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    Corrosion Behavior of Ni-Fe-Mo Deposits Obtained Under Different Electrodeposition Conditions

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    IMEPEG (2021) 30:5593- 5602 inpss/dosorg/10-1007is11665-021-05805-1 ©ASM International 1059-9495/319.00 ® Corrosion Behavior of Ni-Fe-Mo Deposits Obtained under Different Electrodeposition Conditions ‘eyhan Solmaz and B. Deniz Karahan ‘Submitted: 31 December 2020 / Revised: 24 March 2021 / Accepted: 4 April 2021 / Published online: 30 April 2021 ‘Ternary Ni-Fe-Mo coatings have been proposed for anti-corrosion applications to replace chromium coating. To analyze the effects of deposition current and duration six different Ni-Fe-Mo films have been electrodeposited on copper foil. Their morphologies, structures, and chemical compositions of the films hhave been characterized. Potentiodynamic polarization is applicd on each coating and electrochemical Impedance spectroscopy is applied to diseuss their corrosion resistances. Ni-Fe-Mo film that is produced at the lowest current density (5 mA.cm”) for $ min. exhibits a more positive corrosion potential and higher charge transfer resistance. To shed some lights on aging mechanism, the film has been aged for 70 days. The cenhanced protective propertics of the film is atributed to its fine, crack free morphology with high Mo content. The existences of Fe;0,, MoO:, MoOs, and NiO in the passive I barrier protection ability of the film. Keywords conosion resistance, eyelie_volammety, clectodeposition, Ni-Fe-Mo alloys, tfel 1. Introduction Recently, the deposition of metallic and/or metal oxide films ‘on metal substrates has attracted increasing attention especially in the electronic and energy fields since these electrodeposited films have been widely used in memory deviees, micro-electr- ‘mechanical, and energy storage systems (Ref 1), The composite coatings are used to protect the substrates from mechanical ‘wearing and corrosion (Ref 2, 3), These films ane prepared by various deposition methods that include electrochemical depo- sition (Ref 4,5), pulsed laser deposition (Ref 6), cletron beam evaporation (Ref 7), and magnetron sputtering (Ref 8). Among, these methods, electrochemical deposition is preferred due to its low initial investment, material cost, and easy operation, Additionally, the process allows a contrl of chemical compo- tion, thickness, and grain size of the coating at or near room temperature (Ref 9). Chromium coatings have been widely used in decorati aerospace, automotive, and many engineering industries due to their hardness, superior corrosion, and wear properties (Ret 10), However, recently health and environmental concems have ‘caused the restriction inthe use of hexavalent chromium (Cr'®) ‘compounds resulting in increased efforts to develop chromium: free coatinas (Re 1). To this effect, Mo alloys with iron group Reyhan Solmaz, Department of Metallurgical and Materials Engineering, Istanbal Technical University, Maslak, Istanbul 34369, uskey, ahd_B. Denis. Karahan, Civil Engineering. Department, School of Enginering. and. Natural Sciences, Istanbul Medipol University, Beykoz, Istanbul 34810, Turkey: and Research Insite for Health Sciences and Technologies (SABITA), Istanbul Medipol University, eykor, Istanbul 4810, Turkey.” Contact emi ‘edkarahandimedipoledut neering and Performance er substantiate the improved metals (€-g. Ni, Co, Fe) have gained importance because of their particular magnetic, electrical, mechanical, thermal prop: erties, and corrosion resistances (Ref 12) The clectrodeposition of molybdenum with an iron-group clement occurs through “the induced co-deposition” mecha: nism (Ref 13). Therefore, during the induced co-deposition of Mo, the formation ofan intermediate phase with an iron-group element is inevitable. Podlaha and Landolt (Ref 14, 15) have studied the mechanism behind the induced co-deposition of Mo with an iron group element (such as Ni, Co, or Fe), where the electrolyte contains ligands (L such as citrate). The proposed model is based on the adsorption and the reduction of molybdate species on the substrate surface. Accordingly, itis suggested that the formation of surface-adsorbed intermediate, (M(I)LMoO;),x,, compound is the rate-determining step of the deposition process. Once the intermediate compound is adsorbed on the electrode surface, the iron group metal ion acts as catalyst for the reduction of molybdate resulting in Mo coeposition with the iron group metal (M) (Equations 1-4) (Ref 16) MAIL + 6° > M(DLus. (a1) M(I)Lads + — M(s) +L (Eq 2) MoO? + M(IL + 28,0 + 26° —+ [M(H)LMo0:,y,+40H (Eq 3) IM(II)LM00:|,4.+2120 4+ 4e” —> Mo(s) + M(IIL +4011 (Eq 4) There are several studies in the literature on the co- deposition of molybdenum with one or more metas from the iron group such as nickel. As itis known, Ni-Mo coatings have been widely used in the automotive and aviation industries, since they increase the corrosion resistance of the components which operate at elevated temperatures and/or in aggressive environments. Ni-Mo-coated substrates are also studied as electrodes for hydrogen evolution reaction (HER) and fuel cells ‘Volume 30(8) August 20215593 (Ref 16, 17). Zeng et al. (Ref 18) have investigated the co- deposition mechanism of Ni-Mo film by Raman spectroscopy. ‘They have reported that molybdate can only be reduced to a mixture of polyvalent Mo oxides andor hydroxide when the electrolyte has no NiSO, Solution. On the contrary, in the ease of the solution containing NiSO, salt, molybdate is first reduced to Mo (IV) oxide; as an intermediate phase then reduced to Mo in the alloy under the eatalysis effect induced by Ni atoms, In addition to Ni-Mo alloys, Fe-Mo alloys are also preferred duc to their good corrosion and wear resistances, (Ref 19). Additionally, they also have high electrochemical activity and low toxicity. The laters offer outstanding advan- tages to replace chromium coatings (Ref 20, 21), Sanches etal, (Ref 22) have studied electrodeposition of Ni Mo (18.5% 31% Mo) and Fe-Mo (66.9% Fe-11% Mo) alloys on Pt substrates. They have reported that Fe ions in the solution reduce the molybdenum oxides to metallic Mo. A comparison of temary alloy coating’s corrosion potentials to that of the binary alloy has been accomplished by Winiarski et al. (Ref 23), They have fabricated Zn-Fe and Zn-Fe-Mo alloy coatin and proved that the in which the corrosion happens temary alloy coating is different than that ofthe binary alloy ‘They have reported that corrosion potential (E5qq) values for the temary Zn-Fe-Mo coatings (are in the ranges from -980 to - 820 mV (vs. SCE) depending on the Mo amounts) are more positive than the Fayj,( — 1070:mV vs. SCE) ofthe binary Zn Fe films. In addition to plating bath composition, the effeets of {position time and plating current density are also investigated as they lead to different film characteristics (thickness, mor- phology, structure), thus mechanical and corrosion behaviors (Ref 24, 25). Hyie et al. (Ref 24) have studied the effect of ifferent deposition times (15, 30, and 45 min.) on the physical, ‘mechanical, and corrosion properties of Co-Ni-Fe coatings ‘Their results have indicated that in 30 min, deposition duration the deposit reaches optimum thickness and hardness as well as corrosion resistance (Ref 24). Yusof et al. (Ref 25) have investigated the effect of plating current density (1-20 mA.cm?) ‘on the surface morphology of Sn-Ag-Cu alloy coatings. They hhave reported tha atthe current density of 5-10 mA.em”, films with smooth, uniform, compact, and fine grained properties are achieved (Ref 25). Considering the outcomes of the previous works (Ref 22 25), in the present study, a temary coating has been desi where the addition of Fe into the Ni-Mo alloy is expected to ameliorate the corrosion protection properties of the deposit. Unlike to Santana et al. (Ref 26) work where they have analyzed the effect of current density and bath temperature on Ni-Fe-Mo films in an electrolyte containing additives like bboron phosphate, and 1-Na-dodecylsulfate by means of response surface methodology method; herein, metal salts containing electrolyte with no additives has been used to discuss the effects of the deposition current density and deposition time on the electrochemical characteristics of Fe-Mo films. Moreover, first in the open literature, the properties of the passive oxide layer that forms on the TFe-Mo coating afler 70 days of aging is reported to shed some lights on the aging mectanism of the coating. Thus, in pursuit of understanding the corrosion behavior and. ‘aging mechanism of Ni-Fe-Mo coatings, first the deposition current density, then the deposition time have been optimized. Afterwards, the sample with the highest charge transfer 5594 Volume 30(8) August 2021 and the oxide passive layer formed on the sample is characterized to discuss the aging mechanism, Advanced instrumental techniques and methods such as xray diffraction (XRD), secondary electron. micro- scopy (SEM), energy dispersive spectroscopy (EDS), induc- tively coupled plasma (ICP), microwave plasma-atomic emission spectrometer (MP-AES), cyclic voltammetry (CV), electrochemical impedance spectroscopy (FIS), and potentio- ‘dynamic polarization method have been used to support the reasons stated to clucidate the improved corrosion protection ability and the aging mechanism of the Ni-Fe-Mo coating, Experimental 2.1 Electrodeposition of Ni-Fe-Mo Coatings on Copper Foil Electrodeposition of six different Ni-Fe-Mo alloys has been performed galvanostatically by using GW Instek PSP-405 power supplier. The experimental conditions of these six different samples are given in Table 1. The composition of the plating solutions isthe same in all experiments: oF 0.2 M nickel sulfate (NiSO,.6H;0), 02M iron sulfate (FeSO,61,0), 0.1 M sodium molybdate (NagMoO,.2H,0), 0.01 M sodium sulphate (Na,S0,), and 0.001 M_ trisodium citrate (CeHsNaxO,). All chemicals used in the experiments are technical quality and utilized without further purification. The electrolyte is free from any additives such as brighteners. The pHT value of the baths is adjusted to ~5.5 using an ammonia solution (25%). n the electroplating process, the temperature of plating bath is maintained at 30°C and the solution is stired magnetically a « speed of 250 mpm during deposition, Prior to each experiment, the copper fil surface is cleansed with ethanol and subsequently activated by immersing in a solution containing 10 vol% HCl, for 1 min, and finally rinsed with distilled water at room temperature. The clectrodeposition process has been performed in the galvanostatic regime at a current density of 5, 7.5, 10, and 30 mA.cm’ for 10 min, respectively. Afterwards, extra Ni-FeMo films have been produced at S mA.em” deposition current density for 5 and 40 min, respectively. Immediately after deposition, film thick- nesses are measured by Electro-Physic coating thickness gauge, Finally to examine the aging mechanism, Ni-Fe-Mo film with 1 em? open surface area is immersed in 3.5 w.% NaCl solution for 70 days 22 Characterization of the Ni-Fe-Mo Coatings Morphological analyses of the films are carried out with Zeiss Gemini 500 scanning electron microscope (SEM). Inductively coupled plasma (ICP-MS, Perkin Elmer Nexion 300XX ICP-MS) is used to define Mo concentration and microwave plasma-atomie emission spectrometer (AAS, Agi- Tent 4200 MP-AES) is used to determine the Ni and Fe concentration being released from Ni-Fe-Mo films. For ICP~ MS and MP-AES analyses, 1M HNO; solution has been used as the solvent. Copper foils coated with Ni-Fe Mo film, 2 em x 2.em in size, have been immersed in 80 ml of the HINO, solution. After the samples have been completely dissolved, the metal concentrations have been measured. The phases in the coatings are identified by x-ray diffractometer (XRD) (PANalytical X'Pert Pro) using Cu-Kos radiation in the range of 20 = 35-95° with a scan rate of 2°%*minute. The Journal of Materials Engineering and Performance Table 1 Process parameters and thicknesses of Ni-Fe-Mo films Sample ‘Current density, mA.cm™ Sample 30410 0 ample 10-10, 0 Sample 75-10 15 Sample 5 5 Sample 5-5 5 Sample 5-40 5 chemical composition ofthe oxide film is determined by enengy dispersive spectrometer (EDS) (Bruker). 23 Electrochemical Tests Al electrochemical measurements are performed with a Garry Interface 1000E potentiostat using a standard Garry MaltiPort Corrosion Cell Kit with a graphite rod as a counter clectrode and a saturated calomel electrode [SCE, KCI saturated solution (E = + 241 mV vs. normal hydrogen electrode)] as a reference, Al potentials are stated with respect to this reference. Cyelic voltammetry has been performed in three different solutions (sodium sulphate and tr-sodium citrate have been used in all solutions) made of iron sulfate, iron sulfate-sodium ‘molybdate and nickel sulfate-iron sulfate-sodium molybdate at oom temperature in the potential range 0.0V to ~ 1,SV (9s, SCE) with a $mVs" sean rate. For each experiment, a cleansed Cu foil of 1 em? open surface area has been used as the substrate, Polarization and EIS measurements have been carried out based on studies’ results reported in the open literature (Ref 5, 27, 28). The potentiodynamic polarization curves are obtained with a sweep rate of 0.167 mV.s" in a potential range of — 0.250 to + 0.250V in 35 wi% NaCl solution. EIS measurements have been conducted at open: circuit potential, with the perturbation potential amplitude of 5 sm in the frequency range of 10 mHlz to 100 kHz, 3. Results and Discussion 3.1 Morphological, Structural and Compositional Analyses of the Ni-Fe-Mo Coatings Mechanisms behind the Ni-Fe and Fe-Mo film depositions’ processes have been explained based on “anomalous depos tion” and ‘induced. co-depostion” principles, respectively (Ref 14, 29). Therefor, it might be assume thal the proposed film formation of Ni-Fe-Mo is a combination of both anomalous and induced co-depostion mechanisms. XRD results (Fig, 1(@, (b)) substantiate this explanation, The existences of Fe;Mo (ICPDS No. 31-0641) highlight the “co- deposition” of Mo and Fe, as stated in the study of Winiarskia et al, (Ref 23), The remarkable peaks tributed to NiO (ICPDS No. 78-0643) could be relate to “anomolous deposition” of Fe and Ni atoms, as revealed by Shabaan etal. (Ref 30). The patfems have showed sharp narrow peaks that comespond to @ coating with a erystaline stucture. In the sample designated 30-10, deposited withthe highest current density (30 mA.cnY >), its observed that NiO peak has higher intensity and FeMo peak is much more conspicuous. Figure 1(b) shows XRD Pallern of the samples 5-5 and 5-40 (films deposited. with Journal of Materials Deposition time, minute ‘Thickness, 0.5 pm 10 ia 10 37 0 3.68 10 361 5 312 0 1632 5 mA.cm? current density for 5 and 40 min, respectively). In all samples, two peaks corresponding to NiO and Fe;Mo phases are detected (Fig. la). Longer coating period not only leads 10 the peak formation at 68.4° more remarkable (associated with the FesMo phase), but also causes peak broadening and a slight slope formation at low difaction angle. The later could be explained in terms ofthe poor crystallinity or quasi-amorphous structure of the sample 5-40 (Ref 31). ‘Table 2 shows that changes in the current density and the deposition duration lead to challenges among Ni, Fe, and Mo deposition processes. The highest Mo content is achieved when the film is deposited at the lowest current density (5 mA.cm”), in the shortest deposition (5 min.) time. Herein, the reduction ratios of Ni and Fe ions may have decreased and the adsorption of the intermediate reaction (Equation 3) may be increased resulting in high Mo content, as discussed previously (Ref 32), SEM images of six different Ni-Fe-Mo films are presented in Fig. 2a-f) and thickness’ values of all coatings are given in Table |. Deposition in higher current densities and/or longer deposition times lead thicker film formation (Table 1), and itis thought to be the principal cause of the inhomogenities observed in the film morphology. A decrease in the current density leads more homogeneous surface morphology (Fig. 22- 4). Rough and cracked film surfaces are observed at high current densities (Fig. 22-b) which is believed to associate with the induced internal stress of the deposite. Figure 2(d-1) show SEM images of Ni-Fe-Mo films deposited at different ‘deposition times (10, 5, and 40 min, respectively). The deposit wih the thinnest thickness (3.12 jum) and the smallest particle size is obtained when the electrodeposition occurs atthe lowest current density, and the shortest deposition time (5 mA.cm”, 5 min.), Extending the deposition time to 40 min, brings about the formation of micron-size globular particles (Fig. 2e-. 32 Cyclic Voltammetry Curvature Analysis Figure 3(@) shows (ypical eyelic voltammogram for the deposition of ferrous ions. The CV curve shows distinct cathodic and anodie peaks associated with the deposition and dissolution of metallic Fe ions at approximately -I.18 V and = 06 V (vs. SCE), respectively. Figure 3(b) shows that Mo and Fe ions are reduced at around — 1.17 V (vs. SCE), as expected. When Ni, Fe, and Mo ions are all present in the electrolyte, a clear polarization effect is shown to have taken place, as indicated by the shifting of the cathodic ( ~ 1.09 V) and anodic ( — 0.15 V) peaks. This is due to the fact that Ni is relatively more noble in redox reaction compared to Fe and Mo, Moreover, the anodic sean current in CV is noted to crossover the cathodic scan current that is related to the presence of nucleation process (Ref 22, 33, 34). ‘Volume 30(8) August 2021-5595 Relative intensity (a4) @ . Sample 5-40 2 3 2 g & 2 Se © 2meta degree Fig. 1 Xray ditt 5 mA.cm* wit different deposition times (S min. and 40 min.) Table 2_ Concentration (at.%) for Ni, Fe, a Ni-Fe-Mo films Mo in the ample NI Fe Mo ample 30-10 49 36 1s ample 10-10 37 » 6 sa 3 0 sa 4 os 2 2 30 32 8 0 3.3 Potentiodynamic Polarization Measurements Figure 4(a) shows polarization eurves of the sample 30-10, sample 10-10, sample 7.5-10, and sample 5-10 (Ni-Fe-Mo films coated for 10 min with varying current densities ranging from 5 to 30 mA.cm). All measurements have been recorded in 3.5 wL% NaCl solution at room temperature. It apparent that a decrease in the deposition current density results in a 5596 Volume 30(8) August 2021 pastes of Ni-Fo-Mo coatings (a) deposited at dren curent desis (S, 75,10, 30 mA.cm?) (b) deposited at positive shift ofthe corrosion potentials, This behavior may be due to differences in coating morphology and struc ture (Figs. la, b and 2a-f). These results are very promising. when compared to the literature, For example, B. Roozbehania etal. (Ref 35) have investigated the corrosion behavior of the electrodeposited Ni-Mo coatings in NaCl solution. Compared to the film with the best corrosion resistance (corrosion potential: 512 mV vs. Ag/AgCl and corrosion current den- sity: 11.6 wA‘em’) from Ni-Mo costings obtained by B. Roozbehania et al. (Ref 35), Ni-Fe-Mo coating produced in this study at S mA.cm current density has a much better corrosion potential ( — 413 mV vs. SCE) and corrosion current density value (6.8 wAiem'), Tn an effort to determine the most positive corrosion potential, additional coating experiments have been performed for varying time durations at the fixed curent density of 5 mA.cm’, Potentiodynamic polarization curves show that the corrosion potential of the coating deposited for 5 minutes has the most positive value ( — 353 mV vs. SCE) (Fig, 4b), and the sample shows the smallest corrosion current density (4.2 wA/ among all samples. As can be seen from the SEM images, Journal of Materials Engineering and Performance Fig. 2 SEM images from the surface of the coatings (a) sample 30-10 (b) samp 0-10 (¢) sample 75-10 (A) sample 5-10 (e) sample 5-5 () sample 10 ay 2.00. —— 0.0. < — < LIF j = OAs da 240 de de S642 00 02 "Te da da ao So de da G2 00 02 @ Peteta Vs. 208 oy Potent Vs. SCE oasy ‘curren A (©) Potential V vs. SCE Fig. 3 Cyclic voltammograms (a) Fe (b) Fe-Mo (¢) Ni-Fe-Mo (the sean nite is § mVs this fllm (sample 5-5) has the finest grain structure which is B thought to provide an effective barrier to prevent the penetra: tion of the corrosive solution (Ref 36), ure 4(c) shows the effect of corrosive aging in aqueous ‘NaCl solution, on the corrosion potential ofthe sample 5-5 (that is produced with 5 mA.cm’ current density for 5 min). After Journal of Materials Engineering and Performance ‘Volume 30(8) August 20215597 3 ° : i (a) og A cm? tog W Acm” e, i: . a 6 4 () og Ac? Fig. 4 Poteniodysamic polarization curves recorded for Ni-Fe-Mo alloy coatings (2) deposit at various current densities afler 1 hour of Immersion in 3.5 W1% NaCl solution (sample 30-10, sample 10-10, sample 75-1 sample 5-5, sample S-40)(¢) 70 days and 1 hour aged samples deposited at $mA.cm™ for $ min. (sample 55) deposition times (sample 5-1 70 days of immersion in the 3.5 wi% NaCI solution, the comosion potential of the film has been observed with a shit into a more postive value ( ~ 208 mV vs. $CF) witha smaller corrosion eurent density value (2.5 Alm’), This atebuted to the possible formation of a pasive layer aver sample 5-5 ‘which may further enhance its eomosion protective character- ini. In order o evaluate the corosion behavior ofthe samples ‘more accurately, FIS analyses have been conducted ‘34 Electrochemical Impedance Spectroscopy Analysis ‘The Nyquist impedance plots of sample 30-10, sample 10- 10, sample 75-10, and sample 5-10 (Ni-Fe-Mo coatings

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