Scripta Materialia 56 (2007) 10631066 www.elsevier.

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Eect of sintering temperature on the electrochemical, hardness and tribological properties of aluminide-reinforced austenitic stainless steel
S. Balaji, P. Vijay and A. Upadhyaya*
Department of Materials and Metallurgical Engineering, Indian Institute of Technology, Kanpur 208016, UP, India
Received 30 November 2006; revised 19 February 2007; accepted 21 February 2007 Available online 26 March 2007

The present study investigates the eect of aluminide (Fe3Al and Ni3Al) addition and sintering temperature on the densication, hardness, wear and electrochemical behavior of austenitic (316L) stainless steels. As compared to solid-state sintering (1200 C), supersolidus sintering (1400 C) improves the overall performance of both straight 316L as well as 316Laluminide composites. The addition of Ni3Al and Fe3Al to 316L stainless steels improve the mechanical and wear properties without any signicant degradation of corrosion resistance. 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Stainless steels; Sintering; Corrosion; Intermetallics; Wear

The applications of sintered stainless steels are limited by their inferior strength and resistance to wear and corrosion as compared to their wrought and cast counterparts. To enhance the mechanical and tribological properties of the P/M austenitic stainless steels, hard dispersoids such as Al2O3 and SiC have been reinforced and their benecial behavior has been reported by various researchers [1,2]. However, the major drawback of these composites is their inferior densication and corrosion behavior as compared to straight stainless steels which is due to the poor interaction between the matrix and reinforcements. Recently, Shankar et al. [3] have reported that addition of Y2O3 marginally increases the densication of 316L stainless steel compacts. This nding was attributed to the interaction of Cr2O3 with the Y2O3 dispersoids. Subsequent analysis revealed no signicant degradation of the corrosion resistance in 316LY2O3 composites as compared to straight 316L compacts. More recently, Jain et al. [4] too have reported similar observations in YAG-added austenitic (316L) and ferritic (434L) stainless steel composites. Extensive interaction between the intermetallic reinforcements (TiAl, Cr2Al, and TiCr2) and the 316L stainless steel matrix have been reported elsewhere as well
* Corresponding author. Tel.: +91 512 2597672; fax: +91 512 2597505; e-mail: anishu@iitk.ac.in

[5,6]. Based on salt fog tests, Abenojar et al. [6] reported an enhanced corrosion resistance for the Cr2Al reinforcements as compared to oxide and carbide additives in solid-state sintered 316L stainless steel. In recent years, the use of prealloyed stainless steel powders has lent itself to consolidation at higher temperatures through supersolidus liquid phase sintering (SLPS) [7]. Panda et al. [8] reported the onset of melt formation for the prealloyed 316L powder as 1383 C based on dierential scanning calorimetry results. Correspondingly, the supersolidus sintering was carried out at 1400 C and its benecial eects on the densication and corrosion behaviour of particulate-reinforced stainless steel composites have been reported by various researchers [3,9]. The eect of aluminide (Ni3Al and Fe3Al) additions and supersolidus sintering on the densication and corrosion performance of sintered ferritic (434L) stainless steels has recently been detailed [10]. The present work investigates the densication and corrosion response of austenitic (316L) stainless steel aluminide composites along with their mechanical and tribological response. The prealloyed 316L (C: 0.025; Si: 0.93; Mn: 0.21; Ni: 12.97; Cr: 16.5; Mo: 2.48; S: 0.008; P: 0.01; Fe: bal.) stainless steel powders (Ametek Speciality Metal Products, Eighty Four, PA) were mixed with 5 wt.% and 10 wt.% aluminide powders (Ni3Al and Fe3Al) of more than 99.7% purity (Xform Inc., Cohoes, NY), in a

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turbula mixer for 30 min. The uniaxially compacted (at 600 MPa) green compacts were sintered at 1200 C (solid-state sintering) and 1400 C (SLPS) in hydrogen atmosphere (dew point 35 C) for 1 h. The densities were determined from dimensional and weight measurements. The theoretical densities (qth) of the aluminideadded composites were calculated using the inverse rule of mixtures. The green density variation for the aluminide additions is minimal (83 0.2% qth). Table 1 summarizes the sintered density variation of the straight 316L and its aluminide-added composites with sintering temperature. For all compacts, supersolidus sintering at 1400 C results in higher densication as compared to the solid-state sintered samples. Interestingly, the addition of aluminides does not signicantly degrade the sintered density of 316L. In fact, a marginal increase in sintered density was observed for some of the aluminide-added composites; this can be attributed to the interdiusion observed across the 316Laluminide interface at higher sintering temperatures [11]. This is in contrast to the results reported for the other reinforcements [1,2]. Figure 1 shows the optical micrographs of straight and aluminide-reinforced 316L stainless steels sintered at two dierent temperatures. Figure 1a compares the optical micrographs of straight 316L stainless steel sintered at 1200 and 1400 C. Clearly, the porosity level in the straight stainless steels sintered at 1200 C was higher when compared to 1400 C sintered compacts. This correlates with the densication results shown in Table 1. The solid-state sintered stainless steels contain mostly irregular, intergranular pores. In contrast, at higher temperatures microstructural coarsening is observed and the pores are more predominantly intragranular and more rounded. In the case of the aluminide-added composites, the matrix porosity is similar to that of straight stainless steels in both the sintering conditions. From the microstructure it is evident that Ni3Al and Fe3Al retain their identity and appear as distinct phases surrounded by a dark rim. The EDAX analysis at the dark rim portion (316Laluminide interface) conrmed the formation of oxides of aluminium [11].

Figure 1. Optical micrographs of (a) 316L (b) 316L5Ni3Al and (c) 316L5Fe3Al compacts sintered at 1200 C (left) and 1400 C (right). The dark arrows indicate the porosity and the white arrows indicate the respective aluminides.

Table 1. Eect of sintering temperature and aluminide addition on the densication, bulk hardness and specic wear rate of austenitic (316L) stainless steel Sample Sintering temperature (C) 1200 1400 1200 1400 1200 1400 1200 1400 1200 1400 SDa (%) qth 85.8 89.7 85.0 87.5 83.9 90.8 82.6 91.7 80.4 91.4 Bulk hardness (HV5) 98 0.6 102 0.9 111 2.1 102 3.0 112 1.0 122 0.6 106 1.0 131 3.2 90 0.4 124 2.5 Specic wear rate 103 (mm3 N1 m1) 1.7 1.4 1.22 0.41 1.8 0.82 1.83 0.93 1.89 0.69

Straight 316L 316L5Ni3Al 316L10Ni3Al 316L5Fe3Al 316L10Fe3Al

a

Similar observation was also reported by Abenojar et al. [6] for 316L3 vol.% Cr2Al when sintered at 1230 C in hydrogen atmosphere. The bulk hardness of the polished surfaces was measured using a Vickers Hardness Tester (HPO-250, Fritz Heckert, Leipzig, Germany) at 5 kg load. The dry sliding wear behavior of the sintered composites was assessed using a pin-on-disc type wear-testing machine (TR-20, DUCOM, Bangalore, India) against a hardened steel disc (EN31) at a sliding velocity of 1 m s1. Specic wear rate was calculated after 1000 m of sliding using the following expression: Dh A ; 1 F S where Dh is the depth wear loss (mm), A is the apparent contact area (mm2), F is the applied normal load (N) and S is the sliding distance (m). The results of the hardness and wear testing are summarized in Table 1. The increase in bulk hardness of the compacts with increase in sintering temperature is attributed to better densication Specific wear rate mm3 N1 m1

SD, sintered density.

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at higher temperatures. As compared to straight stainless steel, the aluminide-added composites exhibit marginally higher hardness. The addition of both Ni3Al and Fe3Al to 316L stainless steels increases the bulk hardness of the stainless steels. This eect is attributed to the higher hardness of the dispersoid particles. As the sintering temperature increases, the specic wear rate decreases. The addition of both Ni3Al and Fe3Al to 316L stainless steel improves the wear resistance. This is in direct correlation with the reported bulk hardness values. For electrochemical evaluation, the potentiodynamic polarization studies were conducted in freely aerated 0.1 N H2SO4 at a constant scan rate of 1 mV s1 at room temperature using a at cell with standard three-electrode (reference, counter and working) conguration. The reference electrode used for the present experiment was a saturated calomel electrode (SCE) with saturated KCl and the sintered compact was used as the working electrode. A platinum mesh acted as a counter electrode. The pH of the electrolyte was measured using a digital pH meter (MK IV, Systronics, India) and was found to be 1.31. The electrochemical experiments were performed using a potentiostat (PC4, Gamry Instruments, Inc., Warminster, PA) on a CMS100 Framework. Prior to the polarization test, each sample was stabilized for about 3600 s in solution to get a stable open circuit potential (OCP). The cathodic and anodic polarization scans for the straight 316L and aluminide-added composites sintered at 1200 and 1400 C are presented in Figure 2a and b, respectively. Interestingly, straight 316L and all supersolidus sintered compacts exhibit activepassive transition, whereas this was absent in the aluminide-added composites sintered at 1200 C. However, a limit-like current density was discerned in these compacts over a range of potentials at about 25 mA cm2. From the potentiodynamic polarization curves (Fig. 2), the values of critical current density (Icrit), primary passivation potential (Epp), passivation current density (Ipass) and trans-passive potential (Etp) were determined and are presented in Table 2. In comparison, the critical and passivation current densities were relatively more sensitive to the composition and sintering temperature. In case of 1200 C sintered aluminideadded composites, the limit current density was assumed as Ipass. Both Icrit and Ipass increase with an increase in

Figure 2. Potentiodynamic polarization curves for 316L compacts with varying aluminide additions and sintered at (a) 1200 C and (b) 1400 C.

the aluminide content for the solid-state sintered compacts. This indicates that higher porosity (in 1200 C sintered compacts) has overridden any benecial eect of Fe3Al and Ni3Al on the electrochemical response. In contrast to solid-state sintering, the compacts sintered at higher temperature (1400 C) under supersolidus conditions exhibit critical and passivation current densities that are an order of magnitude lower. This is due to the lower porosity levels, which, in turn, decrease the surface area exposed to the corrosive electrolyte. Similar

Table 2. Eect of Ni3Al and Fe3Al addition and sintering temperature on the corrosion results of 316L stainless steels Sample Straight 316L 316L5Ni3Al 316L10Ni3Al 316L5Fe3Al 316L10Fe3Al Temperature (C) 1200 1400 1200 1400 1200 1400 1200 1400 1200 1400 Ecorr (mV) 354 337 370 282 368 323 407 362 417 410 Icrit (lA cm2) 1809 294 2463 66 3131 167 2463 583 3437 332 Epp (mV) 98 213 49 195 122 195 158 195 103 159 Ipass (lA cm2) 550 105 2638 17 1872 123 3200 221 3437 309 Etp (mV) 829 847 700 847 900 847 1171 847 829 847 bc (mV dec1) 384 152 156 161 274 214 206 146 227 250 Icorr (lA cm2) 217 22 96 10 234 30 123 13 278 115 Corrosion rate (mmpy) 2.30 0.24 1.02 0.11 2.50 0.32 1.32 0.15 3.00 1.25

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observations on the eect of higher sintering temperature on the Icrit have been reported elsewhere [12]. There is signicant lowering of Ipass for Ni3Al additions and a marginal increase for Fe3Al additions. The slight increase in Ecorr for the supersolidus temperature indicates its noble behavior as compared to the solid-state sintered compacts of similar compositions. Icorr is measured by extrapolating the linear segments of the cathodic curve and intersecting this extrapolated line with a line drawn from Ecorr parallel to the current density axis [13]. The extrapolation results obtained from the polarization curves are summarized in Table 2. There is a signicant dierence in the Icorr values between the samples sintered at 1200 and 1400 C. Icorr is representative of the corrosion kinetics. Thus, the lower values of Icorr at higher temperature indicate better corrosion resistance in supersolidus sintered samples. The addition of both Ni3Al and Fe3Al results in lower values of Icorr as compared to the straight 316L stainless steels sintered at same conditions. As the amount of aluminides increases, the Icorr increases. Aluminide-added (5 wt.%) composites showed better corrosion resistance than the straight 316L stainless steels. The same trend is also retained in the corrosion rate. For the sintered compacts, the corrosion response was measured over a cross-sectional area of 1 cm2. Most P/M components are typically small and, as compared to conventional casting, sintered microstructures are more homogeneous. Hence, the cross-sectional area over which the corrosion rates were measured gives a good idea about the inuence of alloying additives and porosity on the electrochemical response. Elsewhere, for other sintered multicomponent systems too, potentiodynamic polarization has proven to be an eective technique [1416]. In summary, densication of straight as well as aluminide-reinforced 316L stainless steels increases with

increasing sintering temperature. Irrespective of the aluminide reinforcement and its content, supersolidus sintering enhances both wear and corrosion resistance. As compared to straight 316L compacts, 5 wt.% Ni3Al and Fe3Al-added 316L composites showed a marginal improvement in corrosion and sliding wear resistance.
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