MONITORED DEFORMATION BY POTENTIAL-INDUCED DEFECTS IN CH3(CH2)n−1SH SELF-ASSEMBLED MONOLAYERS ON GOLD: EIS STUDY OF CHAIN LENGTH EFFECT ON SUBDIFFUSION AND SAMs’ HETEROGENEITY

2019 ◽  
Vol 26 (10) ◽  
pp. 1950067 ◽  
Author(s):  
AHMED MOUGARI ◽  
MOKHTAR ZABAT ◽  
SMAIL BOUDJADAR

From the defects-free self-assembled organic layers (SAMs) of CH3([Formula: see text]SH molecules with short chain lengths ([Formula: see text]) electrodeposited on the (111) surface of monocrystalline gold previously prepared, monitored defects (pinholes) were potential-induced from cyclic partial reduction of SAMs at an appropriate potential. Electrochemical impedance measurements were in-situ conducted and [Fe(CN)6][Formula: see text] ions were used as probes for mass and charge transfer. Interface evolution was modeled with an equivalent electrical circuit containing two distinct constant-phase elements (CPEs). One is a generalized semi-infinite Warburg element in series with a charge transfer resistance attributed to subdiffusion phenomenon through leaky sublayers at low frequencies; the other CPE is used for characterizing the interface heterogeneity at medium and high frequencies. At low frequencies, electrochemical impedance measurements show subdiffusion phenomenon, which depends on the remaining sublayer and its thickness. When the defect density increases, diffusion tends to be ordinary, obeying the Fick’s law.

Author(s):  
Dora Zalka ◽  
Soma Vesztergom ◽  
Mária Ujvári ◽  
Gyözö Láng

<p class="PaperAbstract">Time dependence of the electrochemical impedance of an overoxidized glassy carbon|poly(3,4-ethylenedioxytiophene) (PEDOT)|0.1 mol·dm<sup>-3</sup> sulfuric acid (aq.) elec­trode has been investigated. To follow the changes occurring at the film/substrate interface after the overoxidation procedure, successive impedance measurements were carried out. Although the system is intrinsically nonstationary, the charge transfer resis­tance (R<sub>ct</sub>) cor<strong>­</strong>res<strong>­</strong>ponding to different time instants could be determined by using the so-called 4-dimensional analysis method. The same post-experimental mathematic­cal/ana­lytical procedure could be used also for the estimation of the charge transfer resistance corresponding to the time instant just after overoxidation of the PEDOT film. The increase of the charge transfer resistance of the overoxidized system with respect to that of the pristine electrode suggests that during overoxidation the electrochemical activity of the film decreases and the charge transfer process at the metal/film interface beco­mes more hindered. After the overoxidation procedure, when the electrode potential was held in the “stability region” (at E = 0.4 V vs. SSCE in the present case) the R<sub>ct</sub> decre­ased continuously with experiment time to a value somewhat higher than that of the pristine electrode.<strong> </strong>By comparing the properties of the GC|PEDOT|0.1 M H<sub>2</sub>SO<sub>4</sub> and the Au|PEDOT|0.1 M H<sub>2</sub>SO<sub>4</sub> electrodes a possible mechanistic explanation for the observed behavior has been proposed. This is based on the assumption that in the case of the GC|PEDOT|0.1 M H<sub>2</sub>SO<sub>4</sub> electrode two processes may occur simultaneously during the impedance measurements: (a) reduction of the oxidized surface of the GC substrate, including the reduction of the oxygen-containing surface functionalities and (b) read­sorption of the polymer chains (polymer chain ends) on the surface.<strong></strong></p>


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.


Metals ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 98
Author(s):  
Zheng Dong ◽  
Chuanqing Fu ◽  
Amir Poursaee

The present study investigated the galvanic effect between tensile-stressed and non-stressed carbon steels, in addition to the influence of the tensile stress on the passivation and corrosion behavior of steel in a simulated concrete pore solution. Three different levels of tensile stress, ranging from elastic to plastic stress on the surface, were applied by adjusting the displacement of C-shape carbon steel rings. Different electrochemical measurements including the open circuit potential (OCP), the electrochemical impedance spectroscopy (EIS), the zero-resistance ammetry (ZRA), and the cyclic polarization were performed. Based on the results of EIS, the tensile stress degraded the resistance of the oxide film in moderate frequencies while enhancing the charge transfer resistance in low frequencies during passivation. As corrosion propagated, the stressed steel yielded a similar charge transfer resistance to or an even lower charge transfer resistance than the non-stressed steel, especially in the case of plastic tensile stress. The galvanic effect between the tensile-stressed and non-stressed steels increased the chloride threshold value of the tensile-stressed steel, although the susceptibility to pitting corrosion was exhibited after being corroded.


Energies ◽  
2019 ◽  
Vol 12 (23) ◽  
pp. 4507 ◽  
Author(s):  
Yusuke Abe ◽  
Natsuki Hori ◽  
Seiji Kumagai

Lithium-ion batteries (LIBs) using a LiFePO4 cathode and graphite anode were assembled in coin cell form and subjected to 1000 charge-discharge cycles at 1, 2, and 5 C at 25 °C. The performance degradation of the LIB cells under different C-rates was analyzed by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy. The most severe degradation occurred at 2 C while degradation was mitigated at the highest C-rate of 5 C. EIS data of the equivalent circuit model provided information on the changes in the internal resistance. The charge-transfer resistance within all the cells increased after the cycle test, with the cell cycled at 2 C presenting the greatest increment in the charge-transfer resistance. Agglomerates were observed on the graphite anodes of the cells cycled at 2 and 5 C; these were more abundantly produced in the former cell. The lower degradation of the cell cycled at 5 C was attributed to the lowered capacity utilization of the anode. The larger cell voltage drop caused by the increased C-rate reduced the electrode potential variation allocated to the net electrochemical reactions, contributing to the charge-discharge specific capacity of the cells.


2020 ◽  
Vol 92 (6) ◽  
pp. 897-907 ◽  
Author(s):  
Ankita Bhat ◽  
Alexa R. Graham ◽  
Hemang Trivedi ◽  
Matthew K. Hogan ◽  
Philip J. Horner ◽  
...  

AbstractFollowing spinal cord injury, the use of electrodes for neurostimulation in animal models has been shown to stimulate muscle movement, however, the efficacy of such treatment is impaired by increased interfacial impedance caused by fibrous encapsulation of the electrode. Sputter-deposited gold-on-polyimide electrodes were modified by potentiostatic electrodeposition of poly(pyrrole-co-3-pyrrolylbutyrate-conj-aminoethylmethacrylate): sulfopropyl methacrylate [P(Py-co-PyBA-conj-AEMA):SPMA] to various charge densities (0–100 mC/cm2) to address interfacial impedance and coated with a phosphoryl choline containing bioactive hydrogel to address biocompatibility at the ABIO-BIO interface. Electrodes were characterized with scanning electron microscopy (surface morphology), multiple-scan rate cyclic voltammetry (peak current and electroactive area), and electrochemical impedance spectroscopy (charge transfer resistance and membrane resistance). SEM analysis and electroactive area calculations identified films fabricated with a charge density of 50 mC/cm2 as well suited for neurostimulation electrodes. Charge transfer resistance demonstrated a strong inverse correlation (−0.83) with charge density of electrodeposition. On average, the addition of polypyrrole and hydrogel to neurostimulation electrodes decreased charge transfer resistance by 82 %. These results support the use of interfacial engineering techniques to mitigate high interfacial impedance and combat the foreign body response towards epidurally implanted neurostimulation electrodes.


Soft Matter ◽  
2014 ◽  
Vol 10 (34) ◽  
pp. 6467-6476 ◽  
Author(s):  
Choonghyun Sung ◽  
Katelin Hearn ◽  
Jodie Lutkenhaus

Layer-by-layer assemblies exhibit increased conductivity and decreased charge transfer resistance upon heating through the thermal transition.


2020 ◽  
Vol 27 (09) ◽  
pp. 1950208
Author(s):  
K. A. KARTHICK ◽  
D. S. BHUVANESHWARI ◽  
D. UMAPATHI ◽  
PANDIAN BOTHI RAJA

Canthium parviflorum leaf extract (CPLE) was utilized for corrosion prevention against mild steel (MS) in 0.5[Formula: see text]mol[Formula: see text]L[Formula: see text] H2SO4 test medium. Standard corrosion measurement techniques (gravimetric and electrochemical) were employed for this purpose. Gravimetric tests clearly confirmed that the prepared CPLE efficiently performs as corrosion inhibitor. Potentiodynamic polarization measurements (PPM) and electrochemical impedance spectroscopy (EIS) measurements were performed in order to analyze the charge transfer process of CPLE. Polarization curves indicate that CPLE acts through mixed mode inhibition. Impedance study reveals that the CPLE additives enhances the charge transfer resistance values and conversely decreases values of double layer capacitance. Scanning electron microscopy (SEM), Ultraviolet-Visible (UV-Vis) spectroscopy analysis and Fourier-Transform Infrared spectroscopy (FTIR) were done to confirm the Fe-CPLE complex formation on MS. The effect of temperature reveals that the inhibition efficiency increases with decrease in temperature and increase in concentration of CPLE (maximum of 4[Formula: see text]mg[Formula: see text]L[Formula: see text]). The adsorption of CPLE shows that it obeys Langmuir’s isotherm model with free energy of adsorption, [Formula: see text][Formula: see text]kJ mol[Formula: see text]. A suitable adsorption model is also proposed.


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