Applied Surface Science 253 (2007) 43484355 www.elsevier.

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Preparation and characterisation of electrodeposited amorphous SnCoFe ternary alloys

C. Chisholm a, E. Kuzmann b,*, M. El-Sharif a, O. Doyle a, S. Stichleutner b, K. Solymos b, Z. Homonnay b, A. Vertes b
b a Glasgow Caledonian University, Glasgow, Scotland, UK Research Group for Nuclear Methods in Structural Chemistry, Hungarian Academy of Sciences, Department of Nuclear Chemistry, Eotvos University, Budapest, Hungary

Received 23 February 2006; received in revised form 6 September 2006; accepted 22 September 2006 Available online 1 November 2006

Abstract Electrochemical deposition was investigated as a process to obtain alloys of SnCoFe, which to date have not been reported in the literature. A constant current technique was used to electrochemically deposit tincobaltiron alloys from a gluconate electrolyte. The gluconate system was chosen as an electrolyte, which could potentially provide an environmentally safe process. The effect of plating parameters such as current density, deposition time, temperature and pH are discussed. Results are reported for current density and plating time using an electrolyte temperature of 20 60 8C and pH of 7.0 in relation to phase composition, crystal structure and magnetic anisotropy of the deposited alloys. Investigations were conducted using 57Fe conversion electron Mossbauer spectroscopy (CEMS), 119Sn CEMS, transmission Mossbauer Spectroscopy and XRD. The 57Fe and 119Sn CEMS spectra and XRD showed that the dominant phase in the deposits was amorphous SnCoFe. The relative area of the 2nd and 5th lines of the sextets representing the magnetic iron containing phases was found to decrease continuously with increasing current density while at the same time no signicant changes in the magnetic anisotropy was found with plating time. Magnetically split 119 Sn spectra reecting a transferred hyperne eld were also observed. A range of good quality amorphous SnCoFe ternary alloys was obtained over a range of operating conditions from an environmentally acceptable gluconate electrolyte. # 2006 Elsevier B.V. All rights reserved.
PACS : 81.15.Pq; 73.61.At; 61.10.Nz; 61.18.Fs Keywords: Electrodeposition; SnCoFe alloy; XRD; Mossbauer spectroscopy

1. Introduction More recently there has been a resurgence of interest in the use of electrochemical deposition to achieve compositionally modulated alloys, which provide an attractive range of properties through changes to the structure. There is now a growing interest in the potential for electrodeposition to be used to produce environmentally acceptable alloys exhibiting a range of properties correlated to crystal size. As the electrodeposition process is both economic and highly suitable for transfer from laboratory to industrial process [13] it

presents an attractive technique for the development of new alloys such as SnCoFe. A literature search to date shows that there is no documented research to show the development of a tincobaltiron ternary alloy. The aim of the present work was to investigate the possibilities of achieving novel ternary tincobaltiron alloys from an environmentally acceptable electrolyte. 2. Experimental 2.1. Gluconate electrolytes As indicated in the introduction one of the aims of the investigation was to develop an electrolyte, which was environmentally safe, generating no problematic by-products.

* Corresponding author. Tel.: +36 12090555; fax: +36 13722592. E-mail addresses: kuzmann@ludens.elte.hu, kuzmann@chem.elte.hu (E. Kuzmann). 0169-4332/$ see front matter # 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2006.09.045

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Literature research shows that gluconates have been used as successful electrolytes for tin and binary alloys of tincobalt [410]. More recently iron and cobalt have been successfully electrodeposited from gluconated electrolytes [11,12]. The authors also reported successful deposition of CoFe alloys from a gluconate electrolyte [1214,1618]. On the basis of successful codeposition from SnCo and Fe Co gluconate based electrolytes it was decided to take forward the investigation using for deposition a ternary system based on gluconate as the electrolyte. Sodium gluconate (C6H11O7Na) acts as a complexant in the electrolytes and was chosen over other gluconate compounds due to its high electrode potential. Within the electrolyte the Sn, Fe and Co metal ions bond with the gluconate, producing complexes. The complexing in the electrolyte thus facilitates electrode potentials coming together and hence the potential of successful codeposition of SnCoFe as metallic alloys. On the basis of the earlier work reported the electrolytes used for the experimental studies have a composition range and operating conditions as follows:
Sodium gluconate Peptone SnSO4 CoSO4 FeSO4 Electrolyte temperature pH 120 g/l 0.1 g/l 0.020.075 M 0.0750.09 M 0.050.09 M 60 8C 7.0

electrode with 4 M KCl solution was employed in the cell arrangement for the experimental studies. 2.3. Apparatus All the studies were conducted using a two electrode system with a static electrolyte using a galvanostatic mode. The plating cell used had a 375 ml capacity with 300 ml of electrolyte being used for each deposition study. The design of the cell provided the anode and cathode parallel to each other and perpendicular to the cell base to ensure uniform current distribution over the surface of the electrodes. The cell was thermostatically controlled to within 1 8C to ensure accurate experimental results at varying temperatures. 2.4. Deposit quality The deposit quality of the electrodeposits was categorised visually as to whether the surfaces were bright metallic, dull metallic, matte, lustrous or powdery. The visual examination also categorised the partial or total coverage of the cathode by the deposit, whether the deposit was adherent and the presence or otherwise of surface lms on the deposits. The elemental analyses were carried out by electron microprobe analysis. Selected samples were investigated by SEM and EDAX methods. 2.5. XRD Powder X-ray diffractograms of the samples were measured by a computer controlled DRON-2 X-ray diffractometer using Co Ka radiation and b lter. The diffractograms were recorded between 208 and 1408 in 2u, with a goniometer speed of 0.28/ min at room temperature. The evaluations of the XRD patterns were made by the EXRAY code (developed by Klencsar at the Eotvos University, 1996). For identication of the phases the ASTM X-ray diffraction data were used. 2.6. CEMS Fe and 119Sn conversion electron Mossbauer spectra of the samples were recorded by conventional Mossbauer spectrometers (WISSEL) working in constant acceleration mode at room temperature. The conversion electrons were detected by a RANGER type detector. A 50 mCi activity 57Co/Rh source supplied the gamma rays for the measurements. The velocity calibration was performed by a-Fe measurements. The CEMS spectra provided information about the outer most layer of the coatings corresponding to about 1000 A in depth from the coating surface. The evaluation of the Mossbauer spectra was made by the least square tting of Lorentzians using the MOSSWINN programme [15]. 3. Results and discussion of the deposition studies The main parameters for codeposition are shown in Table 1. As can be seen all the alloys were Sn rich across the current density range from 0.5 to 2.5 A/dm2. The visual appearance of
57

It was not clear from published work, which peptones had been used within the reported electrolytes and experimental studies by the authors found that variations in deposit quality correlated to the nature of the peptone used [11]. The experimental studies were conducted using peptone from a meat extract. The electrolytes were prepared immediately prior to each set of studies by independently dissolving the metal sulphates, sodium gluconate and peptone in deionised water. The electrolyte was stirred to help dissolution and provide homogeneity. The alkalinity and acidity of the electrolytes was controlled by either additions of NaOH or HCl, respectively. 2.2. Electrodes Copper cathodes (99.9% pure copper foil) were used with a working surface area of 4 cm2. The cathodes were immersed in acetone for 12 h to ensure degreasing and then rinsed in owing deionised water. Prior to electrodeposition the cathodes were anodically electropolished for 30 s at 1 A in a solution of 80% (v/v) phosphoric acid, 10% (v/v) methanol and 10% (v/v) deionised water. The cathodes were rinsed in owing deionised water and then placed immediately within the electrolyte. Electropolishing was necessary to remove all the surface impurities and any mechanical damage from the cathode substrate. High density graphite passive anodes with a working surface area of 20 cm2 were used and a standard Ag/AgCl reference

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Table 1 The composition of electrodeposits as a function of current density and composition of the plating solution at 60 8C, pH 7.0 for 5 min plating time Sample no. Composition of the electrolyte solution 0.075 M SnSO4, 0.075 M CoSO4, 0.05 M FeSO4 Cathode current density (A/dm2) 0.5 1.0 1.5 2.0 2.5 0.5 1.0 1.5 2.0 2.5 0.02 M SnSO4, 0.09 M CoSO4, 0.09 M FeSO4 0.5 1.0 1.5 2.5 Composition Sn 92.55 92.49 92.34 91.64 93.54 83.97 83.45 82.76 83.24 83.88 45.73 46.84 52.64 58.46 Co 5.39 5.0 4.71 5.40 5.32 8.48 7.86 7.36 7.21 7.01 23.17 20.93 19.62 7.13 Fe 2.06 2.51 2.95 2.96 2.14 7.55 8.69 9.88 9.55 9.11 31.11 32.22 27.34 24.41 All codeposits showed metallic grey character with staining on surface due to H2 evolution Visual description of codeposits

1 2 3 4 5

0.05 M SnSO4, 0.075 M CoSO4, 0.075 M FeSO4

Bright metallic with pitted surface Bright metallic with highly pitted surface Partially bright metallic with H2 gas staining on surface Partially bright metallic with copious H2 gas staining on surface Partially bright metallic with large amounts of H2 gas staining over entire surface High metallic lustre even deposit High metallic lustre with stain free surface Metallic lustre with some H2 gas staining on surface Uneven metallic deposit with some staining

the deposits was affected by changes to the composition of the electrolyte but the cathode current density had no important inuence on this parameter. The decrease of the tin concentration in the electrolytes resulted in a consequent decrease of tin concentration in the alloys. At the lower current densities the brightness of the deposits was higher (in the case of relatively low tin concentration: $80%). It was found that pitting and staining of the surfaces could be eliminated by decreasing the current density to 0.25 A/dm2. Table 2 shows that by extending deposition times that at 0.25 A/dm2 the alloy composition changes signicantly giving rises in the Co and Fe content and a corresponding drop in the tin content. This result suggests that the composition of the layers of electrodeposits is not homogeneous in depth. However at 1 A/dm2 the deposits showed no signicant change in alloy composition, giving a median alloy content of 47.89% Sn,

22.29% Co, 29.82% Fe. While the codeposit thickness increased from 0.99 to 4.5 mm with increased deposition time, the deposition times had no effect on the metallic quality of the codeposits. While 60 8C had been chosen as giving successful deposition for SnCo, and Sn from earlier reported work, studies were conducted to see the effect of electrolyte temperatures from 20 to 60 8C. The results for 20 and 40 8C are shown in Table 3 and the results for 60 8C are shown in Tables 1 and 2. It appears that the ternary electrolyte gives good quality metallic alloys over the temperature range 20 60 8C. While H2 gas staining was found at the higher current densities at 60 8C the deposits at the lower temperatures were free from surface staining for all the current densities studied. Microscopic examination of the codeposits revealed that they were ne grained but exhibited microcracking. The density

Table 2 The compositions of the codeposits as a function of codeposition time and current density at 60 8C and pH 7.0 Sample no. Composition of the electrolyte solution 0.075 M SnSO4, 0.075M CoSO4, 0.05 M FeSO4 6 8 9 10 0.02 M SnSO4, 0.09 M CoSO4, 0.09 M FeSO4 Cathode current density (A/dm2) 0.25 Deposit thickness (mm) Codepostion time (min) 5 15 30 0.99 3.5 3.96 4.5 5 15 20 30 Composition Sn 88.04 68.35 61.54 46.84 46.81 47.56 49.83 Co 9.69 22.18 25.26 20.93 22.11 22.89 23.22 Fe 2.27 9.46 13.20 32.22 31.08 29.55 26.45 High metallic lustre smooth surface with no pitting or staining for all codeposits Even deposit with high metallic lustre and microcracking Slightly uneven metallic deposit with microcracking Uneven deposit but still metallic lustre microcracked Uneven deposit but still metallic lustre and microcracked Visual description of codeposits

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Table 3 Codeposition from 0.02 M SnSO4, 0.09 M CoSO4, 0.09 M FeSO4 plating solution at pH 7.0 as a function of current density, deposition time and temperature Temperature (8C) 20 Depostion time (min) 5 Cathode current density (A/dm2) 0.5 1.0 1.5 2.5 1.0 Composition Sn 41.39 48.99 51.60 57.97 47.33 48,312 49.25 0.5 1.0 1.5 2.5 1.0 42.55 47.15 52.15 58.12 47.68 48.21 49.13 Co 26.75 21.52 20.61 17.48 21.24 21.86 22.41 25.62 22.21 19.75 17.08 22.89 23.05 23.65 Fe 31.85 29.49 23.79 24.55 31.43 30.02 28.34 31.83 30.64 28.10 24.80 29.43 28.74 27.22 Even deposits with high metallic lustre Visual description of codeposits

15 20 30 40 5

High metallic lustre with some microcracking Uneven metallic deposit with some microcracking and surface staining Uneven deposit, metallic stained and microcracked Mattle metallic even deposits

15 20 30

High metallic lustre with microcracks and surface staining Uneven deposit, metallic stained and microcracked Highly uneven but metallic deposit stained and microcracked

of the microcracking increased with increasing temperature. A typical structure is shown in micrograph 1. All the deposits exhibited a degree of microcracking similar to that obtained with decorative chromium deposition. The optimum deposit quality was achieved after 15 min deposition time with a further increase leading to the deposits being deposited unevenly across the cathode surface and exhibiting surface staining due to hydrogen gas evolution at the cathodes. Below pH 5.0 and above pH 7.0 the deposit quality deteriorated leading to very uneven dark grey deposits and at pH 3.0 the deposit appeared to be loosely adherent and powdery. Bright metallic alloys exhibiting microcracking with a median composition of 48% Sn, 22% Co and 30% Fe were obtained within the pH range 5.07.0. Examination of the degree of microcracking in the codeposits revealed that the density of microcracking increased at the more acidic conditions of pH 5.0. Thus by controlling the ratio of the metals in the electrolyte, a range of metallic alloys; 4592%Sn, 525%Co, 330%Fe is possible within a pH range of 5.07.0 and a temperature range of 2060 8C. 4. Results and discussion of XRD and Mossbauer spectroscopy Fig. 1 shows the X-ray diffractograms of SnCoFe electrodeposits plated on a Cu substrate at different conditions as shown in Tables 1 and 2. The sharp peaks at around 2u = 50.8, 60.2 and 88.68 belong to the (1 1 1), (2 0 0) and (2 1 1) reections of Cu substrate for Co Ka (l = 0.1790260 nm) radiation. In Fig. 1 the high intensity peaks at about 60.2 degree were cut in all diffractograms in order to have a more accurate analysis about the small components. In this case, the very intense (2 0 0) reection of Cu substrate becomes highly visible for Co Kb (l = 0.162079 nm) at 2u = 53.1 degree. The lines for Cu are present in all diffractograms because the thickness of the coatings is much smaller than the penetration depth of the X-ray.

In all the X-ray diffractograms, the main peaks, except the lines belonging to the Cu substrate, are very broad, reecting the amorphous or microcrystalline character of the coatings. The relative intensities of the broad lines attributed to SnCoFe coatings compared to those of Cu substrate are consistent with the thickness estimated roughly from the current and time of electrodeposition. XRD has thus revealed the existence of a new metastable amorphous or microctrystalline alloy phase for all electroplating conditions. The amorphous phase is the dominant phase in all SnCoFe deposits. The X-ray diffractograms reect only the amorphous phase for the deposit samples, except for sample 5 and 10. In the latter two cases some small intensity sharp peaks appear indicating the presence of a minute amount of crystalline phases. Co3Sn2 (corresponding peaks at around 2u = 35.38, 50.78 and 658) can be identied for both coatings deposited at the highest current and for the longest time whereas FeSn2 (corresponding peak at around 2u = 41.78) can be identied for sample 5 plated at the highest current. The amorphous character of the samples is consistent with the electronmicrograph (Fig. 2), which shows a homogeneous alloy coating with microcracks on the surface. All 57Fe CEM spectra (Fig. 3) for the SnCoFe electrodeposits exhibit an envelope of magnetically split spectrum with broad lines. These spectra are typical for amorphous alloys. The spectra were decomposed into a dominant magnetically split sextet with broad lines and a minor doublet. The subspectra can be considered as a superposition of a large number of elementary spectra belonging to different microenvironments of iron atoms having various alloying elements in the neighbourhoods. The average Mossbauer parameters of the sextet and the doublet are shown in Table 4. The isomer shift and hyperne eld values are in good agreement with those expected for the SnCoFe randomly distributed alloy phases. The sextet is associated with the ferromagnetic SnCoFe alloy and the doublet is attributed to a paramagnetic SnCoFe alloy phase. The

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Fig. 1. XRD of SnCoFe electrodeposits plated onto Cu substrate at different conditions.

relative spectral areas show that the ferromagnetic amorphous phase is dominant in all samples. At the analysis equal MossbauerLamb factors were supposed which can result in some uncertainty. It was found that the relative area of the doublet increases with the plating current. At the same time the hyperne eld decreases with the increasing deposition current. This can be explained by compositional changes of the amorphous alloy deposited at different current densities. In the case of sample 5 deposited at the highest current density, where the XRD indicated some crystalline phases, the presence of a minute amount of FeSn2 cannot be excluded in the

Fig. 2. SEM micrograph of sample no. 4.

corresponding Mossbauer spectrum. The relatively small hyperne eld value obtained with sample 10 may also be associated with compositional change due to the segregation of the crystalline Co3Sn2 phase which was indicated by XRD and 119 Sn Mossbauer spectroscopy. Alternatively, the presence of FeCo phases in the alloys may be excluded entirely because their characteristic Mossbauer pattern is absent in the 57Fe spectra. The results of 57Fe Mossbauer spectra of SnCoFe electrodeposits are in excellent agreement with the XRD and show the existence of a dominant amorphous ferromagnetic phase and a minor amorphous paramagnetic phase in all electrodeposits. It was also observed that the relative areas of the 2nd and 5th lines of the sextets representing the magnetic iron containing phase decrease continuously with increasing current density. At the same time, no essential change in the relative area of the 2nd and 5th lines was found with the deposition time. The same phenomenon was observed in all Fe-containing deposits (Fe, FeCo [14], FeSn). This indicates that the observed change with the current density is independent from the composition of the coating but is characteristic of the deposition procedure. Since the relative area of the 2nd and 5th lines reveals the average direction of iron magnetic moment relative to the g-ray direction, this nding may provide information about the

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Fig. 3.

57

Fe conversion electron Mossbauer spectra of electrodeposited SnCoFe samples.

distribution of spin direction (domen structure) and about the preferred spin orientation (spin texture) in these electrodeposited materials [14]. The 119Sn conversion electron Mossbauer spectra are shown in Fig. 4. All 119Sn spectra exhibit a magnetically split envelop with very broad lines. This can be considered as a superposition of a number of magnetically split subspectra. Since the Sn is nonmagnetic, the magnetic splitting is probably due to a transferred hyperne eld. It is originated
Table 4 Mossbauer parameters of electrodeposited SnCoFe samples Sample no. 1 Sextet A (%) d (mm s1) B (T) W1,6 (mm s1) Doublet A (%) d (mm s1) D (mm s1) W (mm s1) 86.9 0.13 29.06 1.40 13.1 0.30 0.96 0.57 2 87.4 0.13 29.19 1.33 12.6 0.32 0.83 0.57 3 84.5 0.14 28.53 1.22 15.5 0.29 0.76 0.67 4 85.4 0.13 28.47 1.31 14.6 0.30 0.95 0.61

from the neighboring magnetic atoms. The large number of subspectra with different hyperne elds corresponds well to the number of various microenvironments of Sn in the amorphous SnCoFe alloy. The 119Sn spectra were evaluated with the hyperne eld distribution method. The isomer shift and the magnetic eld data are shown in Table 5. The 119Sn Mossbauer results are consistent with the occurrence of an amorphous SnCoFe phase as was shown by the XRD and 57 Fe Mossbauer results.

5 76.3 0.12 27.91 1.25 23.7 0.29 0.74 0.57

6 85.8 0.11 29.05 1.36 14.2 0.34 0.87 0.50

7 87.9 0.13 28.75 1.35 12.1 0.34 0.93 0.56

8 85.5 0.12 29.32 1.33 14.5 0.30 1.02 0.60

9 76.3 0.14 28.71 1.19 23.7 0.30 0.93 0.52

10 87.7 0.14 21.22 1.01 12.3 0.30 0.74 0.36

The errors of the determination of the isomer shift (d), quadrupole splitting (D), magnetic induction (B) and linewidth (W) are 0.02 mm s1, 0.04 mm s1, 0.2 T and 0.06 mm/s, respectively. W1,6 denotes the linewidth of 1st and 6th lines of the sextet.

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Fig. 4.

119

Sn CEM spectra of electrodeposited SnCoFe alloy coatings.

Table 5 Isomer shift and magnetic eld, derived by hyperne eld distribution method, of Sample no. 1 d (mm s ) B (T)
1

119

Sn Mossbauer spectra of electrodeposited SnCoFe alloy coatings

2 1.82 4.87

3 1.85 4.86

4 1.72 4.86

5 1.98 4.40

6 1.67 5.28

7 1.76 5.32

8 1.73 5.42

9 1.90 4.89

10 1.89 4.97

1.89 5.21

The average width of the hyperne eld distribution was around 2 T. The error of the determination of the isomer shift (d) is 0.04 mm s1.

Sn CEM spectrum of sample 5 (Fig. 4) deposited at the highest current density clearly shows the presence of a small amount of Co3Sn2 (5%) phase (d = 2.01 + 0.03 mm/s, D = 1.21 + 0.04 mm/s) and FeSn2 (4%) phase (d = 2.25 mm/ s, D = 0.85 mm/s), while the spectrum of sample 10 (Fig. 4) exhibits only a little Co3Sn2 (3%) phase which is in excellent agreement with the XRD and 57Fe Mossbauer results. A continuous change in the average hyperne eld (Table 5) was observed with the current density in the 119 Sn CEM spectra. This can be explained by compositional changes of the amorphous alloy deposited at different current densities. This complements well those observed with the 57 Fe CEM spectra. A new metastable ferromagnetic SnCoFe amorphous alloy phase was shown to be present in SnCoFe electrodeposits and this phase is the dominant phase in all the SnCo Fe electrodeposits prepared under the experimental conditions investigated.

119

5. Conclusions A new range of good quality SnCoFe ternary alloys can be successfully deposited from an environmentally acceptable electrolyte based on sodium gluconate. Stable alloy compositions are possible at selected current densities across a range of deposition times thus facilitating deposits of varying thickness. Alloys of varying composition can be obtained by controlling the ratio of metal ions in the electrolyte. XRD and Mossbauer results conrmed the existence of a new metastable amorphous ferromagnetic SnCoFealloy phase within the ternary alloy deposits. The amorphous alloy phase was found to be the dominant phase for all the SnCoFe electrodeposits investigated. Acknowledgement This study was supported by the Hungarian Science Foundation (OTKA T043687).

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