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Square-wave cathodic current modulation was used to electrodeposit fine-grained iron from citric acid bath. The effect of pulse on-time, off-time, peak current density, and total plating time on the grain size, surface morphology, and crystal orientation was determined. X-ray diffraction analysis and modified Williamson–Hall relation were used to determine the average grains size of the coatings. The experimental results showed that an increase in peak current density resulted in considerable refinement in crystal size of the deposits. An increase in the pulse off-time at constant on-time and peak current density resulted in a progressive increase in crystal size. However, the crystal orientation remained unaffected with increasing off-time. The design of the pulse deposition parameters is described in terms of the transport limitations through the diffusion layer and electrochemical interface stability.

The effects of grain size reduction on the corrosion inhibition of sodium nitrite were investigated using polarization curves and electrochemical impedance spectroscopy (EIS). Nanocrystalline iron (~ 45 nm) was produced by pulse electrodeposition using citric acid bath. The grain size of a nanocrystalline surface was analyzed by X-ray diffractometry (XRD) and field emission scanning electron microscopy (FESEM). The most intensive first-order peak (211) of the XRD patterns was taken for detailed analysis using a Gaussian fitting curve. The tests were carried out in 25 mg/lNaCl + 57 mg/lNa₂SO₄ with different concentration of sodium nitrite aqueous solutions.

The results revealed that due to the adsorption process which leads to the formation of a protective layer with a greater charge transfer resistance the inhibition effect and corrosion protection of sodium nitrite inhibitor in near-neutral aqueous solutions increased as the grain size decreased from microcrystalline to nanocrystalline. The standard free energy of adsorption (ΔG_ads) revealed a strong interaction between inhibitor and nanocrystalline surface. This was attributed to the increased number of the active sites caused by nanocrystalline surface.