Electrochemical synthesis and surface protection of polypyrrole-CeO₂ nanocomposite coatings on AA2024 alloy

Kumar, A. Madhan,Babu, R. Suresh,Ramakrishna, Suresh,de Barros, Ana L.F. Elsevier 2017 Synthetic metals Vol.234 No.-

<P><B>Abstract</B></P> <P>A facile approach based on electrochemical polymerization was used to synthesize polypyrrole/CeO<SUB>2</SUB> (PPy/CeO<SUB>2</SUB>) nanocomposite on an AA2024 alloy surface. CeO<SUB>2</SUB> nanoparticles (NPs) embedded in the PPy matrix were observed using FESEM micrographs with EDX analysis. IR and UV–vis spectroscopy were used to characterize the synthesized PPy/CeO<SUB>2</SUB> nanocomposite. The Raman spectra reflected the interactions between the π-conjugated structure of PPy and CeO<SUB>2</SUB> NPs. TGA thermograms revealed improved thermal stability of the synthesized nanocomposite and were used to determine the amount of nano ceria incorporated in the PPy matrix. The electrochemical corrosion behavior of the coated alloys in 0.6M NaCl solution was examined through potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) measurements. From these electrochemical studies, a larger shift of E<SUB>corr</SUB> in the positive direction with a high amount of CeO<SUB>2</SUB> in the nanocomposite was obtained, as well as a maximum corrosion protection efficiency of 99.64% by incorporating 3% of CeO<SUB>2</SUB> NPs in the PPy coatings. EIS studies also confirmed the enhanced corrosion protection behavior of PPy/CeO<SUB>2</SUB> coatings with higher R<SUB>ct</SUB>, R<SUB>f</SUB> and lower CPE<SUB>dl</SUB> values compared to those of pure PPy coatings. The results showed that the PPy coatings with CeO<SUB>2</SUB> nanoparticles can be potential coating materials for the corrosion protection of AA2024 alloys substrates.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Polypyrrole coatings with nanoceria were prepared through electrochemical route. </LI> <LI> Raman studies confirm the interaction between π-conjugated PPy & nano CeO<SUB>2</SUB>. </LI> <LI> TGA reveals improved thermal stability of the synthesized nanocomposite. </LI> <LI> Uniform distribution of nano CeO<SUB>2</SUB> was confirmed by EDX mapping analysis. </LI> <LI> Corrosion test confirms better surface protection of PPy/Ce than pure PPy. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Investigation on the Controlled Degradation and Invitro Mineralization of Carbon Nanotube Reinforced AZ31 Nanocomposite in Simulated Body Fluid

A. Madhan Kumar,S. Fida Hassan,Ahmad A. Sorour,M. Paramsothy,M. Gupta 대한금속·재료학회 2019 METALS AND MATERIALS International Vol.25 No.1

Magnesium (Mg) based implant materials are believed to be the perfect candidates for biomedical applications due to theirversatile properties. However, regulating their corrosion/degradation rate in the biological surroundings is still a noteworthytask. Suitable strategies to overcome this task is to wisely select alloy elements with improved corrosion resistanceand mechanical characteristics. An attempt has been made to enhance the corrosion and biocompatibility performance ofmagnesium alloy AZ31 containing carbon nanotubes (CNTs) as reinforcement and evaluate its degradation and invitromineralization performance in physiological medium. Corrosion behavior of AZ31 alloy with CNTs reinforcement wasinvestigated using electrochemical methods, weight loss, and hydrogen evolution in SBF during short and long-term periods. The obtained results revealed that the corrosion resistance of AZ31 alloy enhanced significantly due to the incorporationof CNTs. Hydrogen evolution test and weight loss tests revealed that the presence of CNTs improves the stability of theMg(OH)2 and efficiently regulate the degradation behavior in SBF. Surface characterization after immersion in SBF revealedthe rapid formation of bone-like apatite layer on the surface, validated a good bioactivity of the AZ31 nanocomposite samples.

Solution processed n-In2O3nanostructures for organic-inorganic hybrid p-n junctions

Kumar, G. Mohan,Kumar, A. Madhan,Ilanchezhiyan, P.,Kang, T. W. The Royal Society of Chemistry 2014 Nanoscale Vol.6 No.19

<P>Solution processed organic-inorganic bulk hybrid heterostructures are nowadays considered as the most promising elements to perform efficient optoelectronic functions. In this regard, In2O3 based hybrid heterostructures were fabricated using polypyrrole and their role as efficient interfacial layers was studied using polypyrrole/ZnO nanowires. The In2O3 nanostructures were synthesized through a facile wet chemical approach at an average scale of less than 10 nm in cubic phase. The presence of O and In related defects was studied through emission spectra; these were also found to exhibit their predominance in Raman measurements. The n-type characteristics and donor density value of around 1020 cm-3 were evaluated for the In2O3 specimens via Mott-Schottky plots. The role of In2O3 nanostructures as active/interfacial layers was then studied using the current-voltage characteristics obtained across the hybrid heterostructures made of polypyrrole/In2O3, polypyrrole/ZnO and polypyrrole/In2O3/ZnO. Organic-inorganic p-n diodes were obtained via in situ chemical polymerization, drop casting and hydrothermal routes. Cyclic voltammograms and Nyquist plots were used to study the reduction mechanism taking place in the nanostructures that actually results with the formation of metallic In, which plays a vital role in establishing the required conduction electrons. The same has been reasoned for the improved rectification characteristics observed across the diodes.</P>

Electrical property studies on chemically processed polypyrolle/aluminum doped ZnO based hybrid heterostructures

Mohan Kumar, G.,Ilanchezhiyan, P.,Madhan Kumar, A.,Yuldashev, Sh.U.,Kang, T.W. Elsevier 2016 Chemical physics letters Vol.649 No.-

<P>A hybrid structure based on p-type polypyrolle (PPy) and n-type aluminum (Al) doped ZnO nanorods was successfully constructed. The effect of Al doping on material properties of wurtzite structured ZnO were studied using several analytical techniques. To establish the desired hybrid structure, pyrrole monomers were polymerized on hydrothermally grown Al doped ZnO nanorods by chemical polymerization. The current-voltage characteristics on the fabricated PPy/A1 doped ZnO heterostructures were found to exhibit excellent rectifying characteristics under dark and illumination conditions. The obtained results augment the prescribed architecture to be highly suitable for high-sensitivity optoelectronic applications. (C) 2016 Elsevier B.V. All rights reserved.</P>

Evidencing enhanced charge-transfer with superior photocatalytic degradation and photoelectrochemical water splitting in Mg modified few-layered SnS₂

Mohan Kumar, G.,Cho, H.D.,Ilanchezhiyan, P.,Siva, C.,Ganesh, V.,Yuldashev, Sh.,Madhan Kumar, A.,Kang, T.W. Elsevier 2019 JOURNAL OF COLLOID AND INTERFACE SCIENCE - Vol.540 No.-

<P><B>Abstract</B></P> <P>Recently there has been immense interest in the exploration of richly available two-dimensional non-toxic layered material such as tin disulfide (SnS<SUB>2</SUB>) for potential employment in energy and environmental needs. In this regard, we report on the synthesis of few-layered Sn<SUB>1−x</SUB>Mg<SUB>x</SUB>S<SUB>2</SUB> nanosheets through a facile one-step hydrothermal route to address all such functions concerning photocatalysis and photoelectrochemical conversion. The crystalline order and structure of processed layered Sn<SUB>1−x</SUB>Mg<SUB>x</SUB>S<SUB>2</SUB> were initially found to exhibit a strong influence on their physicochemical properties. Their optical properties attest the Mg doping in SnS<SUB>2</SUB> to benefit us with enhanced visible-light absorption via red-shift in their absorption edge. In the photoluminescence spectrum the emissions observed along visible and red region signifies the association of Mg related trap states in Sn<SUB>1−x</SUB>Mg<SUB>x</SUB>S<SUB>2</SUB>. Next, the photocurrent and electrochemical impedance spectroscopic results revealed the Mg doping to promote the effective charge transfer process (which was beneficial to enhance their photocatalytic activity). Consequently, the layered Sn<SUB>0.98</SUB>Mg<SUB>0.02</SUB>S<SUB>2</SUB> made photoanodes displayed 1.7 fold higher photocurrent density under simulated solar radiation with respect to their undoped counterpart. Furthermore, the layered Sn<SUB>0.98</SUB>Mg<SUB>0.02</SUB>S<SUB>2</SUB> nanosheets exhibits enhanced visible light decomposition of organic dye while compared with pristine SnS<SUB>2</SUB> nanosheets. The value of rate constants obtained for the Sn<SUB>0.98</SUB>Mg<SUB>0.02</SUB>S<SUB>2</SUB> nanosheets was found to be 1.4 times higher than that of pristine SnS<SUB>2</SUB>. Finally, the results obtained through the present study projects the huge potential of layered Sn<SUB>0.98</SUB>Mg<SUB>0.02</SUB>S<SUB>2</SUB> nanosheets for future multifunctional applications.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Electrochemical studies on two-dimensional ZnInO nanoplates for organic–inorganic hybrid photodiode related applications

Mohan Kumar, G.,Madhan Kumar, A.,Ilanchezhiyan, P.,Kang, T.W. Elsevier 2015 JOURNAL OF ALLOYS AND COMPOUNDS Vol.619 No.-

<P><B>Abstract</B></P> <P>An ultra low cost route has been established to fabricate organic–inorganic hybrid <I>p</I> <I>–</I> <I>n</I> junctions <I>via</I> chemical <I>in-situ</I> polymerization of organic monomers on traditionally drop casted inorganic deposits. In this regard, ZnInO nanoplate-like structures were synthesized through a facile solution based chemical approach and their structural property was studied using X-ray diffraction patterns. The nature of charge carriers and donor density in ZnInO made electrodes were studied using electrochemical impedance spectroscopy. The dissemination of polymer matrices on the ZnInO nanoplates was examined through scanning electron microscopy. The current–voltage characteristics obtained across the polypyrrole/ZnInO made hybrid structures revealed an improved rectifying behaviour under illuminated conditions. The mechanism behind the drastic decrease in resistance values that substantiates the improved electron transfer characteristics across the organic–inorganic structures was studied through cyclic voltammetric measurements.</P>

High performance photodiodes based on chemically processed Cu doped SnS₂ nanoflakes

Mohan Kumar, G.,Xiao, Fu,Ilanchezhiyan, P.,Yuldashev, Sh.,Madhan Kumar, A.,Cho, H.D.,Lee, D.J.,Kang, T.W. Elsevier 2018 APPLIED SURFACE SCIENCE - Vol.455 No.-

<P><B>Abstract</B></P> <P>In this work, Cu doped SnS<SUB>2</SUB> nanoflakes were synthesized through a simple hydrothermal method. The influence of Cu doping on the structural, optical and electrical properties of SnS<SUB>2</SUB> were investigated in detail. Optical properties explores the Cu doping in SnS<SUB>2</SUB> crystal lattice to result with a red-shift in absorption spectrum, which benefits visible-light absorption. Photodiodes were further fabricated by spin coating Cu doped SnS<SUB>2</SUB> nanoflakes on p-type silicon (Si). Electrical and photoelectrical parameters of Cu doped SnS<SUB>2</SUB> nanoflakes were determined by studying their impedance and current–voltage (I–V) characteristics, respectively. The diodes were found to exhibit excellent rectifying behavior and good sensitivity on par to pristine photodiodes. Impedance results identified the resistance of device to reduce considerably on Cu doping. The enhanced photoelectrical properties of the heterojunctions has been ascribed to Cu ions, which act as effective dopant and contribute to the varied carrier concentration in SnS<SUB>2</SUB>. Finally the obtained results suggest the potential of Cu-doped SnS<SUB>2</SUB> for application in photodetection and sensors applications.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Cu doped SnS<SUB>2</SUB> nanoflakes were synthesized in hexagonal phase. </LI> <LI> Nature of charge carriers/carrier density was determined using Mott-Schottky plots. </LI> <LI> Photodiode based on Cu doped SnS<SUB>2</SUB> nanoflakes were fabricated on p-Si substrate. </LI> <LI> Photodiode revealed improved photocurrent and responsitivity values under illumination. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Fabrication of polypyrrole/ZnO nanowires based organic–inorganic hybrid p-n junctions

Mohan Kumar, G.,Madhan Kumar, A.,Ilanchezhiyan, P.,Kang, T. W. Springer Science + Business Media 2015 Journal of materials science Materials in electron Vol.26 No.4

Ultrasonic-assisted synthesis of ZnTe nanostructures and their structural, electrochemical and photoelectrical properties

Ilanchezhiyan, P.,Mohan Kumar, G.,Xiao, Fu,Poongothai, S.,Madhan Kumar, A.,Siva, C.,Yuldashev, Sh.U.,Lee, D.J.,Kwon, Y.H.,Kang, T.W. Elsevier 2017 Ultrasonics sonochemistry Vol.39 No.-

<P><B>Abstract</B></P> <P>Colloidal zinc telluride (ZnTe) nanostructures were successfully processed through a simple and facile ultrasonic (sonochemical) treatment for photoelectronic applications. The particle-like morphological features, phase and nature of valence state of various metal ions existing in ZnTe were examined using electron and X-ray photoelectron spectroscopic tools. Raman spectroscopic measurements revealed the dominance of exciton-phonon coupling and occurrence of TeO<SUB>2</SUB> traces in ZnTe through the corresponding vibrations. Optical bandgap of the ZnTe suspension was estimated to be around 2.15eV, authenticating the direct allowed transitions. The <I>p</I>-type electrical conductivity and charge carrier density of ZnTe were additionally estimated from the Bode, Nyquist and Mott-Schottky type impedance plots. The photoelectrical properties of ZnTe were investigated by fabricating <I>p</I>-ZnTe/<I>n</I>-Si heterostructures and studying their corresponding current-voltage characteristics under dark and white light illumination. The diodes revealed excellent rectifying behaviour with significant increase in reverse current under illumination. The stability of the devices were also affirmed through the time-dependent photoresponse characteristics, which actually suggested the improved and effective separation of photo generated electron hole pairs across the integrated heterojunctions. The obtained results also augment the potential of sonochemically processed ZnTe for application in photo detection and sensor related functions.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Nanostructured ZnTe were ultrasonically processed for photoelectronics. </LI> <LI> Raman, XPS and electron microscopic tools affirmed their physico-chemical traits. </LI> <LI> Electrical properties were studied using Nyquist and Mott-Schottky plots. </LI> <LI> <I>I</I>-<I>V</I> studies augment the improved photo response in p-ZnTe/n-Si heterojunctions. </LI> </UL> </P>

Influence of Organic Acids on the Surface and Corrosion Resistant Behavior of Anodized Films on AA2024 Aerospace Alloys in Artificial Seawater

V. Jothi,Akeem Yusuf Adesina,A. Madhan Kumar,J. S. Nirmal Ram 대한금속·재료학회 2020 METALS AND MATERIALS International Vol.26 No.11

This study aims to evaluate the influence of dicarboxylic acids (oxalic, malonic and succinic acid) used in anodizationbath on the surface and corrosion resistant performance of anodized films on AA2024 aerospace grade alloys. The surfacemorphology, topography, composition and structure of anodized samples were examined by scanning electron microscopy,optical profilometer, X-ray diffraction and attenuated total reflectance-infrared techniques. Characterization results revealedthe effect of dicarboxylic acids addition on the anodized film’s surface with important changes. X-ray Photoelectron Spectroscopicanalysis confirmed the presence of carboxylic groups on the porous anodized layer processed in anodization bathcontaining succinic acid. The electrochemical corrosion tests specified a solid relationship between the corrosion resistanceand the surface microstructure of the anodized layer processed in different dicarboxylic acids.