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Microstructure characteristics of Al2 O3 13 wt.% TiO2 coating plasma spray deposited with nanocrystalline powders
Jianxin Zhang , Jining He, Yanchun Dong, Xiangzhi Li, Dianran Yan
School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China

a r t i c l e
Article history:

i n f o

a b s t r a c t
Nanostructured Al2 O3 13 wt.% TiO2 coating was fabricated by plasma spray with nanocrystalline powders and the microstructures of the feedstock and the coating were characterized by means of XRD, SEM and TEM. It was found that three forms of substructure existed in the coating: one evolving from the unmelted part of the feedstock and showing a roundshaped morphology; one resembling the liquid-phase-sintered structure consisting of the attened partially melted region and fully melted region; another being of the particulatereinforced-solid solution type with ne particles distributed in the matrix. The TEM analysis

Received 3 June 2006 Received in revised form 13 March 2007 Accepted 3 June 2007

Keywords: Nanostructured coatings Microstructure Al2 O3 TiO2 coating Plasma spray

revealed that partially melted -Al2 O3 particles were in the size range of 2070 nm and were embedded in the TiO2 -rich matrix. The mechanism of the substructure formation was also explained in terms of the melting and attening behavior of the powders during plasma spray processing. 2007 Elsevier B.V. All rights reserved.

1.

Introduction

Plasma sprayed ceramic coatings are widely used to protect metallic structural components from corrosion, wear and thermal resistance. Among ceramic coatings, the coatings made of Al2 O3 13 wt.% TiO2 are most commonly employed. In the conventional plasma spray processing, Al2 O3 13 wt.% TiO2 coatings are produced with micron-sized feedstock powders, typical of 20100 m in size and show a layered microstructure containing columnar grains of 100400 nm in diameter and 15 m in length (McPherson, 1981; Bennett and Poulikakos, 1993). In recent years, fabrication of nanostructured ceramic coatings using nanocrystalline powders has become more attractive technologically, because of their excellent properties compared with the conventional counterparts (Karthikeyan et al., 1997; Kear et al., 2000; Wang et al., 2000; Marple et al.,

2000; Gell et al., 2001; Jordan et al., 2001; Lima and Marple, 2005). Different to the conventional coatings, the nanostructured coatings exhibited a distinctive microstructural feature, consisting of unmelted or partially melted (PM) regions and fully melted (FM) regions (Shaw et al., 2000; Lima et al., 2001; Chen and Ding, 2002; Goberman et al., 2002; Lima et al., 2002; Lin et al., 2005). It has been revealed that the nanostructure existing in the PM region was evolved from the non-melted particles and the nanostructure in the FM region was resulted from the molten part of the nanostructured feedstock due to the rapid cooling rate and the nucleation rate (Lima et al., 2001). It is believed that the unique bimodal microstructure contributed to the signicantly enhanced mechanical properties of the nanostructured coatings (Jordan et al., 2001; Bansal et al., 2003). In the present study, nanostructured Al2 O3 13 wt.% TiO2 coating was prepared by atmosphere plasma spraying

Corresponding author. Tel.: +86 22 26564130; fax: +86 22 26564581. E-mail address: zjxhut@126.com (J. Zhang). 0924-0136/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jmatprotec.2007.06.001

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j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 7 ( 2 0 0 8 ) 3135

nanocrystalline feedstock powders and the microstructure of the coating was investigated using SEM and TEM. The microstructural characteristics of the as-sprayed coating were presented and the mechanism of the structure formation was discussed.

Table 1 Plasma spraying parameters used in the study

Spray power (kW) Ar gas ow rate (L/min) H2 gas ow rate (L/min) Powder carrier gas rate (L/min) Gun distance (mm) 3538 85 100120 5 100

2.

Experimental procedure
microscope and a Philips TECNAI-F20 transmission electron microscope.

Commercially available Al2 O3 and TiO2 nano-sized particles of 50110 nm were used as starting materials in the study. Sprayable powders were obtained by spray drying of the slurry containing the nanoparticles in the weight ratio of Al2 O3 13 wt.% TiO2 , and subsequently sintered in the temperature range of 10001200 C. Mild steel substrate samples of 9 mm 8 mm 10 mm were grit-blasted and then coated by plasma spraying Ni/Al powders to form a bonding layer about 100 m thick. The nanostructured Al2 O3 13 wt.% TiO2 coating was deposited by plasma spray using the agglomerated powders and the coating thickness was about 300 m. The plasma spray was carried out on a LP-50B spray system and the parameters used are given in Table 1. The agglomerated nanostructured powders and plasma-sprayed coating were characterized using a PHILIPS X-PertMPD Xray diffractometer, a PHILIPS XL30/TMP scanning electron

3.
3.1.

Results and discussion

Powder characterization

Fig. 1 shows the morphology and X-ray diffraction pattern of the resultant powders after spray drying granulation and sintering treatment. It is seen that the agglomerated powders exhibited well granular and their size ranged from 20 m to 50 m. A high magnication scanning electron micrograph (Fig. 1b) demonstrated that the grain size in the nanostructured granules was about 100 nm and slight necking existed between nanoparticles due to sintering effect, which improved the strength of the connection between nanoparti-

Fig. 1 (a) SEM micrograph of the agglomerated powders, (b) the nanostructured feature and (c) the XRD pattern.

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Fig. 2 SEM micrographs showing: (a) the overall nanostructured coating, (b) the liquid-phase-sintered substructure, (c) the substructure resembling the feedstock powder and (d) the substructure of particulate-reinforced-solid solution.

cles necessary for plasma spraying. The XRD pattern of the agglomerated Al2 O3 13 wt.% TiO2 powders is shown in Fig. 1c. In the heat-treated nanostructured powders, Al2 O3 had the same structure as the raw material and TiO2 changed from anatase to rutile due to an irreversible phase transition occurring at 610 C.

3.2.

Microstructure of the coating

Fig. 2a is a representative cross-sectional SEM micrograph of the Al2 O3 13 wt.% TiO2 nanostructured coating at a relative low magnication. The nanostructured coating had a lamellar composite microstructure, which consisted of not only fully melted splat lamellae but also partially melted regions within splats. This is consistent with what was observed in earlier studies on nanostructured coatings produced using nanocrystalline feedstock (Gell et al., 2001; Jordan et al., 2001; Shaw et al., 2000; Goberman et al., 2002; Lima et al., 2002). It was found through further observations that there were three kinds of substructures presented in the sprayed coating. The major substructure observed in the sprayed nanostructured coating is as shown as in Fig. 2b. It is seen that the attened partially melted region and fully melted region were alternately

built-up to exhibit a layered feature and in some areas the two regions were mixed together without distinct boundaries. This substructure resembled very much the microstructure of liquid-phase-sintered ceramics. On the other hand, the partially melted region in this substructure seemed denser than the feedstock powders (Fig. 1b). Fig. 2c shows the substructure of the partially melted region with a rounded or near spherical morphology, as indicated by the arrow in the gure, surrounded by the fully melted region. This partially melted region showed microstructural characteristics very similar to the agglomerated feedstock. Another substructure of the particulate-reinforced-solid solution type was also observed in the coating, as shown in Fig. 2d. It can be seen that the fully melted region offered a matrix and very ne particles were dispersedly distributed in the matrix phase. Fig. 3 shows a bright-eld TEM image of the PM region in the nanostructured coating and the corresponding EDS spectra from the partially melted particles and the surrounding matrix. It is seen that partially melted particles of about 70 nm in size were embed in the matrix and besides there existed more particles in smaller sizes as pointed by the arrows. These nanoparticles were pure Al2 O3 according to the EDS result, where merely Al and O appeared. In addition to the elements

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In order to introduce nanostructure into thermal-sprayed coatings, it is necessary to use nanostructured powders, usually obtained by agglomeration of nano-sized particles, and to control the plasma conditions to ensure parts of the nanostructure to be retained in the coating. Compared with the conventional powders, the nanostructured powders have a low thermal conductivity and the melting behavior of each individual powder may be different, depending on its size and trajectory in the plasma jet (Lima et al., 2001). Fig. 4 gives a schematic illustration of the melting of the nanostructured powders during plasma spraying and the resultant substructures corporated in the coating. On injected into plasma jet, some of the nanostructured powders can enter into the hottest plasma region and fully melt, resulting in a structure akin to that of the conventional coatings, as demonstrated as the case A in Fig. 4. Besides, there are some powders being melted to such an extent that only their outer portion turns to liquid and the inner remains unmelted. On impacting onto the substrate or previously deposited splats, the liquid shell of these powders tries to atten, but their solid core (i.e. unmelted portion) can be scarcely shaped, see the case B in Fig. 4, thus forming a substructure with a rounded unmelted region surrounded by crystals transformed from liquid, as observed as in Fig. 3c. It is obvious that this unmelted region preserved in the coating holds the microstructural features of the nanostructured feedstock powders. If some of the low melting-point components in the center of the nanostructured powders are melted, but the high melting-point ones cannot, e.g. TiO2 and Al2 O3 respectively in

Fig. 3 (a) TEM micrograph showing the partially melted particles in the PM region and (b) the corresponding EDS spectra from the nanoparticles and surrounding matrix.

Al and O, Ti was also detected in the matrix phase and therefore the matrix must be TiO2 -rich compared with the fully melted regions because of some incompletely melted Al2 O3 retained.

3.3.

Mechanism of the substructure formation

Plasma spray processing is associated subsequently with the injection of feedstock powders into plasma jet, rapid melting and acceleration during their passage through the jet, impact on a substrate and quick solidication to form a coating. The coating such produced is composed of successively deposited splats, the detailed shape of which is determined by the surface tension, density, viscosity and velocity of the liquid droplets (McPherson, 1981). Traditional plasma spraying uses non-nanostructured feedstock powders and the spraying parameters are controlled in such a condition that the powders propelled into the plasma jet are completely melted. On impact, the liquid droplets atten and solidify successively to thin disks and the attening process of the liquid stream results in a layered microstructure of the coating with columnar grains.

Fig. 4 A schematic illustration of the melting of the nanostructured powders during plasma spraying and resultant substructures in the coating.

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our study, the liquid-phase-sintering effect will occur inside the powders during ying in the plasma jet, which is illustrated as the case C in Fig. 4. The attening degree of the powders on impacting onto the substrate is closely related to the degree of the liquid-phase sintering, which determines the deformability of the partially melted powders. Fig. 3b shows the actual substructure produced in this way in the nanostructured coating. Concerning the formation of the particulate-reinforced-matrix substructure, it is thought that the particles in ne size are remains of the incompletely melted Al2 O3 and have been separately distributed within a droplet before reaching the substrate (the case D in Fig. 4). This situation can happen in the feedstock powders with a smaller diameter and a relative higher content of TiO2 and/or may occur in the outer portion of a droplet with an unmelted solid core.

4.

Conclusions

The microstructural characteristics of the plasma sprayed nanostructured Al2 O3 13 wt.% TiO2 coating were investigated in this paper. The results demonstrated that the nanostructured coating exhibited a layered composite structure consisting of the PM region and FM region. Three substructures were observed in the coating. The liquid-phase-sintered substructure was composed of the attened PM region and FM region which were alternately built-up. The substructure of the unmelted part of the feedstock powder had a rounded shape and a microstructural feature of the agglomerated powders. The liquid-phase-sintered substructure consisted of the TiO2 -rich matrix phase and the partly melted Al2 O3 particles distributed within the matrix. The partly melted Al2 O3 particles were nano-sized ranging from about 20 nm to 70 nm. The formation of the substructures is closely related to the melting state of the feedstock powders during ying in the plasma jet and the attening degree on impacting onto the substrate.

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