Measurement of the double layer capacitance of aluminium samples by holographic interferometry

In the present investigation, holographic interferometry was utilized for the first time to measure the double layer capacitance of aluminium samples during the initial stage of anodization processes in an aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out chemically in different sulphuric acid concentrations (0.5–3.125% H₂S0₄) at room temperature. In the meantime, a method of holographic interferometry was used to measure the thickness of anodization (oxide film) of the aluminium samples in aqueous solutions. Along with the holographic measurement, a mathematical model was derived in order to correlate the double layer capacitance of the aluminium samples in solutions to the thickness of the oxide film of the aluminium samples which forms due to the chemical oxidation. The thickness of the oxide film of the aluminium samples was measured by real-time holographic interferometry. Consequently, holographic interferometry is found to be very useful for surface finish industries, especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film as well as the double layer capacitance of the aluminium samples can be determined in situ. In addition, a comparison was made between the obtained data of the double layer capacitance from the holographic measurements and the double layer capacitance data obtained from measurements of electrochemical impedance spectroscopy. The comparison indicates that there is good agreement between the data from both techniques.     

Measurement of the a.c. impedance of aluminium samples by holographic interferometry

In the present investigation, holographic interferometry was utilized for the first time to measure the alternating current (a.c.) impedance of aluminium samples during the initial stage of anodization processes in aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out chemically in different sulphuric acid concentrations (0.5–3.125% H₂SO₄) at room temperature. In the mean time, a method of holographic interferometric was used to measure the thickness of anodization (oxide film) of the aluminium samples in aqueous solutions. Along with the holographic measurement, a mathematical model was derived in order to correlate the a.c. impedance of the aluminium samples in solutions to the thickness of the oxide film of the aluminium samples which forms due to the chemical oxidation. The thickness of the oxide film of the aluminium samples was measured by the real-time holographic interferometry. Consequently, holographic interferometry is found very useful for surface finish industries especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film as well as the a.c. impedance of the aluminium samples can be determined in situ. In addition, a comparison was made between the a.c. impedance values obtained from the holographic interferometry measurements and from measurements of electrochemical impedance spectroscopy. The comparison indicates that there is good agreement between the data from both techniques.     

Interferometric Sensor for Electrochemical Studies of Metallic Alloys in Aqueuos Solution

In a previous study a mathematical model relating surface and bulk behaviors of metals in aqueous solution was developed. The model was established based on principles of holographic interferometry for measuring microsurface dissolution, i.e., mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e., corrosion current. In the present work, an interferometric sensor was built based on the above model, and the corrosion current density of coated copper and brass in seawater were obtained using this sensor. The interferometric sensor was also utilized for the first time to measure the initial stage of the anodization process (oxidation) of aluminium samples in aqueous solution. This was carried out chemically in different acid concentrations (3.125–25% H₂SO₄) at room temperature. The sensor was further used for observation of catalytic activities, i.e., pitting corrosion, which occurred subsequent to the anodization of the aluminium samples in aqueous solutions, after an oxide film had been formed.     

DL capacitance-emission spectroscopy of determining the electrochemical behavior of anodized aluminum in aqueous solutions

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the double layer (DL) capacitance of aluminum samples during the initial stage of anodization processes in aqueous solution without any physical contact. In fact, because the DL capacitance values in this investigation were obtained by holographic interferometry, electromagnetic method rather than electronic method, the abrupt rate change of the DL capacitance was called DL capacitance-emission spectroscopy. The anodization process (oxidation) of the aluminum samples was carried out chemically in different sulfuric acid concentrations (0.5-3.125% H₂SO₄) at room temperature. In the mean time, the real-time holographic interferometry was used to determine the difference of the DL capacitance of two subsequent values, dC, as a function of the elapsed time of the experiment for the aluminum samples in 0.5%, 1.0%, 1.5%, and 3.125% H₂SO₄ solutions. The DL capacitance-emission spectra of the present investigation represent a detailed picture of not only the rate change of the DL capacitance throughout the anodization processes, but also, the spectra represent the rate change of the growth of the oxide films on the aluminum samples in different solutions. Consequently, holographic interferometry is found very useful for surface-finish industries especially for monitoring the early stage of anodization processes of metals, in which the rate change of DL capacitance of the aluminum samples can be determined in situ.     

Measurement of surface resistivity and surface conductivity of anodised aluminium by optical interferometry techniques

Optical interferometry techniques were used for the first time to measure the surface resistivity and surface conductivity of anodised aluminium samples in aqueous solution, without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out in different sulphuric acid solutions (1.0–2.5% H₂SO₄), by the technique of electrochemical impedance spectroscopy (EIS), at room temperature. In the mean time, the real-time holographic interferometric was carried out to measure the thickness of anodised (oxide) film of the aluminium samples during the anodization process. Then, the alternating current (AC) impedance (resistance) of the anodised aluminium samples was determined by the technique of electrochemical impedance spectroscopy (EIS) in different sulphuric acid solutions (1.0–2.5% H₂SO₄) at room temperature. In addition, a mathematical model was derived in order to correlate between the AC impedance (resistance) and to the surface (orthogonal) displacement of the samples in solutions. In other words, a proportionality constant (surface resistivity or surface conductivity=1/surface resistivity) between the determined AC impedance (by EIS technique) and the orthogonal displacement (by the optical interferometry techniques) was obtained. Consequently the surface resistivity (ρ) and surface conductivity (σ) of the aluminium samples in solutions were obtained. Also, electrical resistivity values (ρ) from other source were used for comparison sake with the calculated values of this investigation. This study revealed that the measured values of the resistivity for the anodised aluminium samples were 2.8×10⁹, 7×10¹², 2.5×10¹³, and 1.4×10¹²  Ω cm in 1.0%, 1.5%, 2.0%, and 2.5% H₂SO₄ solutions, respectively. In fact, the determined value range of the resistivity is in a good agreement with the one found in literature for the aluminium oxide, 85% Al₂O₃ (5×10¹⁰ Ω cm in air at temperature 30 °C), 96% Al₂O₃ (1×10¹⁴  Ω cm in air at temperature 30 °C), and 99.7% Al₂O₃ (>1×10¹⁴ Ω cm in air at temperature 30 °C).     

Characterization of native and anodic oxide films formed on commercial pure titanium using electrochemical properties and morphology techniques

Potentiostatically anodized oxide films on the surface of commercial pure titanium (cp-Ti) formed in sulfuric (0.5 M H₂SO₄) and in phosphoric (1.4 M H₃PO₄) acid solutions under variables anodizing voltages were investigated and compared with the native oxide film. Potentiodynamic polarization and electrochemical impedance spectroscopy, EIS, were used to predicate the different in corrosion behavior of the oxide film samples. Scanning electron microscope, SEM, and electron diffraction X-ray analysis, EDX, were used to investigate the difference in the morphology between different types of oxide films. The electrochemical characteristics were examined in phosphate saline buffer solution, PSB (pH 7.4) at 25 °C. Results have been shown that the nature of the native oxide film is thin and amorphous, while the process of anodization of Ti in both acid solutions plays an important role in changing the properties of passive oxide films. Significant increase in the corrosion resistance of the anodized surface film was recorded after 3 h of electrode immersion in PSB. On the other side, the coverage (θ) of film formed on cp-Ti was differed by changing the anodized acid solution. Impedance results showed that both the native film and anodized film formed on cp-Ti consist of two layers. The resistance of the anodized film has reached to the highest value by anodization of cp-Ti in H₃PO₄ and the inner layer in the anodized film formed in both acid solutions is also porous.     

Evaluation of corrosion in electrochemical systems using Michelson interferometry

This work presents the performance of a simple Michelson interferometric configuration, allowing monitoring and evaluation of corrosion and oxide layer growth in aluminium during aqueous corrosion processes in a distilled water solution, without any physical contact with the sample. This alternative experimental arrangement introduces a simpler alignment compared with a preliminary proposal [Habib K. In situ measurement of oxide film growth on aluminium samples by holographic interferometry. Corrosion Sci 2001; 43, 449–55], and the obtained interferograms offer a qualitative and possibly quantitative evaluation of an important physical parameter related to the corrosion process kinetics. Interferograms were obtained as a function of time to register changes related to the corrosion dynamics and oxide growth process. Experimental results correlate with the well-known corrosion process taking place over the aluminium sample under these experimental conditions.     

Characterization of electrodeposited Bi2S3 thin films by holographic interferometry

Optical non destructive evaluation methods, using lasers as the object illumination source, include holographic interferometry. It is widely used to measure stress, strain, and vibration in engineering structures. Double exposure holographic interferometry (DEHI) technique is used to determine thickness and stress of electrodeposited bismuth trisulphide (Bi₂S₃) thin films for various deposition times. The same is tested for other concentration of the precursors. It is observed that, increase in deposition time, increases thickness of thin film but decreases stress to the substrate. The structural, optical and surface wettability properties of the as deposited films have been studied using X-ray diffraction (XRD), optical absorption and contact angle measurement, respectively. The X-ray diffraction study reveals that the films are polycrystalline with orthorhombic crystal structure. Optical absorption study shows the presence of direct transition with band bap 1.78 eV. The water contact angle measurement shows hydrophobic nature of Bi₂S₃ thin film surface.     

Charge transport in activated carbon electrodes: the behaviour of three electrolytes vis-à-vis their specific conductance

In this study, the electrochemical performances of different aqueous electrolytes (6 M KOH, 2 M KCl and 0.5 M K₂SO₄) in activated carbon electrodes are evaluated with regard to their use in electrochemical double layer capacitor (EDLC). The results from cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) were analysed. The lowest value of equivalent series resistance (ESR) and the highest values of specific capacitance and coulombic efficiency were observed, when KOH was the electrolyte. The impedance spectroscopy plots were fitted to an equivalent circuit of ladder type to evaluate the resistances to ion transport at different levels of hierarchies in the pore network. Also, the quality of the double layer capacitance at lower hierarchy that primarily contributes to the overall capacitance of the device was evaluated from the leakage resistance in the equivalent circuit. The fitted circuit parameters were further reviewed vis-à-vis the specific conductance of chosen electrolyte, and the number of successive charge–discharge cycles prior to the EIS measurements.     

Pseudo-capacitive properties of LiCoO<Subscript>2</Subscript>/AC electrochemical capacitor in various aqueous electrolytes

LiCoO₂ particles were synthesized by a sol-gel process. X-ray diffraction analysis reveals that the prepared sample is a single phase with layered structure. A hybrid electrochemical capacitor was fabricated with LiCoO₂ as a positive electrode and activated carbon (AC) as a negative electrode in various aqueous electrolytes. Pseudo-capacitive properties of the LiCoO₂/AC electrochemical capacitor were determined by cyclic voltammetry, charge–discharge test, and electrochemical impedance measurement. The charge storage mechanism of the LiCoO₂-positive electrode in aqueous electrolyte was discussed, too. The results showed that the potential range, scan rate, species of aqueous electrolyte, and current density had great effect on capacitive properties of the hybrid capacitor. In the potential range of 0–1.4 V, it delivered a discharge specific capacitance of 45.9 Fg^–1 (based on the active mass of the two electrodes) at a current density of 100 mAg^–1 in 1 molL^–1 Li₂SO₄ aqueous electrolyte. The specific capacitance remained 41.7 Fg^–1 after 600 cycles.     

Improvement of corrosion resistance of NiTi sputtered thin films by anodization

Anodization of sputtered NiTi thin films has been studied in 1 M acetic acid at 23 °C for different voltages from 2 to 10 V. The morphology and cross-sectional structures of the untreated and anodized surfaces were investigated by field emission scanning electron microscopy (FE-SEM). The results show that increasing anodization voltage leads to film surface roughening and unevenness. It can be seen that the thickness of the anodized layer formed on the NiTi surface is in the nanometer range. The corrosion resistance of anodized thin films was studied by potentiodynamic scan (PDS) and impedance spectroscopy (EIS) techniques in Hank's solution at 310 K (37 °C). It was shown that the corrosion resistance of the anodized film surface improved with increasing voltage to 6 V. Anodization of austenitic sputtered NiTi thin films has also been studied, in the same anodizing conditions, at 4 V. Comparison of anodized sputtered NiTi thin films with anodized austenitic shape memory films illustrate that the former are more corrosion resistant than the latter after 1 h immersion in Hank's solution, which is attributed to the higher grain boundary density to quickly form a stable and protective passive ?lm.     

Holographic interferometry as electrochemical emission spectroscopy of carbon steel in seawater with low concentration of RA-41 corrosion inhibitor

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of carbon steel in blank seawater and with seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion test (EI) spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of RA-41 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which were obtained from the EI spectroscopy. Consequently, holographic interferometric is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

The effect of silicon substrate on thickness of SiO2 thin film analysed by spectral reflectometry and interferometry

Techniques of spectral reflectometry and interferometry are used for measuring small changes in thickness of SiO₂ thin film grown by thermal oxidation on different silicon substrates. A slightly dispersive Michelson interferometer with one of its mirrors replaced by a thin-film structure is used to measure the reflectance and interferometric phase of the thin-film structure at the same time. The experimental data are used to determine precisely the thickness of the SiO₂ thin film on silicon wafers of two crystallographic orientations and different dopant concentrations. We confirmed very good agreement between the experimental data and theory and revealed that the thin-film thickness, which varies with the type of silicon substrate, depends linearly on the wavelength at which minimum in the spectral reflectance occurs. Similar behaviour was revealed for the interferometric phase.     

Electrochemical characterization of Mn: Co3O4 thin films prepared by spray pyrolysis via aqueous route

Present investigation reports, spray pyrolytic deposition of Mn: Co₃O₄ thin films onto the stainless steel by spray pyrolysis, at the deposition temperature 573 ± 2 K via aqueous route. Prepared electrodes were characterized structurally and morphologically by means of XRD and SEM. Also optical and electrochemical characterizations were carried out in depth. Structural characterization confirms face centered cubic and tetragonal body centered crystal structures for Co₃O₄ and Mn₃O₄ respectively. The rough granular morphology is observed form SEM. Electrochemical study reveals the pseudo capacitive as well as double layer behavior with optimum specific capacitance 485.29 F/g at the scan rate 1 mV/s in 1 M KOH electrolyte. Specific energy, specific power and columbic efficiency were calculated using chronopotentiometric technique. Electrochemical impedance spectroscopy was carried out in the frequency range 1 mHz–1 MHz. Randles equivalent circuit parameters associated with the operative cell are reported.     

Studies on electrodeposited As2S3 thin films by double exposure holographic interferometry technique

Arsenic trisulphide (As₂S₃) thin films have been deposited onto stainless steel and fluorine doped tin oxide (FTO) coated glass substrates by electrodeposition technique using arsenic trioxide (As₂O₃) and sodium thiosulphate (Na₂S₂O₃) as precursors and ethylene diamine tetracetic acid (EDTA) as a complexing agent. Double exposure holographic interferometry (DEHI) technique was used to determine the thickness and stress of As₂S₃ thin films. It was observed that the thickness of the thin film increases whereas film stress to the substrate decreases with an increase in the deposition time. X-ray diffraction and water contact angle measurements showed polycrystalline and hydrophilic surface respectively. The bandgap energy increases from 1.82 to 2.45 eV with decrease in the film thickness from 2.2148 to 0.9492 μm.     

Acrylamide based proton conducting polymer gel electrolyte for electric double layer capacitors

A new class of polymer gel electrolyte (PGE) was synthesized using acrylamide as host polymer and LiClO₄ as dopant. The polymer gel was subjected to electrochemical AC impedance analysis and thermal analysis. The polymer has conductivity in the order of 10⁻³ S cm⁻¹ at ambient temperature. Thermogravimetric analysis (TGA) revealed the effect of dopant on host polymer matrix. A supercapacitor was fabricated using acrylamide based polymer gel electrolyte with activated carbon as electrode material and it was subjected to various electrochemical techniques like cyclic voltammetry, electrochemical AC impedance analysis and galvanostatic charge–discharge tests at various current densities. From cyclic voltammetry a specific capacitance of 28 F/g was obtained at a scan rate of 10 mV/s. The capacitor had good self-discharge behavior and good cycle life of more than 10,000 cycles. The coulombic efficiency was more than 95%. These results indicate that this acrylamide-based polymer gel electrolyte doped with LiClO₄ is a potential electrolyte for electric double-layer capacitors (EDLCs).     

Characterisation of passive films formed on low carbon steel in borate buffer solution (pH 9.2) by electrochemical impedance spectroscopy

The comprehension of passivity and its protective character against corrosion is closely connected with the electronic properties of passive films. Passive films formed anodically on carbon steel in borate/boric acid solution, pH 9.2, have been characterised by electrochemical impedance spectroscopy (EIS). Mott-Schottky plots and impedance measurements were made on films formed at different potentials and times. The investigation allowed the determination of the semiconductive properties of the films. The results of the capacitance response indicate that the passive films behave like highly doped n-type semiconductors, showing that the passive film properties are dominated by iron. The value of donors density (N_D) for the passive film is of the order of 10²¹ cm⁻³ and decreases with increasing formation time and potential, indicating that defects decrease with increasing film thickness. Based on the information about the physical phenomena, an equivalent circuit is proposed to fit the experimental data, leading to determination of anodic film capacitance and film resistance.     

由纳米管和纳米颗粒构成的TiO2膜的制备与机理研究

采用聚苯乙烯小球修饰Ti片表面,并进行阳极氧化,制备出一种由纳米颗粒和纳米管构成的TiO₂膜．通过数值模拟,分析了氧化表面附近的局部电场分布对TiO₂膜形貌的影响．结果表明,覆盖物增强了局部电场,从而加快了O^2-与Ti的反应速率,有利于TiO₂的生长;与此同时,[TiF₆]^6-的扩散受到阻碍,使得TiO₂的溶解速率减慢．可见,覆盖物打破了TiO₂纳米管形成的平衡条件,导致纳米颗粒的生成．此外,通过X射线衍射和Raman光谱的测试分析发现,所制备的TiO₂为锐钛矿结构.     

Optical corrosion meter

In a previous study, a mathematical model relating surface and bulk behaviours of metals in aqueous solution has been developed. The model was established based on principles of holographic interferometry for measuring microsurface dissolution, i.e. mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e. corrosion current. In the present work, an optical corrosion meter was built based on the above model. The corrosion meter consists of an electrochemical cell in which the sample is immersed in aqueous solution. Furthermore, the corrosion meter has a holographic camera with a thermoplastic film for in situ processing of holograms in order to obtain real-time holographic interferoms of the sample in the electrochemical cell. Results of the present work indicate that optical holography is a very useful technique for measuring the corrosion current density of different alloys in aqueous solutions. As a result, the corrosion current density of aluminium, stainless steel, and low-carbon steel in 1 M KCl, 1 M NaCl, and 1 M NaOH solutions were obtained. A comparison between the corrosion data of samples showed that the corrosion current density of the stainless steel in 1 M NaCl is nearly three-folds higher than that of the aluminium in 1 M KCl and the low-carbon steel in 1 M NaOH.     

Anodic oxide growth on Zr in neutral aqueous solution

Anodization and subsequent cathodic reactions on a thin-film sample of Zr were studied with in-situ neutron reflectometry (NR) and electrochemical impedance spectroscopy (EIS). The NR results during anodization showed the originally 485 Å thick Zr film generally behaved similar to a bulk electrode in neutral solution. The anodization ratio measured at applied potentials increased in steps of 0.5 V was somewhat higher than the value determined by coulometry, while the Pilling Bedworth ratio is in good agreement with published data. Thickening of the oxide layer, accelerated immediately after each potential increase, gradually decreased over several hours, but remained nonzero even after ～12 h. The thickened oxide eventually cracked when its thickness reached ～120 Å, causing loss of passivation. Surprisingly, neither the anodization ratio nor the Pilling Bedworth ratio showed any discontinuity at the time of oxide cracking, and the EIS behaviour remained qualitatively as before. This observation is taken as the evidence that the cracked and intact regions of the electrode behave more or less independently as parallel electrodes. When the potential was eventually switched to cathodic polarity, NR shows, as expected, that the effects of oxide cracking were irreversible. However, the electrode resistance recovered partially suggesting the cracks were rapidly plugged with newly formed oxide.