- Email: [email protected]
TiNY2O3 composite ceramic coating for metallic parts protection by direct current deposition
Accepted Manuscript Preparation of Ni W/TiN Y2O3 composite ceramic coating for metallic parts protection by direct current deposition Baosong Li, Weiwei Zhang, Dandan Li, Jiajia Wang, Wei Chen, Yuying Liu PII:
S0272-8842(19)30820-X
DOI:
https://doi.org/10.1016/j.ceramint.2019.04.010
Reference:
CERI 21204
To appear in:
Ceramics International
Received Date: 29 November 2018 Revised Date:
7 March 2019
Accepted Date: 1 April 2019
Please cite this article as: B. Li, W. Zhang, D. Li, J. Wang, W. Chen, Y. Liu, Preparation of Ni W/ TiN Y2O3 composite ceramic coating for metallic parts protection by direct current deposition, Ceramics International (2019), doi: https://doi.org/10.1016/j.ceramint.2019.04.010. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Preparation of Ni-W/TiN-Y2O3 composite ceramic coating for metallic parts protection by direct current deposition
RI PT
Baosong Li a, *, Weiwei Zhang b, Dandan Li a, Jiajia Wang a, Wei Chen a, Yuying Liu a a
College of Mechanics and Materials, Hohai University, Nanjing 211100, China
b
College of Mechanical and Electrical Engineering, Hohai University, Changzhou
Corresponding author.
AC C
EP
TE D
E-mail address: [email protected] (B. Li)
M AN U
*
SC
213022, China
ACCEPTED MANUSCRIPT
Abstract A novel Ni-W/TiN-Y2O3 composite ceramic coating has been synthesized by direct current deposition for metallic parts protection. The structural, morphology, hardness and
RI PT
anti-corrosion properties of the Ni-W/TiN-Y2O3 coating have been evaluated by SEM, EDS, TEM, XRD and EIS methods. Results indicated that the samples have uniform and compact nodular structure without defects. It demonstrated that the TiN and Y2O3 nanoparticles had
SC
been uniformly distributed in the composites. The incorporation of TiN and Y2O3 in Ni–W
M AN U
matrix could improve the hardness and anti-corrosion properties. The crystallite size was in the diameter of 13-16 nm. The electrochemical results illustrated that 6-8 Adm-2 and 30 min were beneficial to the improvement of anti-corrosion behaviors of the produced composite coating. After immersed 168 h in 3.5 wt.% NaCl aqueous solution, the coating prepared at 30
TE D
min and 2 A dm-2 owns better anti-corrosion properties. The embedded TiN and Y2O3 nanoparticles in Ni-W matrix could decrease the electrochemical activity and enhance the
EP
protective properties.
Keywords: Ni-W/TiN-Y2O3; Composite ceramic coating; Direct current deposition;
AC C
Corrosion resistance; Hardness
ACCEPTED MANUSCRIPT
1. Introduction In the last few years, Ni-W alloys have obtained much attention for its superior wear resistance, hardness and anti-corrosion properties [1]. Nevertheless, the increasing
RI PT
requirements for better protective performance in aggressive conditions promote the development of metal matrix composites (MMCs) [2]. MMCs were fabricated by incorporation of the reinforcing phase in the metallic matrix, which both have the
SC
predominant features of the metal matrix and the reinforcing phase [3, 4]. Recently, much
M AN U
attention focuses on the preparation of nanoparticle reinforced Ni-W MMCs [5, 6]. Till now, literature reported the addition of nanoparticles such as BN [7, 8], SiC [9, 10], TiO2 [11], ZrO2 [12], WC [13], Al2O3 [14, 15], Si3N4 [4, 16] in Ni-W alloys to fabricate MMCs for enhanced performance. Titanium nitride (TiN) owns good features including
TE D
excellent hardness, superior high-temperature stability and satisfying chemical inertia [17-19] and could be used to reinforce the hardness and corrosion resistance of metallic coating in
EP
various fields [20, 21].
Recently, we found that there are very few reports concerning the co-deposition of more
AC C
than one kind of particles together into one deposit [22]. Limited literature [3] illustrated that a combination of two materials in a desirable fashion might provide better performance than any one of them. Yttria (Y2O3) owns excellent thermal and chemical stability, high mechanical and anti-corrosion properties [23, 24]. Therefore, a novel MMC was designed for enhanced mechanical and anti-corrosion characteristics by incorporation of TiN and Y2O3 particles in Ni-W alloy. However, to the best of our knowledge, the application of direct current (DC) deposition for producing Ni-W/TiN-Y2O3 MMCs has not been yet investigated.
ACCEPTED MANUSCRIPT Till now, no investigation is concerning the morphology, structure, hardness and anti-corrosion behaviors of the Ni-W/TiN-Y2O3 MMCs fabricated by DC deposition. Thus, here, the efforts were made to prepare Ni-W/TiN-Y2O3 MMCs by DC deposition
RI PT
using nanoscale Y2O3 and TiN particles as the reinforcing phase for Ni-W matrix. The microstructure, morphology, hardness and electrochemical properties of the samples were
Ni-W/TiN-Y2O3 MMCs by DC deposition.
M AN U
2. Experimental
SC
studied. To the best of our knowledge, this is the first attempt on the co-deposition of
2.1 Preparation
Ni-W/TiN-Y2O3 MMCs have been synthesized by DC deposition from the following bath solution: 0.12 mol L–1 NiSO4·6H2O, 0.2 mol L–1 Na2WO4·2H2O, 0.4 mol L–1
TE D
Na3C6H5O7·2H2O, 0.5 mol L–1 NH4Cl, 0.001 g L–1 SDS, 30 g L–1 TiN and 6 g L–1 Y2O3 nanoparticles. All chemical reagents were analytical grades supplied by Shanghai Aladdin
EP
Biochemical Technology Co., Ltd and used as received. The particle sizes of TiN (purity＞ 99.9%) were 20-50 nm with face-centered cubic structure purchased from Shanghai Chaowei
AC C
Nanotechnology Co., Ltd. Y2O3 nanoparticles (﹤100 nm, 99.9%) were provided by Shanghai Aladdin Biochemical Technology Co., Ltd. The electrodeposition setup is shown in Fig. 1. A DDK-II high frequency test power (20A/12V, Shaoxing CTN Electronic Co., LTD.) was utilized as a galvanostat (direct current power supply) to electrodeposit the composite coating. If only use a single anode, it just needs to cover the back of the cathode with an insulating plastic membrane. In the process of galvanostatic electrodeposition, the deposition parameters of plating bath temperature, pH value, stirring rate were kept constant at 65±2°C, 8.4±0.1,
ACCEPTED MANUSCRIPT 450±50 rpm, respectively. The effect of current density (2, 4, 6 and 8 A dm-2) and deposition time (15, 30 and 60 min) parameters on the structure and properties of the composite coating were investigated. The cathode and anode were nickel plate and copper sheet, respectively.
RI PT
The distance between the cathode and anode was 3.0 cm. Prior to each experiment, the substrates were cleaned and immersed in 7.2 wt. % HCl solution for 30 s. Before electrodeposition, the solution was agitated for more than 30 min and ultrasonic cleaning for
SC
more than 10 min. It is worth noting that the magnetic stirring and ultrasonic dispersion were
M AN U
continuously performed during the electrodeposition. After electrodeposition, the product was
EP
TE D
ultrasonically treated for 5 min and then washed by purified water.
AC C
Fig. 1. Schematic diagram of the co-electrodeposition setup.
2.2 Characterization
The morphology and composition of the Ni-W/TiN-Y2O3 MMCs were observed by scanning electron microscope (SEM, FEI Inspect F50 and HITACHI S-4800) and the affiliated energy dispersive spectrometer (EDS, Oxford). The structure was analyzed by X-ray diffraction (XRD, Bruker D8 advance). The crystallite size was calculated based on the
ACCEPTED MANUSCRIPT Debye-Scherrer equation. The hardness was measured by a Vickers hardness tester (DHV-1000 type) using 100 g-force load lasting for 10 s. The electrochemical behaviors were investigated in 3.5 wt.% NaCl solutions on CHI 660E potentiostat. The saturated calomel
RI PT
electrode (SCE) was used as reference electrode. The potentiodynamic polarization curves were tested at 5 mV/s. EIS was performed at Eocp at the input amplitude 10 mV ranging from 105 to 10–2 Hz. Before testing, the samples were soaked in 3.5wt.% NaCl solution for 1 h and
SC
168 h, respectively.
M AN U
3. Results and discussion 3.1 Surface morphologies
Fig. 2 describes the SEM images of the as-plated Ni-W/TiN-Y2O3 MMCs in thickness of
TE D
6.7 µm electrodeposited at 4 A dm-2 for 15 min by DC deposition with different magnification. As seen in Fig. 2, all produced Ni-W/TiN-Y2O3 MMCs have compact, uniform structure without defects, exhibiting a nodular surface morphology. In microscale, Fig. 2a exhibits
EP
nodular structure with different dimensions of nodules, circular or quasi-circular in shape,
AC C
which is consistent with the Ni-W composite coating reported by Beltowska-Lehman [12]. It was observed that the nodules diameter varied from 8.5 µm to 0.4 µm. Fig. 2b were the enlarged images of the rectangular region in Fig. 2a. As seen in Fig. 2b, it was found that the granules are composed of many small crystals. Some granules exhibited a needle-like shape. Kalaignan [25, 26] reported that the Ni-W alloy matrix has long needle-shaped particles and the surface morphology was modified to flower like structure after the inclusion of PTFE particles, which is similar with this result. In nanoscale, as shown in Fig. 2b, it was noticed
ACCEPTED MANUSCRIPT that the embedded small particles were evenly dispersed in the Ni-W matrix; and some large
SC
RI PT
needle-shaped Ni-W metallic grains were also observed.
M AN U
Fig. 2. SEM micrograph of Ni-W/TiN-Y2O3 MMCs obtained at 4 A dm-2 for 15 min by DC deposition with magnification times (a) 5×103and (b) 1×105.
Fig. 3 presents the morphology of Ni-W/TiN-Y2O3 MMCs in thickness of 13.4 µm fabricated at 4 A dm-2 and 30 min. It illustrated that the coating prepared at 30 min has
TE D
nodular structure. Compared with the coating deposited at 15 min (Fig. 2), the nodular granules were fine and the coating was smooth and uniform. In the low magnification images
EP
(5×103) as presented in Fig. 3a, the Ni-W/TiN-Y2O3 MMC presents a dense structure with fine nodular granules. It revealed that some dome-like “island” structure appears and the
AC C
amount of the large “island” reduces. In the enlarged images of Fig. 3b (1×105), it was observed that the spherical granules comprising many large crystals and nano-sized particles; and the nanoparticles were uniformly distributed in the obtained coating. Comparing these images, the morphology of the sample produced at 30 min has less irregularity.
RI PT
ACCEPTED MANUSCRIPT
SC
Fig. 3. SEM micrograph of Ni-W/TiN-Y2O3 MMCs fabricated at 4 A dm-2 for 30 min by DC deposition with magnification times (a) 5×103 and (b) 5×104.
M AN U
Fig. 4 shows the morphology of the coating in thickness of 21.6 µm deposited at 4 A dm-2 and 60 min. It was noticed that the dome-like structure diminished and the granules size decreases. Compared with the coating deposited at 15 min (Fig. 2b) and 30 min (Fig. 3b), it was observed in Fig. 4b that more nanoparticles in the dimension of 50 nm have been
TE D
distributed in the metallic matrix. However, it indicated that the size of surface granules made up of needle-shaped Ni-W crystals increased as the deposition time increased. In addition, the
EP
coating presents dense structure without detected cracks. It indicated that the long deposition time is necessary for more nanoparticles incorporated in the metallic matrix, which will be
AC C
beneficial for the improvement of the performances.
ACCEPTED MANUSCRIPT Fig. 4. SEM micrograph of Ni-W/TiN-Y2O3 MMCs fabricated at 4 A dm-2 for 60 min by DC deposition with magnification times (a) 2×105 and (b) 1×105. Fig. 5 presents the TEM image of the coating with thickness 13.5 µm deposited at 4 A
RI PT
dm-2 and 30 min. The white and black areas are attributed to the Ni-W matrix and nanoparticles, respectively. It demonstrated that the nanoparticles were successfully embedded in the metallic matrix. The dimensions of the embedded particles were in the range
SC
of 20-50 nm, which is consistent with the size of the particles used. The Ni-W crystal and
M AN U
TiN-Y2O3 particles in composite coating were in nanometer scale. Although some aggregations of nanoparticles in coating could be observed in TEM surface images, in general, the distribution of particles in composite coating is uniform. In addition, the coating exhibits a dense structure without noticeable cracks, pores or crevices. The interface between particles
TE D
and Ni-W matrix was found to be devoid of cracks or voids, indicating excellent interface bonding. The incorporation of TiN and Y2O3 nanoparticles will be beneficial for the improvement of hardness, wear resistance of Ni-W coating, which was confirmed by the
AC C
EP
existing literature [27, 28].
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 5. TEM image of Ni-W/TiN-Y2O3 MMCs fabricated at 4 A dm-2 for 30 min by DC deposition. 3.2 Cross-sectional observation
TE D
Cross-sectional images and EDS element line scanning of the Ni-W/TiN-Y2O3 composite coating were measured to observe the thickness, interface, as well as the distribution of
EP
embedded nanoparticles in bulk of the coating. Fig. 6a indicates that the coating thickness is 13.5 µm and the calculated growth rate is 0.45 µm min-1 at 4 A dm-2. Fig. 6b shows that the
AC C
bulk of the composite coating is compact and uniform with a good interface with the substrate, suggesting that satisfactory adhesion was obtained for the composite coating. The EDS element line scanning (Fig. 6c) displays the composition of the coating and illustrates that TiN and Y2O3 components were successfully incorporated in Ni-W matrix. Then, it confirms the formation of Ni-W/TiN-Y2O3 composite coating. It was also noticed that the content of Ni, W, Ti, Y is slightly fluctuated with the depth. This may be related to the consumption and the change of the concentration of the metal ions and particles near the cathode, as well as the
ACCEPTED MANUSCRIPT mass transfer process of the supplemental ions (or particles). In nanoscale, Fig. 6d (the enlarged red rectangular region in Fig. 6b) demonstrates that the particles in dimension of
TE D
M AN U
SC
RI PT
20-45 nm have been uniformly distributed in the deposited coating.
EP
Fig. 6. Cross-sectional images (a, b, d) and EDS element line scanning (d) of Ni-W/TiN-Y2O3
AC C
MMCs fabricated at 4 A dm-2 for 30 min by DC deposition. 3.3 XRD and EDS analysis Fig. 7 shows the XRD spectra of the deposited Ni-W/TiN-Y2O3 composite ceramic coating. As seen, all samples present fcc structure with similar XRD spectra which differ in intensity. For comparison, the XRD spectrum of the copper substrate is also shown in Fig. 7a. The diffraction peak at 44.1° attributes to Ni (111) crystal planes. The peaks at 51.5° and 75.5° correspond to Ni (200) and (220) phase, respectively (JCPDS No. 04-0850). It was confirmed
ACCEPTED MANUSCRIPT that the peaks at 42.4°, 49.4°, 72.3° and 87.6° are attributed to the copper substrate (JCPDS No. 04-0836). It needs to be noted that the thickness of coating prepared at 2, 4, 6 and 8 A dm-2 for 15 min were 2.7, 6.7, 8.6 and 10.8 µm, respectively. Due to the X-ray can penetrate
RI PT
the coating more than 10 µm which might be larger than the coating thickness, the peaks of copper substrate were emerged and overlapped the peaks of nickel. As seen, the substrate peaks at 49.4°, 72.3° and 87.6°gradually reduced as the current density increases, indicating
SC
the increase of the coating thickness. The peak of W was not observed, indicating the
M AN U
formation of Ni-W solid solution. The XRD peaks of TiN and Y2O3 particles were also not appeared which is ascribed to the low content of the particles in the coating. The crystallite sizes were calculated according to Scherrer’s equation. The crystallite size is in the dimension of 13-16 nm (Table 1). The preferred orientation at 43.9-44.1° is attributed to Ni (111) phase.
TE D
In Fig. 7a, the coating prepared at 2 Adm-2 has the smallest crystallite size. As the current density increases, the peaks of Ni (220), (200) plane slightly augmented, while the (111) peaks fluctuated. The grain sizes slightly enlarged from 13 nm to 15 nm as current density
AC C
large.
EP
increases from 2 A dm-2 to 8 A dm-2. In general, the change of the crystallite size was not
ACCEPTED MANUSCRIPT Fig. 7. XRD patterns of Ni-W/TiN-Y2O3 MMCs obtained by DC deposition as a function of (a) current density (t=15min) and (b) deposition time (i=4A dm-2). Fig. 7b displayed the XRD spectra of the Ni-W/TiN-Y2O3 MMCs as a function
RI PT
deposition time. As the deposition time increases, the peaks of the substrate gradually disappeared, indicating the increase of the coating thickness. The intensity of the primary (111) diffraction peak decreases as the deposition time increases. The deposition time had no effects
SC
on the diffraction angle. The peak of TiN and Y2O3 particles was not appeared, but the
M AN U
existence was verified by the following EDS results. According to the primary (111) peak at 44.1°, the crystallite size calculated were of 14-16 nm and slightly enlarged as deposition time increases.
Table 1 Crystallite size of Ni-W/TiN-Y2O3 MMCs prepared by DC deposition
TE D
Parameters Current density (A dm-2)
EP
Deposition time (min)
Values 2 4 6 8 15 30 60
Crystal size (nm) 13±1 14±1 14±1 15±1 14±1 15±1 16±1
AC C
Surface element distribution map was measured by EDS. Fig. 8 presents the element distribution map of the sample prepared at 4 A dm-2 for 15 min. It illustrated that the coating consists of Ni, W, Ti, N, Y and O, as well as C component. It indicated that Ni, W elements are homogeneously dispersed in the deposits. It also demonstrated that the TiN and Y2O3 particles were evenly embedded in Ni-W matrix.
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 8. EDS mapping of Ni-W/TiN-Y2O3 composite ceramic coating. Fig. 9 demonstrated that 1.1 wt.% TiN and 0.45 wt.% Y2O3 nanoparticles were incorporated in the Ni-W matrix. It is noted that the contents of TiN and Y2O3 were calculated
TE D
on the basis of the stoichiometric relationships between Ti and TiN, Y and Y2O3, respectively. In addition, the sample comprises 75.2 wt.% Ni and 22.6 wt.% W. It also demonstrated the
AC C
EP
inclusion of the nanoparticles in the produced coating.
Fig. 9. EDS spectra of the electrodeposited Ni-W/TiN-Y2O3 MMCs
ACCEPTED MANUSCRIPT 3.4 Microhardness The hardness was measured with a Vickers hardness tester (DHV-1000 type) at a load of
as follows. =
(1)
RI PT
100 g-force lasting for 10 s. The value of Vickers hardness is calculated by using the formula
where F is the applied load in gram and d is the length of the diagonals of the diamond
SC
pyramidal impression (µm). The quoted hardness value was the statistical average value of 5
M AN U
indentations conducted at different sites on each sample. Fig. 10 shows the hardness of the Ni-W/TiN-Y2O3 MMCs as a function of current density and deposition time. As indicated in Fig 10a, as the current density increases, the hardness first increases from 432 HV to the maximum value of 980 HV at 4 A dm-2. Subsequently, increasing current density, the hardness
TE D
decreases to 773 HV and then keeps almost constant. Sangeetha [25] reported that the improvement of microhardness was due to the more second-phase particle dispersed in the
EP
coating, grain refining and dispersion strengthening of the particles. Allahyarzadeh [14] revealed that the increase of the amounts nanoparticles in the coating and the increase of
AC C
tungsten amount was the main reason for hardness enhancement. When current density is at relatively small value (2-4 Adm-2), the electric field force of the charged nanoparticles will increase with the increase of current density and the transfer rate of the particles to cathode will increase, resulting in more amounts of nanoparticles arrived at cathode and co-deposited in the coating. Therefore, the hardness of the coating increases. However, as well known, the co-deposition rate of nonconducting nanoparticles is less dependent on current density. Hence, continue to increase current density, the deposition rate of nickel will increase larger than that
ACCEPTED MANUSCRIPT of particles. This led to the decrease of the amount (percent by volume) of the embedded nanoparticles in the coating. So, the hardness first increased and then decreased with the increase of current density. In fact, as current density changes, the transfer process of metallic
RI PT
ions and charged particles, especially the transfer rate, have been changed. Consequently, the composition of the coating including the content of embedded particles have been changed, leading to the change of the hardness. In this case, it can be expected that the change of
SC
current density will affect the content of particles and tungsten in the coating, then influencing
M AN U
the hardness. Fig. 10b shows the hardness as a function of deposition time. As presented in Fig. 10b, when deposition time extends from 15 min to 30 min, the hardness of the deposits slightly decreases from 980 HV to 813 HV. Then the hardness increases to 978 HV when deposits for 60 min. Sknar [29] and He [30] reported that the enhanced hardness might be
TE D
caused by two reasons. One is the reinforcing particles in the coatings hinder the matrix grain boundary sliding and the dislocation movement; the other is particles evenly dispersed in the Ni-W matrix resulting in grain refinement and dispersion strengthening effect. As shown in
EP
Table 1, the change of the crystallite size (13-16 nm calculated by Debye-Scherrer equation)
AC C
of the obtained composite coating is small. It indicates that the effect of crystallite size on the hardness of the coating is limited. Therefore, the hardness of the deposited coating is more dependent on the amounts and distribution of nanoparticles embedded in the coating, as well as the nature properties of the particles. Thus, the effect of deposition time on the hardness might be related to the change of particle content in the coatings.
RI PT
ACCEPTED MANUSCRIPT
Fig. 10. Hardness of Ni-W/TiN-Y2O3 MMCs prepared by DC deposition as a function of (a)
M AN U
3.5 Corrosion resistance after immersed 1 h
SC
current density (t=15min) and (b) deposition time (i=4A dm-2).
The corrosion behaviors of the prepared Ni-W/TiN-Y2O3 MMCs were investigated by electrochemical measurements. Fig. 11 shows the Tafel, Nyquist and Bode plots of Ni-W/TiN-Y2O3 composites after immersed in 3.5 wt.% NaCl solution for 1 h. Fig. 11a shows
TE D
the Ecorr shifted to the nobler value and the Icorr decreased, indicating that the corrosion resistance of the coating generally increases as the current density increases. As seen in Fig.
EP
11b, in the initial immersion stage, the Nyquist curves present a semicircular arc shape with different radius, indicating a one time constant. So an equivalent electrical circuit (EEC)
AC C
model as shown in Fig. 12 was used to analyze the corrosion parameters. The corrosion parameters derived from fitting the Nyquist plots of the composite coating after immersed 1 h in 3.5 wt.% NaCl solution were listed in Table 2. As known, in this case, the relative radius of the Nyquist plots could also express the corrosion resistance of the samples [31, 32]. As seen in Fig. 11b (Table 2), when immersed for 1h, as current density increased from 2 Adm-2 to 8 Adm-2, the Rct values firstly decreased from 38.38 kΩ·cm2 at 2 A dm-2 down to 30.27 kΩ·cm2 at 4 A dm-2. Then it gradually increases up to 55.41 kΩ·cm2 as the current density increases to
ACCEPTED MANUSCRIPT 8 A dm-2. It indicated that the corrosion resistance of the deposited coating initially reduces and then improves with the maximum value at 8 A dm-2. As indicated in Fig. 11c, the highest impedance and the broader phase angle peak was obtained at 8 A dm-2 at 1 h, indicating a
RI PT
better corrosion resistance of the coating. Fig. 11d shows that the coating obtained has a dense structure without defects. It should be noted that, in this group of experiments, the deposition time was kept constant at 15 min. So, the thickness of the coating will increase as the current
SC
density increases. The thickness of the coating prepared at 2, 4, 6 and 8 A dm-2 for 15 min
M AN U
were 2.7, 6.7, 8.6 and 10.8 µm, respectively. Hence, the high corrosion resistance of the samples prepared at 8 A dm-2 partly attributed to the larger thickness formed at high current density. The other reason might be due to the compact microstructure and more amounts of
AC C
EP
TE D
nanoparticles incorporated in the coating.
Fig. 11 Tafel curves (a), Nyquist plots (b), Bode plots (c) and SEM images (d) of Ni-W/TiN-Y2O3 composite coating deposited by DC deposition for 15min at different current
ACCEPTED MANUSCRIPT
RI PT
density after immersed 1 h in 3.5 wt.% NaCl aqueous solution.
Fig. 12. Equivalent electrical circuit (EEC) model used to analyze the EIS data.
Fig. 13 indicates the corrosion behavior of the coating fabricated at different deposition
SC
time. Fig. 13a shows the sample obtained at 30 min has higher Ecorr and the lowest Icorr. Fig.
M AN U
13b shows that the impedance of the sample produced at 30 min is larger compared to the coating of 15 min and 60 min. As shown in Table 2, the Rct reaches the maximum values of 71.18 kΩ·cm2 at 30 min, indicating the best anti-corrosion capability. After long time deposition, the Rct value of the coating decreased sharply to 16.27 kΩ·cm2 at 60 min. It is
TE D
associated with the defects formed at long-time deposition, which allows the solution easily permeating through the coating and weakened the protective properties. As seen from Bode plots in Fig. 13c, when immersed for 1 h, the |Z| prepared at 30 min reached the maximal
EP
value at 0.01 Hz. It illustrated that the anti-corrosion properties first enhanced and then
AC C
reduced as the time extends. In this stage, the phase angle curve obtained at 30 min showed the broader hump with the highest phase angle suggesting excellent corrosion resistance. The morphology indicated that the sample obtained at 30 min owns a dense and compact structure without noticeable defects.
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 13. Tafel (a), Nyquist (b), Bode plots (c) and SEM images of Ni-W/TiN-Y2O3 MMCs deposited by DC deposition at 4 A dm-2 for different time after immersed 1 h in 3.5 wt.%
TE D
NaCl solution, The SEM image was obtained at 30 min. Table 2 Corrosion parameters of Ni-W/TiN-Y2O3 composite coating deposited by DC
EP
deposition at different conditions after immersed 1 h in 3.5 wt.% NaCl solution. Rs (Ω·cm2)
Rct (Ω·cm2)
CPEdl (µF cm−2)
n
2 A dm-2, 15 min 4 A dm-2, 15 min 6 A dm-2, 15 min 8 A dm-2, 15 min 15 min, 4 A dm-2 30 min, 4 A dm-2 60 min, 4 A dm-2
7.45 6.23 7.17 6.70 6.23 6.29 5.07
38379 30271 44559 55405 30271 71177 16270
37.56 41.92 41.02 46.51 41.92 39.05 37.47
0.91 0.92 0.90 0.88 0.92 0.91 0.86
AC C
Samples
3.6 Corrosion resistance after immersed 7 days Fig. 14 presents the electrochemical behavior of Ni-W/TiN-Y2O3 MMCs after soaked 168 h in 3.5 wt.% NaCl solution. Table 3 shows the corrosion parameters derived from fitting
ACCEPTED MANUSCRIPT the corresponding EIS diagrams of the composite coating. It was found that the impedance of the sample fabricated at 2 A dm-2 and 30-60 min is higher compared to others. Also, it was noticed that the Rct value of 26.58 kΩ·cm2 of the coating prepared at 2 A dm-2 was larger than
RI PT
that prepared at the higher current density, indicating the better corrosion resistance at 2 A dm-2. Also, it was observed in Table 3 that the CPEdl values (300-768 µF cm−2) are higher than that immersed for 1h (37-47µF cm−2), indicating the rougher surface formed after the
SC
immersion corrosion. The coating prepared at high current density might own more internal
M AN U
stress and potential defects, which could decrease the compactness and then the protective capability of the coating after long time immersion.
After immersed for 168 h, it can be observed from Fig 14 (a, b) that the Ecorr decreases much compared Fig. 11a and 13a. The Nyquist plots of Fig 14 (c, d) also indicated the
TE D
reduced |Z| values. Comparing these plots, the |Z| values of 2 A dm-2 and 30 min were larger than others. Furthermore, the phase angle curve of Fig. 14 (e, f) exhibits one narrow hump with the peak frequency shifting to lower values, indicating a worse corrosion resistance.
EP
After immersed for 168 h, the coating synthesized at 30 min still owns the efficient
AC C
anti-corrosion properties (Rct =27.87 kΩ·cm2). In the initial stage of immersion, the solution has not arrived at the substrate. However, with the extension of immersion time, the dense coating with fewer pores deposited at a relatively low current density (2 A dm-2) will show the highest corrosion resistance. According to Bode plots in Fig. 14f, the |Z| reaches the maximum value at 30 min and 60 min for 168 h. For long-period protection, the coating produced at 30 min has superior protective performance. The Bode plot of Fig. 14f also illustrated the highest |Z| value at 0.01 Hz and the widest hump was obtained for the sample of
ACCEPTED MANUSCRIPT
TE D
M AN U
SC
RI PT
30 min, indicating the excellent anti-corrosion properties.
EP
Fig. 14. Tafel curves, Nyquist and Bode plots of Ni-W/TiN-Y2O3 composite coating after
AC C
immersed 168 h in 3.5 wt.% NaCl solution. (a, c, e) prepared at different current density for 15min; (b, d, f) prepared at 4 Adm-2 for different time.
ACCEPTED MANUSCRIPT Table 3 Corrosion parameters of Ni-W/TiN-Y2O3 composite coating deposited by DC deposition at different conditions after immersed 168 h in 3.5 wt.% NaCl solution. Rs (Ω·cm2)
Rct (Ω·cm2)
CPEdl (µF cm−2)
n
2 A dm-2, 15 min 4 A dm-2, 15 min 6 A dm-2, 15 min 8 A dm-2, 15 min 15 min, 4 A dm-2 30 min, 4 A dm-2 60 min, 4 A dm-2
6.55 4.57 3.69 3.67 4.57 4.33 6.78
26578 18315 23931 25214 18315 27871 23469
300.95 767.33 587.55 574.67 767.33 418.21 278.80
0.92 0.92 0.94 0.94 0.92 0.93 0.92
SC
RI PT
Samples
M AN U
4. Conclusions
In this study, a novel Ni-W/TiN-Y2O3 MMCs were prepared by direct current deposition and the morphology, structure, microhardness and corrosion resistance were investigated. The samples have a dense structure without visible defects. The deposits exhibit nodular structure
TE D
with different dimensions of nodules, circular or quasi-circular in shape. The addition of TiN and Y2O3 particles could improve the hardness and anti-corrosion properties of the metallic matrix. The crystallite sizes were in the diameter of 13-16 nm. EDS mapping demonstrated
EP
that the TiN and Y2O3 particles were evenly distributed in the deposits. The electrochemical
AC C
measurements illustrated that 6-8 Adm-2 and 30 min were the preferred parameters for the best corrosion resistance of Ni-W/TiN-Y2O3 coatings. After immersed 168 h in 3.5 wt.% NaCl aqueous solution, the coating prepared at 30 min and 2 A dm-2 had the best corrosion resistance. This Ni-W/TiN-Y2O3 MMCs have high hardness and superior corrosion resistance, which can be used for metallic parts protection in an aggressive medium.
Acknowledgements We thank the financial support from the National Natural Science Foundation of China
ACCEPTED MANUSCRIPT (Grant No. 51679076), the Fundamental Research Funds for the Central Universities (Grant No. 2019B15914), China.
References
electrochemical deposition, J. Alloys Compd., 702 (2017) 38-50.
RI PT
[1] B. Li, W. Zhang, W. Zhang, Y. Huan, Preparation of Ni–W/SiC nanocomposite coatings by
[2] S. Kumaraguru, S. Mohan, Study of Ni-Bi2O3-CeO2 composite coatings: Hierarchical
SC
microstructure and augmented microhardness for surface engineering application, Surf. Coat. Technol., 349 (2018) 567-575.
M AN U
[3] Y. Wang, Q. Zhou, K. Li, Q. Zhong, Q.B. Bui, Preparation of Ni–W–SiO2 nanocomposite coating and evaluation of its hardness and corrosion resistance, Ceram. Int., 41 (2015) 79-84. [4] B. Li, W. Zhang, Microstructural, surface and electrochemical properties of pulse electrodeposited Ni–W/Si3N4 nanocomposite coating, Ceram. Int., 44 (2018) 19907-19918.
TE D
[5] T. He, Y. He, H. Li, Y. Fan, Q. Yang, Z. He, A comparative study of effect of mechanical and ultrasound agitation on the properties of pulse electrodeposited Ni–W/MWCNTs composite coatings, J. Alloys Compd., 743 (2018) 63-72.
EP
[6] M.H. Allahyarzadeh, M. Aliofkhazraei, A.R. Rezvanian, V. Torabinejad, A.R. Sabour Rouhaghdam, Ni-W electrodeposited coatings: Characterization, properties and applications,
AC C
Surf. Coat. Technol., 307 (2016) 978-1010. [7] H. Li, Y. He, T. He, D. Qing, F. Luo, Y. Fan, X. Chen, Ni–W/BN(h) electrodeposited nanocomposite coating with functionally graded microstructure, J. Alloys Compd., 704 (2017) 32-43.
[8] B. Li, D. Li, T. Mei, W. Xia, W. Zhang, Fabrication and characterization of boron nitride reinforced Ni–W nanocomposite coating by electrodeposition, J. Alloys Compd., 777 (2019) 1234-1244. [9] M.G. Hosseini, M. Abdolmaleki, J. Ghahremani, Investigation of corrosion resistance of electrodeposited Ni–W/SiC composite coatings, Corros. Eng., Sci. Technol., 49 (2013)
ACCEPTED MANUSCRIPT 247-253. [10] B.S. Li, Y.X. Huan, H. Luo, W.W. Zhang, Electrodeposition and properties of Ni–B/SiC nanocomposite coatings, Surf. Eng., 35 (2019) 110-120. [11] K. Arunsunai Kumar, G. Paruthimal Kalaignan, V.S. Muralidharan, Direct and pulse
RI PT
current electrodeposition of Ni–W–TiO2 nanocomposite coatings, Ceram. Int., 39 (2013) 2827-2834.
[12] E. Beltowska-Lehman, A. Bigos, P. Indyka, A. Chojnacka, A. Drewienkiewicz, S.
SC
Zimowski, M. Kot, M.J. Szczerba, Optimisation of the electrodeposition process of Ni– W/ZrO2 nanocomposites, J. Electroanal. Chem., 813 (2018) 39-51.
M AN U
[13] Y. Boonyongmaneerat, K. Saengkiettiyut, S. Saenapitak, S. Sangsuk, Effects of WC addition on structure and hardness of electrodeposited Ni–W, Surf. Coat. Technol., 203 (2009) 3590-3594.
[14] M.H. Allahyarzadeh, M. Aliofkhazraei, A.R.S. Rouhaghdam, V. Torabinejad,
TE D
Electrodeposition of Ni–W–Al2O3 nanocomposite coating with functionally graded microstructure, J. Alloys Compd., 666 (2016) 217-226. [15] B. Li, W. Zhang, Y. Huan, J. Dong, Synthesis and characterization of Ni–B/Al2O3
EP
nanocomposite coating by electrodeposition using trimethylamine borane as boron precursor, Surf. Coat. Technol., 337 (2018) 186-197.
AC C
[16] H. Li, Y. He, T. He, Y. Fan, Q. Yang, Y. Zhan, The influence of pulse plating parameters on microstructure and properties of Ni–W–Si3N4 nanocomposite coatings, Ceram. Int., 42 (2016) 18380-18392.
[17] H. Hassannejad, A. Nouri, Formation of β-NiAl nanocomposite coating by electrodeposition and effect of cerium ion doping on its oxidation mechanism, Ceram. Int., 43 (2017) 9979-9984. [18] M. Karbasi, N. Yazdian, A. Vahidian, Development of electro-co-deposited Ni–TiC nano-particle reinforced nanocomposite coatings, Surf. Coat. Technol., 207 (2012) 587-593.
ACCEPTED MANUSCRIPT [19] Y. Zhou, S. Zhang, L. Nie, Z. Zhu, J. Zhang, F. Cao, J. Zhang, Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy, Trans. Nonferrous Met. Soc. China, 26 (2016) 2976-2987. [20] F. Xia, J. Tian, W. Wang, Y. He, Effect of plating parameters on the properties of pulse
RI PT
electrodeposited Ni–TiN thin films, Ceram. Int., 42 (2016) 13268-13272. [21] C. Ma, X. Guo, J. Leang, F. Xia, Synthesis and characterization of Ni–P–TiN nanocomposites fabricated by magnetic electrodeposition technology, Ceram. Int., 42 (2016)
SC
10428-10432.
[22] M. Ahmadi, M.J.F. Guinel, Synthesis, characterization and understanding of the
M AN U
mechanisms of electroplating of nanocrystalline–amorphous nickel–tungsten alloys using in situ electrochemical impedance spectroscopy, J. Alloys Compd., 574 (2013) 196-205. [23] L.L. Tian, J.C. Xu, Electrodeposition and characterization of Ni-Y2O3 composite, Appl. Surf. Sci., 257 (2011) 7615-7620.
TE D
[24] F. Cai, C.H. Jiang, Z.Q. Zhang, V. Ji, Synthesis and characterization of Ni-Al-Y2O3 composite coatings with different Y2O3 particle content, Ceram. Int., 40 (2014) 15105-15111. [25] S. Sangeetha, G.P. Kalaignan, J.T. Anthuvan, Pulse electrodeposition of self-lubricating
412-419.
EP
Ni–W/PTFE nanocomposite coatings on mild steel surface, Appl. Surf. Sci., 359 (2015)
AC C
[26] K.A. Kumar, G.P. Kalaignan, V.S. Muralidharan, Pulse electrodeposition and characterization of nano Ni–W alloy deposits, Appl. Surf. Sci., 259 (2012) 231-237. [27] B. Li, D. Li, W. Chen, Y. Liu, J. Zhang, Y. Wei, W. Zhang, W. Jia, Effect of current density and deposition time on microstructure and corrosion resistance of Ni-W/TiN nanocomposite coating, Ceram. Int., 45 (2019) 4870-4879. [28] F.F. Xia, W.C. Jia, C.Y. Ma, R. Yang, Y. Wang, M. Potts, Synthesis and characterization of Ni-doped TiN thin films deposited by jet electrodeposition, Appl. Surf. Sci., 434 (2018) 228-233.
ACCEPTED MANUSCRIPT [29] Y.E. Sknar, O.O. Savchuk, I.V. Sknar, Characteristics of electrodeposition of Ni and Ni-P alloys from methanesulfonate electrolytes, Appl. Surf. Sci., 423 (2017) 340-348. [30] T. He, Y. He, H. Li, Z. Su, Y. Fan, Z. He, Fabrication of Ni-W-B4C composite coatings and evaluation of its micro-hardness and corrosion resistance properties, Ceram. Int., 44
RI PT
(2018) 9188-9193. [31] H. Luo, X. Wang, S. Gao, C. Dong, X. Li, Synthesis of a duplex Ni–P–YSZ/Ni–P nanocomposite coating and investigation of its performance, Surf. Coat. Technol., 311 (2017)
SC
70-79.
[32] X. Feng, X. Lu, Y. Zuo, N. Zhuang, D. Chen, The effects of deformation on metastable
M AN U
pitting of 304 stainless steel in chloride contaminated concrete pore solution, Corros. Sci., 103
AC C
EP
TE D
(2016) 223-229.
S0272-8842(19)30820-X
DOI:
https://doi.org/10.1016/j.ceramint.2019.04.010
Reference:
CERI 21204
To appear in:
Ceramics International
Received Date: 29 November 2018 Revised Date:
7 March 2019
Accepted Date: 1 April 2019
Please cite this article as: B. Li, W. Zhang, D. Li, J. Wang, W. Chen, Y. Liu, Preparation of Ni W/ TiN Y2O3 composite ceramic coating for metallic parts protection by direct current deposition, Ceramics International (2019), doi: https://doi.org/10.1016/j.ceramint.2019.04.010. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Preparation of Ni-W/TiN-Y2O3 composite ceramic coating for metallic parts protection by direct current deposition
RI PT
Baosong Li a, *, Weiwei Zhang b, Dandan Li a, Jiajia Wang a, Wei Chen a, Yuying Liu a a
College of Mechanics and Materials, Hohai University, Nanjing 211100, China
b
College of Mechanical and Electrical Engineering, Hohai University, Changzhou
Corresponding author.
AC C
EP
TE D
E-mail address: [email protected] (B. Li)
M AN U
*
SC
213022, China
ACCEPTED MANUSCRIPT
Abstract A novel Ni-W/TiN-Y2O3 composite ceramic coating has been synthesized by direct current deposition for metallic parts protection. The structural, morphology, hardness and
RI PT
anti-corrosion properties of the Ni-W/TiN-Y2O3 coating have been evaluated by SEM, EDS, TEM, XRD and EIS methods. Results indicated that the samples have uniform and compact nodular structure without defects. It demonstrated that the TiN and Y2O3 nanoparticles had
SC
been uniformly distributed in the composites. The incorporation of TiN and Y2O3 in Ni–W
M AN U
matrix could improve the hardness and anti-corrosion properties. The crystallite size was in the diameter of 13-16 nm. The electrochemical results illustrated that 6-8 Adm-2 and 30 min were beneficial to the improvement of anti-corrosion behaviors of the produced composite coating. After immersed 168 h in 3.5 wt.% NaCl aqueous solution, the coating prepared at 30
TE D
min and 2 A dm-2 owns better anti-corrosion properties. The embedded TiN and Y2O3 nanoparticles in Ni-W matrix could decrease the electrochemical activity and enhance the
EP
protective properties.
Keywords: Ni-W/TiN-Y2O3; Composite ceramic coating; Direct current deposition;
AC C
Corrosion resistance; Hardness
ACCEPTED MANUSCRIPT
1. Introduction In the last few years, Ni-W alloys have obtained much attention for its superior wear resistance, hardness and anti-corrosion properties [1]. Nevertheless, the increasing
RI PT
requirements for better protective performance in aggressive conditions promote the development of metal matrix composites (MMCs) [2]. MMCs were fabricated by incorporation of the reinforcing phase in the metallic matrix, which both have the
SC
predominant features of the metal matrix and the reinforcing phase [3, 4]. Recently, much
M AN U
attention focuses on the preparation of nanoparticle reinforced Ni-W MMCs [5, 6]. Till now, literature reported the addition of nanoparticles such as BN [7, 8], SiC [9, 10], TiO2 [11], ZrO2 [12], WC [13], Al2O3 [14, 15], Si3N4 [4, 16] in Ni-W alloys to fabricate MMCs for enhanced performance. Titanium nitride (TiN) owns good features including
TE D
excellent hardness, superior high-temperature stability and satisfying chemical inertia [17-19] and could be used to reinforce the hardness and corrosion resistance of metallic coating in
EP
various fields [20, 21].
Recently, we found that there are very few reports concerning the co-deposition of more
AC C
than one kind of particles together into one deposit [22]. Limited literature [3] illustrated that a combination of two materials in a desirable fashion might provide better performance than any one of them. Yttria (Y2O3) owns excellent thermal and chemical stability, high mechanical and anti-corrosion properties [23, 24]. Therefore, a novel MMC was designed for enhanced mechanical and anti-corrosion characteristics by incorporation of TiN and Y2O3 particles in Ni-W alloy. However, to the best of our knowledge, the application of direct current (DC) deposition for producing Ni-W/TiN-Y2O3 MMCs has not been yet investigated.
ACCEPTED MANUSCRIPT Till now, no investigation is concerning the morphology, structure, hardness and anti-corrosion behaviors of the Ni-W/TiN-Y2O3 MMCs fabricated by DC deposition. Thus, here, the efforts were made to prepare Ni-W/TiN-Y2O3 MMCs by DC deposition
RI PT
using nanoscale Y2O3 and TiN particles as the reinforcing phase for Ni-W matrix. The microstructure, morphology, hardness and electrochemical properties of the samples were
Ni-W/TiN-Y2O3 MMCs by DC deposition.
M AN U
2. Experimental
SC
studied. To the best of our knowledge, this is the first attempt on the co-deposition of
2.1 Preparation
Ni-W/TiN-Y2O3 MMCs have been synthesized by DC deposition from the following bath solution: 0.12 mol L–1 NiSO4·6H2O, 0.2 mol L–1 Na2WO4·2H2O, 0.4 mol L–1
TE D
Na3C6H5O7·2H2O, 0.5 mol L–1 NH4Cl, 0.001 g L–1 SDS, 30 g L–1 TiN and 6 g L–1 Y2O3 nanoparticles. All chemical reagents were analytical grades supplied by Shanghai Aladdin
EP
Biochemical Technology Co., Ltd and used as received. The particle sizes of TiN (purity＞ 99.9%) were 20-50 nm with face-centered cubic structure purchased from Shanghai Chaowei
AC C
Nanotechnology Co., Ltd. Y2O3 nanoparticles (﹤100 nm, 99.9%) were provided by Shanghai Aladdin Biochemical Technology Co., Ltd. The electrodeposition setup is shown in Fig. 1. A DDK-II high frequency test power (20A/12V, Shaoxing CTN Electronic Co., LTD.) was utilized as a galvanostat (direct current power supply) to electrodeposit the composite coating. If only use a single anode, it just needs to cover the back of the cathode with an insulating plastic membrane. In the process of galvanostatic electrodeposition, the deposition parameters of plating bath temperature, pH value, stirring rate were kept constant at 65±2°C, 8.4±0.1,
ACCEPTED MANUSCRIPT 450±50 rpm, respectively. The effect of current density (2, 4, 6 and 8 A dm-2) and deposition time (15, 30 and 60 min) parameters on the structure and properties of the composite coating were investigated. The cathode and anode were nickel plate and copper sheet, respectively.
RI PT
The distance between the cathode and anode was 3.0 cm. Prior to each experiment, the substrates were cleaned and immersed in 7.2 wt. % HCl solution for 30 s. Before electrodeposition, the solution was agitated for more than 30 min and ultrasonic cleaning for
SC
more than 10 min. It is worth noting that the magnetic stirring and ultrasonic dispersion were
M AN U
continuously performed during the electrodeposition. After electrodeposition, the product was
EP
TE D
ultrasonically treated for 5 min and then washed by purified water.
AC C
Fig. 1. Schematic diagram of the co-electrodeposition setup.
2.2 Characterization
The morphology and composition of the Ni-W/TiN-Y2O3 MMCs were observed by scanning electron microscope (SEM, FEI Inspect F50 and HITACHI S-4800) and the affiliated energy dispersive spectrometer (EDS, Oxford). The structure was analyzed by X-ray diffraction (XRD, Bruker D8 advance). The crystallite size was calculated based on the
ACCEPTED MANUSCRIPT Debye-Scherrer equation. The hardness was measured by a Vickers hardness tester (DHV-1000 type) using 100 g-force load lasting for 10 s. The electrochemical behaviors were investigated in 3.5 wt.% NaCl solutions on CHI 660E potentiostat. The saturated calomel
RI PT
electrode (SCE) was used as reference electrode. The potentiodynamic polarization curves were tested at 5 mV/s. EIS was performed at Eocp at the input amplitude 10 mV ranging from 105 to 10–2 Hz. Before testing, the samples were soaked in 3.5wt.% NaCl solution for 1 h and
SC
168 h, respectively.
M AN U
3. Results and discussion 3.1 Surface morphologies
Fig. 2 describes the SEM images of the as-plated Ni-W/TiN-Y2O3 MMCs in thickness of
TE D
6.7 µm electrodeposited at 4 A dm-2 for 15 min by DC deposition with different magnification. As seen in Fig. 2, all produced Ni-W/TiN-Y2O3 MMCs have compact, uniform structure without defects, exhibiting a nodular surface morphology. In microscale, Fig. 2a exhibits
EP
nodular structure with different dimensions of nodules, circular or quasi-circular in shape,
AC C
which is consistent with the Ni-W composite coating reported by Beltowska-Lehman [12]. It was observed that the nodules diameter varied from 8.5 µm to 0.4 µm. Fig. 2b were the enlarged images of the rectangular region in Fig. 2a. As seen in Fig. 2b, it was found that the granules are composed of many small crystals. Some granules exhibited a needle-like shape. Kalaignan [25, 26] reported that the Ni-W alloy matrix has long needle-shaped particles and the surface morphology was modified to flower like structure after the inclusion of PTFE particles, which is similar with this result. In nanoscale, as shown in Fig. 2b, it was noticed
ACCEPTED MANUSCRIPT that the embedded small particles were evenly dispersed in the Ni-W matrix; and some large
SC
RI PT
needle-shaped Ni-W metallic grains were also observed.
M AN U
Fig. 2. SEM micrograph of Ni-W/TiN-Y2O3 MMCs obtained at 4 A dm-2 for 15 min by DC deposition with magnification times (a) 5×103and (b) 1×105.
Fig. 3 presents the morphology of Ni-W/TiN-Y2O3 MMCs in thickness of 13.4 µm fabricated at 4 A dm-2 and 30 min. It illustrated that the coating prepared at 30 min has
TE D
nodular structure. Compared with the coating deposited at 15 min (Fig. 2), the nodular granules were fine and the coating was smooth and uniform. In the low magnification images
EP
(5×103) as presented in Fig. 3a, the Ni-W/TiN-Y2O3 MMC presents a dense structure with fine nodular granules. It revealed that some dome-like “island” structure appears and the
AC C
amount of the large “island” reduces. In the enlarged images of Fig. 3b (1×105), it was observed that the spherical granules comprising many large crystals and nano-sized particles; and the nanoparticles were uniformly distributed in the obtained coating. Comparing these images, the morphology of the sample produced at 30 min has less irregularity.
RI PT
ACCEPTED MANUSCRIPT
SC
Fig. 3. SEM micrograph of Ni-W/TiN-Y2O3 MMCs fabricated at 4 A dm-2 for 30 min by DC deposition with magnification times (a) 5×103 and (b) 5×104.
M AN U
Fig. 4 shows the morphology of the coating in thickness of 21.6 µm deposited at 4 A dm-2 and 60 min. It was noticed that the dome-like structure diminished and the granules size decreases. Compared with the coating deposited at 15 min (Fig. 2b) and 30 min (Fig. 3b), it was observed in Fig. 4b that more nanoparticles in the dimension of 50 nm have been
TE D
distributed in the metallic matrix. However, it indicated that the size of surface granules made up of needle-shaped Ni-W crystals increased as the deposition time increased. In addition, the
EP
coating presents dense structure without detected cracks. It indicated that the long deposition time is necessary for more nanoparticles incorporated in the metallic matrix, which will be
AC C
beneficial for the improvement of the performances.
ACCEPTED MANUSCRIPT Fig. 4. SEM micrograph of Ni-W/TiN-Y2O3 MMCs fabricated at 4 A dm-2 for 60 min by DC deposition with magnification times (a) 2×105 and (b) 1×105. Fig. 5 presents the TEM image of the coating with thickness 13.5 µm deposited at 4 A
RI PT
dm-2 and 30 min. The white and black areas are attributed to the Ni-W matrix and nanoparticles, respectively. It demonstrated that the nanoparticles were successfully embedded in the metallic matrix. The dimensions of the embedded particles were in the range
SC
of 20-50 nm, which is consistent with the size of the particles used. The Ni-W crystal and
M AN U
TiN-Y2O3 particles in composite coating were in nanometer scale. Although some aggregations of nanoparticles in coating could be observed in TEM surface images, in general, the distribution of particles in composite coating is uniform. In addition, the coating exhibits a dense structure without noticeable cracks, pores or crevices. The interface between particles
TE D
and Ni-W matrix was found to be devoid of cracks or voids, indicating excellent interface bonding. The incorporation of TiN and Y2O3 nanoparticles will be beneficial for the improvement of hardness, wear resistance of Ni-W coating, which was confirmed by the
AC C
EP
existing literature [27, 28].
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 5. TEM image of Ni-W/TiN-Y2O3 MMCs fabricated at 4 A dm-2 for 30 min by DC deposition. 3.2 Cross-sectional observation
TE D
Cross-sectional images and EDS element line scanning of the Ni-W/TiN-Y2O3 composite coating were measured to observe the thickness, interface, as well as the distribution of
EP
embedded nanoparticles in bulk of the coating. Fig. 6a indicates that the coating thickness is 13.5 µm and the calculated growth rate is 0.45 µm min-1 at 4 A dm-2. Fig. 6b shows that the
AC C
bulk of the composite coating is compact and uniform with a good interface with the substrate, suggesting that satisfactory adhesion was obtained for the composite coating. The EDS element line scanning (Fig. 6c) displays the composition of the coating and illustrates that TiN and Y2O3 components were successfully incorporated in Ni-W matrix. Then, it confirms the formation of Ni-W/TiN-Y2O3 composite coating. It was also noticed that the content of Ni, W, Ti, Y is slightly fluctuated with the depth. This may be related to the consumption and the change of the concentration of the metal ions and particles near the cathode, as well as the
ACCEPTED MANUSCRIPT mass transfer process of the supplemental ions (or particles). In nanoscale, Fig. 6d (the enlarged red rectangular region in Fig. 6b) demonstrates that the particles in dimension of
TE D
M AN U
SC
RI PT
20-45 nm have been uniformly distributed in the deposited coating.
EP
Fig. 6. Cross-sectional images (a, b, d) and EDS element line scanning (d) of Ni-W/TiN-Y2O3
AC C
MMCs fabricated at 4 A dm-2 for 30 min by DC deposition. 3.3 XRD and EDS analysis Fig. 7 shows the XRD spectra of the deposited Ni-W/TiN-Y2O3 composite ceramic coating. As seen, all samples present fcc structure with similar XRD spectra which differ in intensity. For comparison, the XRD spectrum of the copper substrate is also shown in Fig. 7a. The diffraction peak at 44.1° attributes to Ni (111) crystal planes. The peaks at 51.5° and 75.5° correspond to Ni (200) and (220) phase, respectively (JCPDS No. 04-0850). It was confirmed
ACCEPTED MANUSCRIPT that the peaks at 42.4°, 49.4°, 72.3° and 87.6° are attributed to the copper substrate (JCPDS No. 04-0836). It needs to be noted that the thickness of coating prepared at 2, 4, 6 and 8 A dm-2 for 15 min were 2.7, 6.7, 8.6 and 10.8 µm, respectively. Due to the X-ray can penetrate
RI PT
the coating more than 10 µm which might be larger than the coating thickness, the peaks of copper substrate were emerged and overlapped the peaks of nickel. As seen, the substrate peaks at 49.4°, 72.3° and 87.6°gradually reduced as the current density increases, indicating
SC
the increase of the coating thickness. The peak of W was not observed, indicating the
M AN U
formation of Ni-W solid solution. The XRD peaks of TiN and Y2O3 particles were also not appeared which is ascribed to the low content of the particles in the coating. The crystallite sizes were calculated according to Scherrer’s equation. The crystallite size is in the dimension of 13-16 nm (Table 1). The preferred orientation at 43.9-44.1° is attributed to Ni (111) phase.
TE D
In Fig. 7a, the coating prepared at 2 Adm-2 has the smallest crystallite size. As the current density increases, the peaks of Ni (220), (200) plane slightly augmented, while the (111) peaks fluctuated. The grain sizes slightly enlarged from 13 nm to 15 nm as current density
AC C
large.
EP
increases from 2 A dm-2 to 8 A dm-2. In general, the change of the crystallite size was not
ACCEPTED MANUSCRIPT Fig. 7. XRD patterns of Ni-W/TiN-Y2O3 MMCs obtained by DC deposition as a function of (a) current density (t=15min) and (b) deposition time (i=4A dm-2). Fig. 7b displayed the XRD spectra of the Ni-W/TiN-Y2O3 MMCs as a function
RI PT
deposition time. As the deposition time increases, the peaks of the substrate gradually disappeared, indicating the increase of the coating thickness. The intensity of the primary (111) diffraction peak decreases as the deposition time increases. The deposition time had no effects
SC
on the diffraction angle. The peak of TiN and Y2O3 particles was not appeared, but the
M AN U
existence was verified by the following EDS results. According to the primary (111) peak at 44.1°, the crystallite size calculated were of 14-16 nm and slightly enlarged as deposition time increases.
Table 1 Crystallite size of Ni-W/TiN-Y2O3 MMCs prepared by DC deposition
TE D
Parameters Current density (A dm-2)
EP
Deposition time (min)
Values 2 4 6 8 15 30 60
Crystal size (nm) 13±1 14±1 14±1 15±1 14±1 15±1 16±1
AC C
Surface element distribution map was measured by EDS. Fig. 8 presents the element distribution map of the sample prepared at 4 A dm-2 for 15 min. It illustrated that the coating consists of Ni, W, Ti, N, Y and O, as well as C component. It indicated that Ni, W elements are homogeneously dispersed in the deposits. It also demonstrated that the TiN and Y2O3 particles were evenly embedded in Ni-W matrix.
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 8. EDS mapping of Ni-W/TiN-Y2O3 composite ceramic coating. Fig. 9 demonstrated that 1.1 wt.% TiN and 0.45 wt.% Y2O3 nanoparticles were incorporated in the Ni-W matrix. It is noted that the contents of TiN and Y2O3 were calculated
TE D
on the basis of the stoichiometric relationships between Ti and TiN, Y and Y2O3, respectively. In addition, the sample comprises 75.2 wt.% Ni and 22.6 wt.% W. It also demonstrated the
AC C
EP
inclusion of the nanoparticles in the produced coating.
Fig. 9. EDS spectra of the electrodeposited Ni-W/TiN-Y2O3 MMCs
ACCEPTED MANUSCRIPT 3.4 Microhardness The hardness was measured with a Vickers hardness tester (DHV-1000 type) at a load of
as follows. =
(1)
RI PT
100 g-force lasting for 10 s. The value of Vickers hardness is calculated by using the formula
where F is the applied load in gram and d is the length of the diagonals of the diamond
SC
pyramidal impression (µm). The quoted hardness value was the statistical average value of 5
M AN U
indentations conducted at different sites on each sample. Fig. 10 shows the hardness of the Ni-W/TiN-Y2O3 MMCs as a function of current density and deposition time. As indicated in Fig 10a, as the current density increases, the hardness first increases from 432 HV to the maximum value of 980 HV at 4 A dm-2. Subsequently, increasing current density, the hardness
TE D
decreases to 773 HV and then keeps almost constant. Sangeetha [25] reported that the improvement of microhardness was due to the more second-phase particle dispersed in the
EP
coating, grain refining and dispersion strengthening of the particles. Allahyarzadeh [14] revealed that the increase of the amounts nanoparticles in the coating and the increase of
AC C
tungsten amount was the main reason for hardness enhancement. When current density is at relatively small value (2-4 Adm-2), the electric field force of the charged nanoparticles will increase with the increase of current density and the transfer rate of the particles to cathode will increase, resulting in more amounts of nanoparticles arrived at cathode and co-deposited in the coating. Therefore, the hardness of the coating increases. However, as well known, the co-deposition rate of nonconducting nanoparticles is less dependent on current density. Hence, continue to increase current density, the deposition rate of nickel will increase larger than that
ACCEPTED MANUSCRIPT of particles. This led to the decrease of the amount (percent by volume) of the embedded nanoparticles in the coating. So, the hardness first increased and then decreased with the increase of current density. In fact, as current density changes, the transfer process of metallic
RI PT
ions and charged particles, especially the transfer rate, have been changed. Consequently, the composition of the coating including the content of embedded particles have been changed, leading to the change of the hardness. In this case, it can be expected that the change of
SC
current density will affect the content of particles and tungsten in the coating, then influencing
M AN U
the hardness. Fig. 10b shows the hardness as a function of deposition time. As presented in Fig. 10b, when deposition time extends from 15 min to 30 min, the hardness of the deposits slightly decreases from 980 HV to 813 HV. Then the hardness increases to 978 HV when deposits for 60 min. Sknar [29] and He [30] reported that the enhanced hardness might be
TE D
caused by two reasons. One is the reinforcing particles in the coatings hinder the matrix grain boundary sliding and the dislocation movement; the other is particles evenly dispersed in the Ni-W matrix resulting in grain refinement and dispersion strengthening effect. As shown in
EP
Table 1, the change of the crystallite size (13-16 nm calculated by Debye-Scherrer equation)
AC C
of the obtained composite coating is small. It indicates that the effect of crystallite size on the hardness of the coating is limited. Therefore, the hardness of the deposited coating is more dependent on the amounts and distribution of nanoparticles embedded in the coating, as well as the nature properties of the particles. Thus, the effect of deposition time on the hardness might be related to the change of particle content in the coatings.
RI PT
ACCEPTED MANUSCRIPT
Fig. 10. Hardness of Ni-W/TiN-Y2O3 MMCs prepared by DC deposition as a function of (a)
M AN U
3.5 Corrosion resistance after immersed 1 h
SC
current density (t=15min) and (b) deposition time (i=4A dm-2).
The corrosion behaviors of the prepared Ni-W/TiN-Y2O3 MMCs were investigated by electrochemical measurements. Fig. 11 shows the Tafel, Nyquist and Bode plots of Ni-W/TiN-Y2O3 composites after immersed in 3.5 wt.% NaCl solution for 1 h. Fig. 11a shows
TE D
the Ecorr shifted to the nobler value and the Icorr decreased, indicating that the corrosion resistance of the coating generally increases as the current density increases. As seen in Fig.
EP
11b, in the initial immersion stage, the Nyquist curves present a semicircular arc shape with different radius, indicating a one time constant. So an equivalent electrical circuit (EEC)
AC C
model as shown in Fig. 12 was used to analyze the corrosion parameters. The corrosion parameters derived from fitting the Nyquist plots of the composite coating after immersed 1 h in 3.5 wt.% NaCl solution were listed in Table 2. As known, in this case, the relative radius of the Nyquist plots could also express the corrosion resistance of the samples [31, 32]. As seen in Fig. 11b (Table 2), when immersed for 1h, as current density increased from 2 Adm-2 to 8 Adm-2, the Rct values firstly decreased from 38.38 kΩ·cm2 at 2 A dm-2 down to 30.27 kΩ·cm2 at 4 A dm-2. Then it gradually increases up to 55.41 kΩ·cm2 as the current density increases to
ACCEPTED MANUSCRIPT 8 A dm-2. It indicated that the corrosion resistance of the deposited coating initially reduces and then improves with the maximum value at 8 A dm-2. As indicated in Fig. 11c, the highest impedance and the broader phase angle peak was obtained at 8 A dm-2 at 1 h, indicating a
RI PT
better corrosion resistance of the coating. Fig. 11d shows that the coating obtained has a dense structure without defects. It should be noted that, in this group of experiments, the deposition time was kept constant at 15 min. So, the thickness of the coating will increase as the current
SC
density increases. The thickness of the coating prepared at 2, 4, 6 and 8 A dm-2 for 15 min
M AN U
were 2.7, 6.7, 8.6 and 10.8 µm, respectively. Hence, the high corrosion resistance of the samples prepared at 8 A dm-2 partly attributed to the larger thickness formed at high current density. The other reason might be due to the compact microstructure and more amounts of
AC C
EP
TE D
nanoparticles incorporated in the coating.
Fig. 11 Tafel curves (a), Nyquist plots (b), Bode plots (c) and SEM images (d) of Ni-W/TiN-Y2O3 composite coating deposited by DC deposition for 15min at different current
ACCEPTED MANUSCRIPT
RI PT
density after immersed 1 h in 3.5 wt.% NaCl aqueous solution.
Fig. 12. Equivalent electrical circuit (EEC) model used to analyze the EIS data.
Fig. 13 indicates the corrosion behavior of the coating fabricated at different deposition
SC
time. Fig. 13a shows the sample obtained at 30 min has higher Ecorr and the lowest Icorr. Fig.
M AN U
13b shows that the impedance of the sample produced at 30 min is larger compared to the coating of 15 min and 60 min. As shown in Table 2, the Rct reaches the maximum values of 71.18 kΩ·cm2 at 30 min, indicating the best anti-corrosion capability. After long time deposition, the Rct value of the coating decreased sharply to 16.27 kΩ·cm2 at 60 min. It is
TE D
associated with the defects formed at long-time deposition, which allows the solution easily permeating through the coating and weakened the protective properties. As seen from Bode plots in Fig. 13c, when immersed for 1 h, the |Z| prepared at 30 min reached the maximal
EP
value at 0.01 Hz. It illustrated that the anti-corrosion properties first enhanced and then
AC C
reduced as the time extends. In this stage, the phase angle curve obtained at 30 min showed the broader hump with the highest phase angle suggesting excellent corrosion resistance. The morphology indicated that the sample obtained at 30 min owns a dense and compact structure without noticeable defects.
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 13. Tafel (a), Nyquist (b), Bode plots (c) and SEM images of Ni-W/TiN-Y2O3 MMCs deposited by DC deposition at 4 A dm-2 for different time after immersed 1 h in 3.5 wt.%
TE D
NaCl solution, The SEM image was obtained at 30 min. Table 2 Corrosion parameters of Ni-W/TiN-Y2O3 composite coating deposited by DC
EP
deposition at different conditions after immersed 1 h in 3.5 wt.% NaCl solution. Rs (Ω·cm2)
Rct (Ω·cm2)
CPEdl (µF cm−2)
n
2 A dm-2, 15 min 4 A dm-2, 15 min 6 A dm-2, 15 min 8 A dm-2, 15 min 15 min, 4 A dm-2 30 min, 4 A dm-2 60 min, 4 A dm-2
7.45 6.23 7.17 6.70 6.23 6.29 5.07
38379 30271 44559 55405 30271 71177 16270
37.56 41.92 41.02 46.51 41.92 39.05 37.47
0.91 0.92 0.90 0.88 0.92 0.91 0.86
AC C
Samples
3.6 Corrosion resistance after immersed 7 days Fig. 14 presents the electrochemical behavior of Ni-W/TiN-Y2O3 MMCs after soaked 168 h in 3.5 wt.% NaCl solution. Table 3 shows the corrosion parameters derived from fitting
ACCEPTED MANUSCRIPT the corresponding EIS diagrams of the composite coating. It was found that the impedance of the sample fabricated at 2 A dm-2 and 30-60 min is higher compared to others. Also, it was noticed that the Rct value of 26.58 kΩ·cm2 of the coating prepared at 2 A dm-2 was larger than
RI PT
that prepared at the higher current density, indicating the better corrosion resistance at 2 A dm-2. Also, it was observed in Table 3 that the CPEdl values (300-768 µF cm−2) are higher than that immersed for 1h (37-47µF cm−2), indicating the rougher surface formed after the
SC
immersion corrosion. The coating prepared at high current density might own more internal
M AN U
stress and potential defects, which could decrease the compactness and then the protective capability of the coating after long time immersion.
After immersed for 168 h, it can be observed from Fig 14 (a, b) that the Ecorr decreases much compared Fig. 11a and 13a. The Nyquist plots of Fig 14 (c, d) also indicated the
TE D
reduced |Z| values. Comparing these plots, the |Z| values of 2 A dm-2 and 30 min were larger than others. Furthermore, the phase angle curve of Fig. 14 (e, f) exhibits one narrow hump with the peak frequency shifting to lower values, indicating a worse corrosion resistance.
EP
After immersed for 168 h, the coating synthesized at 30 min still owns the efficient
AC C
anti-corrosion properties (Rct =27.87 kΩ·cm2). In the initial stage of immersion, the solution has not arrived at the substrate. However, with the extension of immersion time, the dense coating with fewer pores deposited at a relatively low current density (2 A dm-2) will show the highest corrosion resistance. According to Bode plots in Fig. 14f, the |Z| reaches the maximum value at 30 min and 60 min for 168 h. For long-period protection, the coating produced at 30 min has superior protective performance. The Bode plot of Fig. 14f also illustrated the highest |Z| value at 0.01 Hz and the widest hump was obtained for the sample of
ACCEPTED MANUSCRIPT
TE D
M AN U
SC
RI PT
30 min, indicating the excellent anti-corrosion properties.
EP
Fig. 14. Tafel curves, Nyquist and Bode plots of Ni-W/TiN-Y2O3 composite coating after
AC C
immersed 168 h in 3.5 wt.% NaCl solution. (a, c, e) prepared at different current density for 15min; (b, d, f) prepared at 4 Adm-2 for different time.
ACCEPTED MANUSCRIPT Table 3 Corrosion parameters of Ni-W/TiN-Y2O3 composite coating deposited by DC deposition at different conditions after immersed 168 h in 3.5 wt.% NaCl solution. Rs (Ω·cm2)
Rct (Ω·cm2)
CPEdl (µF cm−2)
n
2 A dm-2, 15 min 4 A dm-2, 15 min 6 A dm-2, 15 min 8 A dm-2, 15 min 15 min, 4 A dm-2 30 min, 4 A dm-2 60 min, 4 A dm-2
6.55 4.57 3.69 3.67 4.57 4.33 6.78
26578 18315 23931 25214 18315 27871 23469
300.95 767.33 587.55 574.67 767.33 418.21 278.80
0.92 0.92 0.94 0.94 0.92 0.93 0.92
SC
RI PT
Samples
M AN U
4. Conclusions
In this study, a novel Ni-W/TiN-Y2O3 MMCs were prepared by direct current deposition and the morphology, structure, microhardness and corrosion resistance were investigated. The samples have a dense structure without visible defects. The deposits exhibit nodular structure
TE D
with different dimensions of nodules, circular or quasi-circular in shape. The addition of TiN and Y2O3 particles could improve the hardness and anti-corrosion properties of the metallic matrix. The crystallite sizes were in the diameter of 13-16 nm. EDS mapping demonstrated
EP
that the TiN and Y2O3 particles were evenly distributed in the deposits. The electrochemical
AC C
measurements illustrated that 6-8 Adm-2 and 30 min were the preferred parameters for the best corrosion resistance of Ni-W/TiN-Y2O3 coatings. After immersed 168 h in 3.5 wt.% NaCl aqueous solution, the coating prepared at 30 min and 2 A dm-2 had the best corrosion resistance. This Ni-W/TiN-Y2O3 MMCs have high hardness and superior corrosion resistance, which can be used for metallic parts protection in an aggressive medium.
Acknowledgements We thank the financial support from the National Natural Science Foundation of China
ACCEPTED MANUSCRIPT (Grant No. 51679076), the Fundamental Research Funds for the Central Universities (Grant No. 2019B15914), China.
References
electrochemical deposition, J. Alloys Compd., 702 (2017) 38-50.
RI PT
[1] B. Li, W. Zhang, W. Zhang, Y. Huan, Preparation of Ni–W/SiC nanocomposite coatings by
[2] S. Kumaraguru, S. Mohan, Study of Ni-Bi2O3-CeO2 composite coatings: Hierarchical
SC
microstructure and augmented microhardness for surface engineering application, Surf. Coat. Technol., 349 (2018) 567-575.
M AN U
[3] Y. Wang, Q. Zhou, K. Li, Q. Zhong, Q.B. Bui, Preparation of Ni–W–SiO2 nanocomposite coating and evaluation of its hardness and corrosion resistance, Ceram. Int., 41 (2015) 79-84. [4] B. Li, W. Zhang, Microstructural, surface and electrochemical properties of pulse electrodeposited Ni–W/Si3N4 nanocomposite coating, Ceram. Int., 44 (2018) 19907-19918.
TE D
[5] T. He, Y. He, H. Li, Y. Fan, Q. Yang, Z. He, A comparative study of effect of mechanical and ultrasound agitation on the properties of pulse electrodeposited Ni–W/MWCNTs composite coatings, J. Alloys Compd., 743 (2018) 63-72.
EP
[6] M.H. Allahyarzadeh, M. Aliofkhazraei, A.R. Rezvanian, V. Torabinejad, A.R. Sabour Rouhaghdam, Ni-W electrodeposited coatings: Characterization, properties and applications,
AC C
Surf. Coat. Technol., 307 (2016) 978-1010. [7] H. Li, Y. He, T. He, D. Qing, F. Luo, Y. Fan, X. Chen, Ni–W/BN(h) electrodeposited nanocomposite coating with functionally graded microstructure, J. Alloys Compd., 704 (2017) 32-43.
[8] B. Li, D. Li, T. Mei, W. Xia, W. Zhang, Fabrication and characterization of boron nitride reinforced Ni–W nanocomposite coating by electrodeposition, J. Alloys Compd., 777 (2019) 1234-1244. [9] M.G. Hosseini, M. Abdolmaleki, J. Ghahremani, Investigation of corrosion resistance of electrodeposited Ni–W/SiC composite coatings, Corros. Eng., Sci. Technol., 49 (2013)
ACCEPTED MANUSCRIPT 247-253. [10] B.S. Li, Y.X. Huan, H. Luo, W.W. Zhang, Electrodeposition and properties of Ni–B/SiC nanocomposite coatings, Surf. Eng., 35 (2019) 110-120. [11] K. Arunsunai Kumar, G. Paruthimal Kalaignan, V.S. Muralidharan, Direct and pulse
RI PT
current electrodeposition of Ni–W–TiO2 nanocomposite coatings, Ceram. Int., 39 (2013) 2827-2834.
[12] E. Beltowska-Lehman, A. Bigos, P. Indyka, A. Chojnacka, A. Drewienkiewicz, S.
SC
Zimowski, M. Kot, M.J. Szczerba, Optimisation of the electrodeposition process of Ni– W/ZrO2 nanocomposites, J. Electroanal. Chem., 813 (2018) 39-51.
M AN U
[13] Y. Boonyongmaneerat, K. Saengkiettiyut, S. Saenapitak, S. Sangsuk, Effects of WC addition on structure and hardness of electrodeposited Ni–W, Surf. Coat. Technol., 203 (2009) 3590-3594.
[14] M.H. Allahyarzadeh, M. Aliofkhazraei, A.R.S. Rouhaghdam, V. Torabinejad,
TE D
Electrodeposition of Ni–W–Al2O3 nanocomposite coating with functionally graded microstructure, J. Alloys Compd., 666 (2016) 217-226. [15] B. Li, W. Zhang, Y. Huan, J. Dong, Synthesis and characterization of Ni–B/Al2O3
EP
nanocomposite coating by electrodeposition using trimethylamine borane as boron precursor, Surf. Coat. Technol., 337 (2018) 186-197.
AC C
[16] H. Li, Y. He, T. He, Y. Fan, Q. Yang, Y. Zhan, The influence of pulse plating parameters on microstructure and properties of Ni–W–Si3N4 nanocomposite coatings, Ceram. Int., 42 (2016) 18380-18392.
[17] H. Hassannejad, A. Nouri, Formation of β-NiAl nanocomposite coating by electrodeposition and effect of cerium ion doping on its oxidation mechanism, Ceram. Int., 43 (2017) 9979-9984. [18] M. Karbasi, N. Yazdian, A. Vahidian, Development of electro-co-deposited Ni–TiC nano-particle reinforced nanocomposite coatings, Surf. Coat. Technol., 207 (2012) 587-593.
ACCEPTED MANUSCRIPT [19] Y. Zhou, S. Zhang, L. Nie, Z. Zhu, J. Zhang, F. Cao, J. Zhang, Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy, Trans. Nonferrous Met. Soc. China, 26 (2016) 2976-2987. [20] F. Xia, J. Tian, W. Wang, Y. He, Effect of plating parameters on the properties of pulse
RI PT
electrodeposited Ni–TiN thin films, Ceram. Int., 42 (2016) 13268-13272. [21] C. Ma, X. Guo, J. Leang, F. Xia, Synthesis and characterization of Ni–P–TiN nanocomposites fabricated by magnetic electrodeposition technology, Ceram. Int., 42 (2016)
SC
10428-10432.
[22] M. Ahmadi, M.J.F. Guinel, Synthesis, characterization and understanding of the
M AN U
mechanisms of electroplating of nanocrystalline–amorphous nickel–tungsten alloys using in situ electrochemical impedance spectroscopy, J. Alloys Compd., 574 (2013) 196-205. [23] L.L. Tian, J.C. Xu, Electrodeposition and characterization of Ni-Y2O3 composite, Appl. Surf. Sci., 257 (2011) 7615-7620.
TE D
[24] F. Cai, C.H. Jiang, Z.Q. Zhang, V. Ji, Synthesis and characterization of Ni-Al-Y2O3 composite coatings with different Y2O3 particle content, Ceram. Int., 40 (2014) 15105-15111. [25] S. Sangeetha, G.P. Kalaignan, J.T. Anthuvan, Pulse electrodeposition of self-lubricating
412-419.
EP
Ni–W/PTFE nanocomposite coatings on mild steel surface, Appl. Surf. Sci., 359 (2015)
AC C
[26] K.A. Kumar, G.P. Kalaignan, V.S. Muralidharan, Pulse electrodeposition and characterization of nano Ni–W alloy deposits, Appl. Surf. Sci., 259 (2012) 231-237. [27] B. Li, D. Li, W. Chen, Y. Liu, J. Zhang, Y. Wei, W. Zhang, W. Jia, Effect of current density and deposition time on microstructure and corrosion resistance of Ni-W/TiN nanocomposite coating, Ceram. Int., 45 (2019) 4870-4879. [28] F.F. Xia, W.C. Jia, C.Y. Ma, R. Yang, Y. Wang, M. Potts, Synthesis and characterization of Ni-doped TiN thin films deposited by jet electrodeposition, Appl. Surf. Sci., 434 (2018) 228-233.
ACCEPTED MANUSCRIPT [29] Y.E. Sknar, O.O. Savchuk, I.V. Sknar, Characteristics of electrodeposition of Ni and Ni-P alloys from methanesulfonate electrolytes, Appl. Surf. Sci., 423 (2017) 340-348. [30] T. He, Y. He, H. Li, Z. Su, Y. Fan, Z. He, Fabrication of Ni-W-B4C composite coatings and evaluation of its micro-hardness and corrosion resistance properties, Ceram. Int., 44
RI PT
(2018) 9188-9193. [31] H. Luo, X. Wang, S. Gao, C. Dong, X. Li, Synthesis of a duplex Ni–P–YSZ/Ni–P nanocomposite coating and investigation of its performance, Surf. Coat. Technol., 311 (2017)
SC
70-79.
[32] X. Feng, X. Lu, Y. Zuo, N. Zhuang, D. Chen, The effects of deformation on metastable
M AN U
pitting of 304 stainless steel in chloride contaminated concrete pore solution, Corros. Sci., 103
AC C
EP
TE D
(2016) 223-229.