Applied Surface Science 254 (2008) 19661971 www.elsevier.

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Nanocrystalline soft ferromagnetic NiCoP thin lm on Al alloy by low temperature electroless deposition
A. Abdel Aal *, A. Shaaban, Z. Abdel Hamid
Central Metallurgical Research & Development Institute (CMRDI), P.O. 87 Helwan, Cairo, Egypt Received 24 May 2007; received in revised form 5 August 2007; accepted 5 August 2007 Available online 14 August 2007

Abstract Soft ferromagnetic ternary NiCoP lms were deposited onto Al 6061 alloy from low temperature NiCoP electroless plating bath. The effect of deposition parameters, such as time and pH, on the plating rate of the deposit were examined. The results showed that the plating rate is a function of pH bath and the highest coating thickness can be obtained at pH value from 8 to10. The surface morphology, phase structure and the magnetic properties of the prepared lms have been investigated using scanning electron microscopy (SEM), X-ray diffraction analysis (XRD) and vibrating magnetometer device (VMD), respectively. The deposit obtained at optimum conditions showed compact and smooth with nodular grains structure and exhibited high magnetic moments and low coercivety. Potentiodynamic polarization corrosion tests were used to study the general corrosion behavior of Al alloys, NiP and NiCoP coatings in 3.5% NaCl solution. It was found that NiCoP coated alloy demonstrated higher corrosion resistance than NiP coating containing same percent of P due to the Co addition. The NiCoP coating with a combination of high corrosion resistance, high hardness and excellent magnetic properties would be expected to enlarge the applications of the aluminum alloys. # 2007 Published by Elsevier B.V.
Keywords: Electroless NiCoP; Ferromagnetic coatings; Thin lms; Al alloy

1. Introduction The progress in superior soft magnetic materials and lms is the key for making high performance data storage devices. Ni CoP lms are generally used as magnetic recording media for electronic computers and as diffusion barriers [1]. The development of soft magnetic materials with improved performance is considered to be one of the most important features in the eld of information technology. Recently, binary and ternary soft magnetic alloys such as CoNi, NiFe, CoB, CoFeB, CoNiP, are being developed for potential applications in modern high density recording and data storage discs [2,3]. These soft magnetic materials are incorporated in the induction recording heads for writing bit information onto hard disks for several years [4]. Nowadays, nanostructured soft magnetic lms have been effectively used to construct multilayer structures that exhibit

* Corresponding author at: Surface Protection & Corrosion Control Lab, Central Metallurgical Research & Development Institute (CMRDI), P.O. 87 Helwan, Cairo, Egypt. Tel.: +20 122690782; fax: +20 225010639. E-mail address: foralsayed@gmail.com (A.A. Aal). 0169-4332/$ see front matter # 2007 Published by Elsevier B.V. doi:10.1016/j.apsusc.2007.08.017

giant magnetoresistive (GMR) behavior [5]. Soft magnetic thin lms can be used in several functional micro-electromechanical system (MEMS) devices such as, magnetic microactuators, sensors and micromotors [6]. Magnetic thin lms can be deposited by several techniques such as physical vapor deposition (PVD) processes using dc or radio frequency sputtering [7,8] and wet methods by electrochemical or electroless technique [9,10]. However, electroless deposition method can be considered more suitable than electrolytic one due to the possibility of achieving uniform surface coverage and plating micromagnetic patterns on variety of substrates [11]. The autocatalytic electroless can usually be achieved at high temperature (6090 8C) [12]. Besides, it can be performed at lower temperature (35 1 8C) that enables to reduce the energy requirements and facilitate the controlling of solution composition and deposition parameters [13,14]. In this perspective, the present work aims to study the formulation and development of NiCoP electroless plating bath that operate at relatively low temperature, the deposition of electroless NiCoP coatings using such bath and evaluation of coating characteristics such as corrosion behavior and magnetic properties.

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2. Experimental procedures 2.1. Materials and NiCoP deposition Al 6061 alloy with chemical composition (1.0% Mg, 0.6% Si, 0.28% Cu, 0.2% Cr and rest Al) was used as a substrate. Electroless NiCoP deposition on Al alloy usually requires a series of pre-treatment steps to ensure good quality deposits. The pre-treatment series starts by degreasing in order to remove soaks, lubricants and ngerprints followed by acidic etching. Then the main step is the zincate treatment which applied to remove the oxides and deposits a protective zinc layer. It is usually necessary to repeat this process to obtain the best quality converging [15]. For electroless of NiCoP deposition bath, NiSO46H2O and CoSO46H2O were used as the source of nickel and cobalt, respectively. NaH2PO2H2O was used as a reducing agent, which also forms the source of phosphorus in the deposit. Na3C6H5O7 was used as the complexing agent to control the rate of release of free metal ions for the reduction reaction. In addition to other constituents, ammonia solution was added to control the bath pH and the bath was operated at a constant temperature 35 1 8C during the deposition process. The pretreatments, the bath composition and operating conditions employed for preparation are given in Table 1. 2.2. Analysis The electrolessed NiCoP deposit was stripped in 10% HNO3 and the dissolved metal (Co, P and Ni) was determined

by atomic absorption technique using Perkin-Elmer, Atomic Absorption Model, A Analyst 200. The morphology was observed using scanning electron microscopy (JEOL-JSM5410) before and after heat treatment, respectively. Vickers microhardness measurements were carried out using a tukon series B200 microhardness tester with loads of 100 g and indentation time 10 s. The hardness values were measured as average along the specimen surface. The mean hardness of ve readings was calculated for every specimen. Potentiodynamic polarization corrosion tests were used to study the general corrosion resistance of the samples (Al alloy, as-deposited NiCoP) at room temperature using an Auto lab1 Pgstate 30 with corrware software. The electrochemical measurements were made in a conventional three-electrode cell using a saturated calomel electrode (SCE) as a reference electrode and a platinum rod as a counter electrode. After the electrochemical testing system was stable, the measurements were carried out in 3.5% NaCl solution. Potentiodynamic polarization curves of the tested samples were obtained and corrosion rates were determined for comparison. For comparison, the corrosion tests have been applied for NiP coatings containing the same percent of P. The magnetic properties of electroless NiCoP ternary alloy deposits were studied using a vibrating magnetometer device (9600-VSM) at an applied eld of 5 KOe. The magnetic properties, viz. saturation magnetization Ms, remanence Mr, coercivety Hc and the squareness S derived from the hysteresis loop perpendicular to the lm surface with 5 kOe magnetic eld.

Table 1 The bath composition and operating conditions of electrolessed NiCoP lm formation onto aluminum alloys sequences Process 1 Mechanical polishing 2 Alkaline degreaser Composition 600# emery paper then, 380# alumina sand paper Na2CO3 Na3PO4 NaOH HNO3:HF:H2O 9:2:1, v/v NaOH ZnO FeCl3 KNa-tartrate Na3N HNO3 NaOH ZnO FeCl3 KNa-tartrate Na3N NiSO46H2O CoSO46H2O NaH2PO2H2O Na3C6H5O7 H3BO3 525 g/l 10 g/l 10 g/l 10 g/l 1 g/l 50%, v/v 525 g/l 10 g/l 10 g/l 10 g/l 1 g/l 7 g/l 22 g/l 25 g/l 50 g/l 30 g/l 32 g/l 32 g/l 1.5 g/l Operating conditions Time, 2 min, temperature, 50 8C

3 Acidic etching 4 Zincate solution

Time, 1 min room temperature Time, 13 min room temperature

5 Zincate removal 6 Re-zincate solution

Time, 0.5 min room temperature Time, 0.5 min room temperature

7 Electroless NiCoP

pH 811 Time, 1565 min Temperature, 35 1 8C

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Fig. 1. Effect of deposition time and pH on the coating thickness of electroless NiCoP ternary lm deposition.

3. Results and discussion 3.1. Effect of pH and deposition time on the coating thickness The effect of the bath pH on the coating thickness of electroless NiCoP alloys deposit is depicted in Fig. 1a. It is evident that at lower pH values (pH <8), the deposition process is characterized by instability of the bath producing irregular and poor deposits. An increase in the bath pH from 8 to 10 was found to increase the coating thickness with formation of bright and adherent deposits. However, at higher pH values (pH >10), the bath decomposes and the coating thickness drastically decreases. It was reported previously that OH ions concentration increases with pH increasing in range of 810 and the hypophosphite oxidation is the dominant factor in the electroless process [16]. In alkaline media, the oxidation of hypophosphite reaction occurs as follows: H2 PO2 3OH $ H2 PO3 2 2H2 O 2e (1)

the relationship between time and coating thickness is not linear due to the build-up of orthophosphite ions by oxidation of sodium hypophosphite in Eq. (1). The quantitative analysis of NiCoP deposit showed that the contents of Ni, Co and P in the lm are 60, 15 and 25 wt.% for, respectively. 3.2. Phase structure and surface morphology Fig. 2 shows X-ray diffraction patterns of electrolessed Ni CoP deposits before and after annealing at 400 8C for 2 h. XRD pattern of NiCoP as-deposited (without annealing) shows peaks of hcp-Co, fcc-Ni and metastable bcc-Ni7P3 phases. The appearance of Ni7P3 is attributed to the higher phosphorous segregation in grain boundary regions. On the other hand, for the annealed samples, new peaks of stable bctNi3P phase are observed at 36.58, 41.78 and 46.68 in addition to hcp-Co and fcc-Ni peaks. The higher intensity for annealed samples pattern indicates to the higher degree of crystallinity in these samples. During the annealing process, the higher phosphorous regions were supposed to be further increased by

From the above chemical reaction, an increase in bath pH value leads to increasing in the oxidation rate of hypophosphite which in turn accelerates the plating rate. However, the solutions become unstable at higher pH, especially above pH 11.0 where nickel and cobalt hydroxides will precipitate during the deposition process. Hence, higher values of pH were not recommended because of hydroxides precipitation and also because of the microelectronic industry requirements for circuit preservation [17]. In conclusion, it is preferable to use the bath approximately pH 9.5, where there is a good coating thickness as well as the stability of the bath. The variation of coating thickness with the deposition time is illustrated in Fig. 1b. It can be seen that the coating thickness increases with the processing time. This can be ascribed to the autocatalytic nature of the electroless plating process. However,

Fig. 2. XRD patterns of (a) coated NiCoP and (b) annealed NiCoP lms.

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extraction of P dissolved in nickel grains which in turn gave rise to precipitation of the hard inter-metallic Ni3P phase. These transformations support the earlier observation obtained by Sankara et al. [18] and Hur et al. [19]. The surface morphology of the Ni-CoP layer before and after annealing is shown in Fig. 3. The deposit obtained at optimum conditions (pH 9.5 and deposition time 15 min) was compact and smooth with nodular grains as shown in Fig. 3a. The observed randomness in distribution of spherical nanoparticles with size in the range 150250 nm is due to the partially amorphous structure in NiCoP lm grown in perpendicular direction to the substrate surface. Fig. 3b shows SEM of NiCoP coating after annealing at 400 8C for 2 h. It can be observed that there is no signicant change in the crystallite size after annealing process. However, the crystal structure and the phase were converted from bcc-Ni7P3 into bctNi3P as shown in the XRD pattern (Fig. 2b). This transformation in crystal structure is attributed to two reasons. Firstly, the deposit components and substrate, which have different thermal expansion coefcients, undergo different volume changes due to a temperature change by annealing. The evolution of texture during annealing of electroless NiCoP has been studied previously by Lee and Hur [20]. The strains and stresses due to the different thermal expansion coefcients are calculated by the integral equation: eth Z
T

where T and a are temperature and thermal expansion coefcient, respectively. Subscripts 0, s and f indicate initial state, substrate and lm, respectively. Setting T = 400 8C, T0 = 35 8C, as = aAl = 25.8 106 K1, af = aNi = 13.3 106 K1 and the eth = 12.5 106. For more accuracy, the thermal expansion coefcients of fcc-NiCo solid solutions should be used. The thermal expansion coefcient of cobalt (hcp) is 13.8 106 K1 [21], which is very close to that of nickel. Therefore, the closed thermal expansions of these components explain why the coating is not exposed to the delamination during the annealing process. In addition, the formation of nickel phosphide could lead to volume changes [20]. Secondly, NiCoP lm tensile stress (which attributed to the high phosphorus content) is relieved after annealing process, so the lattice parameter of bcc is contract in one dimension along (c-axis) from 8.643 to 4.386 A and the other lattice parameters a, b almost still constant to form bct crystal structure. 3.3. Hardness measurements The microhardness of Al alloy, as-deposited lm and annealed one has been measured by Vickers method. The hardness of Al alloy increased from 66 5 to 287 5 HV100 g after coating. It was found that the microhardness of NiCoP deposits enhanced after annealing (400 8C for 2 h) up to 520 5 VH100 g. Such improvement of the microhardness after annealing can be attributed to the formation of Ni3P intermetallic phase which generated the effect of precipitation hardening [22]. 3.4. Corrosion and polarization measurements Electrochemical potentiodynamic polarization experiment was applied in a 3.5% NaCl solution in order to measure the corrosion resistances of Al alloy and as-deposited NiCoP coating. For comparison, the corrosion properties of Al alloy coated by NiP, deposited from standard bath and containing the same content of P, have been studied (Fig. 4). The

as af dT

(I)

T0

Fig. 3. SEM images of NiCoP lms (pH 9.5 and deposition time 15 min).

Fig. 4. Potentiodynamic curves for (a) uncoated Al alloy and coated by (b) Ni P and (c) NiCoP tested in 3.5% NaCl.

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Table 2 Electrochemical corrosion data related to polarization curves of uncoated Al alloy and coated by NiP and NiCoP tested in 3.5% NaCl solution Sample Uncoated alloy NiP coating NiCoP coating ba 0.062 0.031 0.005 bc 0.032 0.042 0.077 Rp (V/cm2) 129 287 370 Icorr (mA/cm2) 71.1 27.2 5.5 Ecorr (V) 0.733 0.657 0.595 Cr (mpy) 30.81 11.52 2.38

electrochemical parameters obtained from the polarization curves for uncoated Al alloy and the coated alloy by NiCoP and NiP are displayed in Table 2. The corrosion potential of the Al alloy is 0.733 V, which is higher than that of NiP (0.657 V) and NiCoP coated alloy (0.593 V). On the contrary, the corrosion current densities of NiP and NiCoP coated Al alloys are 5.5 and 27.2 mA/cm2, which are somewhat lower than that of uncoated Al alloy 71.1 mA/cm2. The polarization resistance (Rp) of Al, NiP and NiCoP coated alloys are 129, 287 and 370 V/cm2, respectively. It is evident that the NiCoP coating layer provides effective protection for Al alloy than NiP coating. Therefore, the corrosion current Icorr values can be calculated by using the StearnGeary equation with Ozyilmaz et al. [23]. I corr b RP (II)

where b is constant value calculated by the following equation: b b a bc 2:3ba bc (III)

where ba and bc are anodic and cathodic Tafel slopes that were obtained from polarization curves. The value of b were 0.009, 0.007, 0.002 V for Al alloy, NiP and NiCoP coated alloys. Corrosion potential Ecorr is obtained using Tafel extrapolation method and corrosion rate is calculated from the following equation: Corrosion rate mpy 0:13I corr eq: wt: d (IV)

NiP and NiCoP coated Al alloys in 3.5% NaCl solution can be estimated from Icorr and the Faradays law, which are 30.81, 11.52 and 2.38 mpy, respectively. The enhancement in corrosion resistance by NiP and NiCoP deposits is due to the formation of an adsorbed layer of hypophosphite anion H2PO2 on the surface of coatings could provide passivity in aqueous environment [24]. Flis and Duquette reported that phosphorous is enriched on the surface layer by the preferential dissolution of nickel [25]. Then, the passive barrier layer of H2PO2 is formed by reaction of the enriched P with water. By this way, H2PO2 layer will block the supply of water to the electrode surface and prevent the hydration of nickel, which is considered to be the rst step to form either soluble Ni+2 species or a passive nickel lm. Generally, it can be concluded that the improved corrosion resistance obtained for electroless NiCo-P and NiP coatings is due to the enrichment of phosphorous on the electrode surface [26]. Therefore, a conclusion can be drawn that the presence of Co in NiP amorphous deposits improves their corrosion resistance as obtained previously by Parent et al. [27]. Such corrosion resistance improvement can be attributed to the more compact passive lm in NiCoP coatings based on anodic polarization and impedance tests [27]. 3.5. Magnetic properties The magnetic properties of as-plated electroless NiCoP before and after annealing have been studied using a vibrating magnetometer device by applying a magnetic eld of 5 KOe perpendicular to the sample surface. The hysteresis loops of investigated samples are shown in Fig. 5. It can be seen that the hysteresis loops shapes for both of coated and annealed samples are narrow and curved. This shape seems to be very

where (eq. wt.) is the equivalent weight in gram and d is the density in g/cm3 of Al alloy (for uncoated samples) or of Ni (for coated samples). Therefore, the corrosion rates of uncoated,

Fig. 5. The hysteretic behavior of (a) coated NiCoP and (b) annealed NiCoP.

A.A. Aal et al. / Applied Surface Science 254 (2008) 19661971 Table 3 Magnetic parameters of electroless NiCoP ternary alloy deposits Sample Coated alloy Annealed alloy Mr (emu/g) 2.15 3.24 Ms (emu/g) 25.8 23.2 Hc (Oe) 36.5 96.3 HK (Oe) 1194 1196 S 0.08 0.14

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Acknowledgements Help received from both of Dr. W. Agami (Ain Shams University) and F. Abdel Mouez (CMRDI) during the course of this work is greatly acknowledged. References

similar to that exhibited by partially or totally amorphous materials and by an amorphous NiCoP lm [28,29]. It can be mentioned that the prepared electroless NiCoP thin lm of the present study have an amorphous structure with soft magnetic characteristics. The coercivety Hc of annealed Ni CoP lm is affected not only by the grain size but also by impurities and variation of magnetic anisotropy energy governed by shape, lm stress and crystalline anisotropy. Although SEM images showed no signicant change in grain size of NiCoP lm before and after annealing, the coercivety was higher for the annealed ones. This behavior can be attributed to the increasing of the magnetoelastic anisotropy in the lm after stress relief due to the annealing process [30]. The magnetic properties, viz. saturation magnetization Ms, remanence Mr, coercivety Hc and the squareness S of the NiCoP thin lm were derived from the hysteresis loops. The data are summarized in Table 3. It was noticed that both of coated and annealed samples exhibited soft ferromagnetic behavior. Besides, there is no appreciable change in either magnetic properties or the hysteretic behavior by annealing except the increasing in coercivety Hc and the squareness S from 36.5 to 96.3 Oe and from 0.08 to 0.14, respectively. 4. Conclusions - Electrolessed NiCoP lms have been deposited onto Al alloy with nanocrystallite sizes in 150250 nm range. - The coating thickness is dependent of plating parameters (pH and deposition time). - The optimum bath pH and deposition time are of 9.5 and 15 min, respectively, where there are the highest coating thickness (0.92 mm) as well as the stability of the bath. - The NiCoP lms showed short-range order without grain boundaries forming an amorphous phase. However, after annealing (at 400 8C for 2 h), the degree of crystallinity increases and the microhardeness is improved. - The presence of Co in NiP lm improves the corrosion resistance of Al alloy. - The NiCoP coating with a combination of high corrosion resistance and high hardness would be expected to enlarge the applications of the aluminum alloys. - The coated and annealed NiCoP lms deposited onto Al alloys exhibit excellent magnetic recording media properties.

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