Journal of Materials Processing Technology 211 (2011) 16141619

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Journal of Materials Processing Technology

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A novel technique for development of A356/Al2 O3 surface nanocomposite by friction stir processing
Y. Mazaheri , F. Karimzadeh, M.H. Enayati
Department of Materials Engineering, Nanotechnology and Advanced Materials Institute (NAMI), Isfahan University of Technology, Isfahan 84156-83111, Iran

a r t i c l e

i n f o

a b s t r a c t
A356/Al2 O3 surface nanocomposite was produced by friction stir processing (FSP) method. X-ray diffractometery, optical and scanning electron microscopy, microhardness and nanoindentation tests were used to characterize the samples. The results indicated that the uniform distribution of Al2 O3 particles in A356 matrix by FSP process can improve the mechanical properties of specimens. The hardness and elastic modulus of the as-received A356, the sample treated by the FSP without Al2 O3 particles, surface microand nanocomposite specimens were about 75 Hv and 74 GPa, 69 Hv and 73 GPa, 90 Hv and 81 GPa, 110 Hv and 86 GPa, respectively. 2011 Elsevier B.V. All rights reserved.

Article history: Received 8 October 2010 Received in revised form 18 April 2011 Accepted 30 April 2011 Available online 8 May 2011 Keywords: A356 Surface nanocomposite Friction stir processing Nanoindentation

1. Introduction Conventional Al matrix composites (AMCs) reinforced with ceramic particulates, especially Al2 O3 exhibit high strength, hardness and elastic modulus (Tjong, 2007). AMCs are one of the advanced engineering materials that have been developed for weight-critical applications in the aerospace, and more recently in the automotive industries due to their excellent combination of high specic strength and better wear resistance as demonstrated (Surappa et al., 1982). AMCs have been widely studied since the 1920s (Sethi, 2007). A survey of the previous studies indicates that a homogenous dispersion of ne particles in a ne grained matrix is benecial to the mechanical properties of AMCs (Shorowordi et al., 2003). Dispersion of the nano-reinforcements in a uniform manner is a critical and difcult task. There are several methods to fabricate particulate reinforced Al or Mg based composites, including stir casting, squeeze casting, molten metal inltration, and powder metallurgy (Lee et al., 2006). It should be pointed out that the existing processing techniques for forming surface composites are based on liquid phase processing at high temperatures. In this case, it is hard to avoid the interfacial reaction between reinforcement and metal matrix and the formation of some detrimental phases. Furthermore, critical control of processing parameters is necessary to obtain ideal solidied microstructure in surface layer. Obviously,

Corresponding author. Tel.: +98 9173047580; fax: +98 3113912752. E-mail addresses: y.mazaheri@ma.iut.ac.ir, yoosef mazaheri64@yahoo.com (Y. Mazaheri). 0924-0136/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.jmatprotec.2011.04.015

if processing of surface composite is carried out at temperatures below melting point of substrate, these problems can be avoided. Recently, a lot of attention has been paid to friction stir processing (FSP) as a new surface modication technique (Su et al., 2005). Though FSP has been basically advanced as a grain renement technique, it can be readily used for fabricating surface composites. FSP induces intense plastic deformation and mixing of material in the processed zone in which the true strain can be as high as 40 (Ma, 2008). In this way, it is possible to incorporate the ceramic particles into the metallic substrate plate, to form the surface composites. Mishra et al. (2003) reported the rst result on the fabrication of AlSiCp surface composite via FSP. In this way SiC powder was added into a small amount of methanol and mixed, and then applied to the surface of Al plates to form a thin layer of SiC particle. The coated aluminum plates were then subjected to FSP. Additional research efforts were dedicated to fabricating the surface/bulk composites via FSP with improved particle predeposition methods. One of the methods is to produce one or two grooves along the FSP direction to pour the particles inside. Morisada et al. (2006a,b) reported the fabrication of SiC particles and multiwalled carbon-nanotubesreinforced AZ31 surface composites via FSP, using this method. With deeper grooves being cut, Lee et al. (2006) demonstrated a successful fabrication of bulk composites via FSP. More recently, Dixit et al. (2007) successfully dispersed nitinol (NiTi) particles in Al1100 matrix via FSP. They used four small holes drilled below the surface of the Al1100 plate to load the NiTi powders. Subjecting the powder-lled plate to FSP produced an Al1100/NiTi composite with improved mechanical properties. It is important to note that the fabrication of the surface/bulk composites is achieved under a solid-state condition. No interfacial reaction occurs between the

Y. Mazaheri et al. / Journal of Materials Processing Technology 211 (2011) 16141619 Table 1 Chemical composition of A356 bars. Element Composition (wt.%) Al Rem Si 7.44 Mg 0.44 Fe 0.26 Mn 0.07 Cu 0.05 Ti 0.02 Table 2 HVOF parameters for A356Al2 O3 composite powder. Parameters Oxygen ow rate Fuel gas ow rate Spray distance Powder rate Number of passes Unit l min l min1 mm g min1
1

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Value 750 175 350 35 3

reinforcing particles and the metallic matrix, and good interfacial bonding is achieved. According to above researches, surface composites were attempted by changing base materials, reinforced materials and processing way. However, some drawbacks have been revealed when each of these techniques are applied. The agglomeration of the reinforced particles especially in case of nanosized powder is the major limitation of these methods. To overcome this drawback, in this research a new technique was used to incorporate nano-sized Al2 O3 into A356 aluminum alloy to form particulate composite surface layer. The microstructure and mechanical properties of the composite surfaced layer were evaluated in details. 2. Experimental procedure

microscopy (SEM), transmission electron microscopy (TEM) micrographs and Corresponding selected area diffraction pattern (SADP) of as-received materials are shown in Fig. 1. A356 chips were irregular in shape with a size distribution of 200300 m. Microscaled (-Al2 O3 ) and nanoscaled alumina (nAl2 O3 ) powder particles had an angular and nearly spherical shape with a size distribution of 50100 m and 2040 nm, respectively. Several ring patterns and the absence of preferred orientation in the SADP conrmed that the used alumina particles are nanosized. See Fig. 1(c). 2.2. Samples preparation

2.1. Materials The specimens used for the FSP experiments were A356-T6 10 mm 50 mm 250 mm bars. The chemical composition of samples is given in Table 1. Residual machining chips of A356 and micro and nanosized -Al2 O3 powders with purity of 99.9% were used for producing A356/Al2 O3 composite powders. Scanning electron The A356 chips and Al2 O3 powder particles were mixed to achieve A3565 vol.% Al2 O3 composition. Mechanical milling was carried out in a high energy planetary ball mill (Retsch PM100), nominally at room temperature and under Ar atmosphere up to 12 h. The milling media consisted of twenty 20 mm diameter balls conned in a 500 ml volume vial. The ball and vial materials

Fig. 1. Morphology of: (a) A356 chips, (b) microsized alumina, (c) TEM image of nanosized alumina.

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Fig. 2. (a) Dimensions (in mm) and (b) picture of the FSP tool.

were hardened high carbon and chromium steels, respectively. Ball to powder weight ratio was 6:1 and rotation speed of vial was 300 rpm. The total powder mass was 200 g and 0.3 wt.% stearic acid was added as a process control agent (PCA). The as-milled powders were sieved in order to separate 2563 m fraction which is suitable for high velocity oxy-fuel (HVOF) spraying. The composite powders were deposited onto the grit blasted A356-T6 substrates by HVOF spraying (Metallization Met Jet III). The spraying parameters are presented in Table 2. Then plates with preplaced composite coatings were subjected to FSP. The FSP tool was made of H13 steel (Fig. 2). In all FSP experiments tool rotation rate, traverse speed and tilt of the spindle towards trailing direction were kept constant in this study to be 1600 rpm, 200 mm min1 and 2 , respectively. The concept of development of A356/Al2 O3 surface composites design in this study is schematically shown in Fig. 3.

2.3. Analysis techniques Cross-sectioning of the friction stir processed (FSPed) samples in planes perpendicular to the processing direction was performed for metallographic analysis. The samples were prepared according to standard metallographic practice and etched with Kellers reagent (1 ml 48% HF, 1.5 ml HCl and 10 ml nitric acid in 87.5 ml distilled water for 30 s). Transverse sections were examined by optical microscopy (OM) and SEM in a Philips XL30.

The phase composition of the as-received and as-milled powders were analysed by X-ray diffraction (XRD, Philips XPert-MPD) using Cu K radiation ( = 0.15406 nm) generated at 40 kV and 30 mA. The XRD patterns were recorded in the 2 range of 20100 (step size of 0.05 and time per step of 1 s). The hardness prole along the cross-section of FSPed samples was also determined by microhardness test using a Vickers indenter at the load of 100 g and dwell time of 5 s. The average of three measurements for each point was calculated and reported as microhardness value. The hardness and elastic modulus of as-received A356, FSPed sample (no Al2 O3 ) and surface composites were evaluated from the load-penetration depth curves obtained in nanoindentation tests using a nanoindentation tester (NHTX S/N: 01-03119, CSM Instruments) with a Berkovich diamond indenter (B-J87). This method is capable of measuring elastic moduli of the surface composites because of the relatively small volume being tested. Thus, any adverse effects of porosity, commonly obtained in bulk property measurements, can be avoided. Indeed, the properties measured from nanoindentation are the true properties of the surface composite layers. The indentations were made to a maximum load of about 70 mN and under loading and unloading rate of 140 mN/min. In order to take the repeatability into account, the test results were acquired from the average of four indentations. The hardness and elastic modulus were calculated by a standard procedure according to the method of Oliver and Pharr (1992).

Fig. 3. The concept of development design of A356/Al2 O3 surface composites.

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Fig. 4. The XRD patterns of as-received -Al2 O3 , A356 and as-milled A356Al2 O3 composite powders for 12 h.

3. Results and discussions 3.1. Structural evolution A356Al2 O3 composite powder was prepared by 12 h ball milling of A356 machining chips and nanosized as well as microsized Al2 O3 powder. The XRD patterns of powder particles as-received and after 12 h of milling time are shown in Fig. 4. The composites consist only of -Al2 O3 and A356 peaks. Because of the stability of alumina no other reaction product in the compositions

was found. So that after 12 h milling, Al2 O3 peaks was difcult to be detected due to the decrease in intensity and/or overlapping with higher intensity peaks related to A356. All the diffraction peaks from the A356 matrix are clearly seen; however, all the expected diffraction peaks of Al2 O3 are not clearly observed. In comparison to the diffraction peaks from A356, these peaks have a low intensity in the diffraction pattern, which is attributed to the low volume fraction of the Al2 O3 phase and the ne size of the powder in the A356Al2 O3 powder mixture. The as-milled powders were sieved in order to separate 2563 m fraction and used for spraying. Composite coatings were deposited by HVOF process on A356-T6 substrates. After 3 passes, a coating thickness of about 200 m was achieved. The coated specimens were then subjected to FSP. The friction stirred zones were typically about the size of the rotating pin, namely width and depth of 4 and 5 mm, respectively. Nanosized Al2 O3 particles were found to be distributed within this region due to the occurrence of vigorous stirring during the process. Fig. 5 shows the cross-sectional images of the coatings and surface composites. As can be observed in Fig. 5(a) and (c), micrographs of the coatings revealed good homogeneity and uniformity and high-quality contact with substrates. Fig. 5(b) and (d) shows optical micrographs of interface zone between surface composite layers and A356-T6 substrates after FSP. The surface composite layers appeared to be very well bonded to the aluminum alloy substrates, and no defects were visible. Fig. 6 shows SEM images obtained from the surface micro and nanocomposite fabricated by the FSP. The dark particles in Fig. 6(a) and (b) are the broken Si particles dispersed in the Al matrix and

Fig. 5. Cross-sectional microstructure of: (a) A356Al2 O3 composite coating, (b) A356/Al2 O3 surface microcomposite, (c) A356nAl2 O3 composite coating and (d) A356/Al2 O3 surface nanocomposite.

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Fig. 6. SEM micrograph of: (a) A356Al2 O3 and (b) A356nAl2 O3 surface composite.

Fig. 7. The hardness proles along the cross section of the FSPed A356-T6 (no Al2 O3 ) and surface composite layers. Fig. 8. Load versus penetration depth curves of as-received A356, FSPed sample (no Al2 O3 ) and surface composite layers.

the white particles are Al2 O3 particles identied using energy dispersive spectroscopy (EDS). 3.2. Mechanical characterization Fig. 7 shows the hardness prole along the crosssection of samples under the same FSP condition ( = 2 , 1600 rpm200 mm min1 ). The hardness prole was measured along the centerline of the cross-section of the processed zone. According to the previous microstructural results, the effect of FSP on the distribution of hardness on the any sample is justiable. The microstructure of FSPed samples are composed of four primary zones: the base metal (BM), the heat affected zone (HAZ), the thermo-mechanically affected zone (TMAZ) and the stir zone (SZ). The information presented in the publications (Chen and Kovacevic, 2003; Ma et al., 2003) indicate that, FSP generates sufciently high temperatures, at least in some locations, to affect re-solutionizing of the hardening phases in heat treatable Al

alloys reducing the hardness value. On the other hand FSP causes intense plastic deformation resulting in signicant microstructural renement of the processed zone increasing the hardness value. For the FSPed A356-T6 with no alumina powder, microhardness prole shows a general softening and reduction of hardness in the stirred zone in contrast to that of the as-received A356-T6 in spite of smaller grain size. The average hardness values of the BM and SZ were about 80 and 67 Hv, respectively. Others have also found that FSP had a softening effect on A356. As reported in literature studies (Ma et al., 2007, 2008), it seems that the softening of the stirred zone was result of dissolution of strengthening precipitates during FSP. In addition, the heat generated by FSP can increase the temperature of TMAZ and HAZ leading to the full/partial dissolution of the hardening precipitates in heat treatable alloys. Therefore, some softening could also take place in these zones. As can be seen the decrease in hardness for TMAZ and HAZ was

Table 3 Mechanical characterizations of as-received A356, FSPed sample (no Al2 O3 ) and surface composite layers using nanoindentation technique. Parameter Value As-received A356 HIT HV (nanoindentation) HV (microhardness) EIT 783 74.7 0.9 79.6 1.1 74 FSPed sample (no Al2 O3 ) 750 68.9 1.2 66.8 0.9 73 Microcomposite 978 89.6 1.4 89.8 2.6 81 Nanocomposite 1196 109.8 1.1 109.7 2.5 86 MPa Vickers Vickers GPa Dimension

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greater than SZ. The different extent of softening in HAZ and SZ depends on the temperature in each zone, which affects precipitate coarsening, resolution and re-precipitation. But it seems that the less softening in the SZ is due to the fact that SZ additionally includes grain renement effect. The average microhardness values for A356Al2 O3 and A356nAl2 O3 surface composites were about 90 and 110 Hv, respectively, which are higher than that of the as-received and FSPed A356-T6. The HV of the surface layer of aluminum substrates was signicantly enhanced with the incorporation of Al2 O3 particles, and increased as the Al2 O3 particle size was decreased. Al2 O3 particles increased the resistance of aluminum matrix to indentation. The increase in the hardness of the surface composite layer can be explained by the hardening effect of the dispersoids (pinning of dislocations and also of grain boundaries). The mechanical performances of nanoparticle reinforced AMCs are far superior to those of microparticle strengthened composites with a similar volume content of particulate (Tjong, 2007). Fig. 8 shows the loadpenetration depth curves for different samples obtained from nanoindentation test. The difference in hardness of the materials is apparent from the difference in the peak depth. It is clear from the graphs that the hardness of the composites is higher than that of the non-reinforced samples. The mechanical properties of samples obtained from the analysis of load/unload curves, are summarized in Table 3. As mentioned earlier, decreasing microhardness of FSPed sample in comparison with as-received A356 can be related to the precipitation dissolution. The A356/Al2 O3 surface composites showed better microhardness and elastic modulus values in comparison with as-received A356 and FSPed sample (no Al2 O3 ) due to presence of hard alumina particles. The possible strengthening mechanisms which may operate in particle-reinforced MMCs are (Lloyd, 1994): (1) Orowan strengthening. (2) Grain and substructure strengthening. (3) Quench hardening resulting from the dislocations generated to accommodate the differential thermal contraction between the reinforcing particles and the matrix. (4) Work hardening, due to the strain mist between the elastic reinforcing particles and the plastic matrix. According to the characteristics of the microstructure, the better mechanical properties of A356Al2 O3 nanocomposite can be attributed to (1) the nano grain size of the Al matrix following the classical Hall-Petch relationship, and (2) the Orowan strengthening due to the ne dispersion of Al2 O3 particles. This may be explained by the rule of mixtures, applied to composite materials (Dieter, 1976). The hardness values obtained by nanoindentation technique are in good agreement with values measured using Vickers hardness tester (Table 3). 4. Conclusions In the present investigation, the FSP technique has been successfully used for producing the A356/Al2 O3 surface composites.

From the experiments and analyses performed, some conclusions can be drawn: (1) The microstructural study of A356/Al2 O3 surface composite layers fabricated by FSP indicated that Al2 O3 particles were well distributed in the Al matrix, and good bonding with the Al matrix was generated. (2) The FSP with Al2 O3 particles obviously increased the microhardness of the substrates. The microhardness values for A356Al2 O3 and A356nAl2 O3 surface composite were about 90 and 110 Hv, respectively, while that of the sample treated by the FSP without Al2 O3 particles and the as-received A356 were about 67 and 80 Hv, respectively. (3) The results obtained from nanoindentation technique showed better microhardness and elastic modulus values for A356/Al2 O3 surface composites in comparison with as-received A356 and FSPed sample (no Al2 O3 ). (4) The better mechanical properties of A356/Al2 O3 surface nanocomposite can be attributed to the presence of nanosized Al2 O3 particles, which contribute signicantly to the strength through the Orowan mechanism. References
Chen, C.M., Kovacevic, R., 2003. Finite element modeling of friction stir weldingthermal and thermomechanical analysis. Int. J. Mach. Tools Manuf. 43, 13191326. Dieter, G.E., 1976. Mechanical Metallurgy, third ed. McGraw-Hill, Berlin. Dixit, M., Newkirk, J.W., Mishra, R.S., 2007. Properties of friction stir-processed Al1100-NiTi composite. Scr. Mater. 56, 541544. Lee, C.J., Huang, J.C., Hsieh, P.J., 2006. Mg based nano-composites fabricated by friction stir processing. Scr. Mater. 54, 14151420. Lloyd, D.J., 1994. Particle reinforced aluminium and magnesium matrix composites. Int. Mater. Rev. 39, 124. Ma, Z.Y., 2008. Friction stir processing technology: a review. Metall. Mater. Trans. A39, 642658. Ma, Z.Y., Pilchak, A.L., Juhas, M.C., Williams, J.C., 2008. Microstructural renement and property enhancement of cast light alloys via friction stir processing. Scr. Mater. 58, 361366. Ma, Z.Y., Sharma, S.R., Mishra, R.S., 2007. Microstructural modication of as-cast AlSiMg alloy by friction stir processing. Metall. Mater. Trans. A37, 33233336. Ma, Z.Y., Sharma, S.R., Mishra, R.S., Mahoney, M.W., 2003. Microstructural modication of cast aluminum alloys via friction stir processing. Mater. Sci. Forum 426432, 28912896. Mishra, R.S., Ma, Z.Y., Charit, I., 2003. Friction stir processing: a novel technique for fabrication of surface composite. Mater. Sci. Eng. A341, 307310. Morisada, Y., Fujii, H., Nagaoka, T., Fukusumi, M., 2006a. MWCNTs/AZ31 surface composites fabricated by friction stir processing. Mater. Sci. Eng. A419, 344348. Morisada, Y., Fujii, H., Nagaoka, T., Fukusumi, M., 2006b. Effect of friction stir processing with SiC particles on microstructure and hardness of AZ31. Mater. Sci. Eng. A433, 5054. Oliver, W.C., Pharr, G.M., 1992. An improved technique for determining hardness and elastic-modulus using load and displacement sensing indentation experiments. J. Mater. Res. 7, 15641583. Sethi, V., 2007. Effect of aging on abrasive wear resistance of silicon carbide particulate reinforced aluminum matrix composite, MSc Thesis, Univ. of Cincinnati. Shorowordi, K.M., Laoui, T., Haseeb, A.S.M.A., Celis, J.P., 2003. Microstructure and interface characteristics of B4 C, SiC and Al2 O3 reinforced Al matrix composite: a comparative study. J. Mater. Process. Technol. 142, 738743. Su, J.Q., Nelson, T.W., Sterling, C.J., 2005. Friction stir processing of large-area bulk UFG aluminum alloys. Scr. Mater. 52, 135140. Surappa, M.K., Prasad, S.V., Rohetgi, P.K., 1982. Wear and abrasion of cast Alalumina particle composites. Wear 77, 295302. Tjong, S.C., 2007. Novel nanoparticle-reinforced metal matrix composites with enhanced mechanical properties. Adv. Eng. Mater. 8, 639652.