Bis-isoxazolidines: A new class of corrosion inhibitors of mild steel in acidic media

Two new bis-isoxazolidines were synthesized in excellent yields via cycloaddition reaction of 1-pyrroline 1-oxide with 2,7-di(10-undecenyloxy)naphthalene and 1,4-di(10-undecenyloxy)benzene. One of the bis-isoxazolidines, on reaction with two equivalents of 1-bromododecane, afforded a bis-quaternary ammonium salt. All three inhibitor molecules in the presence of 400 ppm at 60 °C achieved inhibition efficiencies (IE) in the ranges 97-98% and 92-96% as determined by gravimetric method for corrosion of mild steel in 1 M HCl and 0.5 M H₂SO₄, respectively. The results obtained by the electrochemical methods using Tafel plots and electrochemical impedance spectroscopy corroborated the findings of the weightloss method. Both bis-isoxazolidines demonstrated remarkable efficiency in the lower range of inhibitor concentrations - in the presence of a meager 1.5 ppm of the inhibitor molecules, IEs of ∼70% in 1 M HCl were achieved. Thermodynamic parameters (, , ) for the adsorption process in the presence of the bis-isoxazolidines were determined. The values of around -90 kJ/mol in 1 M HCl and −50 kJ/mol in 0.5 M H₂SO₄, pointed towards the chemisorption of the inhibitor molecules, especially in HCl media. While the corrosion inhibition by these molecules was predominantly under cathodic control in 1 M HCl, the inhibition in 0.5 M H₂SO₄ was found to be under anodic control. The bis-isoxazolidines were found to provide a suitable inhibition mechanism for the corrosion inhibition in HCl as well as in H₂SO₄ media.     

Inhibitive effect of diethylcarbamazine on the corrosion of mild steel in hydrochloric acid

Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), weight loss measurements and atomic force microscopy techniques were used to investigate the inhibitory effect of diethylcarbamazine (DECM) on corrosion of mild steel in HCl solution. The inhibitor showed >90% inhibition efficiency at 5.01 × 10⁻⁴ M. Results obtained revealed that inhibition occurs through adsorption of inhibitor molecules on metal surface without modifying the mechanism of corrosion process. Potentiodynamic polarization studies suggested that it is a mixed type inhibitor, predominantly controls cathodic reaction. Activation parameters (E_a, ΔH and ΔS) and thermodynamic parameters (, and ) were calculated to investigate mechanism of inhibition.     

Inhibition of mild steel corrosion in acid solution by Pheniramine drug: Experimental and theoretical study

Inhibition of mild steel corrosion in 1 M HCl solution by Pheniramine drug was studied using weight loss, electrochemical impedance spectroscopy, linear polarization resistance, and potentiodynamic polarization measurements. The values of activation energy (E_a) and different thermodynamic parameters such as adsorption equilibrium constant (K_ads), free energy of adsorption , adsorption enthalpy and adsorption entropy were calculated and discussed. The adsorption process of studied drug on mild steel surface obeys the Langmuir adsorption isotherm. Potentiodynamic polarization measurements showed that Pheniramine is mixed-type inhibitor. Further, theoretical calculations were carried out and relations between computed parameters and experimental inhibition efficiency were discussed.     

Effect of Cefazolin on the corrosion of mild steel in HCl solution

The adsorption and inhibition effect of Cefazolin on mild steel in 1.0 M HCl at 308-338 K was studied by weight loss, EIS, potentiodynamic polarization and atomic force microscopy techniques. The results showed that inhibition efficiency increased with inhibitor concentration. The adsorption of Cefazolin on mild steel surface obeys the Langmuir adsorption isotherm equation. Both thermodynamic (enthalpy of adsorption , entropy of adsorption and free energy of adsorption ) and kinetic parameters (activation energy and pre-exponential factor A) were calculated and discussed. Polarization curves showed that Cefazolin acted as mixed-type inhibitor controls predominantly cathodic reaction.     

2,2′-Dithiobis(3-cyano-4,6-dimethylpyridine): A new class of acid corrosion inhibitors for mild steel

The title compound (PyS)₂ has been synthesized and its inhibiting action on the corrosion of mild steel in 1-5 M H₂SO₄ solutions at 35-50 °C has been investigated by polarization resistance (R_p), polarization curves and electrochemical impedance spectroscopy (EIS). (PyS)₂ showed excellent performance and its efficiency did not affect either by increasing the acid concentration or rise of temperature. Polarization curves indicated that (PyS)₂ behaves mainly as anodic inhibitor in 1 M H₂SO₄ solutions and as a mixed-type inhibitor in 3 and 5 M H₂SO₄ solutions at different temperatures. Adsorption of (PyS)₂ on the steel surface followed Temkin’s adsorption isotherm with a very high negative value of the free energy of adsorption . The activation parameters of the corrosion process were calculated. EIS showed that the charge transfer controls the corrosion process in the uninhibited and inhibited solutions.     

Electrochemical behavior of tin in sodium borate solutions and the effect of halide ions and some inorganic inhibitors

The corrosion of tin electrode in sodium borate (Na₂B₄O₇) solutions was investigated using cyclic voltammetry and potentiostatic current transient techniques. In absence of halide ions, the E/j response exhibits active/passive transition. The active region involves one anodic peak corresponding to the formation of Sn(OH)₂ and/or SnO. Addition of Cl⁻, Br⁻ or I⁻ (C ? 0.01 M) ions inhibits the active dissolution of tin, but higher concentrations enhance the active dissolution and tend to breakdown the passive film and induce pitting attack. The effect of , , and as inorganic inhibitors on the pitting corrosion of tin in (0.1 M Na₂B₄O₇ + 0.1 M NaCl) solution has also been studied. The presence of these anions (except ) inhibits pitting corrosion. Chronoamperometry measurements showed that nucleation of pit takes place after an incubation time (t_i). The rate of pit nucleation () increases with increasing halide ions concentration and applied potentials, but decreases with increasing the concentration of the inorganic inhibitors (except ). The inhibition efficiency of these inhibitors decreases in the order:

     

Corrosion of niobium in sulphuric and hydrochloric acid solutions at 75 and 95 °C

New Pourbaix diagrams were calculated at 25, 75 and 95 °C for the Nb-H₂O system. The species and were considered. Potentiodynamic polarization and mass loss experiments (14 days) were conducted in concentrated H₂SO₄ (20, 40 and 80 wt%) and HCl (20 and 38 wt%) solutions at 75 and 95 °C. Nb forms a metastable pentoxide (Nb₂O₅) in H₂SO₄ and HCl solutions which dissolves as . Corrosion rates decrease between the 40% and the 80% H₂SO₄ solutions. SEM micrographs show generalized pitting in the 20% and 40% H₂SO₄ solutions. Mass loss corrosion rates did not exceed 306 μm/yr. Corrosion rates estimated by Tafel extrapolation were within two orders of magnitude of those measured by mass loss and it is shown that this finding is consistent with the thickening of the oxide.     

Effect of the strain rate on stress corrosion crack velocities in face-centred cubic alloys. A mechanistic interpretation

Constant extension rate tests on smooth samples, with strain rate (SR) values from 10⁻⁶ s⁻¹ up to 20 s⁻¹, were used to study stress corrosion cracking (SCC) systems in face-centred cubic alloys. It was found that by increasing the SR a monotonic increase of the (crack propagation rate) takes place. It was also observed that the slope α in vs. plots had different values for different SCC morphologies. Intergranular SCC is more steeply accelerated by SR, α_IG=0.5-0.7, than transgranular SCC, α_TG=0.2-0.3. The differences found between intergranular SCC and transgranular SCC were analysed under the light of the available SCC mechanisms.     

Effect of 4-(N,N-diethylamino)benzaldehyde thiosemicarbazone on the corrosion of aged 18 Ni 250 grade maraging steel in phosphoric acid solution

4-(N,N-diethylamino)benzaldehyde thiosemicarbazone (DEABT) was studied for its corrosion inhibition property on the corrosion of aged 18 Ni 250 grade maraging steel in 0.67 M phosphoric acid at 30–50 °C by potentiodynamic polarization, EIS and weight loss techniques. Inhibition efficiency of DEABT was found to increase with the increase in DEABT concentration and decrease with the increase in temperature. The activation energy E_a and other thermodynamic parameters (Δ, Δ, Δ) have been evaluated and discussed. The adsorption of DEABT on aged maraging steel surface obeys the Langmuir adsorption isotherm model and the inhibitor showed mixed type inhibition behavior.     

Effect of hexamethylpararosaniline chloride (crystal violet) on mild steel corrosion in acidic media

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ and 1 M HCl by hexamethylpararosaniline chloride (HMPC) was investigated using the gravimetric technique in the temperature range 303–333 K. The results indicate that HPMC inhibited the corrosion reaction in both acid media at all temperatures and inhibition efficiency increased with HMPC concentration. The inhibiting action is attributed to general adsorption of protonated and molecular HPMC species on the corroding metal surface. Adsorption followed a modified Langmuir isotherm and the Temkin isotherm, with very high negative values of the free energy of adsorption (). An increase in temperature reduced the inhibition efficiency of HPMC in 0.5 M H₂SO₄ but increased efficiency in 1 M HCl. Activation parameters such as activation energy (E_a), activation enthalpy (ΔH^∗) and activation entropy (ΔS^∗) as well as the adsorption heat (Q_ads) were evaluated from the effect of temperature on corrosion and inhibition processes.     

Perchlorate pitting corrosion of tin in Na2CO3 solutions and effect of some inorganic inhibitors

The anodic behaviour of tin electrode in Na₂CO₃ solutions containing different concentrations of Na₂ClO₄ was studied by potentiodynamic technique and complemented by scanning electron microscope. In perchlorate free carbonate solutions; the polarization curves exhibit two anodic peaks assigned to the electroformation of Sn(II) and Sn(IV) species, respectively, prior to the permanent passivation region. The passivity is due to the presence of SnO and SnO₂ layers on the electrode surface. Addition of to the carbonate solution breaks down the passive layer and initiate pitting corrosion at a certain critical pitting potential. The pitting potential decreases with an increase in concentration but increases with increasing both Na₂CO₃ concentration and scan rate. Addition of increasing concentration of , or causes a shift of the pitting potential in the positive direction indicating the inhibition effect of added anions, while addition of anion accelerates the perchlorate pitting corrosion.     

Influence of anions on the formation of β-FeOOH rusts

The artificial β-FeOOH rusts were synthesized by oxidation of FeCl₂ solutions and hydrolysis of FeCl₃ solutions. Various Na salts such as sulfate, biphosphate, nitrate, and silicate were added to the starting solutions at different anion/Fe molar ratios of 0-0.05. The XRD patterns of the products showed only the diffraction peaks of β-FeOOH. The crystallinity of the products was noticeably reduced by adding and but slightly influenced by adding . The addition of markedly crystallized the products by the hydrolysis of FeCl₃. The N₂ adsorption revealed that the products with were porous particles assembled by β-FeOOH subcrystals. and strongly coordinating to Fe(III) markedly lowered the crystallinity of the products and remained in the formed particles.     

Influence of 1,2-diaminoethane on the mechanism of aluminium corrosion in sulphuric acid solutions

The influence of 1,2-diaminoethane (DAE) on aluminium corrosion in H₂SO₄ solutions (pH 3) was investigated. In pure H₂SO₄, rapid uniform corrosion is followed by inhibition due to the formation of stable Al-sulphate binuclear bidentate metal bound surface complexes via a ligand exchange mechanism with two neighbouring sites. Metastable pitting is also observed. DAE acts as a strong corrosion inhibitor for both uniform and localised corrosion, due to the formation of Al-DAE monodentate hydrogen-bond surface complexes either by direct adsorption of the protonated molecule on Al-OH sites or via a ligand exchange mechanism with the proton of an site.     

Corrosion inhibition of tin, indium and tin-indium alloys by adenine or adenosine in hydrochloric acid solution

The influence of the concentration of adenine (AD), adenosine (ADS) on the electrochemical corrosion behavior of tin, indium and tin-indium alloys in 0.5 M HCl solution at different temperatures was studied. The investigation involved potentiodynamic cathodic polarization and extrapolation of cathodic and anodic Tafel lines techniques. The inhibition efficiency (IE%) increases with an increase in the concentration of adenine or adenosine of all investigated electrodes. The inhibition process was attributed to the formation of adsorbed film on the surfaces of the electrodes that protects the surface against corrosive agent. The data exhibited that the inhibition efficiency slightly decreases with increasing temperature.Frumkin adsorption isotherm fits well the experimental data. The plots of ln K vs. 1/T in the presence of the two studied inhibitors showed linear behavior. The standard enthalpy, , entropy, and free energy changes of adsorption were evaluated; the calculated values of and were negative while those for were positive. Mainly, all the above results are suggestive of physisorption of the inhibitor molecules on the surfaces of the investigated electrodes.     

Stress corrosion cracking of sensitized type 316 austenitic stainless steel in hydrochloric acid solution--effect of sensitizing time

The stress corrosion cracking (SCC) of a commercial austenitic stainless steel type 316 was investigated as a function of sensitizing time (3.6 ks to 1.08 Ms at a sensitizing temperature of 923 K) and test temperature (333-373 K) in 0.82 kmol/m³ hydrochloric acid (HCl) solution by using a constant load method. From the applied stress dependence of the three parameters (, steady state elongation rate, t_ss, transition time, t_f, time to failure), the relationships between applied stress and the three parameters were divided into three regions that are dominated by either stress, SCC or corrosion. In the SCC-dominated region, the was a linear function of the logt_f regardless of applied stress and test temperature for each sensitized specimens, showing that became a useful parameter for prediction of t_f. Furthermore, the results obtained indicated that the degree of sensitization increased with increasing sensitizing time, reached a maximum at a sensitizing time of around 360 ks and then began to decrease at 1.08 Ms by Cr healing. On the basis of the results obtained, the effect of sensitizing time on SCC and the IGSCC mechanism were discussed.     

Effects of temperature and aggressive anions on corrosion of carbon steel in potable water

Experiments on the corrosion of carbon steel in three kinds of artificial potable waters containing different concentrations of aggressive anions, Cl⁻ and , open to air in the temperature range from 5 to 60 °C were conducted using weight loss and electrochemical methods. The corrosion rate increased in proportion to the concentration of aggressive anions and with increasing temperature. At lower concentrations of aggressive anions and temperatures, the corrosion rate was lower and the corrosion potential was higher, at intermediate concentrations and temperatures, the corrosion rate increased logarithmically with decreasing potential, and at higher concentrations and temperatures, the corrosion rate was higher and the potential was lower. The corrosion behavior in potable water can be determined by the balance between inhibitive action of oxygen (passive film formation) and aggressive action of Cl⁻ and ions.     

Experimental and theoretical investigation of organic compounds as inhibitors for mild steel corrosion in sulfuric acid medium

Three synthesized organic compounds were tested as corrosion inhibitors for mild steel in sulfuric acid medium by potentiostatic polarization, FTIR spectroscopy and SEM techniques. Quantum chemical parameters were also calculated to characterize adsorption mechanism. Acceptable correlations were obtained between inhibition efficiency and the calculated quantum chemical parameters. It was found that the investigated compounds exhibit a good inhibition effect especially at 8-10 ppm range concentration, which makes them commercially important. The adsorption of inhibitors on the surface obeys Langmuir adsorption isotherm. The values of activation energy and the thermodynamic parameters, such as K_ads, , and were calculated.     

Hydrophobic-tailed bicycloisoxazolidines: A comparative study of the newly synthesized compounds on the inhibition of mild steel corrosion in hydrochloric and sulfuric acid media

The cycloaddition reactions of the cyclic nitrones 1-pyrroline 1-oxide and 3,4,5,6-tetrahydropyridine 1-oxide with alkenes, 11-phenoxy-1-undecene and 11-p-methoxyphenoxy-1-undecene, afforded cycloaddition products (bicyclic isoxazolidines) in excellent yields. One of the cycloadducts on reaction with propargyl chloride and ring opening with zinc in acetic acid afforded quaternary ammonium salt and aminoalcohol, respectively. All the new inhibitor molecules in the presence of 400 ppm at 60 °C achieved inhibition efficiencies, determined by gravimetric method, in the range 99-99.6% and 85-99% for mild steel in 1 M HCl and 0.5 M H₂SO₄, respectively. Comparable results were obtained by the electrochemical methods using Tafel plots and electrochemical impedance spectroscopy for the synthesized compounds. The isoxazolidine derivatives were also found to be good inhibitors of mold steel corrosion in synthetic brine. Negative values of in the acidic media ensured the spontaneity of the adsorption process. While the corrosion inhibition by these molecules was predominantly under cathodic control in 1 M HCl, the inhibition in 0.5 M H₂SO₄ was found to be under anodic control. The isoxazolidines and their derivatives were found to be among a rare class of molecules, which provide suitable inhibition mechanism for the corrosion inhibition in HCl as well as in H₂SO₄ media.     

Photoelectron spectroscopy study of the inhibition of mild steel corrosion by molybdate and nitrite anions

Passive films formed on mild steel in aqueous 8.6 mM NaCl solutions (pH 8), containing either or , have been studied with X-ray photoelectron spectroscopy. For either anion these films are ∼5 nm deep, and the primary chemical state of iron is Fe³⁺. Following exposure to , the film consists of a sub-layer (∼4.1 nm) composed largely of ferric oxide/hydroxide, overlaid by Fe₂(MoO₄)₃ (∼0.6 nm). As regards , spectra are consistent with the film being closely related to γ-Fe₂O₃. Furthermore, a reduction product of , potentially N₂, is present, displaying a depth profile comparable to that of molybdate.