Surface & Coatings Technology 206 (2011) 137142

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Surface & Coatings Technology

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Electrodeposition of high Mo content amorphous/nanocrystalline NiMo alloys using 1-methyl-imidazolium chloride ionic liquid as an additive
M.H. Allahyarzadeh a, B. Roozbehani a, A. Ashra c, S.R. Shadizadeh b,
a b c

Department of Technical Inspection Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran Department of Materials Engineering, Faculty of Engineering, Shahid Chamran University, Ahvaz, Iran

a r t i c l e

i n f o

a b s t r a c t
Amorphous/nanocrystalline NiMo alloy containing more than 49 wt.% Mo has been electrodeposited onto mild steel from aqueous ammonia citrate solution by pulse plating technique in the presence of ionic liquid additive 1-methyl-imidazolium chloride. The deposits were quite bright, compact, metallic and adherent. In the presence of ionic liquid and pH = 8.5, deposits containing over 49 wt.% Mo have been obtained while in the absence of ionic liquid no deposit was obtained at the same conditions. Microstructure, morphology and chemical composition of the NiMo coatings were investigated using scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis respectively. The textural components of the coatings were also evaluated employing X-ray diffraction spectra. 2011 Elsevier B.V. All rights reserved.

Article history: Received 11 March 2011 Accepted in revised form 1 July 2011 Available online 13 July 2011 Keywords: Electrodeposition High Mo content Ionic liquid NiMo coating 1-Methyl-imidazolium chloride

1. Introduction Molybdenum alloys can be produced by electrodeposition. Theoretically electrodeposition of these alloys is an example of the induced codeposition mechanism which was proposed by Brenner [1]. The electrodeposition of pure molybdenum from aqueous solutions has been unsuccessful [2,3] due to the high overvoltage of molybdenum or the low overvoltage of hydrogen on Mo [4]. Mo can be co-deposited with an iron group metal, forming an alloy. The induced codeposition of molybdenum with cobalt, iron, chromium or nickel has been investigated in the literature [2,3,510]. Molybdenum alloys are used in variety of applications. They serve as electrodes in the process of the hydrogen evolution reaction [1214], as catalysts for hydroprocessing of aromatic oils and gas phase hydrogenation of benzene [15]. This electrocatalytic activity is due to the low overvoltage of hydrogen on Mo and Ni [16]. Moreover electrodeposited NiMo alloys are interesting materials because of their high corrosion resistance [1722]. In many cases of codeposition of nickelmolybdenum, citrate is used as complexing agent in order to establish electrodeposition conditions that lead to homogeneous deposits with different compositions. Citrate in the electrolyte assures that the pH remains stable during the deposition phenomena [11]. The electrodeposition of high-molybdenum-content alloys from the citrateammonia solution is possible. However, very-high-molybdenum-content alloys (38 at.% or
Corresponding author at: Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Northern Bowarde, Abadan 6318714331, Iran. E-mail address: shadizadeh@put.ac.ir (S.R. Shadizadeh). 0257-8972/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2011.07.004

50 wt.% of Mo), independent of the alloy deposition rate, exhibit cracks and small pits which diminish their practical importance and application [9]. Most of these deposits exhibited a dense net of bumps and cracks. It is also reported that the NiMo alloys electrodeposited by pulse current, might contain up to 41 at.% or 53 wt.% of Mo [23]. Ionic liquids are dened as molten salts with a melting point below 100 C [2429]. In general, they are composed of organic cations, such as substituted imidazolium ions or tetra-alkyl-ammonium ions, and of inorganic or organic anions, such as AlCl4 , PF6 , BF4 , CF3SO3 , and (CF3SO2)2N . Ionic liquids show an extraordinarily high chemical and thermal stability as well as wide electrochemical window [24,28]. Recently, it is reported that nanocrystalline aluminum, with an average crystallite size of 34 nm, can be electrodeposited without any additives in the ionic liquid 1-butyl-1-methylpyrrolidinium-bis (triuoromethylsulfonyl) imide saturated with AlCl3 [24]. Furthermore ionic liquids (IL) have very low vapor pressures, even at temperatures as high as 300 C [24]. Application of ionic liquids as an additive in deposition solution has not been well revealed. Recently Zhang et al. studied the effect of ionic liquid [BMIM] HSO4 as an additive on the electrochemically deposition of copper in sulfate electrolyte. Their results showed that the addition of IL leads to more leveled and ne-grained cathodic deposits [29]. The following research is going to investigate the effects of ionic liquid 1-methyl-imidazolium chloride as an additive on the morphology and chemical composition of NiMo coatings onto mild steel substrate. All the results are compared with those plated without additive. NiMo coatings were plated on mild steel substrates which have been prepared in two different methods include mechanically and electrochemically polishing. The morphology of NiMo coatings deposited on mechanically polished and electrochemically polished

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substrates was quite different. Although advances have been made, there are still many unknown aspects concerning the mechanism of additive behaviors. 2. Material and methods The mild steel specimens were disk shape mounted samples, having the exposed area of 0.81 cm2. Prior to the deposition, the substrate was mechanically polished from 280 to 1200 grit emery papers. Some of the specimens were electrochemically polished using 95% acetic acid and 5% percholoric acid solution for about 1 min at the constant potential of 6 V. After that, the specimens were washed with distilled water and immediately placed into the electroplating bath. The mechanically polished specimens were activated before plating in 10% HCl aqueous solution. The bath utilized for electrodeposition of the NiMo alloy, contained 0.1 M nickel sulfate (NiSO46H2O), 0.1 M nickel chloride (NiCl26H2O), 0.03 M sodium molybdate (Na2MoO42H2O) and 0.25 M sodium citrate (Na3C6H5O72H2O) as complexing agent. The ionic liquid which was used as additive was 1-methyl-imidazolium-chloride (95%) from Sigma Aldrich. Distilled water was used for electrolyte preparation. The pH of the solution was adjusted using ammonium hydroxide or sulfuric acid. (In the case of ionic liquid additive only ammonium hydroxide is used.) The pulse plating was carried out using a computer controlled AutoLab PGSTAT302N potentiostat system and Nova 1.6 software for application of pulse current and collecting the experimental data. Electrochemical deposition was conducted in a 250 mL beaker with conventional three electrode cell system. Ag/AgCl was considered as reference electrode and 316 stainless steel was used as counter electrode. The pulse parameters such as pulse current density, duty cycle and frequency were set as 8 A/dm 2, 0.3 and 10 Hz respectively. Deposition was conducted at four different temperatures of 30 C, 40 C, 50 C and 60 C. For investigating the effect of pH variations, pH was varied from 8.5 to 10.5. During the electrodeposition, temperature and pH were kept xed and the electrolyte was stirred at 200 rpm using magnetic stirrer. Characterization of the NiMo coatings was performed using X-ray diffraction technique (XRD) and the patterns were collected using a Bruker AXS D8ADVANCE X-Ray Diffractometer, with Cu K radiation, step size of 0.02 and the dwell time of 1 s. The surface morphology and the microstructure of the electrodeposited layers were characterized by scanning electron microscopy (SEM) using a SERON AIS-2100 scanning electron microscope. The chemical composition of the NiMo alloy was also determined by energy dispersive X-ray analysis (EDX) using SERON AIS-2100. 3. Results and discussion 3.1. Electrochemical deposition of NiMo without IL additive Nickelmolybdenum alloy coatings were deposited from citrate ammonia bath using pulse plating technique. As mentioned in the experimental procedure, Ni ions were provided by equal concentration of nickel sulfate and nickel chloride. Moreover, Mo ions were supplied in the form of sodium molybdate compounds. Fig. 1 shows the morphology of nickelmolybdenum coatings on electrochemically polished substrate (Fig. 1(a) and (b)) and on mechanically polished one (Fig. 1(c) and (d)). It should be noted that both of them were plated in the absence of 1-methyl-imidazolium-chloride. The bright surface of NiMo coatings includes bumps and some micro-sphere fragments. These electrodeposits were obtained at 40 C and pH 9.5. At this condition, the alloy deposition efciency is high and the crack-free deposits can be produced according to the literature [30,31]. At these conditions, EDX spectra clearly specify the amount of Mo content in the NiMo electrodeposits in both mechanically (23 wt.%) and electrochemically (26 wt.%) polished specimens. Based on the literature [32] this range of %Mo is

reported to be the best corrosion resistant nickelmolybdenum electrodeposits. Temperature and pH were varied to investigate their effects on Mo content in the electrodeposition process onto both mechanically polished and electrochemically polished substrates. Three pH values have been chosen as 8.5, 9.5 and 10.5 and they were kept during each deposition so that temperature was maintained constant at 40 C. The EDX spectra obviously demonstrate that at pH 8.5 NiMo deposits were plated very poorly so that a sharp Fe peak is observed over there so that, the amount of Fe content and Mo content was specied as 76 wt.% and 14 wt.% respectively. This fact could be due to very low cathodic current efciency as a result of hydrogen evolution reaction (HER) and lack of appropriate condition for alloy deposition. Nickel and specially molybdenum promote hydrogen evolution reaction, on the other hand hydrogen in its turn has very low overpotential for HER on these two metals [16]. In Fig. 2 the relationship between pH and Mo content in the nickelmolybdenum electrodeposits is clearly observed. Acidity is one of the major important deposition parameters, which plays an important role during alloy deposition. Experimental results showed that the Mo contents obtained at pH 8.5 and 10.5 are less than that of electrodeposit at pH 9.5. Ernst et al. have investigated the effect of pH on Mo content of NiMo deposits in sulfate solution. Their experiments included a wide range of acidity and alkalinity, (pH = 212). Their results indicated that in the range of pH from 12 to 8 as pH decreases the Mo content is decreased [33]. They showed that the lowest amount of Mo in nickelmolybdenum occurs at approximately pH 8.0. It is reported that the effect of pH at the higher values might be due to the complexing action of NH3 and not to the OH concentration [33]. The same behavior was observed in pyrophosphate electrolyte [4]. Fig. 2 also exhibits that at higher pH, more Mo content is plated on electrochemically polished substrates than those which are mechanically polished. It seems that surface preparation may affect on chemical composition of alloy deposits, however more investigation is required to discuss about that. As it would be discussed in the following section, the present research by adding a new additive to the deposition electrolyte at pH about 8.5, led to interesting results that are different from above results. Fig. 3 illustrates the relationship between temperature and Mo content in the nickelmolybdenum deposits. EDX spectra show that the Mo contents of NiMo coatings onto mechanically and electrochemically polished substrate are quite different. It is clear that at different temperatures and xed pH (9.5), Mo content on electrochemically polished substrate is more than those on mechanically polished one. Fig. 3 also indicates that at pH = 9.5 and constant pulse parameters from 30 C to 40 C, as the temperature increases, the Mo content decreases, and from 40 C to 60 C, Mo content increases with increasing the temperature. Such behavior is observed for both coatings on mechanically polished substrate and electrochemically polished one. Considering temperature variations, it is reported that from 30 C to 70 C the amount of %Ni in nickelmolybdenum deposits decreased from 83.4 wt.% to 78.8 wt.% therefore resulted in increasing Mo content [33], these results are obtained if direct current was applied and bath pH varied between 9.5 and 10.5. It is also reported that the same behavior was obtained at 80 mA/cm 2, 2000 rpm rotation rate and pH about 9.2 [9]. The effect of temperature on Mo content in NiMo coatings has been veried in pyrophosphate bath, and results were quite opposite of sulfate solution [4]. 3.2. Electrochemical deposition of NiMo in the presence of IL additive Various concentrations of 1-methyl-imidazolium-chloride ionic liquid have been added as an additive into the sulfatechloride solution to deposit the nickelmolybdenum coating on mild steel. This research is concentrated on investigation of the effect of 100 ppm of 1-methyl-imidazolium chloride ionic liquid as an additive on the electrodeposition process. As discussed in previous section, despite of

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Fig. 1. SEM micrographs of NiMo deposits in additive free sulfatechloride using pulse technique at pH = 9.5 and 40 C on electrochemically polished substrate (a, b) and on mechanically polished substrate (c, d).

poor electrodeposition of NiMo at pH 8.5 in additive free solutions, in the presence of IL additive, promising results were obtained at exactly the same conditions on both mechanically and electrochemically polished surfaces. EDX spectra obviously demonstrated that in the presence of only 100 ppm 1-methyl-imidazolium chloride ionic liquid, the Mo content of nickelmolybdenum coatings exceeds 50 wt.% on electrochemically polished substrate (50 wt.%). This amount is about 47 wt.% for mechanically polished one. So it could be observed that, electrodeposition of high Mo content NiMo alloy coatings were carried out in the presence of just 100 ppm ionic liquid with above mentioned condition (pulse current density 8 A/dm 2, frequency f = 10 Hz and duty cycle = 0.3). Other researchers deposited high Mo content NiMo alloy coatings under very high forced convection with 4000 rpm rotation rate [9,34]. Maximum Mo

content which can be obtained under a high forced convection and 4000 rpm rotation rate was 48 wt.% [9,34], whereas in the presence of 100 ppm 1-methyl-imidazolium chloride ionic liquid and onto electrochemically polished substrate 50.1 wt.% Mo was obtained only with 200 rpm rotation rate. Fig. 4 depicts the morphology and microstructure of NiMo coating from citrate ammoniacal electrolyte in the presence of 100 ppm ionic liquid 1-methyl-imidazolium chloride onto mechanically polished substrate. By comparison, it is very obvious that the morphology of coating in the presence and absence of ionic liquid are quite different. Fig. 1 shows the morphology of NiMo coating in the absence and Fig. 4 exhibits the NiMo coating morphology in the presence of ionic liquid additive. It also seems that surface preparation has inuenced on morphology of NiMo coatings in the presence of

Fig. 2. Relationship between pH and Mo content on both mechanically and electrochemically polished substrates at 40 C in additive-free solution.

Fig. 3. Relationship between temperature and Mo content on both mechanically and electrochemically polished substrates at pH 9.5 in additive-free solution.

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Fig. 4. SEM micrographs of NiMo deposits in sulfatechloride bath in the absence of 1-methyl-imidazolium chloride additive using pulse technique at pH = 8.5 and 40 C on mechanically (a, b) and electrochemically (c, d) polished substrates.

ionic liquid. Fig. 4(c) and (d) indicate the NiMo coating morphology onto electrochemically polished substrate and Fig. 4(a) and (b) represent the coating morphology onto mechanically polished substrate. Comparison between the above mentioned morphologies in Fig. 4 demonstrates that surface preparation apparently can inuence the morphologies of NiMo electrodeposits in the presence of ionic liquid additive. To study the effect of temperature on the NiMo coatings in the presence of 100 ppm 1-methyl-imidazolium chloride ionic liquid, temperature was varied from 40 C to 60 C while pH was kept xed at 9.5 (pulsing parameters were kept also xed). Fig. 5 illustrates the variation of Mo content as a function of temperature at constant pH 9.5. Fig. 5 shows that in the presence of 100 ppm ionic liquid and onto electrochemically prepared substrate, Mo content is increased by increasing the temperature, but a dissimilar behavior can be observed for mechanically polished substrate. These two different trends may be due to the surface preparation method, but it needs more investigations. Fig. 6 illustrates the morphology and microstructure of NiMo coatings onto electrochemically polished substrate at different temperatures of 50 C and 60 C. Fig. 6(a) and (b) compares the microstructure and morphology of alloy coatings at two different temperatures. By comparison between Fig. 6(a) and (b), it is revealed that by increasing the temperature, surface smoothness decreases and at higher temperatures, coatings with higher roughness could be obtained. Moreover pH variations have been also investigated. Fig. 7 shows that in the presence of 100 ppm 1-methyl-imidazolium chloride ionic liquid, high Mo content NiMo coatings were obtained only at pH = 8.5. As mentioned before, this considerable results were obtained at pH = 8.5 onto either electrochemically or mechanically polished substrate whereas in the absence of ionic liquid additive and at mentioned acidity, the coating cannot be deposited. EDX spectra represent the Mo content of NiMo deposit in the presence of ionic liquid additive at pH = 8.5 and 40 C temperature exceeds 47 wt.% while in the absence of ionic liquid additive and at the same condition (pH = 8.5 and 40 C temperature) no

coatings were deposited. SEM micrographs (Fig. 8) represent that at higher pH, smoother coatings were deposited. Fig. 8(b) shows the morphology of NiMo coating at temperature 40 C and pH 10.5 in the presence of 100 ppm 1-methyl-imidazolium chloride ionic liquid additive, and Fig. 8(a) illustrates NiMo deposit with more surface roughness at the same condition and pH 9.5. 3.3. X-ray diffraction analysis The structural properties of the deposits were determined using X-ray diffraction method (Fig. 9). Patterns A and B are related to NiMo deposits in the presence of 1-methyl-imidazolium chloride ionic liquid as an additive and pH 9.5 onto electrochemically and mechanically

Fig. 5. Relationship between temperature and Mo content in the presence of 1-methylimidazolium chloride additive on both mechanically and electrochemically polished substrates at pH 9.5.

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Fig. 6. SEM micrographs of NiMo deposits in sulfatechloride bath in the presence of 100 ppm 1-methyl-imidozalium chloride using pulse technique at pH = 9.5 onto electrochemically polished substrate at 50 C (a) and 60 C (b).

Fig. 8. SEM micrographs of NiMo deposits in sulfatechloride bath in the presence of 100 ppm 1-methyl-imidozalium chloride using pulse technique at temperature 40 C onto mechanically polished substrate at pH = 9.5 (a) and pH = 10.5 (b).

polished substrate respectively. A brief analysis of the X-ray spectra of the NiMo coatings deposited from the citrate ammoniacal bath, leads to a conclusion that at above conditions, the structure of the electrodeposited NiMo alloy becomes amorphous-like due to the appropriate widening of the diffraction peaks. The diffractograms obtained for NiMo coatings exhibit the shapes typical for the nanostructured deposits and contain one broad peak; the (1 1 1) preferred orientation becomes more pronounced. Such X-ray pattern and preferred orientation is also reported by other researcher [32,37,38]. The crystal sizes could be estimated from the peak width using the Scherrer's equation modied by Warren and Biscoe [35]:

where is the grain size, is the position of the peak in the diffractogram, is the wavelength (in ), and is an integral the peak broadening (in radians) which approximated [36] as full width at half maximum (FWHM). For estimating the crystal size, an average value is considered for FWHM (or ). The mean crystal sizes determined from the peak width using above formula are 10 nm for coatings onto both mechanically and electrochemically substrate at pH 9.5. Table 1 represents the mean crystal size of NiMo deposits at different pH. All results in Table 1 demonstrate that at present condition, nickelmolybdenum coatings have been deposited with amorphous/nanocrystalline structure. The

0:94 cos

Fig. 7. Relationship between pH and Mo content in the presence of 1-methyl-imidazoliumchloride additive on both mechanically and electrochemically polished substrates at 40 C.

Fig. 9. X-ray diffractograms obtained for NiMo alloys plated from sulfate chloride solution and in the presence of 100 ppm 1-methyl-imidazolium-chloride at temperature 40 C on mechanical polished substrate at pH= 9.5 (A) and pH= 8.5 (C), on electropolished substrate at pH= 9.5 (B) and pH= 8.5 (D).

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Table 1 Estimated grain size of amorphous/nanocrystalline NiMo coatings electrodeposited from sulfatechloride solution at 40 C in the presence of 1-methyl-imidazolium chloride additive. Mo content (wt.%) 46.9 50.1 32.6 33.1 28.2 24.9 Bath pH 8.5 8.5 9.5 9.5 10.5 10.5 Surface preparation Mechanically polished Electrochemically polished Mechanically polished Electrochemically polished Mechanically polished Electrochemically polished Estimated grain size (nm) 38 45 10 10 15 9

results obtained in this work agree well with the calculations and experiments done by Donten et al. [37] and Chassaing [32]. It is reported that, when the Mo content exceeds 20 at.% the alloy gives wide X-ray diffractograms, which prove that the deposit is nanostructured [37]. 4. Conclusions NiMo alloy coatings containing more than 49 wt.% Mo have been electrodeposited onto mild steel from aqueous ammonia citrate solution with pulse plating technique in the presence of ionic liquid 1-methyl-imidazolium-chloride additive. These high Mo content deposits were plated in the presence of ionic liquid additive at pH 8.5, whereas at this pH no proper coatings were deposited without additive. Present condition leads to amorphous/nanocrystalline NiMo coatings. It also concluded that surface preparation has signicant effect on coating morphology. Acknowledgment The authors would like to acknowledge Mr. Shali and Mr. Pouransari for their support. Also the authors wish to gratefully appreciate Dr. Nabhani, Mr. Sayyar and Mr. Salehi for their kind assistance. References
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