Journal of the Australian Ceramic Society Volume 46[1], 2010, 63-70

Response of Detonation Sprayed Ceramics to Abrasive Working Environment

A.Kharim Kutty 1*, R.Krishnamurthy 2 and M.M.Mayuram 3
1

Research Scholar, 2 Emeritus Professor, 3 Professor Indian Institute of Technology Madras, Chennai, India.

*Email: Kharimkutty@gmail.com Available Online at: www.austceram.com/ACS-Journal-2010vol1.asp

ABSTRACT Tribological contact pairs usually encounter solid-solid or solid-fluid interface experiencing thereby surface originated failures through abrasion, erosion and corrosion. To combat these modes of wear and enhance the life, surface depositions like plasma spraying and detonation spraying are being practiced. In detonation spraying the particle undergoing an interaction with combustion flame splashes with high velocity on the substrate; the resultant microstructure of the deposition is largely dependant on the particle velocity and consequent temperature. In the case of plain alumina deposition, the deposition is a layer of lenticulted splats with certain porosity However with alumina-titania composite; the deposition is relatively denser presenting a structure similar to liquid phase sintered. This can influence the tribological response of the ceramic depositions. The present study illustrates the relatively distinct response of detonation sprayed Alumina and Alumina-Titania ceramic composite. KEYWORDS: Detonation spraying, aluminium oxide, AT-13, static indentation, erosion wear, abrasion wear.

1. INTRODUCTION Surface engineering involves the application of traditional and innovative surface technologies to engineering parts in order to produce a component with properties unattainable in either the bulk or the surface material [1]. Among the available deposition techniques, thermal spray deposition is one of the pragmatic methods to deposit a wide range of materials from polymers to ceramics and is well practised by the manufacturing industries [2]. Among the thermal spray deposition techniques, plasma spray deposition and detonation spray deposition find increasing applications. In plasma spraying, the particles introduced into the plasma jet (ionic state) are ionized and rapidly heated to molten state. The molten particles are impinged on to the substrate, which are splatcooled to form a layered structure. However in detonation spraying, the particles are introduced into a gun barrel, mixed up with combustion products, heated up to a plastic state and thrown on to the substrate with very high velocity. In thermal spray processing, the parameters influencing coating formation and subsequent structural properties are the size, temperature and velocity of the particle to be sprayed [3]. 63

Normally high particle velocity will lead to production of dense coating with low porosity. However, it may not facilitate good mechanical properties owing to lower particle temperature [4]. Lamellar bonding of plasma spray deposition with good particle cohesion is due to particle temperature rather than particle velocity. Despite lamellar bonding, plasma spray deposition results in a structure with defects such as porosity, unmelted particles and cracking due to thermal shock [5]. In detonation spraying, the high velocity impingement induces high compressive stresses followed by occurrence of rarefaction causing tensile stresses and cracking of the coating substrate interface region [6]. This dynamic damage can result in uncertainties in the performance of detonation sprayed deposition. According to Tucker [7] in detonation spraying the combination of particle plasticity/fluidity and velocity must be high enough to allow the particle to flow into a thin lenticular shape that molds itself to the topology of the substrate. Some particles rupture into sub-droplets resulting in higher porosity, poor intracoating fracture strength and higher roughness.

A.Kharim Kutty, R.Krishnamurthy, and M.M.Mayuram

Also the micro-structure can be amorphous near the substrate, followed by a crystalline state. Further, the high temperature impingement can result in high temperature phases. This can influence the response of the deposition to the working environment. From this it can be inferred that it is necessary to go in for finer particles to minimize the uncertainties unlike the case of plasma spraying which calls for relatively coarser particles to sustain the chemistry of the deposition, especially with the case of ceramic composite. Thus it can be seen that both the processes are associated with constraints, influencing their performance. A study has been undertaken to assess the response to static indentation and tribological characteristics of spray deposited Alumina (Al2O3) and Alumina Titania (AT-13) ceramic composite. The results are presented in this paper. 2. METHODS AND PROCEDURES The Ceramic spray deposits of plain alumina and alumina-titania composite (500m thickness coatings) were prepared by detonation spraying on low carbon steel (30mm x 10 mm dia). These specimens were subjected to static indentation tests. Test specimens were polished to a mirror finish using 1-m diamond paste. During the indentation test, the prepared specimen was placed in the specimen holder and properly aligned beneath the Rockwell C diamond indenter. After positioning of the indenter close to the specimen surface, controlled loading was applied at a fixed ram displacement rate of 0.5mm/min for 1-500N load, using a standard Instron Universal Testing machine. (Three trials were conducted and the average was taken). The progressive response of the material such as crack initiation and propagation was monitored on-line through piezoelectric type acoustic emission sensor using an AET-5500 data acquisition system. The loading was continued at the same rate even after flexure was observed in order to record the total response of the system. Apart from Static indentation test, Slurry jet erosion test was carried out using Erosion wear test apparatus. A slurry of 1 wt% 212/300 m (ASTM 70/50) silica particles was prepared in water of pH 7. The slurry was directed at the specimens (75x18x5 mm low carbon steel coated with Al2O3 and AT-13 of 500 m thickness) at 12.4 m/s with a flow rate of 21 LPM, at nominal impingement angles of 90, chamber pressure 0.8 kg/cm2 and at a nozzle-specimen distance of 6mm.

The tests were carried out for 10,20,30 and 40 minutes with fresh slurry. Weight loss from each exposure was determined after washing and drying of specimen to constant weight. Results are recorded as loss of material eroded. Abrasive wear test were carried out using the Dry sand / Rubber wheel apparatus as per ASTM G 65 [8]. The dry sand / rubber wheel abrasion test set up involves the abrading of a standard test specimens with a grit of controlled size and composition of 150/200m (ASTM 70/100) angular dry silica particles . The abrasive was introduced between the test specimen and a rotating wheel. This test specimen was pressed against the rotating wheel at a specified force by means of a lever arm while a controlled flow of grit abrades the test surface. The rotation of the wheel was such that its contact face moves in the direction of the sand flow. The tests were carried out for 4, 6, 8 and 10 min. with fresh abrasive. Specimens were weighed before and after the test and weight loss was recorded. To understand the nature of response of the ceramic deposition to the different tests, scanning electron micrographs of the tested specimens were studied. Details are presented below 3. RESULTS AND DISCUSSION Static Indentation - Response Static indentation test was carried out in a Standard (Instron) Universal Testing Machine (UTM). During indentation, the depth of penetration with respect to indentation load was monitored. Typical load-penetration characteristics of alumina and the alumina-titania composite monitored during the test are illustrated in Fig. 1

0.5
Al2O3
penetration (mm)

AT-13

0.45

0.4 0.35

0.3 0 50 100 150 200 250 300 350 400 450 500 load (kg)

Figure 1: Typical variation of indentation depth with normal load

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Journal of the Australian Ceramic Society Volume 46[1], 2010, 63-70

100X 200X Figure 2a &2b: SEM Photograph of detonation sprayed alumina coating-exposed to static indentation

100X 200X Figure 3a &3b: SEM Photograph of detonation sprayed AT-13 coating-exposed to static indentation

Referring to the illustration on load-penetration, it is seen that around 100 kg of indentation load, a rise in depth of penetration occurs for alumina deposition, while around 150 kg, a rise in penetration depth occurs in the case of aluminatitania composite. These loads can be considered as critical normal loads for the first occurrence of fissures/local distress in the test material. The relatively denser, particulate reinforced ceramic composite exhibits a higher critical load. The observation on static-indentation study shows better response of the alumina-titania ceramic composite to indentation/normal load, unlike the response to flexure. Even in the flexural response, a change-over in the trend of load-deformation characterization is seen to occur at lower loads for Al2O3 compared to AT-13 ceramic composite. Indentation Morphology Typical micrographs of indentation morphology with alumina deposition pertaining to the critical load is illustrated in Figs.2a and 2b, incidence of lateral cracking around the eye of the indentation can be seen. Typical observed morphology of indentation with alumina-titania composite material at the critical load of 150 kg is illustrated in Figs.3a and 3b. It is seen that in the critical load region

alumina-titania exhibits side flow of material around with mild cracking in the eye region. Monitoring of acoustics emission during static indentation Apart from load-penetration characteristics, response of the detonation sprayed alumina deposit to static indentation was evaluated by monitoring the AE signals. Typical power spectra of the signal monitored during static indentation on alumina are illustrated in Fig. 4 (a to d). During early phases of indentation (up to 100 kg load) the monitored signal was of relatively low power with the power spectrum containing dominant low frequency peaks (Fig. 4a).This can be attributed to progressive deformation of the material statically indented. During the trend-change over phase i.e., around 100-150 kg of indentation load range, AE signal of increased power was monitored. Accordingly the power spectrum contains dominant high frequency peaks (Fig.4b). A progressive rise in the loaddeformation characteristics observed over the load range of 150-350 kg was associated with increased power of AE signal monitored as shown in Fig. 4c.The rise in the load penetration characteristics observed around 350 kg of indentation load is associated with a power spectra of high intensity, high frequency peaks, indicating localized burst emission.(Fig. 4d). 65

A.Kharim Kutty, R.Krishnamurthy, and M.M.Mayuram

Figure 4: Typical power spectra of the AE signals monitored (alumina) during static indentation test at different intervals

Figure 5: Typical power spectra of the AE signals monitored (AT-13) during static indentation test at different intervals

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Journal of the Australian Ceramic Society Volume 46[1], 2010, 63-70

The test specimen of sprayed alumina is of 500m thickness. With penetration reaching around 450 m the indenter would be close to the substrate. This could have resulted in differential stressing of the coating system causing the burst emission. Beyond this load, signal of mixed mode with low amplitude peak was observed as illustrated in Fig. 4c & 4d. This can be attributed to the emission of the material over the bond region. The response of the detonation sprayed aluminatitania composite of 500 m thickness during static indentation was also evaluated by monitoring the AE signal. Typical power spectra of AE signal monitored during different load ranges are illustrated in Fig. 5 a & b. Comparing the emission of sprayed alumina deposits relatively lower emission of AE signal was monitored for sprayed alumina-titania composite. The application of static indentation stress would have been contained by the particulate reinforced ceramic composite structure. i.e, unlike flexure testing (induction of tensile stresses). The application of normal stresses would have been resisted better by the ceramic composite. It is seen that aluminatitania ceramic composite exhibited a better response to the indentation by way of reduced magnitude of penetration. This can be attributed to the relatively denser deposition of the AT-13 composite.
0.95
AE (rms)

Beyond a particular depth of penetration, the alumina deposit exhibit an increasing trend of AE rms, indicating a larger energy release rate; however the observed more or less steady AE rms value in the case of alumina-titania ceramic composite shows steady material response. The above observation indicates the effectiveness of dispersion strengthening of alumina-titania ceramic composite structure. Wear Testing Response Slurry Erosion Wear Test Typical monitored slurry erosion wear propagation for both detonation sprayed Al2O3 and AT-13 composite are illustrated in Figs. 7a and 7b. It is seen that both the progressive wear propagation. However, the AT-13 ceramic composite, exhibit greater resistance to erosion wear. This can be attributed to a relatively more compact/dense structure of AT-13 composite; also the dispersion strengthened ceramic composite material can resist crack propagation and thereby restrict the wear.

Alumina

AT-13

0.75

(a)
0.55 0.35 0.35

0.40

0.45

0.50

Depth of penetration (mm)

Figure 6: Typical variation of indentation depth with AE-rms Apart from the observation on power spectra the nature of variation of AE signal with indentation was evaluated in terms of rms values of signal emitted.

(b)
Typical observed variation of the rms value of the monitored AE signal during static indentation is shown in Fig. 6. It is seen that both alumina and alumina-titania composite exhibit higher rms value during initial load phase indicating higher energy release. The observed reduction in the AE rms value is attributable to progressive penetration load characteristics. Figure 7: Typical variation of mass loss of alumina and AT-13 at different intervals of slurry erosion

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A.Kharim Kutty, R.Krishnamurthy, and M.M.Mayuram

Typical observed SEM of a worn-out Al2O3 coating is shown in Fig. 8. The worn-out surface undergoes localized glazing and pull out of material. The formation of surface cracks can be seen. It is seen that the specimen experiences maximum erosion at the impingement spot, around which the rate of erosion decreases. Since the impingement and subsequent flow of the erodent is randomly oriented, the orientation can be seen in the eroded surface texture, with distinct splat formation and the amount of erosion experienced by the surface around the core. This will facilitate further pull out of material from the surface. Typical scanning electron micro graph of the worn-out AT-13 ceramic surface is illustrated in Fig. 9. The surface material has experienced deformation and glazing, the formation of numerous white boundaries are the deformed titania material around the sprayed alumina splat, and the eroded surface texture is rather uniformly glazed, with the absence of pre-erosion texture.

Dry Abrasion Wear Test Typical monitored sliding wear propagation for both detonation sprayed Al2O3 and AT-13 composite are illustrated in Fig. 10a and 10b. It is seen that both plain alumina and alumina-titania exhibit progressive wear up to a certain exposure time, beyond which enhanced erosion wear occurs with alumina deposition. The liquid phase sintered structure of alumina-titania deposition and the dispersion strengthening of the ceramic-composite can resist the exfoliation (mechanism of material removal in erosion) of splats better.
0.18

Mass loss, g

0.14

0.1 Alumina 0.06 2 4 6 8 Tim e, m in 10 12

(a)

0.16

Mass loss, g

0.12 0.08 AT-13 0.04 2 4 6 8 10 12 Tim e, m in

100X

Figure 8: SEM Photograph of detonation sprayed alumina coating-exposed to slurry erosion

(b) Figure 10: Typical variation of mass loss of alumina and AT-13 at different intervals Typical observed SEM of detonation sprayed alumina deposition are presented below highlighting the nature of a flexible abrasion experienced. Fig. 11 illustrates micrograph of worn out alumina deposition. It is seen that the abrasion wear track is randomly oriented, due to the nature of abrasive flow; also the closed boundaries of abrasive flow patterns can be pertaining to localized dislodgment due to abrasive impingement. During flexible abrasion, with random impinging orientation, it is possible that certain region is impinged with higher order impingement force (depending on the impingement angle, and consequent abrasion wear.

100X

Figure 9: SEM Photograph of detonation sprayed AT-13 coating-exposed to slurry erosion

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Journal of the Australian Ceramic Society Volume 46[1], 2010, 63-70

The as sprayed surface presents dimples (marked) indicating the occurrence of pin holes / cavities, possibly due to dynamic damage induced during splat formation. The observed region (Fig. 11) shows a relatively smoother surface, indicating higher order flexible abrasion around the dynamically damaged portion of the deposition. Scanning Electron Micrographs of flexible abraded Alumina-Titania deposition are presented in Fig. 12. Typical formation of splats surrounded by solidified liquid phase of low melting titania can be seen. The surface is more compact / coherent compared to plain alumina deposition.

The micrographs of the abraded (flexible) aluminatitania illustrate smoothing of the surface texture, with localized spalling of the individual splat. The micrograph of abraded alumina-titania composite shows smoothing of the texture with localized surface cracking. This can be attributed to the formation of harder / brittle alumina-titania compound over the intersplat region during spraying. 4. CONCLUSIONS The study on static indentation shows better response of AT-13 ceramic composite to indentation/normal load. The resistance of AT-13 composite structure to normal load can be attributed the relatively denser structure Study on slurry erosion has shown that both plain alumina and alumina-titania exhibit progressive wear up to a certain exposure time, beyond which enhanced erosion wear occurs with alumina deposition. The liquid phase sintered structure of alumina-titania deposition and the dispersion strengthening like particulate reinforcement of the ceramiccomposite can resist the exfoliation (mechanism of material removal in erosion) of splats better. Observations on the abrasion wear have shown that relatively the porous alumina deposition experiences more wear. The dense / compact alumina-titania deposition exhibits a relatively low order of wear during early exposure. This can be attributed to possible rebouncing of the abrasives impinging on a dense / compact surface. Alumina and AT-13 exhibit progressive wear propagation; comparatively AT-13 exhibits greater resistance to sliding wear.

100X

Figure 11: SEM Photograph of detonation alumina coating exposed to dry abrasion

5. ACKNOWLEDGEMENTS The authors would like to gratefully acknowledge the contributions made to this research by Shafel Tech Thermal Spray Coating Unit, Chennai, and testing facilities provided by the parent institute.

100X

Figure 12: SEM Photograph of detonation sprayed AT-13 coating-exposed to dry abrasion

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6. REFERENCES 1. Sharma, A.K. (2002) Microwave glazing of plasma sprayed ceramic composite coatings and their characterization, Ph.D.Thesis, I.I.T. Madras, Chennai, India. Venkataraman.R., (2003) Study on the phase stability and correlation to the adhesive strength of as plasma sprayed oxide ceramic coatings, Ph.D.Thesis, I.I.T. Madras, Chennai, India. Chang-Jiu Li and Akira Ohmori, (1996) The lamellar structure of a detonation gun sprayed Al2O3 coating, Surface coatings technology, Volume 82, 254-258 Houben.J.M.,(1980) Remarks concerning a rational plasma for thermal spraying, General Aspects of Thermal Spraying, Preprints 9th Int. Thermal Spraying Conf., Hogue, Nederland institute voor Lastechnick, 143-154. Psyllaki. P.P, Jeandin.M, and Pantelis. D.I, (2001) Microstructure and wear mechanisms of thermal-sprayed alumina coatings, Journal of Materials Letters, Volume 47, 77-82. 6. Buravova, S.N., Goncharov, A.A. and Ju. N. Kiseley (1996) Surface damage under dynamic loading, Tribology international, Volume 29, 357-363. Tucker, R.C. (1994) Thermal Spray Deposition Techniques, Hand Book on Technology for Development of Thin Films and Depositions, Ed. Bhunshah, R.F. Noyes Publications, 591-627. ASTM G65-04 Standard Test Method for Measuring Abrasion using the Dry Sand/Rubber wheel Apparatus Active standard ASTM G65 Developed by subcommittee G02.30 Books of standards Volume: 03.02.

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