Accepted Manuscript Enhanced texture and microhardness of the nickel surface using Bi2O3 particles via electrodeposition technique for engineering application S. Kumaraguru, Gopika G. Kumar, S. Shanmugan, S. Mohan, R.M. Gnanamuthu PII:
S0925-8388(18)31227-1
DOI:
10.1016/j.jallcom.2018.03.350
Reference:
JALCOM 45580
To appear in:
Journal of Alloys and Compounds
Received Date: 3 November 2017 Revised Date:
19 March 2018
Accepted Date: 27 March 2018
Please cite this article as: S. Kumaraguru, G.G. Kumar, S. Shanmugan, S. Mohan, R.M. Gnanamuthu, Enhanced texture and microhardness of the nickel surface using Bi2O3 particles via electrodeposition technique for engineering application, Journal of Alloys and Compounds (2018), doi: 10.1016/ j.jallcom.2018.03.350. 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
Enhanced texture and microhardness of the nickel surface using Bi2O3 particles via electrodeposition technique for engineering application S. Kumaraguru a, Gopika G. Kumar a, S. Shanmugan a, S. Mohan b, RM. Gnanamuthua* SRM Research Institute & Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur-
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a
603203, Chennai, Tamilnadu, India. b
Electroplating and Metal Finishing Technology Division, CSIR – Central Electrochemical Research Institute,
Karaikudi – 630003, Tamilnadu, India.
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Abstract
In this study, we explore the structure and mechanical properties of nickel-bismuth oxide
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(Ni-Bi2O3) composite material, for the first time, prepared via electrodeposition technique. The emerging of Bi2O3 particles is improving the microhardness, wear resistance and roughness of the Ni coating when compared with pure nickel deposit. X-ray diffraction analysis revealed that the crystallite size of the Ni-Bi2O3 coating diminishes with amplification in the concentration of
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Bi2O3 particles. The preferred crystalline orientation of Ni-Bi2O3 coating has been distorted from the most intense (200) texture to polycrystalline orientation. The scanning electron morphologies (SEM) show that pyramid-like and cauliflower-like structures and it has observed from Ni and
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Ni-Bi2O3 deposits, respectively. A maximum bismuth content of 10.71% is embedded at a loading of 50 g/L. The Ni-Bi2O3 composite exhibits an average microhardness value of 730
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HV50. This is approximately three times higher than nickel deposit. Therefore, the prepared NiBi2O3 composite material is a suitable candidate for engineering uses. Keywords: Microhardness; Texture; Composite coating; Electrodeposition; AFM
*Corresponding author: Tel.: 044-24712606, Fax. +91-44-2745-6702 Email:
[email protected] (RM. Gnanamuthu) 1
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1. Introduction Damage to metallic parts was induced by corrosion activities via the chemical reaction
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and environmental issues. As a consequence of this, enormous economic losses in the past years [1]. Coatings can protect the steel surface from corrosion by acting as a barrier between environment and steel surface [2,3]. Over the last several decades, electrodeposition is most widely utilized technique to modify the surface with metals or alloys, by virtue of its simplicity,
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reproducibility, less expensive, rapid deposition rate and working at an ambient condition [4].
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Researchers much interested in the technological development of metal matrix composite (MMC) coatings [5], MMCs thin films containing reinforcement particles like carbides, hard metal oxides, diamond and carbon nanostructures etc., dispersed in a metal matrix [2,6] and have unique mechanical, optical and magnetic properties [7]. The characteristics of the composite films were controlled by several parameters such as electrolyte concentration [8], applied current
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density [9], additives [10], pH of the bath [11], surfactant [12] and the nature of the reinforced particle (size, conductivity and surface charge) [13]. Among these deposition variables, surfactant was very much essential in the case of metal matrix composite deposition, since
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surfactant in the bath will reduce the agglomeration of inert particles [9]. N. Parhizkar et al. reported the upshot of sodium dodecyl sulfate (SDS) surfactant on the electrodeposited Ni-TiN
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nanocomposite and found that the addition of SDS considerably improved the incorporation of TiN particles in the nickel matrix [12]. Bismuth oxide (Bi2O3) is recognized as an oxygen ion conducting ceramic material
[14,15]. It exists in a variety of crystalline orientation and phases, includes α, β, γ, δ and ω [16]. The structure, conductivity and stability properties of the electrodeposited Bi2O3 were extensively studied by several research groups [15,17]. It possesses interesting properties such as 2
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a high refractive index, dielectric permittivity, a large energy band gap, photoconductivity and photoluminescence [18]. Therefore, it will be effectively used in sensors [19], fuel cells [20], supercapacitor [21] and photocatalysis [22]. Specifically, L. Cao et al. reported that porous
dendritic
Bi/Bi2O3
exhibits
superhydrophobic
surfaces
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electrodeposited
[23].
Y. Nakabayashi et al. studied that CuBi2O4 thin film fabricated using anodic electrodeposition
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employed for the hydrogen production under solar light irradiation [24].
Nickel is most widely used engineering material to protect the steel surface by
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electrodeposition [25]. Nickel-based composite coatings as an alternative to the chromium deposited from hexavalent chromium ions, which can cause environmental pollution and carcinogenic to human health [26,27]. The inclusion of reinforcement particles in the nickel metal matrix significantly improved the hardness, anti-oxidation, corrosion and wear resistance of the coatings [1]. Nickel-based composite coatings displayed a wide variety of applications.
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Recently, G. Zhoa et al. specified the superhydrophobic property of one-step electrodeposited Ni/WS2 [28]. Electrodeposited nickel composites such as Ni-CeO2 [29], Ni-LaNiO3 [30], Ni-W [31] and Ni-Mo [32] were evaluated for hydrogen evolution reaction. M. Uysal et al. fabricated
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the Sn-Ni/MWCNT composite using electrodeposition technique and studied Li-ion battery
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performance [33]. However, a Ni-Bi2O3 composite coating was not much more explored. Definitely, Ni-Bi2O3 composite coatings will be a promising candidate for the various kinds of applications and replacement for hexavalent chromium. Now, the strategy of the work is that to prepare the Ni-Bi2O3 composite deposits and
optimizes the concentration of the reinforcement particles to insert the number of Bi2O3 particles in the nickel matrix. The influence of crystal orientation, composition and morphology of the deposits on microhardness and wear resistance were inspected. 3
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2. Materials and methods 2.1. Materials
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In this work, the following chemicals NiCl2.6H2O (99%, Merck), NiSO4.6H2O (99%, Fisher Scientific), H3BO3 (99.5%, Fisher Scientific), bismuth oxide (Bi2O3, 99.9%, 80-200 nm, Alfa Aesar) and sodium lauryl sulfate (99%, SRL) were used in the preparation of electrolyte.
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Na2CO3 (99%, Merck), NaOH (99%, SRL) and HCl (35-38%, Rankem) were used to prepare the solution for pretreatment process. All the chemicals were utilized without any further
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purification. The experimental solutions were prepared using Millipore water and these were utilized in the electrochemical deposition process. 2.2. Experimental details
Electrodeposition of Ni-Bi2O3 composite coatings was carried out from Watts electrolyte
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and prepared by 200 ml of the electrolyte was taken in a beaker and Bi2O3 particles were added. The concentration of the Bi2O3 particles was varied. Before performing the co-deposition process, the bath was vigorously agitated well for 24 hours by using a magnetic stirrer at 1000
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rpm. Each time, concentration variation was studied by use of newly prepared electrolyte. With
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the intention of avoiding pits in the deposit and evade agglomeration of Bi2O3 particles, a small quantity of sodium lauryl sulfate (surfactant) was added into the bath. More details of the bath composition and operating parameters were shown in Table 1. Electrodeposition experiments were executed with conventional two electrode system using direct current (DC) power supply. Nickel sheet was used as an anode and mild steel plate as the cathode, respectively. Firstly, mild steel plates were mechanically polished and degreased with acetone. Prior to a deposition, the plates were sequentially pretreated with alkaline (Na2CO3+NaOH). The surface of the nickel 4
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sheet and mild steel plates were activated by dipping in 10% HCl for 20 seconds and washed with distilled water. Throughout the experiment, deposition was effectuated at a current density of 5 A/dm2 and bath was constantly stirred at a speed of 400 rpm. The pH of the electrolyte
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ranges from 3.5 to 4.5. The deposition was accomplished at room temperature for 60 minutes. An identical procedure was followed to prepare the samples for abrasive wear study. But the mild steel plates with the size of 10 × 10 cm2 were used for the deposition of the Ni-Bi2O3
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composite. The deposition process was conducted with the concentration of 50 g/L for the period
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of 60, 90 and 120 minutes.
The deposition experiment was implemented by means of Aplab L3210 regulated DC power supply. The crystalline phases of the composite were tested using Bruker D8 Advance Xray diffractometer (XRD) equipped with Cu Kα radiation (wavelength: 0.15406 nm). The angle (2θ) ranges from 10 to 110⁰ at a measuring speed of 6⁰/min. The crystallite size was determined
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using the Debye-Scherrer equation [26]:
= ⁄βcos
Where k is the shape factor (0.9), λ is the wavelength of X-rays (0.15406 nm), β is the full
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width at half maximum, θ is the angle of diffraction. To estimate the preferred crystal orientation
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of the composite deposits, the relative texture coefficients (RTC) were appraised by using the formula as follows [10]:
#!
() 1 [ ]() % = " $ × 100 () () ()
!
Where () is the diffraction intensities of the (hkl) reflection of the Ni-Bi2O3 composite
deposits, () is the intensities of a standard Ni sample randomly oriented, n is the number of
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diffraction peaks used in the calculations. The most important reflections such as (111), (200), (220), (311) and (222) were exploited to calculate the texture coefficient (n=5). The composition of the Ni-Bi2O3 composite coatings was assessed with HORIBA XGT-
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5200 Energy Dispersive X-ray Fluorescence analyzer (ED-XRF). The surface morphology of the deposits was scrutinized by the Tescan scanning electron microscope (SEM) integrated with the Vega3sem software. The roughness parameter and topography was recorded with the Agilent
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Technologies 5500 Series Atomic force microscopy (AFM). The microhardness of the composite coating was surveyed by the Vicker’s hardness tester. Hardness measurements were performed at
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a load of 50 g with the dwell time of 5 s. Each coating was an indentation at five different locations. The abrasive wear resistance was fulfilled through Taber industries, 5135 Abraser, rotary platform abraser equipped with ‘CS-10’ wheel consisting of silicon carbide particles. The wear index (I) was calculated using the formula:
['( − * + × 1000]
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=
Where A is the weight of the coated specimen before abrasion in mg, B is the weight of
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the coated specimen after abrasion in mg and C is the number of cycles of abrasion recorded. The abrasion test was done up to 8000 cycles at a load of 1000 g. The weight differences
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between every 1000 cycles were recorded. 3. Results and discussion 3.1. Structural analysis
The XRD patterns of the Ni and incorporated Bi2O3 particles as Ni-Bi2O3 composite deposited at various concentrations as shown in Fig. 1. The XRD pattern of the Ni surface illustrates (200) plane {i.e. (100) plane}. While all other planes of the Ni surface such as (111),
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(220), (311) and (222) were observed with very low intensity. This may be due to the surfactant existing in the electrolyte reduces the surface energy of the (200) plane than that of the other plane. Encapsulation of Bi2O3 particles in the nickel matrix induces a modification in the texture
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of the deposits. The initial addition of Bi2O3 (10 g/L) dwindles the intensity of (200) plane and enhance the intensity of all other planes. Further increment in the concentration of Bi2O3 particles (20 g/L) suppresses the (200) crystal plane and random crystal orientation was
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perceived with the preferred orientation of (111) plane. But the intensity of (200) plane remains constant at a Bi2O3 concentration of 30 g/L. At the same time, slight shrinkage in the (111)
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orientation was observed and minor increment was detected for the other less intense planes. At high concentration of Bi2O3 (50 g/L), the intensity of the crucial planes (111) and (200) was contracted. Bi2O3 particle loading in the electrolyte elevates crystallite size of the composite coating decreases and shows the minimum value of crystallite size was 20 nm as shown in
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Table 2. The remarkable transformation of crystalline planes arises due to the adsorptiondesorption phenomena takes place in the cathode interface. When Bi2O3 particles emerged in the electrolyte, it dispersed and charged on the surface by the ionic species present in the bath. These
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surface-charged oxides arrived at the catholyte area and loosely adsorbed on the surface. During the deposition process, rise in pH at the catholyte interface and formation of Ni(OH)2 at the
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interface. At that time, the adsorbed surface-charged oxides will condense the amount of hydrogen adsorption (Hads). Therefore, the formation of Ni(OH)2 at the interface was hindered. Accordingly, the adsorption of insoluble species hindered the nucleation of preferred orientation and grows in the less common crystallographic direction [1,13]. In order to analyze the quantity of Ni and Bi present in the composite coatings were investigated using EDXRF technique as depicted in Fig. 2. The observed nickel and bismuth 7
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percents were 99.27% and 0.73%, respectively at a concentration of 10 g/L. Upon increasing the concentration of Bi2O3 particles in the Watts bath leads to enriching the bismuth content in the composite coatings. A higher bismuth content of 10.71% (approx.) in the composite coating was
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achieved at a loading of 50 g/L Bi2O3. The augmentation in bismuth content ascribed to the fact that the mechanical agitation given to the electrolyte enhances the mass transport at the cathodeelectrolyte interface region. So, the number of surface-charged species available for the
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discharge reaction is enriched. As a result, the bismuth content in the deposits increases with the
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rise in the concentration of Bi2O3 particles.
Figure 3 portrays the SEM images of the nickel and Ni-Bi2O3 composite coatings deposited from the bath containing various concentrations of Bi2O3 particles. Electrodeposited nickel exhibits pyramidal morphology with the size of approximately 5 µm as shown in Fig. 3A. This morphology arises due to the surfactant present in the Watts electrolyte. The addition of
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Bi2O3 particles shrinks the pyramidal shape to 2 µm and Bi2O3 particles not homogeneously distributed in the metal matrix due to the formation of whirls in the electrolyte. The symmetric pyramidal morphology was uniformly distributed throughout the surface in figure 3B. In Fig. 3C
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illustrates that the number of pyramidal shape particles drops off and displays pseudo-pyramid
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like structure. Some faces of the pyramid were destroyed and edges of the grains become fuzzy. Because of the number of entrenched Bi2O3 particles. A further rise in the concentration of Bi2O3 particles produces cauliflower like morphology and also shows micro-cracks that are seemed due to the stress in the deposit as shown in fig. 3D. Moreover, the agglomeration of the composite was completed at higher concentration (50 g/L) of Bi2O3 and forms bigger particles in Fig. 3E. The formation of these kinds of morphologies attributed to the absorption of Bi2O3 particles on
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the steel surface, then nickel begins to start to nucleate around the cathode surface, ingraining the particles.
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Figure 4 shows the cross-sectional micrographs of the Ni and Ni-Bi2O3 composite deposit acquired with the Bi2O3 concentration of 50 g/L are investigated. Ni and Ni-Bi2O3 composite expose the granular structure as shown in Fig 5A and B. Both the deposits were densely and
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compactly packed. It can be seen that the higher number of Bi2O3 particles inserted in the Ni matrix. Although the coatings were micro-cracks free but showed the presence pinholes at higher
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magnification. Figure 5C and D demonstrate that the thickness of the Ni and Ni-Bi2O3 composite deposits were measured, approximately 40 µm and lack of defects in the interface indicate that good adhesion was found between the deposited film and the steel substrate. Figure 5 illustrates the three-dimensional view of the surface morphology of the nickel
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and Ni-Bi2O3 composite coatings produced from the Watts electrolyte. The nickel deposit exhibits smooth surface and measured roughness value of less than 10 nm in Fig. 4A. The surface profile analysis shows the presence of void space in Fig. 4B. It arises due to the presence
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of second phase particles in the Ni matrix. It is obvious that the use of Bi2O3 (10 g/L) particles results in the formation of grain like structure and homogeneously distributed on the surface. The
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Ra, Rq, Rz values of the Ni-Bi2O3 composite deposit were 45.7 nm, 53.3 nm, 213 nm as shown in Table 3. It was quite high compared to all other deposits. There is less number of grains were observed at 20 g/L of Bi2O3 and also roughness value was declined as shown in Fig. 4C. Overall, at high concentrations agglomeration of Ni-Bi2O3 composite occurred as a consequence of this cluster was formed as presented in Fig. 4D and 4E.
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3.2. Mechanical properties The microhardness of the Ni-Bi2O3 composite coatings as a function of the concentration
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of Bi2O3 particles is exposed in Fig. 6. In composite plating, the hardness of the deposits was controlled by the reinforcement particles arise in the electrolyte [3]. The microhardness of the electrodeposited nickel shows a maximum value of 279 HV50. It has been observed that the
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introduction of the Bi2O3 particles in the bath, supplement the hardness of the Ni-Bi2O3 composite coating compared to that of nickel. Higher the amount of Bi2O3 particles embedded in
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the Ni matrix led to the significant improvement in the microhardness value. The enhancement of hardness attributed to the grain refinement and dispersion hardening. The presence of surfactant in the electrolyte, launch a higher number of Bi2O3 particles uniformly distributed in the nickel matrix contributing dispersion hardening. The reinforcement particle acts as an obstacle while gaining load by the matrix. Even though the stress of the motions of locked
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dislocation between two particles augmented (Orovan effect) but the movement of dislocations was prevented by forming dislocation pileups at grain boundaries, ensuring the hard deposit. Grain refinement guided the nucleation of small grains around the hard particles, is constituted
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by the Hall-Petch equation [34].
,- = , + / #!⁄0
Where HV is the measured Vicker’s hardness, d is the average crystallite size, H0 and k
are the constants. The average hardness value of 730 HV50 was achieved for the composite coating with 10.71% of Bi2O3 particles. The influence of deposition time on the abrasion rate of the Ni-Bi2O3 composite was displayed in Fig. 7. It is interesting to note that the mass loss (abrasion rate) of the samples step10
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up with increasing deposition time. This is due to the engrained Bi2O3 particles which directed to the irregular surface growth and the roughness of the deposits surface. Thus the coated surface abraded well. Initially, all the coatings show a heavy weight loss of 24.6, 26.4, 29.4 mg for the
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deposition time of 60, 90 and 120 minutes respectively. This was observed at after the completion of 1000 cycles. Upon add-on the wear cycles, The Taber wear index was gradually lessened. Above 5000 cycles, the mass loss was less, because the surface of the deposits became
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smooth.
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5. Conclusions
We have successfully prepared Ni-Bi2O3 composite material on mild steel via electrodeposition technique. The prepared materials were compared with nickel surface that NiBi2O3 composite was better characteristic behavior such as crystalline orientation, microhardness
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and wear resistance. The different compositions of Bi2O3 particles were examined and the result delivered that the microhardness value was 730 HV50. The crystallite size of the composite coating was attained a minimum value of 20 nm. The maximum incorporation amount of
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bismuth was 10.71% and it has achieved at a current density of 5 A/dm2. Thus, the effects of Bi2O3 with nickel as a composite material have a superior microhardness and wear resistance that
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it may be a suitable material for the automobile engineering application.
Acknowledgement
This work was supported by Science and Engineering Research Board (SERB), a statutory body of the Department of Science & Technology, government of India. File No. ECR/2017/001156.
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Table 1. Chemical composition and operating parameters of the electrolyte utilized for the
NiCl2.6H2O
45
NiSO4.6H2O
240
H3BO3
35
Sodium lauryl sulphate Bi2O3 (50-200 nm)
Anode: nickel sheet
Cathode: mild steel plate
Deposition time: 60 min
10,20,30,50
Stirring speed: 400 rpm
35
pH: 3.5-4.5
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25
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Current density: 5 A/dm2
0.02
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Na2CO3 NaOH
Operating conditions
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Concentration (g/L)
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Bath constituents
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fabrication of Ni-Bi2O3 composite coatings.
Room temperature (32±2 ⁰C)
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Table 2. Calculated crystallite size and texture coefficient of the Ni-Bi2O3 composite coatings
Concentration
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electrodeposited at a current density of 5 A/dm2. Relative Texture Coefficient [RTC] (%)
Crystallite
of Bi2O3 (g/L)
(111)
(200)
(220)
(311)
Bare Ni
6.51
484.21
0.76
3.62
4.83
126.87
10
33.49
395.04
10.57
32.21
28.69
125.95
20
146.24
70.15
77.72
100.77
105.10
53.48
30
115.09
70.88
81.95
84.39
147.66
21.61
50
112.06
66.04
100.30
86.29
135.29
20.16
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TE D EP AC C
(222)
Size (nm)
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Table 3. Roughness parameters of the Ni-Bi2O3 composite coatings electrodeposited at a current
Concentration of
Roughness (nm)
Bi2O3 (g/L)
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density of 5 A/dm2.
Rq
Bare Ni
0.91
1.27
7.61
10
45.7
53.3
213
20
28.9
35.2
141
30
27.1
38.3
217
50
21.8
28.0
118
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Rz
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Ra
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Figure captions Fig. 1. X-ray diffractogram of Ni composite coatings produced at a current density of 5 A/dm2:
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(A) Ni and Ni-Bi2O3 composite coatings deposited from electrolyte containing 10 g/L Bi2O3 (B) 20 g/L, 30 g/L and 50 g/L Bi2O3.
Fig. 2. Describe the bismuth content in the composite deposits as a function of concentration of
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Bi2O3 particles in the electrolyte.
Fig. 3. Representative SEM micrographs show the surface morphology of (A) Ni and Ni-Bi2O3
Bi2O3 and (E) 50 g/L Bi2O3.
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composite coatings deposited in the presence of (B) 10 g/L Bi2O3, (C) 20 g/L Bi2O3, (D) 30 g/L
Fig. 4. Cross-sectional morphology of the (A) Ni and (B) Ni-Bi2O3 composite coating deposited at 50 g/L. Cross-sectional SEM images for deposit thickness measurement of: (C) Ni and (D) Ni-
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Bi2O3 (50 g/L) functional composite coating.
Fig. 5. AFM 3D images of Ni deposits with different concentration of Bi2O3 particles in the electrolyte: (A) Ni deposit and Ni-Bi2O3 composite coatings deposited from the bath containing
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(B) 10 g/L Bi2O3, (C) 20 g/L Bi2O3, (D) 30 g/L Bi2O3 and (E) 50 g/L Bi2O3.
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Fig. 6. Show the plot of microhardness of prepared Ni and Ni-Bi2O3 composite deposits versus concentration of Bi2O3 particles in the electrolyte. Fig. 7. Taber wear index as a function of number of cycles for 50 g/L Bi2O3 in the electrolyte.
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AC C
EP
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Fig. 1
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AC C
EP
Fig. 2
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EP
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Fig. 3
AC C
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Fig. 4
AC C
EP
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Fig. 5
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AC C
EP
Fig. 6
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AC C
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Fig. 7
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Highlights Ni-Bi2O3 composite, for the first time, prepared via electrodeposition technique. Ni-Bi2O3 composite shows cauliflower like morphology.
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A maximum bismuth content of 10.71% was incorporated at a concentration of 50 g/L. The maximum hardness value of 279 HV50 and 730 HV50 was observed from Ni and Ni-
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EP
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Bi2O3 composite coatings.
