Electrochemical synthesis of Fe-W and Fe-W-P magnetic amorphous films and Fe-W nanowires

Accepted Manuscript Electrochemical synthesis of Fe-W and Fe-W-P magnetic amorphous films and Fe-W nanowires

E.P. Barbano, I.A. Carlos, E. Vallés PII: DOI: Reference:

S0257-8972(17)30550-9 doi: 10.1016/j.surfcoat.2017.05.071 SCT 22390

To appear in:

Surface & Coatings Technology

Received date: Revised date: Accepted date:

22 March 2017 23 May 2017 24 May 2017

Please cite this article as: E.P. Barbano, I.A. Carlos, E. Vallés , Electrochemical synthesis of Fe-W and Fe-W-P magnetic amorphous films and Fe-W nanowires, Surface & Coatings Technology (2016), doi: 10.1016/j.surfcoat.2017.05.071

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Electrochemical synthesis of Fe-W and Fe-W-P magnetic amorphous films and Fe-W nanowires E.P. Barbano[a], I.A. Carlos [a], E. Vallés [b][,c]*

Departamento de Química, Universidade Federal de São Carlos, CP 676, 13565-905, São Carlos-

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[a]

SP, Brazil

Ge-CPN (Thin Films and Nanostructures Electrodeposition Group), Dpt. Ciència de Materials i

Química Física, Martí i Franquès 1, 08028 Barcelona, Spain

Institute of Nanocience and Nanotechnology (IN2UB), Universitat de Barcelona

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[c]

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[b]

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*Corresponding Author: Prof. Elisa Vallés

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e-mail: [email protected] Fax: +34 934021231

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Abstract

Binary and ternary Fe-W and Fe-W-P films have been obtained electrochemically by using an alkaline stable bath of Fe(III) with a new complexing agent (nitrilotriacetic acid trisodium salt

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monohydrate-NTA), adequate to avoid carbon incorporation in the deposits and assure the bath durability. The different stages to obtain the alloy deposits through induced co-deposition have

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been proposed. Significant tungsten percentages in the deposits have been obtained, resulting stable amorphous films with soft-magnetic properties. However, it has been necessary to simplify the deposition process to obtain Fe-W alloy nanowires by means of induced co-deposition in the interior of polycarbonate membranes. For first time, Fe-W magnetic nanowires have been synthesised by templated induced co-deposition.

Keywords: Iron-tungsten films and nanowires, amorphous alloys, magnetic binary and ternary iron alloys, induced co-deposition

ACCEPTED MANUSCRIPT 2 1. Introduction

Amorphous alloys present increasing interest due to the absence of order in the atom arrangement. They can be formed by means of rapid cooling to obtain non-equilibrium conditions [1], but the electrochemical pathway has demonstrated its capability as an alternative method to

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prepare amorphous alloys of modulated composition. Some metastable alloys have been electrochemically prepared, without observing a variation of its properties with time. In our

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laboratory, we have obtained some amorphous alloys electrochemically, by means of selected

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electrolytic baths and/or applying significantly fast deposition rates [2]. High deposition rates

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favour the formation of alloys different than those predicted from the phase diagram [3]. However, when very negative potentials or current densities are applied for electrodeposition of

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alloys at high speed, frequently powders are formed instead of uniform and compact films.

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Some researchers prepare electrochemically Fe-W quasi-amorphous powders [4] with moderate

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tungsten percentages. Our interest is the use of electrochemical techniques to prepare, at room temperature, homogenous and compact amorphous Fe-W magnetic films. The amorphous alloys are very interesting due to their habitual soft-magnetic behaviour, being applicable in sensors,

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transformers’ cores, inductive devices, recording media and magneto resistive applications. The

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Fe-W alloy can be a promising material for these applications [5]. The presence of tungsten alloyed with ferromagnetic metals confers them durability and heat resistance [6] because increase the nobleness of the metallic material. The amorphous structure confers stability to the alloy respect to similar crystalline alloy because improves corrosion resistance [7]. Tungsten can be electrochemically deposited only in the presence of metals such as nickel or cobalt, through an induced co-deposition [8]. A few authors obtained Fe-W alloy by means of electrodeposition in citrate-containing solutions [9-13], although in this case a few carbon can be incorporated during the formation of the deposits. A general accepted mechanism for induced co-deposition of Mo or

ACCEPTED MANUSCRIPT 3 W with iron-group metals (M) in the presence of citrate implies the formation of M(II)-citrate complexes, which favour molybdate or tungstate reduction to form adsorbed species composed of Mo or W oxides with the citrate complexes, evolving to metallic Mo or W [13,14].

The objective of the present work is the electrochemical preparation of Fe-W and Fe-W-P

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compact amorphous films and the characterization of their magnetic properties. A new alkaline electrolytic bath containing Fe(III) and nitrilotriacetic acid trisodium salt monohydrate (NTA) as

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complexing agent is selected, with the objective of avoiding the reduction of the ligand during the

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deposition, because we have found that several proportion of molybdate can be co-deposited

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with iron group metals from the proposed bath [15]. In the present work, we have tested, therefore, the induced co-deposition of Fe and W in the proposed bath. The incorporation of

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phosphorous in the alloy have been also tested, because its presence usually enhances the

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tendency of formation of amorphous deposits.

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Also, the possibility, for the first time, of obtaining electrochemically magnetic Fe-W nanowires is analysed. Induced co-deposition to grow Fe-W nanowires has been tested and the magnetic

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properties of the nanowires have been compared with those of the corresponding films.

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2. Experimental section

The electrodeposition baths for obtaining Fe-W and Fe-W-P films were aqueous solutions of 0.022M FeCl3 + 0.0275M Na2WO4 + 0.176M NTA (Fe-W bath) and 0.022M FeCl3+ 0.0275M Na2WO4 + 0.0385M Na2H2PO2 + 0.176M NTA (Fe-W-P bath), being the formula of NTA: N(CH2COONa)3 · H2O.The pH of each solution was adjusted to 8.0. Fe(III) salt was used to confer stability to the bath, significant concentration of tungstate allows to obtain deposits with high proportion of tungsten and, then, with amorphous structure, and high concentration of NTA assures iron ions

ACCEPTED MANUSCRIPT 4 complexation. On the other hand, alkaline pH is adequate to minimize hydrogen evolution during the co-deposition. For Fe-W nanowires preparation, a 0.022M FeCl2 + 0.088M sodium citrate+ xM Na2WO4(x between 0.0069 and 0.0275M) was used, adjusting the pH at 4.0. A simpler bath was selected to obtain the nanowires after detecting the difficulty of grown the nanowires by means of the initial

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complex bath to induce the deposit formation in the interior of the channels of the membrane.

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All the reagents were of analytical grade and the water was purified by means of a Millipore MilliQ system.All electrochemical experiments were carried out at room temperature (20 °C) with

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a Ag/AgCl/3.0M KCl/Luggin capillary as reference electrode and a Pt plate as a counter electrode.

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The Fe-W and Fe-W-P deposition process was studied over Cu disks (0.5 cm2) as working electrode. The deposits of Fe-W and Fe-W-P were obtained over both Cu disks or

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Si/Ti(10nm)/Au(100nm) pieces (prepared in the Institute of Microelectronics of Barcelona IMBCNM (CSIC)). Fe-W nanowires were grown in track edged polycarbonate (PC) membranes

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(Millipore), 20 µm thick, with nominal pore’s density of 1x108–2.5x109 pores cm-2and 100 nm of

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pore’s diameter, with an evaporated gold layer of 100 nm in one side of the membrane to enable

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conductivity.

Voltammetric studies and Chronoamperometric curves were recorded with a microcomputer-

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controlled AUTOLAB potentiostat/galvanostat PGSTAT 30 equipment and processed with the GPES software. Field-emission Scanning Electron Microscope (SEM) photographs were obtained with a JEOL JSM 6510 equipment. Semi-quantitative chemical analysis of the electrodeposits was performed by means of Energy-Dispersive X-ray Spectroscopy (EDS), by using Oxford Microanalysis System INCA software. Thickness of the coatings was measured using a Zygo NEW VIEW 100 white-light interferometer together with SensoScan DCM 3D Optical image profiler software.

ACCEPTED MANUSCRIPT 5 X-ray diffraction (XRD) profiles were recorded with Cu K radiation (1.5406Å), using a X-ray generator equipped with a goniometer, in 2scanning mode (from 2 = 10.0o to 120.0o in steps of 0.033oand a time per step of 600 s). Magnetic curves were recorded at room temperature (300 K) in helium atmosphere using a Superconducting Quantum Interference Device (SQUID) magnetometer. The magnetization-magnetic field curves were recorded by applying the magnetic

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field in parallel or perpendicular configuration to the samples.

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3. Results and discussion

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The voltammetric study of the Fe-W and Fe-W-P electrodeposition processes in the selected electrolytic bath allowed us to define the potentials range in which electrodeposition was

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possible, avoiding both the formation of tungsten oxides and a significant hydrogen evolution. The voltammetry curves in Figure 1 show, after the Fe(III) to Fe(II) reduction process, at around -

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0.3 V, new reduction current at more negative potentials, assigned to a first tungstate reduction

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(started at -1.1 V) to form tungstate oxides. This is proposed according to similar behaviour observed in molybdate-containing solutions [15], and corroborated by the detection of only

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tungstate oxides in this potential zone. At more negative potentials, from -1.3 V, alloy formation (Fe-W or Fe-W-P) and hydrogen evolution take place. Alloy oxidation was detected in a single

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peak centred at -0.75 V, a peak obtained only when the cathodic limit was more negative than 1.3 V. Similar voltammetic curves were obtained for the deposition process on Cu and on Si/Ti/Au substrates.

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10

FeW FeWP

0 -10 0

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C1 -3

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j / mA cm-2

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-30

-1.8

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Figure 1. Cyclic voltammogram at 10 mV s-1 of Fe-W (solid line) and Fe-W-P solutions (dashed line)

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on copper substrate.

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The same potentials were selected for form both Fe-W and Fe-W-P films because very similar

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voltammetric curves were obtained in both cases, which reveals that the presence of hypophosphite in the electrodeposition bath does not disturb the mechanism of the Fe-W electrodeposition. The deposits were prepared potentiostatically on both copper and Si/Ti/Au

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substrates. The same morphology and composition of the deposits were obtained over the two

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substrates. Si/Ti/Au were preferred as substrate for the deposits characterization because they are flat and thinner and, moreover, the thin Ti/Au conductive seed-layer does not interfere in the compositional analysis and magnetic response of the deposits. Two representative Chronoamperometric curves of Fe-W and Fe-W-P potentiostatic deposition process over Si/Ti/Au are shown in Figure 2. The shape of the curves is typical of a nucleation and growth process in stirring conditions [16], although the increase of the current density with time can be justified by the increase of the roughness of the deposits that implies a gradual increase of the effective area [17].

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FeW FeWP

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j / mA cm-2

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Figure 2. Chronoamperometric curves, at -1.8 V of the electrodeposition of Fe-W (dark grey line)

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and Fe-W-P (black line) on Cu substrate.

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By applying potentials more negative than -1.3 V, Fe-W or Fe-W-P films were obtained, depending

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on the bath composition. Figure 3 shows the binary and ternary deposits obtained at two different potentials; irregular Fe-W deposits were obtained (Figure 3(a) and (b)), which were more uniform and fine-grained when they contained phosphorous (Figure 3, (c) and (d)). The deposits

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prepared in the Fe-W-P solution show evident round holes consequence of simultaneous

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hydrogen bubbles formation, but the size of the voids minimized when the deposition potential was more negative. The presence of Na2H2PO2 in the solution led to a greater uniformity of the films.

The results show that induced co-deposition took place in the presence of Fe, because W was not obtained in the absence of iron. Similar induced co-deposition was observed for Fe-Mo alloy in an electrolytic bath containing NTA [15]. In the accepted mechanism of CoMo or NiMo induced codeposition in the presence of citrate [13,14,18,19], molybdenum oxides are initially formed by

ACCEPTED MANUSCRIPT 8 reduction of the molybdate of the electrolytic bath, followed by the formation of an adsorbed (Cocit- or Nicit- molybdenum oxide) intermediary that, finally, promotes the molybdenum oxides reduction next to the metal deposition. In a similar way, the formation of Fe-W deposits can occur through the formation of Fe-WO4-NTA adsorbed species, precursor for the Fe-W alloy deposition. From voltammetric results the following stages are proposed to justify the induced co-deposition:

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Reduction of Fe(III)-NTA complexes; tungstate reduction to form tungsten oxides, and adsorption of NTA-Fe(II) complexes with the oxides to promote the deposition of W that incorporates in the

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Fe deposit. Binary and ternary iron-alloy deposits could be, therefore, obtained by

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electrodeposition in the selected baths, with significant W percentage to confer durability,

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stability to the deposits and to induce amorphous structure with specific magnetic properties.

Figure 3. SEM images of deposits (0.5 µm thick) on Si/Ti/Au substrate, obtained in Fe-W solution ((a) -1.5 V, (b) -1.8 V,) and in Fe-W-P solution ((c) -1.5 V, (d) -1.8 V). Scale bar: 5 µm.

ACCEPTED MANUSCRIPT 9 Table 1.-Composition (by EDX) of the binary and ternary deposits prepared at two potentials on Si/Ti/Au substrates

Fe-W E/V

Fe-W-P W/

Fe /

W/

P/

wt.%

wt.%

wt.%

wt.%

wt.%

-1.5

72

28

69

29

-1.8

68

32

71

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Fe /

4

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25

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The magnetic properties of the films prepared over Si/Ti/Au substrates were determined by

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recording the magnetization-magnetic field hysteresis curves of the samples, by applying the magnetic field parallel or perpendicular to the substrate. Figure 4 shows that the two magnetic

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curves, in parallel or perpendicular configuration, attain the magnetization of saturation at

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different applied magnetic fields. This can be justified because the electrodeposits have shape anisotropy (2D shape, with 5 mm long, 5 mm wide, 0.5 µm thick, aspect ratio: 2000), which

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favours an easy magnetisation in the direction parallel to the samples [20]. In general, thin films are less magnetized when the field is applied perpendicularly to the film plane because the

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inverse magnetic poles that are generated on the films surfaces imply a large demagnetizing field. The samples show a very vertical magnetic curve and a low coercivity (30-70 Oe), as it corresponds to a soft-magnetic behaviour. The incorporation of P in the deposits doesn’t modify significantly the coercivity of the films.

The X-ray diffraction profiles of the Si/Ti/Au/Fe-W(P) samples show the absence of narrow diffraction peaks of the coatings, which allows to propose the formation of non-crystalline deposits. Gold diffraction peaks, especially those corresponding to the Au(111) and Au(222)

ACCEPTED MANUSCRIPT 10 reflections, are significant, which demonstrates the clear preferred orientation of the gold seedlayer; also, the silicon response is observed at around 70 °2θ (Figure 5). The presence of the Fe-W or Fe-W-P films on the substrate is reflected in the high background in the diffractograms respect to those of the substrate, as a consequence of the iron absorption, and in wide band partially masked by the presence of the (111) peak of gold. Therefore, amorphous films (or highly nano-

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crystalline) seem to be formed due the presence of high proportion of W in the deposits and they

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are also favoured by the incorporation of P in the ternary deposits.

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Figure 4.Magnetization curves of Fe-W and Fe-W-P deposits (0.5 µm) prepared at -1.8 V.

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Figure 5. X-Ray diffractograms of Fe-W and Fe-W-P films (5 µm) obtained at -1.8 V over Si/Ti/Au pieces.

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From the obtained results, the preparation of amorphous magnetic Fe-W based alloys by means

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of induced co-deposition in a simple electrolytic bath has been possible. Moreover, in this work the possibility of obtaining Fe-W or Fe-W-P nanowires into gold-coated polycarbonate membranes has been tested for a first time. However, from the selected bath, no alloy wires were obtained by applying deposition potentials in the -1 to -1.8 V range and using different concentrations of NTA (0.176 M, 0.083 M) or deposition charges. We then tried to electrodeposit pure iron nanowires from Fe(III) + NTA or Fe(II) + NTA solutions at different pH (8 and 4) with negative results. Therefore, the presence of very complexated metals and the use of Fe(III) salts involves an added difficulty for the formation of metallic nanowires in the narrow channels of the

ACCEPTED MANUSCRIPT 12 membranes. Therefore, in order to favour the formation of iron nanowires, solutions of Fe(II) salts without complexing agents or with moderate citrate concentration (0.083 M) have been tested, resulting in the formation of well-defined Fe nanowires. In order to obtain Fe-W nanowires, solutions containing FeCl2, 0.083 M of citrate and different concentrations of sodium tungstate have been tested (Table 2), by applying in all cases a deposition potential of -1.5 V. Fe-W

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nanowires were formed in these conditions, detected as black wires in the inner of the polycarbonate membrane. After removing the gold seed layer using a saturated solution of I2/I-,

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the polycarbonate membrane was dissolved with chloroform. The nanowires were exhaustively

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cleaned with chloroform, ethanol and water in order to observe them by means of SEM. The

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magnetic character of the nanowires allowed us an easy manipulation and retention of the

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nanowires by using a magnet.

Table 2. Composition of the electrolytic solutions used to obtain Fe-W nanowires and composition

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of the corresponding nanowires

[Sodium

Electrolytic

[FeCl2]

[Na2WO4]

citrate] /

/M

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solution

pH /M

Fe /

W/

wt.%

wt.%

Nanowires

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0.176

0.0275

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70

30

0.022

0.088

0.0137

4

85

15

0.022

0.088

0.0069

4

95

5

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Figure 6. SEM images (Scale bar: 2 µm) and magnetization-magnetic field curves of the Fe-W

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nanowires obtained in the conditions of Table 2

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In all cases well defined nanowires, of a few microns length and 100 nm of diameter, were obtained (Figure 6) with a tungsten percentage depending on the tungstate concentration in the solution (Table 2). The magnetic behaviour of the nanowires was analysed by recording the

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magnetization curves, maintaining the nanowires inside the membranes and applying the

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magnetic field parallel or perpendicularly to the nanowires axis (Figure 6). No differences between the magnetic responses in parallel or perpendicular configuration were observed except for the nanowires with higher W percentage, in which the nanowires show a faster response when applying the field perpendicularly to the nanowires axis. Moderate coercivities were obtained in all cases, in the 50-100 Oe range. Magnetic nanowires of modulated behaviour as a function of the composition were obtained.

ACCEPTED MANUSCRIPT 14 The induced co-deposition of W with Fe in the interior of the nanochannels of the polycarbonate membranes is more difficult that the corresponding deposition on flat substrates, requiring a simplification of the system. Direct reduction of the Fe(II) to Fe and citrate medium has been demonstrated useful to favour the tungstate oxides reduction leading to Fe-W nanowires.

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Conclusions

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The use of an electrolytic bath containing nitrilotriacetic acid trisodium salt monohydrate-NTA as

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complexing agent for Fe(III) has permitted, in alkaline solutions, the formation of Fe-W and Fe-W-

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P alloy films, which reveals that induced co-deposition of tungsten with iron has been possible, avoiding the use of usual acidic citrate baths. The high W percentages in the deposits make that

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they present amorphous (or nanocrystalline) structure, which induces a soft-magnetic behaviour in the films, which easily respond to the action of a magnetic field, especially when it applies in

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the direction parallel to the films. Phosphorous can incorporate during the deposition and the

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resulting ternary films maintain their amorphous and magnetic character. Fe-W nanowires are not formed by using the Fe(III)-NTA solution selected, which reveals that induced co-deposition is more difficult in the interior of the membrane’s channels. However, a

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simplified electrolytic bath containing lower concentrations of complexing agent (now citrate) and

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direct reduction of iron from Fe(II) has permitted a successful electrochemical synthesis of magnetic Fe-W nanowires by means of an induced co-deposition. It is the first time in which magnetic nanowires are obtained from induced co-deposition in the interior of membranes.

Acknowledgements

This work was supported by the EU ERDF (FEDER) funds and the Spanish Government grant TEC2014-51940-C2-2-R from Ministerio de Economía y Competitividad (MINECO).

ACCEPTED MANUSCRIPT 15 The authors thank the CCiT-UB for the use of their equipment. E.P.Barbano is grateful to the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) by the grant 2015 / 21788-0

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Graphical abstract

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FeW nanowires obtained for the first time by electrodeposition

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Binary FeW and ternary FeWP amorphous films from a new environmentally friendly electrolytic bath Control of the induced codeposition in films and nanowires

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Tuneable magnetic properties of films and nanowires as a function of the W percentage

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