Surface & Coatings Technology 202 (2008) 51515157

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Electroless NiP coating of different magnesium alloys

N. El Mahallawy a, A. Bakkar c,e, M. Shoeib b, H. Palkowski d, V. Neubert c,
a

Engineering and Material Science Department, The German University in Cairo, Egypt Surface Coating Department, Central Metallurgical Research & Development Institute (CMRDI), Helwan, Egypt c Institut fr Materialprfung und Werkstoffkunde, Clausthal-Zellerfeld, Germany d Metal Forming and Processing, Institute of Metallurgy, TU Clausthal, Clausthal-Zellerfeld, Germany e Metallurgical and Materials Engineering Department, Faculty of Pertoleum and Mining Engineering, Suez Canal University, P.O. Box 43721 Suez, Egypt
b

A R T I C L E

I N F O

A B S T R A C T
Coating of AZ31B, AE 42 and ZRE1 wrought magnesium alloys was carried out using electroless Ni plating technique in a solution of nickel sulphate, sodium hypophosphite, ammonium hydrogen uoride and glycine with a zinc immersion pre-treatment. The results of SEM/EDX investigations and X-ray diffraction indicate that the coat exhibit a typical surface morphology with compact nodules with good adherence to the substrate. The coat was composed of amorphous structure, which transformed to a mixture of crystalline Ni and Ni3P precipitates after heat treatment at 673K for 1 h. The phosphorous (P) content increased gradually from the substrate towards the surface reaching a maximum of 10 wt.% to 18 wt.% on the surface depending on the substrate alloy and the thickness of deposit. The hardness of the coat was found to increase with the P content and also after heat treatment. The electrochemical corrosion test in NaCl solution indicated a great improvement in the corrosion resistance of the Mg substrates and that a noble behaviour of NiP was obtained regardless of the heat treatment process. The forming ability test indicates that hot rolling of the coated substrate does not succeed to keep a continuous coat due to cracking of the coat in both as-coated and heat treated specimens. 2008 Elsevier B.V. All rights reserved.

Article history: Received 24 October 2007 Accepted in revised form 17 May 2008 Available online 29 May 2008 Keywords: Magnesium Electroless Ni Morphology Composition Hardness Corrosion

1. Introduction Magnesium alloys have several attractive properties which make them promising for several industrial applications based on their low density. They also have the advantage of high specic strength and modulus and excellent anti-shock resistance. Therefore, they are attractive in aerospace and automotive industries, in manufacturing electrical equipment such as cellular phones, television, and in sporting industries like golf heads [1]. Due to their heat conductivity and electromagnetic shielding effectiveness they are also attractive for IT industry [2] and for communication satellites travelling wave tubes (TWT) for amplication of signals [3]. However, magnesium has a drawback which is its poor atmospheric corrosion resistance. It is also a difcult metal for electrochemical treatment because of its high chemical afnity to aqueous solutions. Furthermore, the presence of alloying elements introduces an electrochemical heterogeneity which makes the situation even more complex [3]. Furthermore, increase of surface roughness reduces the corrosion resistance [4]. Modication of microstructure through heat treatment also affects the corrosion rate [5]. Therefore, surface treatment of magnesium alloys is important for many applications. A wide variety of coating techniques and surface
Corresponding author. Tel.: +49 5323 989890; fax: +49 5323 989899. E-mail addresses: Nahed.elmahallawy@guc.edu.eg (N. El Mahallawy), volkmar.neubert@tu-clausthal.de (V. Neubert). 0257-8972/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2008.05.037

modication for magnesium is present in the literature [616]. Surface treatment by coating is among the commonly used treatments including inorganic, organic, metallic, and ceramic as well as composite coatings. The different coating techniques have been summarized in a previous work [6]. A critical review on the protective coatings of magnesium alloys is given previously [7]. In most cases, the coating was not completely satisfactory or needed several steps to reach satisfaction. Electroless NiP coats are being increasingly used as a protective layer against wear and corrosion, and a uniform coat is formed on the product surface with no restriction on the shape [1720]. They provide a high degree of corrosion resistance at elevated temperatures as well as a good solderability and wettability to the soldering materials [3]. The nickel coat is of special importance in electronic industry due to its conductivity and magnetic properties. The NiP deposit results in a coat with less porosity and of higher hardness (480 HV) than electro deposited metal (200 HV) because phosphorous is incorporated in the structure [17,18]. With further heat treatment at 673K for 1 h, the hardness of the deposit increases. A good wear resistance, low ductility (13% elongation), low porosity, excellent solderability and brazability are provided in addition to low labour cost and improved corrosion resistance compared to that of the magnesium substrate. An enhancement of the electroless NiP layer was obtained either by the application of multi-layer NiP with higher P content on the surface or the use of multi-layer solgel or the use of direct current electroplating following the electroless deposition layer [2123].

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N. El Mahallawy et al. / Surface & Coatings Technology 202 (2008) 51515157 Table 2 Solutions and processes used in nickel plating Step no. 1 2 3 Process and solutions Condition

Electroless plating involves the deposition of coatings from non electrolyte solutions of metallic salts and reducing agents through the application of moderate heat [17,18]. The surface preparation and pretreatment prior to electroless coating is of prime importance for a successful coat [2426]. Different pre-treatments were applied prior to the electroless deposition mainly zinc immersion or zincating [26]. Special attention was recently given to the formation of an intermediate layer by successive immersions [27], by the application of a phosphatemanganese lm [28] or by the deposition of an organic layer [29]. The role of the intermediate layer on the substrate is to reduce the potential difference between the magnesium and the Ni top coat and to reduce the corrosion of the magnesium during the NiP plating process. In general, the application of electroless NiP on Mg alloys surfaces is a promising process. Therefore, it is the purpose of this work to investigate the possibility of application of electroless NiP coating on several magnesium alloys, namely AZ31, AE42 and ZRE1, keeping the plating bath and procedure constant. The study includes the surface roughness, morphology, hardness, adhesion, formability and corrosion resistance of the as-coated surfaces as well as the effect of post heat treatment on these characteristics. 2. Experimental details The magnesium alloys AZ31B, AE42 and ZRE1 were received as rolled sheets of different thicknesses up to 2.0 mm. The chemical composition of the alloys is given in Table 1. Samples with size 20 20 mm were cut, prepared and coated using the electroless coating technique following the procedure given in Table 2. All solutions used were freshly prepared from analytical grade reagents and monodistilled water. Water rinse was applied after each step. The use of nickel sulphate solution in electroless plating has been selected as it was successfully used for plating steel and aluminium surfaces [1820] as well as magnesium in a previous work of the authors [6]. The zincate pre-treatment also called zinc immersion has been used to remove the residual oxides and hydroxides and to produce a thin layer of zinc to prevent re-oxidation of the magnesium surface, as reported previously [7]. The substrate becomes catalytically active after the surface oxides are dissolved into the plating bath which made the replacement reaction between the substrate and nickel ion to happen. In the present work, the process steps, the solutions and plating conditions are given in Table 2. Half the samples were further heat treated at 673K for 1 h in a mufe furnace in air, then air cooled. The samples before and after heat treatment were investigated for surface roughness and surface morphology using SEM. The coat characteristics, including thickness, adhesion and chemical composition, were investigated. The micro-hardness, forming ability and corrosion resistance of the samples have also been determined. AZ31 coated samples were investigated with X-ray diffractometry using a Siemens D 5000/Kristalloex diffractometer in the /2 modus with CoK radiation (40 KV, 40 nA). An adjustable sample holder was used to position the sample surface in the incidence plane of X-rays. Peaks were identied using a standard data base. In order to study the adhesion and thickness of the coat, all samples were carefully cut across the section using a thin diamond cutter. The samples were mounted, ground and polished and the cross sections were studied by Scanning Electron Microscope (SEM).
Table 1 Chemical composition of Magnesium alloys used in wt.% Alloy AZ31 AE42 (nominal) ZRE1 (nominal) Al 2.92 b4.0 Zn 1.15 1 RE b2.0 b1.0 Si 0.022 Mn 0.16 Cu 0.002 Fe 0.002

Mechanical polishing Ultrasonic cleaning Alkaline cleaning Sodium carbonate 25 g/l Sodium hydroxide 15 g/l 65 C, 5 min Acid pickling Chromium trioxide CrO3 180 g/l NaF 3.5 g/l Room temp., 5 s Acid activation Phosphoric acid, H3PO4 200 ml/l Ammonium hydrogen uoride, 30 C, 5 min NH4HF2 100 g/l Alkaline activation: Tetra sodium pyrophosphate 40 g/l Sodium tetraborate 70 g/l Sodium uoride 20 g/l Room temp., 5 min Zincating (zinc immersion) 23 mm thickness Zinc sulphate 30 g/l Tetra sodium pyrophosphate 120 g/l pH 1010.6 Sodium uoride 5 g/l Room temperature, 5 min Electroless nickel plating with uoride activators: NiSO4 30 g/l Sodium hypophosphite 25 g/l Ammonium hydrogen uoride 15 g/l pH 9, 70 C, 35 min. Glycine 15 g/l

The hardness of the coated samples was measured using a microhardness tester Wolpert Diatestor using 16.5 g for 15 s. More than 15 indentations were made on each sample on the cross sections. Only the readings corresponding to full indentation away from the Mg substrate were taken into consideration. For potentiodynamic polarisation tests, the samples were tied to copper wires and coated with lacquer for exposing a free test surface of 1 cm2, cleaned in ethanol in an ultrasonic cleaner, then suspended in the electrolyte. All experiments were carried out at (298 1)K. Potentiodynamic polarisation experiments were carried out using a Wenking LB 94 L Laboratory Potentiostat. The specimens were immersed in 3% NaCl solution for 15 min. prior to polarisation, by which time the open circuit potential (OCP) was monitored. With reference to saturated calomel electrode, the polarisation was obtained by scanning from about 500 mV more negative than the OCP at a rate of 1 mV/s. 3. Results and discussion 3.1. Coat surface roughness In general, from the appearance point of view, the coating caused some slight darkening of the surface due to the deposition of the nickel alloy, while further colouring was obtained after the heat treatment process due to formation of the nickel oxides The surface roughness was measured using the Tencor Surface Proler Alpha-Step 500. The results given in Table 3 indicate that a relatively smooth surface was obtained in all samples with Ra of less than 1 m in most samples and an Rz value of 2.8 to 5.9 m. Substrate material AZ31 gave

Table 3 Surface roughness of coated samples before and after heat treatment Alloy AZ31 AE42 ZRE1 Condition Non heat treated Heat treatment Non heat treated Heat treatment Non heat treated Heat treatment Ra, m 0.6 0.5 1.1 0.8 0.9 0.8 Rz, m 4.9 2.8 5.9 4.2 4.5 4.7

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Fig. 1. Surface morphology of coated samples: a) AZ31, general overview, b) ZRE1, detail. Fig. 2. Surface morphology after heat treatment a) ZRE1, = 2000, b) AE42, = 5000, showing ne sub-micro nodules.

the lowest roughness followed by ZRE1. In a recent work [30] where NiP was deposited on pure magnesium, AZ31 and AZ91, the lowest surface roughness was obtained on AZ31. It is to be noted from the results in Table 3 that the surface roughness has decreased in most samples after the heat treatment process. 3.2. Surface morphology The surface morphology of the present samples was studied using the SEM, Figs. 1 and 2. It was found that the deposit is uniform, defect free, with no pores or cracks. It is composed of compact ne nodules uniform in size with some coarser cauliower nodules. Those nodules consist of a number of very ne sub-micro nodules which are resolved at higher magnication (Fig. 2b). After heat treatment( HT), the deposit was similar in shape and quality, but with a smaller amount of cauliower nodules (Fig. 2). This result might explain the decrease in surface roughness after HT due to coalescence and coarsening of nodules. 3.3. X-ray diffraction Fig. 3 shows the results for both, the as-coated (1) and the heat treated sample (2) obtained using step size 0.025 and dwell time of 1 s. For the as-deposited coating, curve (1), it is noticed that for 2 = 48 to 62, a broad peak occurs as a result of the superposition of Ni and NiP compounds peaks. This peak corresponds to an amorphous material whereas the peak is broad with a width larger than 10. Sharp

peaks are for crystalline Mg (notation M) from the substrate effect, but no sign of pure P or Ni3P precipitates. After HT, sharp peaks were obtained, curve (2) in Fig. 3. Those peaks correspond to the Mg substrate (M) and crystalline Ni (N). New peaks (P) which are very probably Ni3P containing about 15 wt% P. However, other NixPy compounds cannot be excluded. Pure elemental P was not found. In a previous work [16] on electroless deposition of NiP on AZ91 alloy, X-ray diffractogram showed a broad peak at diffraction angle 2

Fig. 3. XRD plot of as-coated (curve 1) and heat treated (curve 2).

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Fig. 4. SEM photomicrographs of cross sections for some coated samples: a) AZ31 as-coated, b) AZ31 heat treated, c) AE42 as-coated, and d) ZRE1 as-coated.

between 40 and 50 corresponding to the dominant peak of Ni, similar to that of the present work. The structure was said to be amorphous with microcrystalline areas. In another work [3], it was mentioned that the as-deposited coat is amorphous, containing Ni and P separately, and that this deposit crystallises and forms Ni3P phase only after heat treatment. The broad peak in (curve 1), (Fig. 3a) might also be Ni only and P may not be visible, because it is amorphous. In general, previous qualitative observations indicate that ner grain sizes on micro-scale are obtained in NiP deposits on steel surfaces with increase of P content [31,32] and when plating with adding W to the NiP deposit [20]. However, no quantitative measurements of the grain size were made. When the process of electroless nickel plating on magnesium alloys was investigated [33], it was found that the bath composition and pH affect the P content by varying concentration of complexing agent and pH of the bath. Moreover, DSC curves of their deposits revealed that the microstructure changes from crystalline to amorphous with the increment of the P content.

3.4. Coat characteristics: thickness and adhesion For illustration of the coat characteristics, the micrographs of the sections for AZ31, AE42, and ZRE1 samples are given in Fig. 4. The micrographs indicate that in all cases, the coat has a uniform thickness with no defects such as cracks or pores. The absence of gaps at the interface indicates a good adherence to the magnesium substrates. The coat thickness was measured from SEM photomicrographs and the results given indicate that the coat thickness ranged between 8 and 9.5 m. The average coat thickness was somewhat different depending on the alloy type, being maximum for AE42 and minimum for ZRE1. The coat thickness is usually function of the rate of deposition which depends on the bath and plating conditions [17,34] and complex agents [33]. As the bath composition and plating time conditions are kept constant, the difference in thickness is thought to be due to the difference in substrate compositions. The high pH used in the present work is more favourable for Mg alloys because the etching rate

Table 4 EDX elemental analysis (wt.%) of some selective points, as represented in Fig. 4b for the coated AZ31 Mg alloy Condition As-coated Point X1 X2 X3 X4 X5 X1 X2 X3 X4 X5 Ni 87.91 0.36 89.20 0.39 90.96 0.82 0.70 0.15 0.22 0.07 86.28 0.80 89.67 1.13 91.27 0.36 3.53 0.68 0.47 0.05 P 10.72 0.23 8.41 0.27 4.17 0.09 0.08 0.03 0.06 0.02 11.26 0.07 7.67 1.14 4.07 0.14 0.06 0.01 0.0 Mg 1.13 0.16 2.15 0.58 4.25 0.75 93.37 0.87 95.23 1.32 2.0.9 0.16 2.36 0.25 4.42 0.22 92.62 0.69 95.81 0.06 Al 0.04 0.03 0.09 0.08 0.22 0.11 4.01 0.34 3.08 0.24 0.02 0.01 0.16 0.10 0.19 0.03 2.10 0.75 3.11 0.08 Zn 0.04 0.03 0.24 0.07 0.21 0.04 0.44 0.19 0.63 0.05 0.26 0.20 0.04 0.03 0.35 0.07 0.54 0.02 0.48 0.09

Heated

Fig. 5. Phosphorous distribution from the substrate towards the coat surface in not heat treated condition for different Magnesium alloys.

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Table 5 EDX elemental analysis (wt.%) in the coat onto AZ31 after removal of the substrate Condition As-coated Point X1 X2 X3 Ni 87.87 1.07 90.82 2.59 93.50 1.35 P 10.76 0.39 7.48 1.42 4.27 1.08 Mg 1.04 0.7 1.49 1.46 1.8 1.25 Al 0.08 0.06 0.04 0.04 0.12 0.10 Zn 0.14 0.08 0.10 0.10 0.17 0.05

Fig. 6. Phosphorous distribution from the substrate towards the coat surface for different Mg alloys; heat treated.

decreases with increase in pH. Further study relating the growth of the coat to microstructure phases is still needed in this respect. 3.5. EDX analysis of the coat The chemical analysis of the coat is one of the parameters that determine its chemical, physical and mechanical properties. The EDX elemental analysis on the cross section of the coat was made at three positions: on top, in the center and close to the magnesium substrate, as represented by points X1, X2 and X3 in Fig. 4b. On the substrate, two points close to the coat (pointed out by X4 and X5, Fig. 4b) were also analysed. Table 4 exemplies the typical elemental analysis undertaken for a coated Mg alloy. The concentration of P in the coat and across the interface is plotted in Figs. 5 and 6 for the as-coated and for the heat treated specimens, respectively. The results indicate that the phosphorous (P) content increased gradually from the substrate towards the surface in all cases and that there is no sensitive effect of heat treatment on P redistribution. As the thickness of the deposit increases, the maximum P content reached on the coat surface also increases as illustrated in Fig. 7. It was recently observed by Gu [35] after electroless NiP plating on AZ91 that Ni was rst deposited on the Mg surface after 15 min plating while P content was very low, based on the deposition mechanism of electroless plating on Mg alloys suggested by Gu [36]. The increase in P content may also result from the variation of the pH of the solution adjacent to the coating, resulting in a change in potential of the substrate associated with increase in bath acidity, hence, P content deposited [37]. As the plating conditions were kept constant, the substrate alloy is thought to affect the P content. However, the dependence of the deposition on the alloying elements still needs further investigation. Magnesium is also detected in the coat, ranging from 1 to 2% on the surface, and its content increases towards the substrate. This is due to the dissolution during uoride activation and further co-deposition with the Ni. In order to exclude the effect of the substrate on the results of EDX analysis, the composition of coat was measured sepa-

rately by etching away the substrate for a coated and not heat treated AZ31 specimen. Three points in the cross section of coat, in the same arrangement in Fig. 4b, were selected for analysis. The results in Table 5 indicate a good agreement with those listed in Table 4. The P content in the deposit depends on bath temperature, composition and plating conditions. Deposits with different P contents were obtained by varying the concentration of complexing agents and reductants and pH of the bath [33]. It was found that there is a tendency for a lower P content with increasing bath pH [19,34]. The bath pH may also change during coating time, and consequently affects the P content through the coat layer. In general, the P concentration in the present coats, reaching 15 and 17 wt% towards the outer surface, are higher than that reported in previous work as the analysis was made on cross sections not on the outer top surface as the latter would give an average value over the thickness of the coat [6,16]. Previous work has indicated that the alloy composition of the substrate and its structure had an effect on the structure of the deposit by affecting the nucleation and growth mechanisms [38]. However, no previous study on its effect on the chemical composition of the deposit was found available. 3.6. Coat hardness The results of hardness, listed in Table 6, are plotted versus P wt% in Fig. 8 together with those of previous work using the same heat treatment as that of the present work. It can be noticed that the hardness of the non heat treated samples ranged between 420 and 520 HV, and between 680 and 760 HV after heat treatment. These values are comparable to those of previous work for similar baths [18], as illustrated in the gure. The results in Fig. 8 indicate that the hardness increases as the P content increases in the coat. The addition of P to the Ni bath has the advantage of increasing the hardness of the coat by forming an alloy with Ni as reported in [17], where a maximum value of 650 HV could be reached for the coat containing more than 10 wt% P in the as-coated deposit on steel substrate. However, no correlation between the hardness and P content was given. In [34] it was found that the hardness increased slightly from 650 to 685 HV with increase in P content. In general, it is advantageous to reach a high hardness in the as-coated soft products such as plastics, aluminium and printed circuits which cannot be subjected to post heat treatment. Other additives to the bath give higher hardness [20,39]. In previous work [16], a wide range of hardness values were found, depending on bath composition, plating parameters, concentration of ammonium bi-uoride, also resulting in different P content. The results in Table 6 and Fig. 8 indicate an increase in hardness after heat treatment at 400C for 1 h, in agreement with previous work.

Table 6 Surface micro-hardness of coated samples Alloy AZ31 AE42 Fig. 7. Effect of coat thickness on the phosphorous content on the surface of the substrates before and after heat treatment. ZRE1 Condition As-coated Heat coated As-coated Heat coated As-coated Heat coated HV average 421.5 696.75 512.0 756.1 505.8 684.3 P (wt.%) in center of coat 8.35 7.5 15.2 14.9 10.5 9.7

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N. El Mahallawy et al. / Surface & Coatings Technology 202 (2008) 51515157 Table 7 Electrochemical parameters of bare, electroless Ni coated, and heat coating of AE42 and ZRE1, obtained by polarization in 3% NaCl solution Sample AE42-Mg alloy Coated AE42 HT coated AE42 ZRE1- Mg alloy Coated ZREI HT coated ZREI OCP, mV 1601 463 1381 1514 1188 217 Ecorr, mV 1535 474 1339 1518 1210 228 Icorr, A/cm2 15.77 0.75 21.44 75.24 380.59 0.95

Fig. 8. Effect of P wt% on the micro-hardness of the coat in as-deposited and after heat treatment conditions.

This increase is related to the crystallisation and formation of Ni3P. Previous work explained the increase in hardness as a result of the precipitation of Ni3P from the supersaturated solid solution, so that a hardness of 1000 to 1170 HV was measured on the coat surface [34], where the substrate was platinum and the bath was pyrophosphate. On the other hand, an increase in the hardness only by 55 to 65 HV after a HT at 230 C for 2 h was found [3]. This was thought to be associated with structural transformations, precipitation and/or agglomeration of nickel phosphide (Ni3P) particles after heat treatment. The micro-

structure in the as-coated condition was found to contain a ne dispersion of a thin layer of precipitated P in Ni, whereas the structure after heat treatment showed dispersion of Ni in a matrix of nickel phosphide [3]. Further increase in hardness could be obtained in the NiP deposits by the addition of other elements, such as tungsten [11] or cobalt [40] due to the formation of supersaturated solid solution, even with the presence of low P content in the deposit. Also the addition of uoborate anions in the bath with concentration up to 0.04 mol corresponding to 7.6 wt% P resulted in increasing the hardness due to inhibition of crystal growth during deposition, thus producing ner and more homogeneous grains [18]. However no quantitative measurements of the grain size were given. 3.7. Electrochemical tests Fig. 9 shows the potentiodynamic polarisation curves for the bare, electroless Ni coated, and heat treated after coating AE42 and ZRE1 Mg alloys. The results illustrate that, regardless the effect of heat treatment, some coats have noble corrosion potential (Ecorr) values characteristic

Fig. 9. Potentiodynamic polarisation diagrams for AE42 and ZRE1 in 3% NaCl solution: a) bare, electroless Ni coated, b) heat treated after coating.

Fig. 10. Corrosion surfaces following potentiodynamic polarisation in 3% NaCl solution for electroless Ni coated AE42 specimen (a) and after heat treatment (b).

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of the NiP layer and greatly signicant low corrosion current densities (Icorr), and others monitor Ecorr values close to that of the Mg alloy substrates and Icorr values relatively higher than that of the Mg alloy substrate, see Table 7. This can be attributed to the presence of very ne pores in the coat layer within the corrosion-tested area. These pores may exist occasionally and are hardly observed as they were not observed in the SEM investigated areas. One open pore sufces for arising of the corrosion characteristics of the Mg substrate. The open and continuous pores permit the corrosion solution to reach to the substrate and, hence, lead to the formation of galvanic cells between the extremely active Mg and the noble NiP coat. The resultant Icorr is, consequently, higher than that of the bare Magnesium alloy. The post heat treatment has no effect on the porosity, if found, even though it inuences the corrosion morphology. Fig. 10 shows the microscopic observation of the corroded surfaces of coated AE42, with and without heat treatment, after polarisation to about 900 mV beyond the Ecorr. The as-coated specimen has exfoliation in some points, where some parts of the coat detached from the surface are clearly seen, Fig. 10a. In contrast, the heat treated sample does not show this deleterious defect after polarisation. Continued microdefects could, however, be observed as pointed out by the arrows in Fig. 10b. The interfacial layers evolved as a result of the heat treatment prevent the propagation of deleterious corrosion arising beneath the coat due to the occasionally appearing pores. Consequently, it can be stated that the electrochemical polarisation test can be used for indication of the presence of porosity in the coated Mg alloys. In recommendation, further work should be directed to apply a surface modication process for Mg alloys, e.g. conversion coating, prior to electroless plating to verify high corrosion resistance against aggressive aqueous solutions. Nevertheless, the coat layer is resistant for atmospheric corrosion, e.g. humidity test, as previously examined by the authors [26]. 3.8. Formability test In order to investigate the possibility to deform the coated alloys, strips of AZ31 were hot rolled in the as-coated condition at 350 C, and in the HT condition at 500 C. No defects were observed with the naked eye. However, SEM investigations indicate the formation of very ne cracks in the coat after the rst pass with 14% reduction in the ascoated condition and with 17% reduction (pass 2) in the HT condition. This is due to the low ductility of NiP-phase. Some magnesium oxide was also formed under the cracked coat due to heating at 500 C. However, no separation between the coat and substrate was observed. These results indicate that a redesign of the coat material is necessary, if the coated strips are to be further formed. 4. Conclusions 1. The results indicate that it is possible to coat different wrought magnesium alloys, namely AZ31, AE42 and ZRE1, by electroless NiP plating using a nickel sulphate bath after a prior zincating pretreatment. The resulting coat is uniform in thickness and produces no residual stresses after coating due to the low temperature involved in the electroless plating technique. 2. After a plating time of 35 min, the thickness of the coat reaches 8 to 9.5 mm, indicating a good rate of deposition. 3. The deposit surface morphology reveals the presence of ultrane nodules which are gathered in a micro-scale cauliower shape.

They are compact, uniform in size, without detectable defects or porosity and with excellent adhesion to the substrates, before and after heat treatment (HT). The deposited coat contains amorphous Ni and NiP mixture, while after heat treatment crystalline NiP compounds are precipitated. 4. The P wt.% increases gradually in the coat from the substrate towards the surface before and after HT which affects the surface micro-hardness of the deposit. The hardness increases continuously with P content and reaches between 420 and 512 HV while it increases to 700 to 760 HV after HT. 5. A tremendous improvement in the corrosion resistance of the Mg substrate is obtained after NiP coating especially after HT. The potentiodynamic measurements indicate that some coats exhibit the corrosion characteristics of the noble NiP layer. 6. Forming tests by hot rolling result in cracking of the coat due to its low ductility. Therefore, a redesign of the coat material is necessary if the coated material has to be formed. References
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