J. Mater. Sci. Technol., 2010, 26(9), 783-786.

Synthesis and Characterization of Fe50 Cr14 Mo14 C14 B6 Gd2 Bulk Amorphous Steel
M. Iqbal1) , J.I. Akhter1) , H.F. Zhang2) and Z.Q. Hu2)
1) Physics Division, Pakistan Institute of Nuclear Science & Technology, P.O. Nilore, Islamabad, Pakistan 2) Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
[Manuscript received August 10, 2009, in revised form March 31, 2010]

Bulk amorphous steel having 7 mm thickness was synthesized to evaluate its thermal stability and mechanical properties. The steel was synthesized by Cu mold casting technique using 1-2N pure metals. Characterization of the material was done by X-ray diraction, dierential scanning calorimetry and scanning electron microscopy. The activation energies were calculated by Kissinger equation and it was found that the steel had better stability against crystallization. Mechanical properties like Vicker s hardness, nanohardness, elastic modulus and elastic recovery of as-cast and annealed samples were measured. It was concluded that the present steel had good glass-forming ability (GFA) and mechanical properties. KEY WORDS: Bulk amorphous steels; Activation energy; Glass-forming ability; Mechanical
properties

1. Introduction Structural amorphous steels (SASs) have attracted considerable attention during the last few years because these materials have shown higher strength and hardness as well as better corrosion resistance compared to the conventional steels[14] . However, limited glass-forming ability (GFA) is the major restriction in the production of thicker ingots required for structural applications. There have been a number of eorts to improve the GFA of SASs for the production of bulk samples with large critical size to enhance their structural utilization. A number of non-magnetic Fe-based amorphous alloys that can be cast in the bulk form with varying diameter have been reported[4,5] . In addition, the production of SASs from inexpensive constituents is also considered worth examination from the cost eectiveness point of view[6] . Addition of small amounts of rare earth elements has shown improvement in
Corresponding author. Ph.D.; Tel.: +92 51 2207224; Fax: +92 51 9290275; E-mail address: akhterji@pinstech.org.pk, jiakhter@yahoo.com (J.I. Akhter).

the thermal and mechanical properties of many bulk metallic glasses (BMGs). Recently, Iqbal et al.[4] synthesized two bulk amorphous steels (BASs), namely, Fe50 Cr14 Mo14 C14 B6 Y2 and Fe50 Cr14 Mo14 C14 B6 Dy2 using conventional technique of Cu mold casting. Both the steels showed good GFA and superior hardness. However, the materials developed crystalline phases during casting as the diameter was increased to 5 mm. The present study was conducted to develop structural amorphous steel with increased diameter. Therefore, 2 at. pct Gd (having bigger atomic size), was added in the Fe50 Cr14 Mo14 C14 B6 base material and 7 mm thick BMG was produced and characterized. 2. Experimental The steel having composition Fe50 Cr14 Mo14 C14 B6 Gd2 was synthesized using 1-2N pure metals Fe, Cr, Mo, C and Gd along with the Fe-B master alloy. The materials mixture was rst melted in an arc-melting furnace at least 4 times to get the extended chemical homogeneity of the alloy buttons. Bulk ingots of

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Cr

23

C -1
6

13

Fe Mo C-2
3 3

Fe-3 12 212
(c)

2 1 2 1 12 1 1 12 3 2 2 2 11 3
1

Intensity / a.u.

1123 K/20 min

(b)

873 K / 20 min

(a)

As-cast

20

30

40

50

60

70

80

/ deg.

Fig. 1 XRD patterns of the as-cast and annealed samples

7 mm diameter with 50 mm length and sheets of size 60 mm5 mm2.5 mm were synthesized by Cu mold casting technique. For structural characterization, X-ray diraction (XRD) was conducted using D/Max-2500 Rigaku diractometer (Japan) with CuK1 (=0.154056 nm) radiation. In order to determine the thermal parameters, low and high temperature dierential scanning calorimetry (DSC) was performed using NETZSCH DSC 404C under high purity Ar atmosphere. Samples were annealed at 873 and 1123 K for 20 min to study crystallization behaviour. As-cast and annealed samples were examined by scanning electron microscopy (SEM, Leo440i, UK) to reveal the microstructure. Analysis of the samples was carried out by energy dispersive spectroscopy (EDS, Oxford, UK) attached with the SEM. Nanohardness H and elastic modulus E of the as-cast and annealed samples were measured using a MTS Nanoindenter XP with Berkovich indenter under a load (P ) of 10 mN. Vicker s hardness HV was measured by MVK-H3 Mitutoya hardness testing machine under appropriate load. 3. Results and Discussion Chemical analysis of the as-cast alloy revealed its composition close to the designed composition Fe50 Cr14 Mo14 C14 B6 Gd2 . Figure 1(a) shows the XRD patterns of the as-cast sample of 7 mm diameter taken from the central portion of the ingots. The broad band observed in the XRD pattern indicates the amorphous nature of the material. The physical appearance of the ingots and sheets showed excellent metallic luster which also indicates amorphous nature of the steel. XRD patterns of the samples annealed at temperatures 873 and 1123 K for 20 min are also shown in Fig. 1(b) and (c), which indicate sharp diraction peaks of crystalline phases. Three phases are identied in the annealed samples as -Fe, Cr23 C6 and -Fe3 Mo3 C, i.e. similar to those identied by Mssbauer spectroscopy[7] in steels having Y o and Dy as additives. EDS analysis also conrmed the presence of these precipitates in the annealed samples.

Fig. 2 SEM image of the as-cast steel (a) and sample annealed at 1123 K/20 min (b)

SEM examination of as-cast sample reveals featureless surface without any appreciable second phase particles as shown in Fig. 2(a), indicating the amorphous nature of the material. Precipitation is observed in the annealed samples as shown in Fig. 2(b) for annealing temperature 1123 K. The large size precipitates (rich in Fe and Mo) are corresponding to phase, while small size precipitates, rich in Cr and C, are likely to be Cr23 C6 phase. Figure 3(a) shows high temperature DSC scans at heating rates of 20 and 40 K/min. In order to determine the precise thermal parameters, low temperature DSC was conducted at 10 K/min and the plot is given in Fig. 3(b), which clearly reveals presence of three stage crystallization. Various thermal parameters like glass transition temperature Tg , crystallization temperature Tx , peak temperature Tp , melting and liquid temperatures Tm and Tl , obtained from the DSC plots, are given in Table 1. The supercooled liquid region Tx (=Tx Tg ), reduced glass transition temperature Trg1 (=Tg /Tm ) and Trg2 (=Tg /Tl ), parameter (=Tx /(Tl +Tg ))[1,4] and (=Tx /(Tl Tg ))[8] were evaluated to determine GFA of the alloy. These parameters are summarized in Table 1. It is clear that the values of these parameters are close to those reported for steels containing Y and Dy[4] , which indicates the good thermal stability and GFA of this steel. The activation energy for crystallization was evaluated by using the DSC data taken at various heat2 ing rates. A plot of 1000/Tp vs ln(r/Tp ) is shown in Fig. 4 for rst and second stage crystallization, where Tp is the peak temperature and r is the heating rate. The data was tted to Kissinger equation 2 ln(r/Tp )=Eac /RTp + constant[9] , where R is real

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Table 1 Thermal parameters (in K) obtained from DSC results r 10 20 40 Tg 813 831 840 Tx1 864 885 899 Tx 51 54 59 Tp1 888 895 908 Tx2 903.0 919.4 918.7 Tp2 929 939 949 Tm 1380 1385 Tl 1414 1435 Trg1 0.602 0.606 Trg2 0.587 0.585 0.394 0.399 1.52 1.51

Table 2 Mechanical properties and elastic recovery Sample As-cast 873 K/20 min 1123 K/20 min HV 1155 1233 1426 H/GPa 15.2 17.3 21.5 E/GPa 245 285 327 H/E 0.0621 0.0608 0.0658 hf /nm 136 128 110 hmax /nm 189 181 165 hf /hmax 0.716 0.707 0.667 %R/% 28.4 29.3 33.3

4
(a)

Tm T l
-10.0

3
Heat flow / mW

T
20 K/min

-10.5

40 K/min
0

ln (

r/T

Eac2
-11.0

Eac1

Tp1
600 750 900

p2

-1 1050 1200 1350 1500

-11.5 1.06 1.08 1.10
-1

T/K
1.3 (b) 1.2

1.12

(1000 / T ) / K
p

Heat flow / mW

Fig. 4 Kissinger plot for rst and second stage crystallization

1.1 10 K/min 1.0

10
Tp1 Tp2 Tp3
Load / mN

As-cast

0.9

8 6 4 2 0

873 K/20 min 1123 K/20 min

0.8

Pop-out Loading curves

0.7 450 600 750 900 1050 1200

Pmax

T/K
Fig. 3 DSC scans at high temperature (a) and low temperature (b)

Pop-in mark

hf hmax
0 50 100
Penetration depth,

Unloading curves

150

200

gas constant 8.3145 J/molK. The value of the slope B was measured from the plots. Putting the values of R and constant B into the Kissinger equation, the rst stage activation energy Eac1 and second stage activation energy for crystallization Eac2 were calculated to be 449.8 and 489.8 kJ/mol, respectively. It is interesting to note that the rst stage activation energy of the present steel is about 28% higher than that of the previously reported steels[4] . It indicates the promising thermal stability of the steel and high resistance against crystallization. The disorder produced by Gd addition in the base material is the main cause of the increase in the activation energy. Results on Vicker s hardness (HV ) of the as-cast

h / nm

Fig. 5 P -h curves of as-cast and annealed samples

and annealed samples are given in Table 2. The hardness of as-cast steel is found to be 1155 which is comparable to steels reported by Lu et al.[1] and Iqbal et al.[4] . The hardness of samples annealed at temperatures 873 and 1123 K was measured to be 1233 and 1426, respectively. Hess et al.[10] reported the Vicker s hardness of Fe48 Cr15 C15 Mo14 B6 Er2 amorphous steels (DARVA-Glass 101) in the range of 960 1150. Ponnambalam et al.[11] reported the Vicker s hardness of Fe-based BMGs in the range of 1200

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1300. The loading and unloading curves (P -h curves) obtained by nanoindentation of as-cast and annealed samples are shown in Fig. 5. Here P represents the applied load and h is the displacement of the indenter. Displacement discontinuities (pop-in marks) in few loading curves and pop-out marks in unloading curves have been observed, which indicate sudden penetration of the tip of the indent into the sample due to crack formation. Similar pop-in marks have been reported elsewhere[1,4,12,13] in loading curves of various BMGs. Dierent parameters obtained from the P -h curves are given in Table 2. The results on nanohardness parameters (penetration depth h and nal depth hf ) of the present steel are comparable with previously reported steels[1,4] . The as-cast steel has nanohardness 15.2 GPa, which increases by annealing. The elastic modulus E is one of the fundamental properties of materials as it shows the bonding between the atoms and is dependent on interatomic distances[13] . The elastic modulus of the present steel is also given in Table 2. The elastic modulus of the as-cast steel is found to be 245 GPa, which is higher than many BMGs. The enhancement in hardness and elastic modulus of the annealed samples is due to nucleation of hard intermetallics in the amorphous matrix[14] . Using the values of the nal indentation depth hf and the maximum penetration depth of the indenter hmax , the elastic recovery hf /hmax and percentage elastic recovery of displacement on unloading %R=((hmax hf )/hmax )100%[15,16] were evaluated. The elastic recovery limits in present case are found to be in the range of 0.6670.716, while percentage elastic recovery %R ranges between 28.4%33.3%. The fracture strength f of the as-cast steel was calculated to be 5 GPa from the correlations f H/3[17] and E/f =50[2] proposed for BMGs. The results indicate high strength of the SAS similar to that reported for other SASs[1,5] . 4. Conclusion High strength structural amorphous steel Fe50 Cr14 Mo14 C14 B6 Gd2 having 7 mm diameter was synthesized by Cu mold casting. DSC results revealed very good glass-forming ability of the material. The material also showed high hardness as well as high strength. The activation energy for crystallization

was found to be very high, which indicated high thermal stability of the present steel. Annealing at 873 and 1123 K produced three types of phases which enhanced mechanical properties.

Acknowledgements Dr. M. Iqbal acknowledges the nancial support provided by the Chinese Academy of Sciences. Help extended by Prof. Wang and members of DL/MSG, Physics Division, PINSTECH is highly appreciated. REFERENCES [1 ] Z.P. Lu, C.T. Liu, J.R. Thompson and W.D. Porter: Phys. Rev. Lett., 2004, 92, 245503-1. [2 ] Y.H. Zhao, C.Y. Luo, X.K. Xi, D.Q. Zhao, M.X. Pan and W.H. Wang: Intermetallics, 2006, 14, 1107. [3 ] J. Shen, Q.J. Chen, J.F. Sun, H.B. Fan and G. Wang: Appl. Phys. Lett., 2005, 86, 151907-1. [4 ] M. Iqbal, J.I. Akhter, H.F. Zhang and Z.Q. Hu: J. Non-Cryst. Solids, 2008, 354, 3284. [5 ] X.J. Gu, S.J. Poon and G.J. Shiet: J. Mater. Res., 2007, 22, 344. [6 ] C.Y. Luo, Y.H. Zhao, X.K. Xi, G. Wang, D.Q. Zhao, M.X. Pan, W.H. Wang and S.Z. Kou: J. Non-Cryst. Solids, 2006, 352, 185. [7 ] M. Sidique, M. Iqbal, J.I. Akhter and M. Ahmad: J. Alloy. Compd., 2009, 482, L25. [8 ] Q.J. Chen, J. Shen, D.L. Zhang, H.B. Fan, J.F. Sun and D.G. McCartney: Mater. Sci. Eng. A, 2006, 433, 155. [9 ] H.E. Kissinger: Anal. Chem., 1957, 29, 1702. [10] P.A. Hess, S.J. Poon, G.J. Shiet and R.H. Dauskardt: J. Mater. Res., 2005, 20, 783. [11] V. Ponnambalam, S.J. Poon and G.J. Shiet: J. Mater. Res., 2004, 19, 1320. [12] M. Iqbal, J.I. Akhter, H.F. Zhang and Z.Q. Hu: J. Non-Cryst. Solids, 2008, 354, 3291. [13] J.G. Wang, B.W. Choi, T.G. Nieh and C.T. Liu: J. Mater. Res., 2000, 15, 798. [14] Y.F. Wang, C. Wang, X. Pan and C. Dong: Mater. Lett., 2005, 59, 2574. [15] S.V. Hainsworth, H.W. Chandler and T.F. Page: J. Mater. Res., 1996, 11, 1987. [16] A. Bolshakov and G.M. Pharr: J. Mater. Res., 1998, 13, 1049. [17] D.C. Qiao, G.Y. Wang, P.K. Liaw, V. Ponnambalam, S.J. Poon and G.J. Shiet: J. Mater. Res., 2007, 22, 544.