Electrochemical determination of sulfite and phenol using a carbon paste electrode modified with ionic liquids and graphene nanosheets: Application to determination of sulfite and phenol in real samples

Benzoylferrocene was used to construct a modified-graphene paste electrode. Also, hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) was used as a binder to prepare the modified electrode. The electro-oxidation of sulfite at the surface of the modified electrode was studied using electrochemical approaches. This modified electrode offers a considerable improvement in voltammetric sensitivity toward sulfite, compared to the bare electrode. Square wave voltammetry (SWV) exhibits a linear dynamic range from 5.0 × 10⁻⁸ to 2.5 × 10⁻⁴ M and a detection limit of 20.0 nM for sulfite. The diffusion coefficient and kinetic parameters (such as electron transfer coefficient and the heterogeneous rate constant) for sulfite oxidation were also determined. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of sulfite and phenol that makes it suitable for the detection of sulfite in the presence of phenol in real samples.     

Electrocatalytic determination of captopril using a modified carbon nanotube paste electrode: Application to determination of captopril in pharmaceutical and biological samples

A carbon paste electrode modified with carbon nanotube and benzoylferrocene (BF) was fabricated. The electrochemical study of the modified electrode, as well as its efficiency for electrocatalytic oxidation of captopril (CAP), was described. The electrode was employed to study the electrocatalytic oxidation of CAP, using cyclic voltammetry (CV), chronoamperometry (CHA) and square wave voltammetry (SWV) as diagnostic techniques. It has been found that the oxidation of CAP at the surface of modified electrode occurs at a potential of about 85 mV less positive than that of an unmodified CPE. SWV exhibits a linear dynamic range from 1.0 × 10⁻⁷ to 3.5 × 10⁻⁴ M and a detection limit of 3.0 × 10⁻⁸ M for CAP. Finally the modified electrode was used for determination of CAP in CAP tablet and urine sample.     

The design of polyaniline based sensor for the qualitative estimation of malonaldehyde

The detection of contaminated food in every stage of processing required new technology for fast identification and isolation of toxicity in food. Since effect of food contaminant are severe to human health, the need of pioneer technologies also increasing over last few decades. In the current study, MDA was prepared by hydrolysis of 1,1,3,3-tetramethoxypropane in HCl media and used in the electrochemical studies. The electrochemical sensor was fabricated with modified glassy carbon electrode with polyaniline. These sensors were used for detection of sodium salt of malonaldehyde and observed that a high sensitivity in the concentration range ∼1 × 10⁻¹ M and 1 × 10⁻² M. Tafel plots show the variation of over potential from − 1.73 V to − 3.74 V up to 10⁻⁵ mol/L indicating the lower limit of detection of the system.     

Determination of haloperidol drug in ampoules and in urine samples using a potentiometric modified carbon paste electrode

A modified carbon paste electrode for haloperidol drug based on haloperidol-phosphomolybdate (HP-PM) as an ion-exchanger dissolved in plasticizer DBP and its potentiometric characteristics were discussed. The electrode exhibited a good Nernstian slope of 56.9 ± 0.3 mV/decade with a linear concentration range from 3.2 × 10⁻⁶ to 1.0 × 10⁻² M for the haloperidol ion. The limit of detection (LOD) was 1.5 × 10⁻⁶ M. It had response time of 5–8 seconds (s), useable in pH range of 6.2–8.6 and temperature of 20–60 °C. The electrode shows clear discrimination of haloperidol drug from several inorganic ions, sugars and some common drug excipients. The sensor was applied for determination of haloperidol drug in urine and in pharmaceutical formulations using potentiometric determination, standard addition and the calibration curve methods. The results are satisfactory with excellent percentage recovery comparable or better than those obtained by other routine methods.     

Development of a simple ‘temperature versus sliding speed’ wear map for the sliding wear behaviour of dissimilar metallic interfaces

The variation in wear behaviour during limited debris retention sliding wear of Nimonic 80A versus Stellite 6 (counterface) between room temperature and 750 °C, at sliding speeds of 0.314, 0.654 and 0.905 m s⁻¹, was investigated. At 0.314 m s⁻¹, mild oxidational wear was observed at all temperatures, due to transfer and oxidation of Stellite 6-sourced debris to the Nimonic 80A and resultant separation of the Nimonic 80A and Stellite 6 wear surfaces. Between room temperature and 450 °C, this debris mostly remained in the form of loose particles (with only limited compaction), whilst between 510 and 750 °C, the particles were compacted and sintered together to form a wear protective ‘glaze’ layer.At 0.654 and 0.905 m s⁻¹, mild oxidational wear due to transfer and oxidation of Stellite 6-sourced debris was only observed at room temperature and 270 °C (also 390 °C at 0.654 m s⁻¹). At 390 °C (450 °C at 0.654 m s⁻¹) and above, this oxide was completely absent and ‘metal-to-metal’ contact resulted in an intermediate temperature severe wear regime—losses in the form of ejected metallic debris were sourced almost completely from the Nimonic 80A. Oxide debris, this time sourced from the Nimonic 80A sample, did not reappear until 570 °C (630 °C at 0.654 m s⁻¹), however, were insufficient to eliminate completely severe wear until 690 and 750 °C. At both 0.654 and 0.905 m s⁻¹, the oxide now preventing severe wear at 690 and 750 °C tended not to form ‘glaze’ layers on the surface of the Nimonic 80A and instead supported continued high wear by abrasion. This abrasive action was attributed to the poor sintering characteristics of the Nimonic 80A-sourced oxide, in combination with the oxides’ increased mobility and decreased residency.The collected data were used to compose a simple wear map detailing the effects of sliding speed and temperature on the wear of Nimonic 80A slid against Stellite 6, at these speeds and temperatures of between room temperature and 750 °C.     

Studies of high temperature sliding wear of metallic dissimilar interfaces IV: Nimonic 80A versus Incoloy 800HT

Wear variations of Nimonic 80A slid against Incoloy 800HT between room temperature (RT) and 750 °C, and sliding speeds of 0.314 and 0.905 m s⁻¹ were investigated using a ‘reciprocating-block-on-cylinder’, low debris retention configuration. These were considered alongside previous observations at 0.654 m s⁻¹.Different wear types occurring were mapped, including high transfer ‘severe wear’ (RT and 270 °C, also 0.905 m s⁻¹ at ≤570°C), low transfer ‘severe wear’ (0.314 m s⁻¹ at 390 °C to 510 °C oxide abrasion assisted at 510 °C), and ‘mild wear’ (0.314 m s⁻¹ at ≥570 °C; 0.905 m s⁻¹ at ≥630 °C). Wear surfaces at 750 °C were cross-sectioned and profiled.     

Effect of SiC particles on the friction and wear behavior of Ti3Si(Al)C2-based composites

The non-lubricated, sliding friction and wear behavior of Ti₃Si(Al)C₂ and SiC-reinforced Ti₃Si(Al)C₂ composites against AISI 52100 bearing steel ball were investigated using a ball-on-flat, reciprocating tribometer at room temperature. The contact load was varied from 5 to 20 N. For monolithic Ti₃Si(Al)C₂, high friction coefficients between 0.61 and 0.90 and wear rates between 1.79 × 10⁻³ and 2.68 × 10⁻³ mm³ (N m)⁻¹ were measured. With increasing SiC content in the composites, both the friction coefficients and the wear rates were significantly decreased. The friction coefficients reduced to a value between 0.38 and 0.50, and the wear rates to between 2.64 × 10⁻⁴ and 1.93 × 10⁻⁵ mm³ (N m)⁻¹ when the SiC content ranged from 10 to 30 vol.%. The enhanced wear resistance of Ti₃Si(Al)C₂ is mainly attributed to the facts that the hard SiC particles inhibit the plastic deformation and fracture of the soft matrix, the oxide debris lubricate the counterpair, and the wear mode converts from adhesive wear to abrasive wear during dry sliding.     

A sensitive nanocomposite-based electrochemical sensor for voltammetric simultaneous determination of isoproterenol,acetaminophen and tryptophan

The electrooxidation of isoproterenol (ISPT), acetaminophen (AC) and tryptophan (Trp) and their mixture has been studied using an 8,9-dihydroxy-7-methyl-12H-benzothiazolo[2,3-b]quinazolin-12-one modified multiwall carbon nanotubes paste electrode (DMBQ-MCNTPE). The novel sensor exhibited potent and persistent electron mediating behavior followed by well separated oxidation peaks towards ISPT, AC and Trp with activation over-potential. The peak currents were linearly dependent on ISPT, AC and Trp concentrations using square wave voltammetry (SWV) method in the range of 0.04–400, 5.0–500, and 10.0–800 μmol L⁻¹, with detection limits of 0.009, 1.0, and 4.0 μmol L⁻¹, respectively. The modified electrode was used for the determination of ISPT, AC and Trp in biological and pharmaceutical samples.     

Nanocomposite polymer electrolyte based on rice starch/ionic liquid/TiO2 nanoparticles for solar cell application

Nanocomposite polymer electrolyte (NCPE) was prepared using solution cast technique. Rice starch (RS), lithium iodide (LiI), 1-methyl-3-propylimidazolium iodide (MPII) as ionic liquid and TiO₂ nanopowder (RS:LiI:MPII:TiO₂) were introduced to prepare the sample. The conductivity of 3.63 × 10⁻⁴ S/cm was achieved by introducing 30 wt.% of 1-methyl-3-propylimidazolium iodide (MPII) as ionic liquid and 2 wt.% of TiO₂. Temperature-dependent conductivity and dielectric behavior were analyzed in this work. Dye sensitized solar cell was fabricated using the nanocomposite film for this sample and analyzed.     

1-N-alkyl -3-methylimidazolium ionic liquids as neat lubricants and lubricant additives in steel–aluminium contacts

The influence of the alkyl chain length and of the anion on the lubricating ability has been studied for the room-temperature ionic liquids (IL) 1-n-alkyl-3-methylimidazolium X⁻ [X = PF₆; n = 6 (L-P106). X = BF₄; n = 2 (L102), 6 (L106), 8 (L108). X = CF₃SO₃; n = 2 (L-T102). X = (4-CH3C6H4SO3); n = 2 (L-To102)]. Neat IL have been used for AISI 52100 steel-ASTM 2011 aluminium contacts in pin-on-disk tests under variable sliding speed. While all IL give initial friction values lower than 0.15, real-time sharp friction increments related to tribochemical processes have been observed for L102 and L-P106, at room-temperature and at 100 °C. Electronic microscopy (SEM), energy dispersive (EDS) and X-ray photoelectron (XPS) spectroscopies show that wear scar surfaces are oxidized to Al₂O₃ and wear debris contain aluminium and iron (for L102) fluorides. For L-P106, the steel surface is covered with a P-containing tribolayer. A change of anion (L-T102; L-To102) reduces friction and wear, but the lowest values are obtained by increasing the alkyl chain length (L106; L108). When the more reactive L102 and L-P106 are used as 1 wt.% base oil additives at 25 °C, tribocorrosion processes are not observed and a friction reduction (69–75% for 1 wt.% L102) and a change from severe (10⁻³ mm³ m⁻¹) to mild wear (10⁻⁴ to 10⁻⁶ mm³ m⁻¹) is obtained with respect to the neat IL. 1 wt.% IL additives also show good lubricating performance at 100 °C.     

Measurement of seed spacing uniformity performance of a precision metering unit as function of the number of holes on vacuum plate

The objective of the study was to determine the seed spacing uniformity performance of a precision metering unit when vacuum plates with different number of holes were used. In order to meet this objective, the performances of vacuum plates with different number of holes were evaluated in the laboratory conditions by employing sticky belt tests and seed spacing values were measured computerized measurement system (CMS) for the cotton and corn seeds. Quality of feed index, multiple index, miss index as well as coefficient of precision (CP3) were considered as the performance indicators for precision seeding. The forward speed values were as selected as 1.0, 1.5 and 2.0 m s⁻¹ while vacuum plates with hole diameter of 3.5 mm for cotton and 4.5 mm for corn seeds were used. For both, cotton and corn seeds, five different vacuum plates (20, 26, 36, 52, and 72 holes) were considered in the experiments. In the experiments, vacuum pressure was applied at 6.3 kPa. Based on the findings in this work it appears that 1.0 and 1.5 m s⁻¹ of forward speed values were found to provide the highest performance levels for all vacuum plates. However such performance substantially decreased when forward speed increased to 2.0 m s⁻¹. In overall, the highest performance was determined when 26 and 36 holes were used for cotton and corn, respectively.     

Modified nanoporous carbon as a novel sorbent before solvent-based de-emulsification dispersive liquid–liquid microextraction for ultra-trace detection of cadmium by flame atomic absorption spectrophotometry

Combination of different extraction methods is an interesting work in the field of sample pretreatment. In the current study, for the first time, solid phase extraction combined with solvent-based de-emulsification dispersive liquid–liquid microextraction (SPE-SD-DLLME) was developed for preconcentration and trace detection of cadmium in water samples using flame atomic absorption spectrophotometry (FAAS). The adsorbed cadmium ions on prepared SPE (75 mL of aqueous solution) were eluted by optimized elution solvent and introduced to the second microextraction step. The effective variables of SPE including the pH of sample, flow rates, type, concentration and volume of the eluent and the effect of potentially interfering ions of the separation of cadmium were evaluated and optimized. Also, several factors that influence the SD-DLLME step such as pH, neocuproine concentration (the cadmium binding ligand), type of dispersed/de-emulsifier solvent, volume of disperser/de-emulsifier solvent and type and volume of extraction solvents were investigated. SPE-SD-DLLME provides a preconcentration factor of 165 for cadmium ions. Calibration plot was linear in the range of 0.1–50 μg L⁻¹ with correlation of determination (r²) of 0.988. The precision and limit of detection of proposed method were 5.1% (RSD%, n = 8) and 0.03 μg L⁻¹, respectively.     

Determination of the thermal conductivity of composted material

The objective of this study was to develop a reliable method for the determination of the thermal conductivity of composted material using the TP08 probe. Study was set out to determine whether the selection of a signal fragment used to establish thermal conductivity (λ), has a significant influence on the results. Also minimum number of measurements was determined for every phase of the composting process. No significant differences were reported between results, but certain changes in the value of λ were noted. In successive stages of the process, thermal conductivity of composted material were: 0.31 ± 0.09, 0.45 ± 0.14, 0.27 ± 0.03 and 0.37 ± 0.17 W m⁻¹ K⁻¹.     

AC conduction mechanism and battery discharge characteristics of (PVC/PEO) polyblend films complexed with potassium chloride

New K⁺ ion-conducting polymer blend electrolyte films based on amorphous polymer poly(vinyl chloride) (PVC) and semicrystalline polymer poly(ethylene oxide) (PEO) complexed with KCl salt were prepared using a solution-cast technique. The maximum value of ionic conductivity of a PVC/PEO:KCl (42.5:42.5:15) system is 8.29 × 10⁻⁶ S/cm at 303 K. The absorption edge was found at 4.30 eV for undoped film, while it was observed at 4.03 and 3.93 eV for 10 and 15 wt% KCl doped films, respectively. The direct band gaps for these pure and salt doped PVC/PEO films were found to 4.10, 3.86 and 3.74 eV, respectively, whereas the indirect band gaps were determined as 4.15, 3.72 and 3.64 eV. Transference number values showed that the charge transport in this electrolyte system is predominantly due to ions (t_ion = 0.97). The discharge capacity for PVC/PEO:KCl (42.5:42.5:15) polymer blend electrolyte system is 11 μA/h.     

A comparative study on the wear properties of coarse-grained Al6061 alloy and nanostructured Al6061–Al2O3 composites

Wear behavior of nanostructured Al6061 alloy and Al6061–Al₂O₃ nanocomposites produced by milling and hot consolidation were investigated. The samples were characterized by hardness test, pin-on-disk wear test, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Nanocomposites containing 3 vol% Al₂O₃ showed a maximum hardness of 235 HV and optimum wear rate of 4×10⁻³ mg/m. Increasing the amount of Al₂O₃ up to 5 vol% resulted in decrease in hardness values (∼112 HV) and a sharp rise in wear rate (∼18×10⁻³ mg/m).     

Adsorption effect of a cationic surfactant at carbon paste electrode as a sensitive sensor for study and detection of folic acid

The present study is the first report on the effect of cetyltrimethylammonium bromide (CTAB) on the electrochemical behavior of folic acid (FA) at the surface of carbon paste electrode (CPE) in real samples. The studies were performed by cyclic voltammetry (CV), chronocoulometry and differential pulse voltammetry (DPV). CTAB, with a hydrophobic C–H chain, could absorb at the CPE surface by hydrophobic interaction and then changed the electrode/solution interface, and eventually affects the electrochemical response of FA, confirming from the remarkable oxidation peak current enhancement. For investigation of the electrode properties, CV technique was used at the various scan rates. Electrochemical parameters including diffusion coefficient (D), electron transfer coefficient (α) and ionic exchanging current density (j_o) were determined for the FA at the surface of the electrode. Under optimized conditions, the proposed method showed acceptable analytical performances for FA in terms of linearity (over the concentration range from 0.01 to 1.5 and 1.5 to 10.0 μM), detection limit (2.89 nM), repeatability (1.37%) and stability (13% reduction in peak current after 60 days). After studying on the effect of probable interferences it was found that the method was free of the interferences. Finally, the proposed method was successfully applied for the determination of FA in real samples.     

Rapid and simultaneous determination of tetracycline and cefixime antibiotics by mean of gold nanoparticles-screen printed gold electrode and chemometrics tools

The screen-printed gold electrode (SPGE) modified with the formation of self-assembly monolayer (SAM) of cysteine (Cys) on gold-nanoparticles (Au_nano) was utilized for rapid and simultaneous determination of tetracycline and cefixime antibiotics by square wave voltammetry (SWV). Electrochemical investigation and characterization of the modified electrode was achieved using cyclic voltammetry (CV) and scanning electron microscopy (SEM). A principal component artificial neural network (PCANN) with three layer back-propagation network was utilized for the analysis of the voltammogram data. It is possible to simultaneously determine the tetracycline and cefixime concentrations in the ranges of 10⁻⁵ and 10⁻³ mol L⁻¹, under the optimum conditions. Moreover the SPGE-Au_nano-Cys biosensor together with chemometrics tools was successfully applied to the determination of tetracycline and cefixime in biological fluids, which may provide a promising alternative in routine biosensing applications.     

Electrochemical Impedance Spectroscopy: Insights for fretting corrosion experiments

Using Electrochemical Impedance Spectroscopy (EIS), in the tribocorrosion field, especially in fretting corrosion, is new. The key point of this work is using EIS. The influence of ionic strength (I_c) and a model protein, albumin, on passive layer behavior was studied. At cathodic applied potential, E=−400 mV(SCE), fretting leads to an increase of corrosion current, without albumin. The current drop increases with the ionic strength. With albumin of 20 g L⁻¹, I is constant whatever the ionic strength: albumin acts as a corrosion inhibitor. Thanks to EIS, the degradation of passive layer due to fretting-corrosion is assessed by the fall of Polarization Resistance (R_p) and exponent of constant phase element (n), and the rise of constant phase element (Q).     

Effect of carbide volume fraction on erosive wear behaviour of hardfacing cast irons

The present work reports the effect of carbide volume fraction on erosive wear behaviour of hardfacing cast irons. Five different grades of weld hardfacing cast irons were selected for the present investigation. The solid particle erosion experiments were carried out with blast furnace sinter, silica sand and alumina particles under mild (53–75 μm, 25 m s⁻¹), moderately severe (125–150 μm/100–150 μm, 50 m s⁻¹) and under severe erosion conditions (300–425 μm, 90 m s⁻¹) at impingement angles of 30 and 90°. The variation in erosion rate with carbide volume fraction was observed to be strong function of the erodent particle hardness, impingement angle and the impact velocity. Under mild erosion conditions, erosion rate decreased with increasing carbide volume fraction (CVF), whereas erosion rate increased with CVF under moderately severe erosion condition with alumina particles. With silica sand particles under moderately severe erosion conditions the beneficial effect of large volume fraction of carbides could only be observed at 30°, whereas at normal impact erosion rate increased with increasing CVF. The erosion rate showed power law relationship with ratio of hardness of erodent particle to that of the target material (H_e/H_t) and expressed as E=c(H_e/H_t)^p.With increasing severity of erosion conditions erosion rate showed stronger dependence on H_e/H_t as compared to those under mild and moderately severe erosion conditions. The mechanism of materials removal from the carbides involved Hertzian fracture with softer sinter particles, whereas harder alumina particles could plastically indent and cause gross fracture of the carbides.     

Silver nanoparticles/polymethacrylic acid (AgNPs/PMA) hybrid nanocomposites-modified electrodes for the electrochemical detection of nitrate ions

AgNPs/PMA hybrid nanocomposite materials with different Ag loadings have been synthesized using a simple chemical route assisted by UV irradiation. The hybrid composites were characterized by means of SEM and TEM, UV–vis spectroscopy and XPS. The as synthesized hybrid samples, composed of small Ag nanoparticles (AgNPs) embedded within the PMA (poly-methacrylic-acid) matrix, have been used to modify the working electrode of disposable screen printed carbon electrodes (SPCEs). It has been observed that hybrid composite with the lowest Ag loading forms dendritic silver structures on the surface of working electrode, whereas at higher loadings massive structures were formed. The electrocatalytic properties of the AgNPs/PMA/SPCEs were investigated toward the reduction of nitrate at neutral pH. Based on these modified electrodes, both voltammetric and amperometric sensors were developed for the electrochemical sensing of nitrate. Voltammetric sensor showed a wide linear range (0–20 mM) and high sensitivity (130 μA mM⁻¹ cm⁻²).