that the monolayer approaches an ideal dielectric (α = 0.992) under prolonged incubation, which is attributed to the reduction of pinholes and defects in the monolayer during coalescence and annealing of SAM chains. The SAMs behave as insulators until a critical potential, Vc, is exceeded in both cathodic and anodic regimes, where electrolyte ions are believed to penetrate the monolayers. Using a Randles circuit model for these cases, the variation of the capacitance and charge transfer resistance with applied dc potential shows decreased permeability to ionic species with prolonged incubation time. The EIS data show that UDT (methylene chain length n = 10), incubated for 120 h, forms a monolayer whose critical voltage range extends from −0.3 to 0.5 V versus Ag/AgCl, previously attained only for alkanethiol at n = 15. At low frequencies where ion diffusion occurs, almost pure capacitive phase (−89 deg) was attained with lengthy incubation.


Sensors ◽  
2021 ◽  
Vol 21 (6) ◽  
pp. 1929
Author(s):  
Alexander Rodríguez ◽  
Francisco Burgos-Flórez ◽  
José D. Posada ◽  
Eliana Cervera ◽  
Valtencir Zucolotto ◽  
...  

Neuronal damage secondary to traumatic brain injury (TBI) is a rapidly evolving condition, which requires therapeutic decisions based on the timely identification of clinical deterioration. Changes in S100B biomarker levels are associated with TBI severity and patient outcome. The S100B quantification is often difficult since standard immunoassays are time-consuming, costly, and require extensive expertise. A zero-length cross-linking approach on a cysteamine self-assembled monolayer (SAM) was performed to immobilize anti-S100B monoclonal antibodies onto both planar (AuEs) and interdigitated (AuIDEs) gold electrodes via carbonyl-bond. Surface characterization was performed by atomic force microscopy (AFM) and specular-reflectance FTIR for each functionalization step. Biosensor response was studied using the change in charge-transfer resistance (Rct) from electrochemical impedance spectroscopy (EIS) in potassium ferrocyanide, with [S100B] ranging 10–1000 pg/mL. A single-frequency analysis for capacitances was also performed in AuIDEs. Full factorial designs were applied to assess biosensor sensitivity, specificity, and limit-of-detection (LOD). Higher Rct values were found with increased S100B concentration in both platforms. LODs were 18 pg/mL(AuES) and 6 pg/mL(AuIDEs). AuIDEs provide a simpler manufacturing protocol, with reduced fabrication time and possibly costs, simpler electrochemical response analysis, and could be used for single-frequency analysis for monitoring capacitance changes related to S100B levels.


Electrochemical hydrogenation, lithiation and sodiation of the phases GdFe2–xMx and GdMn2–xMx (M=Mn, Co, Ni, Zn, and Mg) and the influence of doping components on electrochemical characteristics of electrode materials on their basis were studied using X-ray powder diffraction method, scanning electron microscopy, energy dispersive X-ray analysis, X-ray fluorescent spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Phase analysis showed a simple correspondence between unit cell parameters of the phases and atomic radii of doping elements. Electrode materials based on GdFe2 and GdMn2 doped with 2 at.% of Co, Ni and Mg demonstrated better hydrogen sorption properties than those doped with Mn and Zn. Corrosion resistance of the doped electrodes was also better than of the binary analogues (e.g. corrosion potential of the GdFe2-based electrode was –0.162 V whereas that of GdFe1.96Ni0.04 was –0.695 V). The capacity parameters were increased in the following ranges: Zn<Mn<Mg<Co<Ni and Zn<Fe<Mg<Co<Ni for GdFe2–xMx and GdMn2–xMx, respectively. After fifty cycles of charge/discharge, we observed the changes in surface morphology and composition of the electrode samples. In the structure of studied Laves type phases with MgCu2-type structure, the most suitable sites for hydrogen atoms are tetrahedral voids 8a. During lithiation and sodiation of the phases, the atoms of the M-component of the structure are replaced by the atoms of lithium, and the atoms of gadolinium are replaced by the atoms of sodium. This difference in interaction is due to the difference in atomic sizes of the atoms. No insertion of lithium or sodium into the structural voids of the phases was observed.


2021 ◽  
Author(s):  
Antonio Tannas

In order to replace hazardous molten lead baths in the heat treatment of carbon steel wire with environmentally friendly fluidized bed furnaces a better understanding is needed of their heat transfer rates. There has been considerable work done in examining heat transfer rates to large cylinders immersed in fluidized beds, and some on wire sized ones as well, but all previous studies have been conducted on static cylinders. In order to gain a deeper understanding of heat transfer rates to a moving wire immersed in a fluidized bed furnace an apparatus has been constructed to move a wire through a fluidized bed. The heat transfer rates were calculated using the difference in inlet and outlet temperatures, wire speed and the bed temperature. As predicted, correlations for static wire were found to under-predict heat transfer rates at higher wire speeds, so a new correlation was developed by modifying an existing one.


2021 ◽  
Vol 12 (5) ◽  
pp. 7075-7091

The extract of Fucus spiralis (FS) was tested as a corrosion inhibitor of carbon steel in a 1M HCl medium. The anti-corrosion properties were analyzed by gravimetric and electrochemical techniques such as potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). The surface characterization of carbon steel submerged in the optimal solution was carried out using UV-Visible, UV-Vis-NIR, and Optical microscopy analyses. Electrochemical and gravimetric results demonstrated that inhibitory efficiencies increase with increasing inhibitor concentration and the efficiency reaches 87% at a concentration of 0.5 g/L. According to Tafel extrapolated polarisation measurements, the FS also worked as a mixed-type corrosion inhibitor and changed the mechanism of anodic reactions. EIS analysis showed that a depressed capacitive loop dominates the Nyquist plot of impedance and enhances the polarization resistance (Rp) to 161.9 Ω cm2 with a reduction of the double layer capacity (Cdl) of carbon steel to 61.8 μF/cm2. This protection is assured by an adsorption mechanism based on the isothermal Langmuir adsorption model, which positively affects the thermodynamic parameters. UV-Visible, UV-Vis-NIR analyses exhibited that inhibitor decreases the iron oxides like hematite, Magnetite, and Goethite, Maghemite, Lepidocrocite, δ-FeOOH of the metal surface and delays the dissolution of the bare metal of iron to the ferrous ions, notably that optical morphology showed that FS extract decreases the aggressivity of HCl.


Author(s):  
I.V. Frolov ◽  
◽  
V.A. Sergeev ◽  
A.M. Hodakov ◽  
S.A. Zaytsev ◽  
...  

The paper presents the results of studies of changes in the characteristics of LED COB matrices of the GW P9LR31.EM - DURIS S 8 type as part of a LED luminaire when tested under the direct current in a continuous mode and in an electrocycling mode. The arrays consist of eight InGaN/GaN LED dies connected in series, coated with a phosphor. Calculation in the Comsol Multiphtsics environment of the temperature field of the luminaire at the rated operating current and free convection heat transfer showed that the maximum overheating of the matrices does not exceed 46 K, and the difference in their temperatures is 2 K. At the same time, the experimental values of the thermal resistances of the matrices of a real lamp vary from 42 to 58 K/W. Before testing, the I-V characteristics of the matrices differ markedly in the level of leakage current in the voltage range from 14 V to 19 V, and the LEDs in the luminaire matrices have a significant spread in the brightness of emission in the microcurrent mode. The degree of this scatter within each matrix was estimated by measuring the luminescence brightness of each die of the matrix and calculating the coefficient of variation γ. It was found that the coefficient of variation of the emission brightness of the COB matrix dies measured at a current of 100 nA strongly correlates with the leakage current. When testing a luminaire under the direct current, the most significant changes in the electrophysical and optical characteristics of COB matrices are observed in the range of microcurrents: the distribution of the emission brightness of the matrix dies at a current of 100 nA becomes more uniform. The greatest changes in matrix characteristics were observed after the first 700 hours of testing, that is, at the running-in stage. At the same time, no correlation was found between the degree of change in the characteristics of the matrices during tests and their thermal resistances.


2013 ◽  
Vol 833 ◽  
pp. 50-55 ◽  
Author(s):  
Lu Zheng ◽  
Liang Bin Liu ◽  
Xiao Jing Zhou ◽  
Yu Zhong Guo

Li (Ni1/3Co1/3Mn1/3) O2 cathode materials doped by Zn were synthesized by a co-precipitation routine, the first delithiation process of the samples with 0-4wt% of Zn doping were studied by electrochemical impedance spectroscopy (EIS) under the polarized voltage of 2.8-4.6V. The fitting results based on EIS data indicate that delithiation reactions happen within the voltage range of 3.7-4.4V ; The resistances of SEI film and charge transfer are both decreased significantly, whereas Li+ diffusion ability through layered crystalline lattice is improved largely with the increase of zinc doping from 0 to 4wt%.


MRS Bulletin ◽  
1999 ◽  
Vol 24 (2) ◽  
pp. 39-43 ◽  
Author(s):  
Daniel Josell ◽  
Frans Spaepen

It is generally recognized that the capillary forces associated with internal and external interfaces affect both the shapes of liquid-vapor surfaces and wetting of a solid by a liquid. It is less commonly understood that the same phenomenology often applies equally well to solid-solid or solid-vapor interfaces.The fundamental quantity governing capillary phenomena is the excess free energy associated with a unit area of interface. The microscopic origin of this excess free energy is often intuitively simple to understand: the atoms at a free surface have “missing bonds”; a grain boundary contains “holes” and hence does not have the optimal electronic density; an incoherent interface contains dislocations that cost strain energy; and the ordering of a liquid near a solid-liquid interface causes a lowering of the entropy and hence an increase in the free energy. In what follows we shall show how this fundamental quantity determines the shape of increasingly complex bodies: spheres, wires, thin films, and multilayers composed of liquids or solids. Crystal anisotropy is not considered here; all interfaces and surfaces are assumed isotropic.Consideration of the equilibrium of a spherical drop of radius R with surface free energy γ shows that pressure inside the droplet is higher than outside. The difference is given by the well-known Laplace equation:This result can be obtained by equating work done against internal and external pressure during an infinitesimal change of radius with the work of creating a new surface.


2014 ◽  
Vol 2014 ◽  
pp. 1-12 ◽  
Author(s):  
José I. López-Pérez ◽  
Edwin O. Ortiz-Quiles ◽  
Khaled Habiba ◽  
Mariel Jiménez-Rodríguez ◽  
Brad R. Weiner ◽  
...  

AlPO4 nanoparticles were synthesized via chemical deposition method and used for the surface modification of MoO2 to improve its structural stability and electrochemical performance. Structure and surface morphology of pristine and AlPO4-coated MoO2 anode material were characterized by electron microscopy imaging (SEM and TEM) and X-ray diffraction (XRD). AlPO4 nanoparticles were observed, covering the surface of MoO2. Surface analyses show that the synthesized AlPO4 is amorphous, and the surface modification with AlPO4 does not result in a distortion of the lattice structure of MoO2. The electrochemical properties of pristine and AlPO4-coated MoO2 were characterized in the voltage range of 0.01–2.5 V versus Li/Li+. Cyclic voltammetry studies indicate that the improvement in electrochemical performance of the AlPO4-coated anode material was attributed to the stabilization of the lattice structure during lithiation. Galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) studies reveal that the AlPO4 nanoparticle coating improves the rate capability and cycle stability and contributes toward decreasing surface layer and charge-transfer resistances. These results suggest that surface modification with AlPO4 nanoparticles suppresses the elimination of oxygen vacancies in the lattice structure during cycling, leading to a better rate performance and cycle life.


CORROSION ◽  
10.5006/2755 ◽  
2018 ◽  
Vol 74 (11) ◽  
pp. 1259-1271 ◽  
Author(s):  
Jalal Kangazian ◽  
Morteza Shamanian ◽  
Ali Ashrafi

Surface features of a dissimilar friction stir weld between Incoloy 825 Ni-based alloy and SAF 2507 super duplex stainless steel were investigated using scanning electron microscopy, microhardness test, cyclic potentiodynamic polarization, and electrochemical impedance spectroscopy. The surface of the weldment showed lower general corrosion resistance in comparison to the base metals. Areas under the weld shoulder exhibited weak pitting resistance because of the deformed structure and/or chromium nitride precipitates. Incoloy 825 located under the shoulder also displayed the highest susceptibility to pit growth because of the austenite matrix containing titanium nitride phases. Overall, the obtained results demonstrated that the friction stir welding method could significantly deteriorate the surface corrosion behavior of the processed regions.


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