Materials Science and Engineering A352 (2003) 105 /111 www.elsevier.

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Mechanical alloying of MoSi2 with ternary alloying elements. Part 1: Experimental

A.J. Heron, G.B. Schaffer *
Division of Materials, School of Engineering, The University of Queensland, Brisbane, Qld 4072, Australia Received 22 July 2002

Abstract Phase evolution during the mechanical alloying of Mo and Si elemental powders with a ternary addition of Al, Mg, Ti or Zr was monitored using X-ray diffraction. Rietveld analysis was used to quantify the phase proportions. When Mo and Si are mechanically alloyed in the absence of a ternary element, the tetragonal C11b polymorph of MoSi2 (t -MoSi2) forms by a self-propagating combustion reaction. With additional milling, the tetragonal phase transforms to the hexagonal C40 structure (h -MoSi2). The mechanical alloying of Al, Mg and Ti additions with Mo and Si tend to promote a more rapid transformation of t -MoSi2 to h MoSi2. In high concentrations, the addition of these ternary elements inhibits the initial combustion reaction, instead promoting the direct formation of h -MoSi2. The addition of Zr tends to stabilise the tetragonal phase. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Mechanical alloying; Molybdenum disilicide; Rietveld

1. Introduction Mechanical alloying (MA) is well known as a nonequilibrium powder processing technology and has been applied to many systems, including MoSi2 [1 /8]. The MA of molybdenum and silicon has been studied extensively with most researchers reporting a spontaneous high temperature synthesis reaction after only a few hours of milling to form the tetragonal C11b structure (t -MoSi2). Continued high energy deformation induced by mechanical milling has also been shown to favour the formation of the hexagonal C40 polymorph (h -MoSi2). Alloying of MoSi2 with a third element to remove oxygen is one strategy used to reduce the deleterious effects of SiO2 at elevated temperatures [9]. The alloying behaviour of MoSi2 has been widely studied, particularly with Al to form Mo(Si,Al)2 [9 /12]. As shown in the

* Corresponding author. Tel.: '/61-7-3365-4500; fax: '/61-7-33653888. E-mail address: g.schaffer@minmet.uq.edu.au (G.B. Schaffer).

ternary phase isotherms proposed by Brukl et al. at 1600 8C [13] and by Yanigahara et al. [14] at 1550 8C, Al has some solubility in MoSi2 and in concentrations in excess of 3 at.%, promotes the formation of the C40 structure. The Al substitutes for the Si atoms on the {110} planes of the C11b structure, which are equivalent to the close-packed {0001} planes in C40. This coincides with a minor charge transfer away from the Al sites, which bond covalently with the Mo [15]. The MA of MoSi2 with Al has recently been investigated by Costa e Silva and Kaufman [9]. The h -MoSi2 phase is also stabilised by both Ti and Mg, although the Ti subsitutes for the Mo and forms a stable disilicide with the C54 structure. The C40 structure is stable at intermediate Ti levels [16,17]. The aim of this work was to study the MA of Mo with Si to form MoSi2 and its alloying with Al, Mg, Ti or Zr. These elements were chosen for their strong chemical affinity for oxygen. This paper shows the progress of the reactions using X-ray diffraction, analysed using Rietveld analysis. A companion paper presents a computer simulation of the reactions as they occur during MA [18].

0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 1 - 5 0 9 3 ( 0 2 ) 0 0 8 6 4 - X

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2. Experimental The powders were obtained from Cerac Inc., the powder details are presented in Table 1. The mechanical alloying was performed in a Spex 8000 mixer/mill. The powders were placed in a high strength steel vial with 20 )/8.4 g hardened steel ball bearings. The powders were mixed in proportion such that the total powder mass of each mill was 8.4 g, giving a constant charge ratio (ball mass to powder mass, Cr) of 20. The vial was sealed in an inert argon atmosphere with an oxygen concentration B/1000 ppm. Prior to each mill, the vial was cleaned by milling with alcohol for 1 h and then sand blasted and the loose powder was removed by compressed air. Molybdenum and silicon powder were milled for times between 2.5 and 100 h with up to 16.7% of Al, Mg, Ti or Zr (all concentrations in at.% unless otherwise specified). After each mill, the loose powder was removed for analysis.

3. Rietveld analysis Diffraction patterns were collected using a Phillips Xray diffractometer with Cu Ka radiation and a nickel filter. Scans were performed using a low angle background holder with diffraction angles 15 /908, a step size of 0.058 and a scan speed of 18 min (1. The phases present were identified using the mPDSM search/match program. Due to the large discrepancy in the initial powder sizes, it was difficult to obtain X-ray diffraction patterns for the unmilled powder mixes. The X-ray diffraction patterns from the powders after 2 h of milling were, therefore, used as a reference for the powders milled for longer times. The X-ray patterns were analysed using the LHPM9 Rietveld program [19] to give the phase proportions. Rietveld analysis refers to any method that uses a mathematical description of the crystal structure to calculate a theoretical X-ray diffraction pattern. The description of the crystal structure includes information such as the space group, atomic positions and lattice site occupancy, preferred orientation and unit cell size. In

Table 1 The size and purity of the starting powders Powder Mo Si Al Mg Ti Zr Size (/325 mesh 3 /6 mm (/325 mesh (/325 mesh (/150 to '/325 mesh 1 /3 mm Purity (%) 99.9 99.999 99.5 99.6 99.5 99.8

order to determine a theoretical diffraction pattern, the X-ray diffraction process, including source of experimental error, is also modelled using parameters for the radiation wavelength, background noise and adjustment to peak shape due to grain size, peak asymmetry and adsorption effects. The theoretical pattern is then compared to the experimentally observed pattern and recursively refined to minimise the difference between them. The computer generated diffraction patterns are governed by several parameters, including unit cell parameters, atomic positions, scale factors and terms to define the peak shape. The refined scale factor from Rietveld analysis gives an indication of the integrated peak intensities. The broad, low intensity of the peaks are accounted for by increasing the Lorentzian parameter. Hence, if two diffraction patterns with the same phase proportions are analysed, one with tall sharp peaks and the other with low broad peaks, Rietveld would keep the scale factor constant and vary the Lorentzian parameter to account for the peak shape. The Rietveld method can only match phases in the experimental patterns that are included in the input file. Thus, a traditional search/match process must first be undertaken to determine which phases are observable before the Rietveld analysis can be initiated. Due to the broad peaks in several of the diffraction patterns, especially in the mills with high proportions of Ti and Zr, it is difficult to determine all the phases present with complete certainty. This is particularly problematical for amorphous phases. The converse of this problem must also be considered. If a phase is selected in the input file but is only just resolvable above the background in the experimental pattern, or not observable at all, the Rietveld analysis tends to overestimate the phase proportion by keeping the scale factor constant and increasing the Lorentzian parameter. Hence the experimental pattern is matched by a broad, low intensity peak with a large integrated area. When this was observed during the Rietveld refinement process, the phase in question was considered not to be present in significant proportions and was removed from the input file. It is for this reason that Rietveld occasionally does not report the existence of a particular phase when it may be argued that its peaks can indeed be observed. To account for amorphous phases and those that fall below the detectable limit, the phase proportions were corrected by assuming that the Mo never becomes unobservable and is always accounted for as either elemental Mo or in the MoSi2 phase. This assumption is based on the high atomic scattering factor of Mo, particularly compared to Si. The corrected molar phase proportions and the associated error analysis are derived in Appendix A.

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107

Fig. 1. X-ray diffraction patterns for the mechanical alloying of 33.3 Mo /66.7 Si.

Fig. 2. The Rietveld renement for the sample containing Mo and Si powder, without a ternary element, milled for 2.6 h.

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Fig. 3. The change in the relative phase proportions during the mechanical alloying of 33.3 Mo /66.7 Si, as determined by Rietveld analysis.

4. Results and discussion Fig. 1 shows the X-ray diffraction patterns for the mechanical alloying of Mo and Si in the absence of

ternary additions. After 2.5 h of milling, the diffraction pattern shows strong Mo peaks with relatively weak and broad Si peaks. The reduction in the intensity of the Si peaks during the early stages of mechanical alloying is commonly observed and is attributed to the intimate mixing of the two elements and the strong absorption of Mo [2,8]. At 2.6 h, the elemental precursor powders have transformed to t -MoSi2 and the peaks are sharp and well defined. This is indicative of a combustion reaction between 2.5 and 2.6 h. A large portion of Mo is still evident after combustion. It is possible that some regions of the powder mixture were physically isolated from the combustion front, or were not involved in sufficient deformation events for the combustion reaction to proceed. The diffraction peaks after 10 h have broadened considerably compared to the peaks for the pattern after 2.6 h of milling, indicating deformation and grain size refinement. The tetragonal structure transforms to the hexagonal structure as milling continues up to 100 h. The Rietveld analysis immediately

Fig. 4. X-ray diffraction patterns for the mechanical alloying of 27.8 Mo /55.6 Si /16.7 Al after (a) 2, (b) 5, (c) 10, (d) 20 and (e) 50 h.

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Fig. 5. X-ray diffraction patterns for the mechanical alloying of 27.8 Mo /55.6 Si /16.7 Zr after (a) 2, (b) 5, (c) 10, (d) 20 and (e) 50 h.

following combustion is shown in Fig. 2 and the relative phase proportions over the entire milling period are shown in Fig. 3. After 100 h, t -MoSi2 and h -MoSi2 reach steady state proportions of 31.7 and 68.3 mol%, respectively. After 2 h of milling, the powders containing 16.7% Al, Mg and Ti have not reacted and still show strong elemental peaks. As milling continues for up to 50 h, Al, Mg and Ti additions promote the formation of h -MoSi2, and other than the powder containing Ti, exhibit sharp diffraction peaks. The series containing 16.7% Ti exhibits very broad, low intensity peaks after 50 h, indicating a fine nanocrystalline structure. The X-ray diffraction patterns of the system with 16.7% Al are shown in Fig. 4. In contrast to the systems containing Al, Mg and Ti, the system containing Zr largely inhibits the formation of the hexagonal polymorph. The X-ray diffraction patterns of the system with 16.7% Zr is shown in Fig. 5. The ZrSi2 phase has the C49 structure and the C40 phase does not form in the quasi-binary ZrSi2 /MoSi2 system [17].

The effect that each element has on the relative phase proportions after 50 h of milling are shown as a function of alloy content in Fig. 6. As shown above, the addition

Fig. 6. The concentration of the tetragonal C11b polymorph as a proportion of the total MoSi2 content after 50 h of milling showing that Zr stabilises the tetragonal phase whereas Al, Mg and Ti stabilise the hexagonal C40 phase.

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of Al, Mg or Ti to MoSi2 favours the formation of the hexagonal C40 polymorph over the tetragonal C11b phase and complete transformation to the hexagonal variant occurs at some critical level of alloying element. In contrast, the tetragonal phase persists for all Zr concentrations tested.

The atomic phase fractions are, therefore, given by    1 1 NA pMo ' pMoSi2 AMo 0 Atotal 3 ASi 0    2 NA pSi ' pMoSi2 Atotal 3 1 1 (NA pA ) Atotal 1 (NA pU ) Atotal (A2)

5. Conclusions The crystallographic structure of mechanically alloyed molybdenum and silicon with various ternary additions was monitored using X-ray diffraction and Rietveld analysis. In the absence of a third alloying element, the reactants combust during milling to form MoSi2. Initially, this has the tetragonal C11b structure, but this decomposes during further milling to the hexagonal C40 phase. The addition of titanium promotes the transformation of the tetragonal MoSi2 polymorph to the hexagonal one. Magnesium and aluminium additions also sustain the transformation, but to a lesser extent. Zirconium stabilises the tetragonal phase.

AA 0

AU 0

Since AMo is constant and equal to the initial atomic phase fraction, given by 1 AMo 0 (1 ( AI ) 3 (A3)

where AI is the initial atomic fraction of the additive, the first line in Eq. (A2) may be rewritten as   1 NA pMo ' pMoSi2 1 3 (1 ( AI ) 0 (A4) 3 NA (pMo ' pSi ' pA ' pMoSi2 ' pU ) Rearranging to solve for pU gives 1 pMo ' pMoSi2 3 pU 0 ( (pMo ' pSi ' pA ' pMoSi2 ) 1 (1 ( A I ) 3

Acknowledgements This work was funded by the Australian Research Council.

(A5)

The total number of moles in the sample is given by Appendix A Rietveld analysis may be used to estimate the relative phase proportions of the observable phases within a sample. However, if a phase becomes amorphous or the quantity falls below the detectable limit for Rietveld analysis then the phase proportion cannot be accounted for in the determination of the observable phase proportions. To account for the unobservable phases, it is assumed that the Mo never becomes unobservable and is always present as either elemental Mo or in the MoSi2 phase. The total number of atoms within the sample may be determined from the experimental molar phase proportions Atotal 0 NA (pMo ' pSi ' pA ' pMoSi2 ' pU ) (A1) Mtotal 0 pMo ' pSi ' pA ' pMoSi2 ' pU (A6)

? , of Therefore, the normalised phase proportion, pU unobservable Si and additive phase relative to the total number of moles is given by

pU ? 0

pU Mtotal

(A7)

? of the phases were unobservable It follows that if pU then the initially determined experimental molar phase ? ) of the moles proportions represented only (1(/pU present in the sample. Therefore, the corrected molar phase proportions are given by

pMo ? 0 ( 1 ( p? U )pMo pSi ? 0 (1 ( pU ? )pSi pA ? 0 (1 ( p? U ) pA pt ?-MoSi2 0 (1 ( p? U )pt-MoSi2

where pU is the number of unobservable moles of (Si'/ additive), NA is Avagadros number and the relative molar phase proportions, determined experimentally from Rietveld analysis, are given by pMo, pSi, pA and pMoSi2 for the Mo, Si, addition and MoSi2 phases, respectively.

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111

ph ? -MoSi2 0 (1 ( pU ? )ph-MoSi2

(A8)

Similarly, the lower bound may be found fp( 0 pp ? ;calc pp ? ;calc ' pU ? '
n (1 ' R p ) X

The errors in the relative phase proportions may be calculated from the Rp counting statistic returned by the Rietveld analysis program, LHPM9 [19,20]. Rp is defined as the absolute error between the calculated and observed diffraction intensity, summed over all data points in the specified diffraction angle range. P jyi;obs ( yi;calc j Rp 0 (A9) P yi;obs If Sp ,obs and Sp ,calc are the observed and calculated scale factors, and y1 i is the true intensity for data point i , then P j jSp;obs yi1( Sp;calc yi1 (A10) Rp 0 P Sp;obs y1 i P jSp;obs ( Sp;calc j y1 i Rp 0 (A11) P Sp;obs y1 i Rp 0 jSp;obs ( Sp;calc j Sp;obs (A12)

(A19) pi?;calc

(1 ( R p )

i"p

For the data here, the residual error, Rp , was typically less than 0.15, and the proportion of unobservable phase was typically less the 30%. Using these values it may be shown that the corrected phase proportions are bounded by an error of 10 mol%.

References
[1] R.B. Schwarz, S.R. Srinivasan, J.J. Petrovic, C.J. Maggiore, Mater. Sci. Eng. A155 (1992) 75. [2] A.J. Heron, G.B. Schaffer, J. Mater. Synth. Proc. 2 (1994) 335. [3] B.K. Yen, T. Aizawa, J. Kihara, Mater. Sci. Eng. A220 (1996) 8. [4] B.K. Yen, T. Aizawa, J. Kihara, J. Am. Ceram. Soc. 79 (1996) 2221. [5] E. Ma, J. Pagan, G. Cranford, M. Atzmon, J. Mater. Res. 8 (1993) 1836. [6] S.N. Patankar, S.-Q. Xiao, J.J. Lewandowski, A.H. Heuer, J. Mater. Res. 8 (1993) 1311. [7] D.L. Zhang, J. Mater. Sci. Lett. 14 (1995) 1508. [8] L. Liu, F. Padella, W. Guo, M. Magini, Acta Metall. Mater. 43 (1995) 3755. [9] A. Costa e Silva, M.J. Kaufman, Mater. Sci. Eng. A195 (1995) 75. [10] A. Costa e Silva, M.J. Kaufman, Scripta Metall. Mater. 29 (1993) 1141. [11] J.S. Jayashankar, E.N. Ross, P.D. Eason, M.J. Kaufman, Mater. Sci. Eng. A239 /240 (1997) 485. [12] M. Fu, J.A. Sekhar, J. Am. Ceram. Soc. 81 (1998) 3205. [13] C. Brukl, H. Nowotny, F. Benesovsky, Monatsh. Chem. 92 (1961) 967. [14] K. Yanigahara, T. Maruyama, K. Nagata, Metall. Mater. Trans. 12 (1993) 1200. [15] A. Arvantis, S. Diplas, P. Tsakiropoulos, J.F. Watts, M.J. Whiting, S.A. Morton, J.A.D. Matthew, Acta Mater. 49 (2001) 1063. [16] W.J. Boettinger, J.H. Perepezko, P.S. Frankwicz, Mater. Sci. Eng. A155 (1992) 33. [17] H. Nowotny, H. Kudielka, E. Parthe, Plansee Proceedings, 1955, p. 166. [18] A.J. Heron, G.B. Schaffer, Mater. Sci. Eng. A, in press. [19] C.J. Howard, R.J. Hill, AAEC Report no. M112, 1986. [20] R.A. Young (Ed.), The Rietveld Method, Oxford University Press, 1993.

The error in the absolute phase proportion is jpp;obs ( pp;calc j jSp;obs Zp Vp ( Sp;calc Zp Vp j 0 0 Rp pp;obs Sp;obs Zp Vp (A13)

' ( The upper, pp , and lower pp , limits of the corrected phase proportions for phase p , may be determined by

pp ? ;obs 0 pp ? ;calc 9 Rp pp ? ;obs p' p 0 p( p 0 pp ? ;calc (1 ( Rp ) pp ? ;calc (1 ' Rp )

(A14) (A15) (A16)

Considering the unobservable phase in Eq. (A7) the upper limit for the relative phase proportions may be calculated as fp' 0 pp ? ;calc pp ? ;calc ' pU ? '
n (1 ( R p ) X

(A17) pi?;calc

(1 ' Rp ) i"p