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Thin Solid Films 388 Ž2001.

208᎐212

Interfacial phenomena in the plasma spraying Al 2 O 3 q 13 wt.%


TiO 2 ceramic coating

Yang YuanzhengU ,a , Liu Zhiguo a , Liu Zhengyi b , Chuang Yuzhi b


a
Faculty of Materials and Energy, Guangdong Uni¨ ersity of Technology, Guangzhou, 510090, PR China
b
Department of Mechanical and Electronic Engineering, South China Uni¨ ersity of Technology, Guangzhou, 510461, PR China

Received 15 January 2000; received in revised form 20 December 2000; accepted 19 January 2001

Abstract

The interface between the bond layer and ceramic layer as well as between the bond layer and the substrate in a duplex coating
system consisting of a NiCrAl bond coat layer and an Al 2 O 3 q 13 wt.% TiO 2 ceramic coat layer has been investigated by
scanning electron microscopy and transmission electron microscopy. The lamellar bond layer mainly consists of lamellae aligning
approximately parallel to the substrate surface, in which the individual lamellae consist of a thin outer amorphous and
nanocrystalline film, an intermediate layer of fine columnar and equiaxed grains and an inner microcrystalline region of big
columnar grains. The morphology of the interfacial regions of the above two interfaces is shown to be similar and consists of a
thickness of 0.7 ␮m, or far less, of a mixture of amorphous and nanocrystalline phases. However, besides a certain percentage of
area of perfect contact, a small amount of area of non-contact has also been detected among the lamellae or at the interfaces.
䊚 2001 Elsevier Science B.V. All rights reserved.

Keywords: Aluminium oxide; Coating; Interfaces; TEM

1. Introduction microscopy ŽTEM. w6,7x due to the difficulty in prepara-


tion of the specimens for TEM observation. In this
Plasma spraying has been widely used to obtain paper, the microstructure of the bond layer and the
ceramic coatings to strengthen the surface of metal characteristics of interface between the bond layer and
substrates w1,2x. However, to a certain degree, the low the substrate as well as between the bond layer and
adhesion between ceramic coating and the substrate ceramic layer in the Al 2 O 3 q 13 wt.% TiO 2 coating
and the low cohesion within the coating seriously re- have been reported.
strict the applications of plasma sprayed ceramic coat-
ing w2,3x. Therefore, it is necessary to understand fully 2. Experimental procedures
the nature of bonds within the coating and between the
coating and the substrate. However, studies of the The starting materials used in this investigation were
interfacial microstructure have been focused on the commercial compound powders of the metal NiCrAl
ZrO 2 coating system w4,5x. Up to now, only a few and ceramic Al 2 O 3 q 13 wt.% TiO 2 of sizes in the
studies have been made into the interfacial phenomena range of 75᎐143 ␮m and 37᎐105 ␮m, respectively. Mild
in Al 2 O 3 ceramic coating using transmission electron steel plates, approximately 40 mm in diameter and
10-mm thick, were used as substrates for spraying.
After pre-cleaning and a fine grit blast, the specimens
U
Corresponding author. Tel.: q86-20-877-660-69; fax: q86-20-
were deposited with a duplex coating consisting of a
877-765-97. NiCrAl bond coat layer approximately 50-␮m thick and
E-mail address: yangyz@gdut.edu.cn ŽY. Yuanzheng.. an Al 2 O 3 ceramic coat layer approximately 200-␮m

0040-6090r01r$ - see front matter 䊚 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 1 . 0 0 8 0 6 - 9
Y. Yuanzheng et al. r Thin Solid Films 388 (2001) 208᎐212 209

thick by atmospheric plasma spraying. On the same


spraying condition, the single ceramic coating on the
substrate Žwithout bond layer. was also prepared. The
plasma spraying operating condition can be seen else-
where w8x. The pull test showed that the average bond
strength for the duplex coating was approximately 27.1
MPa, appreciably higher than 16.8 MPa for the single
coating. In view of engineering applications, high bond
strength is beneficial to improvement of the life of the
coating. So the present study is concentrated on the
interfacial microstructure of the duplex coating.
The phase composition of the spray coatings was
determined using a Y-4 X-ray diffractometer. The mor- Fig. 1. SEM morphology of Al 2 O 3 q 13 wt.% TiO 2 coating in cross-
section: Ža. ceramic and bond layers; and Žb. within bond layer.
phology of these coatings was investigated with an
S-505AMERY scanning electron microscope ŽSEM.
and a JEM-200CX TEM or JEM-2000EX II High unmelted particles can be observed. The morphology of
Resolution TEM. The cross-section specimens for SEM the bond layer with a high magnification shows that,
observation were prepared by cutting, grinding and besides the area of perfect contact, at the corner or
polishing. To prevent charging of the insulating cer- edge of some lamellae there exists a small amount of
amic by the electron beam, all the specimens were area of non-contact, at which the gap may be up to
coated with a layer of carbon approximately 20-nm approximately 0.1᎐2-␮m thick.
thick. The TEM morphology of the bond layer near to the
The preparation of cross-sectional foils for TEM substrate is presented in Fig. 2. The lamellar structure
examination, which contains the interface between the of the bond layer is much clearly illustrated. The thick-
ceramic and bond coat layer as well as between the ness of the lamellae is non-uniform and can extend up
bond coat layer and the metal substrate, is relatively to approximately 8 ␮m as shown in Fig. 2a. The interfa-
difficult. After a series of steps of preparation with a cial regions within the lamellae or between the lamel-
special method, we got some thin disk specimens, ap- lae and the substrate are clearly of a definite thickness
proximately 500-␮m thick and containing the desired and non-uniform. From the bright and dark images,
interface. Next these disks were petrographically Fig. 2b,c, it is obviously demonstrated that the lamellae
thinned to a thickness of approximately 20᎐30 ␮m and mainly consist of columnar crystallites, which are ap-
then attached by refractory conductive adhesive to a proximately 0.1᎐1 ␮m in diameter and 3᎐4-␮m long
special brass ring, which is hollow in the center, with an and almost vertical to the substrate surface. In addition
outside diameter of 3 mm and inside of 2.4 mm. Fi- to the columnar grains, some approximately equiaxed
nally, the thin disks were dimpled to 5᎐10 ␮m and then grains, up to 160 nm in diameter, are observed in the
ion thinned by an ion-beam milling technique until outer surface of the lamellae.
perforated. The ion beam was produced from argon On close examination of the selecting area electron
and the incidence angle was changed from 15⬚ at the diffraction for the area containing the interfacial re-
beginning of thinning to 8⬚ at the end of thinning in gion between lamellae, one may observe that, besides
order to increase the area of thinning. During the the crystallite diffraction points, there exists a very
thinning the disc was rotated at 5 rev.rmin in order to faint spot ring caused by nano crystallites and a very
change the direction of bombardment. faint diffuse ring by glassy matrix. This phenomenon is
also detected in the latter observation for interfacial
3. Results zone between the bond coat layer and the substrate.

3.1. Morphology of the bond layer 3.2. The interface between the bond coat layer and the
substrate
The SEM morphology of the coating in cross-section
is shown in Fig. 1. The ceramic layer and bond layer As shown in Fig. 2a, the morphology of the interfa-
mainly display a lamellar structure, in which the lamel- cial regions between bond lamellae and between
lae of both the ceramic layer and bond coat layer are lamellarsubstrate is quite similar. The gap, approxi-
almost parallel to the substrate surface. The shapes of mately 0.7-␮m thick as shown in Fig. 2a᎐c, is precisely
lamellae of the bond layer are rather regular strips the interfacial region between the bond layer and the
Žstrictly speaking: are regular disks.. However, for the substrate owing to the fact that the interfacial phases
ceramic layer, in addition to the lamellae, spheres and are ready to be perforated during ion bombardment.
shapes intermediate between them as well as some Such a typical interface and the selecting area electron
210 Y. Yuanzheng et al. r Thin Solid Films 388 (2001) 208᎐212

Fig. 2. TEM morphology of the bond layer near to substrate: Ža. bond layer near the substrate; Žb. bright image of a bond lamella; and Žc.
corresponding dark image.

diffraction pattern are shown in Fig. 3. The side of totally up to 0.7 ␮m or possibly far less, and consists of
columnar structure pertains to the bond layer and the amorphous phases and nanocrystalline grains layer,
other side to the steel substrate, in which there exists whereas for the region of imperfect contact at the
almost no thin region owing to the difficulty in perfo- edges of the lamellae there may exist an extremely thin
rating during ion bombardment. The selecting area gap.
diffraction pattern shows that, besides crystallites of Ni
Žcorresponding to diffraction points., some amount of 3.3. The interface between the bond coat layer and ceramic
nano crystallites NiO and a certain amount of amor- coat layer
phous phases Žcorresponding to the diffraction spot
ring and faint diffuse ring, respectively.. Thus, it can be The typical morphology of the interfacial region
concluded that the interfacial region of perfect contact between the ceramic layer and bond metal layer and
between the bond metal layer and the substrate may be the selecting area electron diffraction are shown in

Fig. 3. Ža. Local interface between the bond layer and the substrate and Žb. the selecting area electron diffraction.
Y. Yuanzheng et al. r Thin Solid Films 388 (2001) 208᎐212 211

Fig. 4. A typical morphology of the interfacial region between the ceramic coating and bond metal layer at two magnification Ža, b. and the
selecting area electron diffraction pattern Žc..

Fig. 4. The thickness of the interfacial region exhibits mately equiaxed grains, and inner main sub-layer of
also non-uniform, possibly extending up to approxi- larger columnar grains. Furthermore, within the experi-
mately 0.7 ␮m. The selecting area diffraction pattern mental accuracy, the XRD results show that the NiCrAl
shows that micro crystallites of Al 2 O 3 and TiO 2 , nano compound powder transfers into a supersaturated solid
crystallites of NiO, and amorphous phases exist. It is solution NiŽCr,Al. after plasma spraying w9x. Thus, due
demonstrated that the interfacial region is not only to the oxidation of the outermost region of bond lamel-
non-uniform but also contains amorphous phases, nano lae with the entrapped gas in plasma jet w7,10x, NiO
and micro crystallites. wmore accurately maybe NiŽCr,Al.Ox rather than Al 2 O 3
phase is to be expected at the interface. In short, the
interfacial region between the bond lamellae of perfect
4. Discussion contact consists of the outer amorphous films of neigh-
boring lamellae.
In the interfaces within bond lamellae and between
As we know, the morphology of the characteristic the bond layer and substrate as well as between cer-
lamellar microstructure is associated with the mecha- amic and bond layer, the presence of amorphous film
nism of the impact of a liquid droplet on the substrate. may mainly result from the same reasons. Besides, the
The ultra-rapid solidification of the surface of a flat- morphology of the interfacial regions of these inter-
tening droplet caused by impact results in the forma- faces is also quite similar. However, there exists some
tion of amorphous and nanocrystalline constituents in subtle differences between them as follows. Generally,
the contact layer due to homogeneous nucleation and during spraying the higher current of spraying, the
preventing grain growing. Since the amorphous film higher heat of liquid droplets. In the present study, the
acts as a thermal barrier, the rate of cooling decreases current used for spraying the ceramic and bond layers
with the depth and hence leads to formation of another is 530 and 450 A, respectively. Thus, the heat of cer-
region characterized by fine columnar and equiaxed amic droplets and the energy of impact may melt a part
grains. For the inner major part of the flatted droplet, of the bond layer hence the interface between the
the cooling rate now reduces low enough to permit the ceramicrbond layer will be widened and contain some
growth of big columnar grains, which are aligned to the compositions of bond metal. However, the liquid
surface of lamellae and oriented parallel to the direc- droplets of bond metal can melt almost no substrate
tion of the maximum heat transfer. Therefore, each owing to the lower heat of droplets and the more rapid
lamella of the bond layer may consist of an outermost heat conduction of the substrate, thus the bondrsub-
thin amorphous and nanocrystalline film, an intermedi- strate interface contains no composition of the sub-
ate region of fine columnar crystallites and approxi- strate or only a very small amount for the composition
212 Y. Yuanzheng et al. r Thin Solid Films 388 (2001) 208᎐212

thermal diffusion. Therefore the interface between the 5. Conclusion


ceramicrbond layers might be divided into three sub-
layers. The first one is adjacent to the metal bond layer The microstructure within bond layer and the inter-
mainly consisting of metal composition; the second facial phenomena within the bond layer and between
region is the main amorphous sub-layer containing ceramicrbond layer as well as between bondrsubstrate
ceramic and metal composition; the third belongs to a in a duplex coating system consisting of a NiCrAl bond
ceramic sub-layer of nano or micro crystallites mainly coat layer and an Al 2 O 3 q 13 wt.% TiO 2 ceramic coat
of ceramic composition. layer have been studied. The plasma spraying bond
It is surprising that the thickness of the interfaces layer is of a characteristic overall lamellar nature,
between ceramicrbond and between bondrsubstrate is which is associated with the mechanism of the impact
accidentally almost equal. Generally, the cooling rate of a liquid droplet. Each droplet forms a single lamella.
of ceramic droplets is lower than that of bond metal The individual platelet consists of an outer amorphous
droplets due to the higher rate of heat conduction of and nanocrystalline film, an intermediate layer made
the substrate than that of bond lamellae with an amor- up of fine columnar and equiaxed grains, and a main
phous film. As a result, the outermost amorphous film inner part of big columnar crystallites extending
of ceramic lamellae neighboring the bond layer is thin- through their thickness. The NiCrAl bond layer is
ner than that of bond metal lamellae adjacent to the beneficial to the adhesion strength of the ceramic coat-
substrate. On the other hand, ceramic droplets can ing, which is discussed with respect to the improvement
melt a part of the bond layer then widen the interfacial of mechanical andror physical bonding at the cer-
amorphous film. Therefore, the thickness of interfacial amicrmetal interface.
amorphous film between ceramicrbond including the The morphology of the interfacial regions of the two
outer amorphous films of neighboring ceramic and interfaces between ceramicrbond and between
bond lamellae might be accidentally equal to that of bondrsubstrate looks similar and consists of a certain
the amorphous film between bondrsubstrate. thickness of a mixture of amorphous and nanocrys-
As mentioned in Section 2, the average bond strength talline phases. These interfacial phases are formed due
for the duplex coating is approximately 27.1 MPa, ap- to the ultra-rapid solidification of liquid droplets during
preciably higher than 16.8 MPa for the single coating. plasma spraying. Furthermore, within the bond lamel-
It suggests that the NiCrAl bond layer is beneficial to lae and at the interface between bondrceramic lamel-
the adhesion strength of the ceramic coating. From the lae as well as between bondrsubstrate, besides a cer-
above discussion, in the duplex coating there exists four tain percentage of area of perfect contact, a small
kinds of interfaces, namely, ceramicrceramic, cer- amount of area of non-contact is also detected at the
amicrbond, bondrbond and bondrsubstrate, while in edges or corner of the lamellae.
the single coating system, only two types of interfaces,
ceramicrceramic and ceramicrsubstrate. Since the in- Acknowledgements
terfaces within bond lamellae and between bondrsub-
strate have greater chemical, i.e. metallurgical bonding This work was supported by Doctor Foundation of
resulting from interatomic forces and the generation of Ministry of Education of China and by the Natural
interdiffusion zones, such metalrmetal interfaces will Sciences Foundation of Guangdong Province, China.
own relatively high adhesion strength. Additionally, the
interfaces within ceramic lamellae in the single and References
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