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Materials Chemistry and Physics 113 (2009) 562566

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Materials Chemistry and Physics


journal homepage: www.elsevier.com/locate/matchemphys

A study on preparation of Mo0.6Ti0.2Zr0.02C alloy by mechanical alloying and hot isostatic pressing, and its characterization
S. Majumdar a, , I.G. Sharma a , S. Raveendra b , I. Samajdar b , P. Bhargava b , R. Tewari c
a b c

Materials Processing Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology, Powai, Mumbai, India Materials Science Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India

a r t i c l e

i n f o

a b s t r a c t
Mo0.6Ti0.2Zr0.1C alloy was prepared by mechanical alloying (MA) and subsequently consolidated by powder processing techniques. The pellets prepared from the ne size MA powder showed a high rate of densication during sintering in the temperature range of 13001500 C. Close to theoretical density was attained by hot isostatic pressing (HIP) at 1250 C and TEM studies revealed the uniform distribution of complex carbide precipitates (<100 nm) in the ne grain microstructure of the consolidated alloy. The alloy consolidated by HIP showed a high hardness of the order of 500 HK due to the presence of the carbides in the ne grain microstructure. 2008 Elsevier B.V. All rights reserved.

Article history: Received 7 April 2008 Received in revised form 2 June 2008 Accepted 3 August 2008 Keywords: Powder metallurgy Sintering Electron microscopy Carbides

1. Introduction Molybdenum base alloys such as Mo30W and TZM, TZC, etc. possess excellent creep and tensile properties beyond 1000 C. Better corrosion resistance against liquid metal (Pb or PbBi) and good high temperature properties make these alloys suitable as structural materials for advanced high temperature nuclear reactors [1,2]. Conventionally molybdenum base alloys are prepared through melting followed by casting. But it is very difcult to achieve compositional homogeneity in this approach. Mechanical alloying is the technique that allows production of homogeneous materials starting from blended elemental powder mixtures [3]. In the mechanical milling process elemental powders are repeatedly involved in collisions between milling tools [46]. Repeated welding and fracturing of the powder due to these collisions lead to the formation of alloy powder. Size reduction during milling also produces nanocrystalline materials during mechanical alloying [710]. However, consolidation of powder produced by MA is a necessary step for producing the alloy of full-density maintaining a ne grain structure. The powder processing techniques best suited for the purpose are hot isostatic pressing, spark plasma sintering, explo-

sive compaction, pressure-less sintering, explosive compaction, hot pressing, etc. [11]. Hot isostatic pressing is the most promising consolidation method for producing ne gain, uniformly dense bulk material by careful control of the temperature, isostatic pressure and processing time [12]. Not much of data is existent in the current literature on the phase formation of MoTiZrC base alloy systems by mechanical alloying followed by consolidation. The aim of the present investigation was to prepare Mo0.6Ti0.2Zr0.02C (wt%) alloy powder by mechanical alloying and subsequent consolidation by powder metallurgical techniques such as (i) compaction followed by sintering and (ii) hot isostatic pressing. X-ray diffraction (XRD), scanning electron microscopy (SEM), TEM and OIM analysis were conducted to characterize the alloy powder as well as the consolidated alloy.
2. Experimental procedure Initially high purity molybdenum metal powder (11.5 m) was prepared by hydrogen reduction of MoO3 at 900 C for 150 min. The Mo powder was mixed thoroughly with pure titanium, zirconium and graphite (C) powder of required quantities and of nearly similar size range and mechanically milled in a planetary ball mill (Insmart, Hyderabad, India). 10 mm diameter WC balls were used and ball to powder weight ratio (BPR) was maintained at 3:1. After charging the powder mixture, the vial was air tightened with the lid using O ring and clamped with the mechanical arm. Maintaining a milling speed of 400 rpm, the powder mixture was milled for a maximum period up to 120 h. The alloy powder produced after different milling time was characterized by XRD and SEM.

Corresponding author. Tel.: +91 22 25590183. E-mail address: sanjib@barc.gov.in (S. Majumdar). 0254-0584/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2008.08.013

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Fig. 3. Sintering behavior of pellets of (a) mixed and (b) mechanically alloyed powder.

and compaction process was performed by varying pressures up to 350 bar at 1250 C for 4 h. Density measurements (using Archimedean technique), XRD investigations, knoop hardness measurements and transmission electron microscopic studies were conducted for characterizing the consolidated alloy. Thin slices were cut from the alloy and 3 mm diameter TEM samples were prepared by optimizing jet thinning parameters as 30 V, 210 mA and 50 C using the electrolyte consisting of 20 vol% perchloric acid and methanol solution. Orientation imaging microscopic (OIM) studies were conducted after careful preparation of the sample metallographically and nal polishing for 4 h on colloidal silica.

3. Results and discussions


Fig. 1. XRD patterns of powder mixture, 20 h MA, 60 h MA, 120 h MA and HIP consolidated alloy.

3.1. Mechanical alloying Fig. 1 shows the XRD patterns of the parent powder mixture, mechanically alloyed powder and bulk alloy after consolidation by HIP. The peaks obtained from the powder mixture were due to the reections only from body centered cubic (bcc) molybdenum, because contents of Ti and Zr in the mixture were very low. As the alloying elements had the similar atomic size as that of Mo, no detectable shift on the Mo peaks occurred on the dissolution of the elements during MA. A gradual broadening of the

The powder processing techniques applied to study the consolidation behavior of both the parent powder mixture and mechanically alloyed powder are (i) cold uniaxial and isostatic compaction (CIP) followed by sintering between 1000 and 1800 C for 1 h in an atmosphere containing He 15 vol% H2 and (ii) hot isostatic pressing at 1250 C. For hot isostatic pressing (HIP), the preforms were made by CIP and subsequent heating at 950 C for 2 h under hydrogen ow for removing traces of oxygen from the 15 mm diameter green rods. The preforms were encapsulated under vacuum using thin stainless steel tubes. The capsules were placed inside the chamber

Fig. 2. SEM images of (a) as reduced Mo; (b) 60 h MA and (c) 120 h MA powder.

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XRD reections with higher milling time was observed due to both crystallite size renement and structural disorder accumulation processes occurred parallel to MA. Not a signicant difference in peak broadening was detected on increasing the duration of mechanical alloying from 60 to 120 h. The mean particle size and the mean lattice strains were calculated from the XRD data by applying WilliamsonHall method [13]. The mean lattice strain () of MA 20, 60 and 120 h powder were 0.9%, 0.79% and 1.15% and the mean powder diameters (d) were 714, 179 and 179 nm, respectively.

The actual powder size measured by SEM was 728, 325 and 233 nm, respectively indicating slightly higher value than that was obtained by WilliamsonHall technique. The reduction of mean lattice strain in MA 60 h compare to MA 20 h samples was due to the signicant reduction in crystallite size and recovery due to heating during milling. Not much of reduction in the particle size was observed between 60 and 120 h milled samples. As a result, an increase in the mean lattice strain was detected in MA 120 h samples. SEM images of powder before and after milling are presented in Fig. 2. As reduced molybdenum metal powder was spherical in

Fig. 4. TEM images of HIP alloy (a) bright eld image showing carbides; (b) dark bright-eld image; (c) selected area diffraction pattern showing rings: the inner ring r1 and r3 for (0 0 2) and (1 0 1) of (Mo0.54 Ti0.46 )C, r2 and r5 for (0 4 0) and (1 7 1) of (Mo0.72 Ti0.28 )C and r4 and r6 for (1 1 0) and (2 0 0) of Mo matrix and (d) dark eld image showing ne grains with precipitates.

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morphology and average powder size was 11.5 m (Fig. 2a). MA 60 and 120 h powder are shown in Fig. 2(b and c), respectively. Apart from slightly higher agglomeration tendency of MA 120 h powder, no signicant size difference is evident from the gures. After milling for this much of time, steady-state equilibrium is attained when a balance is achieved between the rate of welding and the rate of fracturing. Smaller particles are able to withstand deformation without fracturing and tend to be welded into larger pieces, with an overall tendency to drive both very ne and very large particles towards an intermediate size [14]. 3.2. Compaction and sintering The green densities of uniaxially compacted pellets prepared from the parent powder mixture and MA 120 h powder were 76% and 62% of the theoretical density (10.16 g cc1 ), respectively. The alloy powder was hard and brittle producing a lower green density although having a much lower particle size (233 nm) than the parent powder (11.5 m). Fig. 3 represents the densication behavior of both types of pellets during sintering between 1000 and 1800 C for 1 h in reducing atmosphere. Because of lower particle size the rate of densication of the alloy powder compact was much higher in the intermediate temperature range (13001500 C). This could be due to the availability of higher specic surface area and faster grain boundary diffusion in this temperature range. The sintering kinetics was much slow beyond this temperature for both the pellets. A maximum of 97.7% of the theoretical density was attained on sintering at the highest attempted temperature of 1800 C. 3.3. Hot isostatic pressing The density better than 99.9% of the theoretical value (10.16 g cc1 ) was achieved by hot isostatic pressing of the compact prepared from the alloy powder. Only 92% densication was observed for the parent powder under the application of same isostatic pressure of 350 bar. Therefore, the powder size reduction from 1 to about 0.23 m increased the densication rate producing near theoretical (100%) density by hot isostatic pressing at the temperature as low as 1250 C. XRD peaks (Fig. 1) obtained from the consolidated alloy were much sharper than those of

milled powder due to decrease in mean lattice strain at high temperature. Fig. 4(a) and (b) is the bright eld and the dark eld TEM images obtained from the jet thinned foil of hot isostatically pressed alloy showing uniform dispersion of second phase precipitates in the matrix. Diffraction rings (Fig. 4c) obtained from the selected area presented in the dark eld image are from (0 0 2), (1 0 1) of hexagonal (Mo0.54 Ti0.46 )C, (0 4 0), (1 7 1) of orthorhombic (Mo0.72 Ti0.28 )C and (1 1 0), (2 0 0) of Mo matrix. Initially diffraction patterns from the matrix and the different carbide phases were captured by properly adjusting the electron beam. The diffraction patterns from the individual phases were indexed and analyzed to detect the matrix (Mo) and carbides. The diffraction rings in Fig. 4(c) were indexed accordingly. Hence a mixture of complex molybdenumtitanium carbides was formed in the molybdenum matrix during the mechanical alloying. Formation of the complex carbides is a thermodynamically feasible process. The size of the carbide precipitates ranged from 40 to 100 nm. The complex carbide precipitates improving the creep strength of the arc consolidated TZM alloy was reported earlier [15]. Fig. 4(d) is a dark eld image showing the overall microstructure containing ne grains and carbide precipitates. The grains were not perfectly equiaxed in nature and the average grain size varied between 1 and 1.5 m indicating a little grain growth. During the consolidation process, the material was exposed to 1250 C for certain time that led to grain growth. As the grain growth is a diffusional phenomenon and diffusion coefcient decreases with pressure [16], the grain growth is restricted in hot isostatic pressing due to simultaneous application of high pressure at elevated temperature. The absence of voids or pores inside the grains, grain boundaries and interfaces between the carbide particle and matrix indicated the achievement of near theoretical density by HIP. The alloy was further annealed at 1700 C for 1 h under reducing atmosphere. The average knoop hardness values measured at 0.98 N loads for hot isostatically pressed and annealed alloy were 500 HK and 352 HK, respectively. The hardness of the annealed alloy was higher than that reported for the arc consolidated TZM alloy [15] whereas the hot isostatically pressed alloy exhibited the hardness value comparable with that of MoSiB alloy possessing superior high temperature strength [15]. Higher

Fig. 5. EBSD images along with inverse pole gures of (a) HIP and (b) HIP and annealed alloy samples.

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hardness of the alloy consolidated by HIP was a combined consequence of precipitation hardening and formation of ne grain structure. Electron back scattered diffraction (EBSD) images of as consolidated alloy are presented in Fig. 5(a). The black areas appeared in the image are from the no-indexed grains. Color code and inverse pole gure indicate the orientation of the grains along different directions. Fig. 5(b) represents the EBSD image of the annealed alloy. A signicant amount of grain growth was observed and average grain size was 7.027 m. The lower hardness of the annealed alloy compared to that of the hot isostatically pressed alloy was due to the grain growth during annealing. 4. Conclusions Mo0.6Ti0.2Zr0.02C alloy was prepared by mechanical alloying. Faster sintering kinetics of the compact prepared from ne size alloy powder was observed between 1300 and 1500 C. HIP produced the alloy having near theoretical density and uniform distribution of mixed carbides in a ne grain microstructure. A high hardness of the order of 500 HK was observed for as consolidated alloy, while a lower hardness of 352 HK was detected for the annealed alloy due to grain coarsening.

Acknowledgements The authors wish to thank Dr. Ritu (WIP) and Mr. R. Fotedar (MPD) of Bhabha Atomic Research Centre for their valuable support in performing HIP experiments. References
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