Surface and Coatings Technology 172 (2003) 298307

Electroless NiCoP ternary alloy deposits: preparation and characteristics

T.S.N. Sankara Narayanana,*, S. Selvakumarb, A. Stephenb
a

National Metallurgical Laboratory, Madras Centre, CSIR Complex, Taramani, Chennai 600 113, India b Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai 600 025, India Received 2 December 2002; accepted in revised form 31 January 2003

Abstract Electroless NiCoP ternary alloy deposits were prepared by varying the metallic ratio and were characterized using X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and vibration sample magnetometer. The plating rate of electroless NiCoP deposits is a function of concentration of sodium hypophosphite, pH of the plating bath, plating time and the metallic ratio. With increase in metallic ratio, the cobalt content of the deposits increases with a simultaneous decrease in the nickel content, while the phosphorus content decreases slightly. The electroless NiCoP deposits of the present study are amorphous in their as-deposited condition. The DSC trace exhibits three distinct exothermic peaks, corresponding to the relaxation of lattice strain during the phase separation, the phase transformation of amorphous phase to nickel and nickel phosphide phases and the transformation of metastable phases to stable nickel phosphide phase. The XRD pattern of electroless NiCoP deposits confirms the formation of Ni, Ni5 P2 , Ni12 P5 and Ni3 P phases during annealing at 300 and 400 8C for 1 h. Thermomagnetic study exhibits the Curie transition of nickel and non-stoichiometric Ni3 Co based alloys. Being amorphous in nature, the electroless NiCoP deposits exhibit soft magnetic characteristics. The saturation magnetization, remanence and coercivity increase with cobalt content of the deposit. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Electroless deposition; NiCoP alloy; Phase transition; X-ray diffraction

1. Introduction Electroless deposition process experienced numerous modifications to meet the challenging needs of a variety of industrial applications since Brenner and Riddell invented the process in 1946 w1x. Development of electroless nickel polyalloy deposits is considered as the most effective method to alter the chemical and physical properties of binary NiP and NiB alloy deposits w2 4x. The choice of the additional element is made based on the chemicalyphysical property to be imparted in the deposit. Cobalt is considered to be the most common additional element for imparting magnetic properties in the deposits w5,6x. Although a variety of techniques are available for preparing magnetic films, electroless plat*Corresponding author. Tel.: q91-44-254-2077; fax: q91-44-2541027. E-mail address: tsnsn@rediffmail.com (T.S.N. Sankara Narayanan).

ing is found to be the most suitable method because of its ability to provide a uniform surface and the costeffectiveness of the process w7x. Electroless CoNiP alloy films were studied for their use as a thin film magnetic recording media w611x. However, the magnetic properties of the electroless CoNiP films strongly depend on their thickness and microstructure w8,12,13x. The microstructure of electroless CoNiP films is, in turn, dependent on the chemical species present in the plating bath and the operating conditions employed w8,1416x. The dependence of magnetic properties on the microstructure enables the possibility to deposit electroless NiCoP films with different magnetic properties from the same solution by changing the conditions of deposition. The use of programmed variation of rotational speed of the substrate and simultaneous electrolysis during electroless plating were successfully adopted to manipulate the magnetic properties of electroless NiCoP films w1720x. In this

0257-8972/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0257-8972(03)00315-3

T.S.N. Sankara Narayanan et al. / Surface and Coatings Technology 172 (2003) 298307 Table 1 Bath composition and operating conditions employed for preparing electroless NiCoP ternary alloy deposits Type of deposit Sample designation Metallic ratio Bath composition NiSO46H2O CoSO47H2O Na3C6H5O72H2O Na2H2PO2H2O NH4Cl Operating conditions pH Temperature Time Deposit composition Nickel (wt.%) Cobalt (wt.%) Phosphorus (wt.%) Electroless NiCoP NCP3 0.3 0.035 M 0.015 M 0.15 M 0.30 M 0.50 M 9.0 80"1 8C 60 min 60.00% 31.00% 9.00% NCP5 0.5 0.025 M 0.025 M 0.15 M 0.30 M 0.50 M 9.0 80"1 8C 60 min 51.40% 40.00% 8.60% NCP7 0.7 0.015 M 0.035 M 0.15 M 0.30 M 0.50 M 9.0 80"1 8C 60 min 39.70% 52.20% 8.10%

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perspective, the present work aims to prepare electroless NiCoP ternary alloy deposits, and to evaluate their characteristic properties and magnetic behaviour. 2. Experimental details Nickel sulphate hexahydrate and cobalt sulphate heptahydrate were used as the source of nickel and cobalt, respectively. Sodium hypophosphite was used as the reducing agent, which also forms the source of phosphorus in the deposit. Trisodium citrate was used as the

complexing agent to control the rate of release of free metal ion for the reduction reaction. In addition to other constituents, ammonium chloride was added to impart buffering action. During plating, the bath was maintained at a temperature of 80"1 8C by a constant temperature bath. Besides, the pH of the bath was also maintained constant during the plating process with the addition of NaOH. Electroless NiCoP ternary alloy deposits having different amounts of nickel, cobalt and phosphorus were prepared by varying metallic ratio (CoSO4 yCoSO4qNiSO4 ), viz., 0.3, 0.5 and 0.7. The phosphorus content of the deposit was determined using atomic absorption spectrophotometer. The cobalt content of the deposit was determined spectrophotometrically using nitroso-R-salt as the reagent whereas the nickel content of the deposit was determined after precipitating nickel as Nidimethyl glyoxime complex. The bath composition, operating conditions employed for preparing electroless NiCoP ternary alloy deposits and the deposit composition are given in Table 1. The electroless NiCoP ternary alloy deposits prepared using different metallic ratios, viz., 0.3, 0.5 and 0.7 were designated as NCP3, NCP5 and NCP7, respectively. These deposits were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermomagnetic measurement and vibrating sample magnetometer (VSM) to determine their crystal structure, phase transformation behaviour, Curie transition and magnetic properties, respectively. XRD patterns were obtained using a copper target (ls1.540598 A) in Rich Seifert (model 3000) XRD. The DSC traces were recorded using a Perkin-Elmer DSC-7 in the temperature range of 220

Fig. 1. Effect of sodium hypophosphite concentration on the plating rate of electroless NiCoP ternary alloy deposit (CoSO4 7H2 Os0.025 M; NiSO46H2Os0.025 M; Na3C6H5O7s0.15 M; NH4Cls0.50 M; pH 9.0; Temperatures80 8C; Times60 min).

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Fig. 2. Effect of pH of the plating bath on the plating rate of electroless NiCoP ternary alloy deposit (CoSO4 7H2 Os0.025 M; NiSO46H2Os 0.025 M; Na3C6H5O7s0.15 M; NH4Cls0.50 M; NaH2PO2s0.30 M; Temperatures80 8C; Times60 min).

Fig. 3. Effect of plating time on the plating rate of electroless NiCoP ternary alloy deposit (CoSO4 7H2 Os0.025 M; NiSO4 6H2 Os0.025 M; Na3C6H5O7s0.15 M; NH4Cls0.50 M; NaH2PO2s0.30 M; pH 9.0; Temperatures80 8C).

520 8C at a heating rate of 10 8Cymin in argon atmosphere. The thermomagnetic study was performed using a Perkin Elmer TGA-7 in the temperature range of 150800 8C at a heating rate of 10 8Cymin in argon atmosphere in the presence of a horseshoe magnet. The native weight of the electroless NiCoP alloy deposits is first made as 0 and the weight due to the magnetic field is taken as the weight of the deposit, which is equated to 100% weight so that the 100% weight is entirely due to magnetic attraction. The magnetic prop-

erties, viz., saturation magnetic moment (ss), remanence (Mr) and coercivity (Hc), were determined using EG&G Princeton Applied Research VSM (model 4500). 3. Results and discussion The plating rate of electroless NiCoP alloy deposit as a function of concentration of sodium hypophosphite (0.10.3 M), pH of the plating bath (8.011.0), plating time (1060 min) and the metallic ratio (CoSO4 y

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Fig. 4. Effect of metallic ratio (CoSO4y(CoSO4 qNiSO4 )) on the plating rate of electroless NiCoP ternary alloy deposit (Na3C6H5O7s0.15 M; NH4Cls0.50 M; NaH2PO2s0.30 M; pH 9.0; Temperatures80 8C; Times60 min).

CoSO4qNiSO4) is depicted in Figs. 14, respectively. The plating rate increases with increase in sodium hypophosphite concentration in the range from 0.1 to 0.3 M (Fig. 1). However, the extent of increase is not linear throughout. This is due to the fact that even though the available electrons for metal ion reduction increases with increase in concentration of sodium hypophosphite, the rate at which the availability of the metal ion is limited by the amount of complexing agent present in the bath.

The plating rate is found to increase with increase in pH from 8.0 to 10.0, beyond which, the bath becomes destabilized and approximately pH 11.0, decomposition of the bath is quite evident (Fig. 2). Hence, it is safer to use the bath approximately pH 9.0, where there is good plating rate as well as the stability of the bath. The plating rate increases with increase in processing time throughout the 60 min of plating (Fig. 3). This can be ascribed to the autocatalytic nature of the electroless plating process. However, the extent of increase in

Fig. 5. Effect of metallic ratio (CoSO4y(CoSO4qNiSO4 )) on the chemical composition of the electroless NiCoP ternary alloy deposit.

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Fig. 6. XRD pattern of electroless NiCoP ternary alloy deposits in their as-plated condition (a) NCP3; (b) NCP5; and (c) NCP7.

plating rate observed for every 10 min period is not linear. This is due to the build-up of orthophosphite ions following oxidation of sodium hypophosphite. The plating rate of electroless NiCoP deposit decreases with increase in metallic ratio (CoSO4 y CoSO4qNiSO4) (Fig. 4). This behaviour is attributed to the fact that nickel possesses a higher catalytic activity than cobalt. Matsubara and Yamada w18x and Kim et al. w7x have also reported a decrease in plating rate with increase in cobalt content in the plating bath. These results indicate that it is possible to vary the composition of the alloy deposit by varying the metallic ratio. Based on these results NiCoP ternary alloy deposits with different metallic ratios are produced and characterized. The nickel, cobalt and phosphorus content of the electroless plated NiCoP ternary alloy deposit as a function of metallic ratio (CoSO4 yCoSO4 qNiSO4 ) is given in Fig. 5. With increase in metallic ratio, the

cobalt content of the deposit increases with a simultaneous decrease in the nickel content. Younan et al. w21x also reports a similar trend. Tarozaite and Jusys w9x have also observed the dependence of composition of the electroless NiCoP deposit with wCo2qx:wNi2q x ratio. There is only a slight change in phosphorus content of the electroless NiCoP deposit with increase in metallic ratio. The phosphorus content of electroless CoNi P deposit increases with an increase in nickel sulphate concentration of the plating bath and a corresponding increase in nickel content of the deposit. This has resulted due to the comparatively higher phosphorus codeposition with nickel than with cobalt w9x. XRD patterns of electroless NiCoP ternary alloy deposits, prepared using a metallic ratio (CoSO4 y CoSO4qNiSO4) of 0.3, 0.5 and 0.7 (NCP3, NCP5 and NCP7, respectively) in their as-deposited condition are shown in Fig. 6. A broad peak centered at approximately 458 2u is evident in all the three samples studied, which indicates the amorphous nature of the deposits. In electroless deposition process, the extent of segregation of metalloid alloy (phosphorus or boron) in the coating determines its crystallinity. Since the required amount of phosphorus segregation (8.19.0 wt.% for samples NCP3, NCP5 and NCP7) is relatively large, nucleation of nickelycobalt phase is prevented, and this has resulted in amorphous structure. The broad peak could either due to hcp-Co(0 0 2) or the fcc-Ni(1 1 1). The phase transformation behaviour of electroless Ni CoP ternary alloy deposits was studied using DSC. The DSC trace obtained for electroless NiCoP deposits (NCP3, NCP5 and NCP7) at a heating rate of 10 8Cymin in argon atmosphere is depicted in Fig. 7. The DSC trace exhibits three distinct exothermic peaks in the temperature range of 260400 8C. It has been established that the peak temperature is very sensitive to the phosphorus content w2224x. Surprisingly, for electroless NiCoP ternary alloy deposits of the present study there is not much change in the phosphorus content. However, it is interesting to note that with increase in cobaltydecrease in nickel content of the deposit, there observed to be a small change in peak temperature for Peak I whereas a decrease in peak temperature is noted for Peaks II and III. Based on this observation, first exothermic peak (Peak I for NCP3, NCP5 and NCP7) could be either due to structural relaxation or due to the separation of fcc nickel from the amorphous matrix, whereas, the second exothermic peak with peak temperature at approximately 329337 8C (Peak II for NCP3, NCP5 and NCP7) might be due to the phase transformation of amorphous phase to crystalline nickel and nickel phosphide phases, and, the third exothermic peak with peak temperature at approximately 347383 8C (Peak III for NCP3, NCP5 and NCP7) may possibly be due to the transformation of metastable to stable phase.

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Fig. 7. DSC trace of electroless NiCoP ternary alloy deposits (a) NCP3; (b) NCP5; and (c) NCP7.

To ascertain the phases formed at the respective peak temperatures, electroless NiCoP deposits were annealed at 300 and 400 8C for 1 h and the corresponding XRD patterns are shown in Figs. 8 and 9, respectively. It is evident from Fig. 8 that the amorphous nature of the deposits still remains, even after annealing at 300 8C for 1 h. Hence, the first exothermic peak (Peak I for NCP3, NCP5 and NCP7) is due to the relaxation of lattice strain during the phase separation. The XRD pattern of electroless NiCoP deposits annealed at 400 8C for 1 h reveals the presence of fcc nickel and bct nickel phosphide (Ni3P) phases. Based on this, the exothermic peak with peak temperature at approximately 329337 8C (Peak II for NCP3, NCP5 and NCP7) could be attributed to the phase transformation of amorphous phase to nickel and nickel phosphide phases. The exothermic peak with peak temperature approximately 347383 8C (Peak III for NCP3, NCP5 and NCP7) could not be accounted for recrystallization and growth of Ni3P phase as such an occurrence is expected only approximately 400 8C w20x, and hence, is due to the transformation of metastable phases to stable nickel phosphide phase. XRD pattern of NCP3 annealed at 300 8C for 1 h reveals the presence of hexagonal Ni5P2 phase (Fig. 8). The presence of tetragonal Ni12P5 phase is evident even after annealing at 400 8C for 1 h (NCP3, NCP5 and NCP7) (Fig. 9).

Lee and Hur w25x and Hur et al. w26x reported the formation of Ni5P2 phase upon annealing of electroless NiCoP and NiCuP deposits at 325 8C. Yo et al. w27x have also observed the formation of Ni5P2 and Ni12P5 phases during the phase transformation of electroless Ni18.0Cu9.3P deposits upon annealing. The electroless NiCoP deposits of the present study have a high phosphorus content (Fig. 5), which enables a higher phosphorus segregation in the grain boundary region. During annealing the high phosphorus region is further increased by the extraction of phosphorus atoms dissolved in nickel grains, which in turn gave rise to precipitation of the Ni5P2 and Ni12P5 phases. These metastable phases get transformed into stable Ni3P phase at higher temperatures, supporting the observations made earlier by Lee and Hur w25x, Hur et al. w26x and Yu et al. w27x. The various stages of phase transformation of the electroless NiCoP deposit are depicted in Fig. 10. The thermogravimetric analysis (TGA) trace of the electroless NiCoP ternary alloy deposit (NCP7) upon annealing at a heating rate of 10 8Cymin in argon atmosphere in presence of a magnetic field is shown in Fig. 11. The initial weight gain is not a real weight gain but a magnetic flux gain following the removal of occluded hydrogen in the electroless NiCoP ternary alloy deposit. The first Curie transition noted at 326.69

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Fig. 8. XRD pattern of electroless NiCoP ternary alloy deposits heat-treated at 300 8C for 1 h (a) NCP3; (b) NCP5; and (c) NCP7.

Fig. 9. XRD pattern of electroless NiCoP ternary alloy deposits heat-treated at 400 8C for 1 h (a) NCP3; (b) NCP5; and (c) NCP7.

Fig. 10. Schematic of the sequential transformation of phases of electroless NiCoP deposits following heat treatment at 300, 400 and )400 8C for 1 h.

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Fig. 11. TGA trace of electroless NiCoP ternary alloy deposit (NCP7) obtained in presence of magnetic field.

8C is the Curie transition (Tc) of nickel. Tc for standard nickel is 354 8C and for electrodeposited nickel it is approximately 320 8C. The decrease in magnetic flux after the first Curie transition is due to the formation of non-magnetic phases, viz., Ni5P2, Ni12P5, Ni3P, etc. The DSC and XRD studies confirm the formation such phases. The second Curie transition is noted above 520 8C and this Curie transition increases with increase in cobalt content of the deposit (Table 2). This may be due to the non-stoichiometric Ni3Co and NiCo based alloys. After the second Curie transition, there observed to be a gain in the magnetic flux. This may be due to NiCo alloy formation. Further studies are required to ascertain the nature of alloy formed under such conditions. The magnetic properties of electroless NiCoP ternary alloy deposits were studied in their as-deposited condition. The hysteresis loop obtained for as-plated
Table 2 Curie transitions of electroless NiCoP ternary alloy deposits Sample designation NCP3 NCP5 NCP7

electroless NiCoP deposits (NCP3, NCP5 and NCP7) is shown in Fig. 12. The magnetic properties, viz., saturation magnetic moment (ss), remanence (Mr) and coercivity (Hc), derived from the hysteresis loop, are given in Table 3. The shape of the hysteresis loops seems to be very similar to that exhibited by partially or totally amorphous materials w28x. Fenineche et al. w29x have also observed a similar type of narrow hysteresis loop for NiCoP deposits electrodeposited at 2 Aydm2, which has an amorphous structure. It is well known that magnetic characteristics of amorphous materials are significantly smaller than those of crystalline materials w30x. Being amorphous in nature, the electroless NiCoP deposits of the present study exhibit soft magnetic characteristics. According to Tarozaite et al. w19x the formation of certain crystallites shape, which determines high coercivity, takes place only at definite phosphorus content. The phosphorus content,

First Curie transition (Tc1) (8C) 315 317 327

Second Curie transition (Tc2) (8C) 625 607 529

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4. Conclusions The plating rate of electroless NiCoP deposits is a function of concentration of sodium hypophosphite, pH of the plating bath, plating time and the metallic ratio. With increase in metallic ratio, the cobalt content of the deposits increases with a simultaneous decrease in the nickel content, while the phosphorus content decreases slightly. Electroless NiCoP deposits are amorphous in their as-deposited condition. The DSC trace exhibits three distinct exothermic peaks, corresponding to the relaxation of lattice strain during the phase separation, the phase transformation of amorphous phase to nickel and nickel phosphide phases and the transformation of metastable phases to stable nickel phosphide phase. The XRD pattern of electroless NiCoP deposits confirms the phases formed during annealing at 300 and 400 8C for 1 h. Thermomagnetic study exhibits the Curie transition of nickel and non-stoichiometric Ni3Co and NiCo based alloys. Being amorphous in nature, the electroless NiCoP deposits of the present study exhibit soft magnetic characteristics. The saturation magnetization, remanence and coercivity are found to increase with cobalt content of the deposit. Acknowledgments The authors express their sincere thanks to Prof. S.P. Mehrotra, Director, National Metallurgical Laboratory, Jamshedpur, Dr S. Srikanth, Scientist-in-Charge, NML Madras Centre, CSIR Complex, Chennai and Prof. P.R. Subramanian, Professor and Head, Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai, for their constant support and encouragement to carry out this work. References
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Fig. 12. Hysteresis loop obtained for electroless NiCoP ternary alloy deposits in their as-plated condition (a) NCP3; (b) NCP5; and (c) NCP7.

necessary for the formation of grains boundaries, differs for the films, deposited under different conditions, because of the grains with different size and shape formation. According to them, electroless NiCoP deposits exhibit a high coercivity when the phosphorus content of the deposit lies between 4 and 6 wt.%. When the phosphorus content is lower than 4 wt.%, films of coarse crystallites are deposited, resulting in lower coercivity. If phosphorus content exceeds 6 wt.%, films consisting of very fine grains are deposited which also leads to a decrease in coercivity. A comparison of the magnetic characteristics of electroless NiCoP deposits of the present study reveals that the saturation magnetization and remanence are found to increase with cobalt content of the deposit (Table 3). Rivero et al. w31x report a linear increase in magnetic moment with increase in cobalt content for electrodeposited NiCoP amorphous ribbons. An increase in saturation magnetization of electroless Ni CoP deposits with increase in cobalt content of the deposit was also reported by Matsubara and Yamada w18x.
Table 3 Magnetic properties of electroless NiCoP ternary alloy deposits Sample Saturation Remanence (Mr) Coercivity (Hc) designation magnetization (ss) (emuyg) (Oe) (emuyg) NCP3 NCP5 NCP7 11.54 28.10 59.41 3.16 7.74 20.03 67.62 64.65 63.70

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