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2013, Brno, Czech Republic, EU

EFFECT OF SPRAY PARAMETERS ON THE PROPERTIES OF HVOF SPRAYED COATINGS WITH CHANGING CO CONTENT BASED ON TUNGSTEN CARBIDE Jan SCHUBERTa, rka HOUDKOVa, Zdenk ESNEKa, Michaela KAPAROVa
a VZ Plze s.r.o., Tylova 46, 301 00 Plze, Czech republic, schubert@vzuplzen.cz

Abstract Thermal sprayed coatings based on tungsten carbide are the most durable and much sought materials in terms of wear resistance. Although they are not suitable for high temperature applications, they can be applied in many areas of industry due to the combination of very hard carbides and tough matrix. The hardness and toughness rate of WC-Co coatings is, in the case of thermal sprayed coatings, determined by mutual proportion of carbide phase and matrix, and by spraying parameters. The presented study was conducted to determine the effect of spraying parameters and cobalt matrix content on the resulting coating mechanical properties. Samples were prepared using the HVOF (high velocity oxy-fuel) spraying equipment TAFA JP-5000. Three powder types with different cobalt matrix content, namely WC-12Co, WC-17Co and WC-25Co, were used. Two sets of samples were prepared in order to determine the effect of spray parameters on the final properties of the coatings from each of powder. The first set was prepared using the default parameters. Spraying of the second set was carried out by different parameters that were newly tested. The basic mechanical properties were evaluated for each of Co content and spray parameters. Special attention was focused on comparison of changes in the abrasive wear resistance evaluated by Dry Sand Rubber Wheel test (performed according to ASTM G-65) and on changes in sliding friction assessed by a test pin-on-disc (according to ASTM G-99). The conclusion of study is devoted to the evaluation of application potential of WC-Co coatings, depending on the preparation parameters and on varying content of Co matrix. Keywords: coating, wear resistance, HVOF, tungsten carbide, cobalt matrix 1. INTRODUCTION

WC-Co cermet coatings are nowadays a common method used mainly to improve wear resistance of the majority of machine components. The thermal spraying methods for coating deposition are mainly used in practice. High Velocity Oxygen Fuel (HVOF) is a leading representative of thermal spraying methods [6, 8]. This technology enables deposition of wide range of coatings characterized by low or medium melting temperature. The advantage of HVOF compared with other thermal spraying technologies is the possibility to accelerate the melted particles of deposited powder at relatively high speeds ensuring relatively thick and particularly compact layers with thick microstructure. Moreover, the lower temperate deposition mode of HVOF compared with plasma spraying technology enables lower degree of carbide decarburization (in our case WC-Co) [10, 11]. On the other hand, HVOF has also its disadvantages. In comparison with sintered WC-Co, HVOF coatings suffer from carbide decarburisation and decomposition processes, as it has been proved by many authors. These processes result in formation of undesirable phases such is W 2C etc. [5]. Pin-On-Disc results has shown that cermet coatings form a smooth compact tribofilm, which provides these coatings with similar properties as Cr2O3 coatings and with better properties compared with Al2O3 TiO2based coatings. The stability of frequently brittle / fragile tribofim is a vital parameter to reach the best cermet coatings properties [12]. Therefore, the spraying parameters must be well optimized to ensure stable tribofilm formation and to prevent from premature coating spalling and subsequent serious component wear [5]. This paper presents results of three WC-Co cermets differing in cobalt bonding matrix phase content (12, 17 and

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25 wt% Co). Coatings were deposited by HVOF thermal spraying technology; and the influence of spraying parameters on final mechanical properties and wear resistance was evaluated. 2. EXPERIMENTAL

The determination of new spraying parameters influence on the final WC-Co coating properties with respect to the changing cobalt matrix content is the main aim of this research. Three WC-Co coating variations with cobalt matrix contents of 12%, 17% and 25% were used (FST K 624.23, K 674.23 and Fujimi DTS-W817). Six sets of samples were prepared. Three sets were deposited under standard parameters set on the basis of previous optimization. Three sets were deposited under new parameters. Coating deposition was realized in VZ Plze. Mechanical properties and wear resistance were examined on these sample sets. 2.1 Deposition parameters

Spraying parameters and powder materials used are shown in the Tab. 1. Grain size of individual powders is in the range of 15 - 45 m. The substrate surface was degreased and blasted before coating deposition. Brown corundum F22 with grain size 0.8 1.0 mm was used as abrasive medium. Tab. 1 Spraying parameters Pressure in the combustion chamber [bar] 8,80 7,20 Deposition distance [mm] 380 380

Parameters A B
2.2

Equivalent ratio
0,75 1,10

Barrel

150 mm 150 mm

Measurement conditions

Microstructure evaluation was conducted by scanning electron microscope SEM (FEI Quanta 200) in NTC ZU. Surface hardness HR15N was evaluated by Rockwell HT 8003 hardness test on unpolished coating surface. Results were calculated as an average of five measurements conducted in laboratories of VZ Plze. Microhardness HV0.3 was evaluated on the coating cross section. Results were calculated as an average of seven measurements conducted similarly in VZU Plze with LECO DM400A device. Abrasive wear resistance measurements were conducted by Dry Sand Rubber Wheel test in VZ Plze s.r.o. Test parameters were following. Al2O3 (abrasive grain size 212-250 [m]) sand was used as an abrasive material. Pressure force was 22N. Wheel speed was 180rev/min and the total measurement track was 718m. Wheel rubber was BR-60-z 10mm with hardness 60 sh. Test procedure followed ASTM G-65 norm requirements [1]. Pin-On-Disc test was conducted in the laboratory of NTC ZU according to ASTM G-99 norm [2]. The test conditions were the same for all samples and the final value was calculated as an average of several measurements. Linear sliding speed was 10 cm/s; norm load was 10N; used balls had diameter of 6mm (steel and corundum balls were used); and samples were cleaned with ethanol. Slide track was constant during all tests (50 000 cycles). The environmental conditions of relative moisture and temperature were approximately Hr = 15

20% a 20 C, resp. and stayed constant during the test. Wear rate after the pin-on-

disc test was evaluated in NTC ZU using profilometer (KLA-Tencor P-6 Profiler). 3. 3.1 RESULTS AND DISCUSSION Microstructure

Coating microstructure is shown on Fig. 1. The quality of evaluated coating is suitable: low porosity, adhesion to the substrate and absence of cracks. Nevertheless, there is a visible difference between WC-

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12%Co coatings prepared under A and B parameters. The coating WC-12%Co deposited under the B parameters has appreciable lower porosity comparable with coating deposited by parameters B. The difference in porosity between the WC-Co 17 and 25% sprayed by parameters A and B is no longer visible. The 25%Co coating is slightly inhomogeneous due to the higher matrix amount. The matrix was formed into elongated formations after the deposition.

a)

b)

c)

d)

e)

f)

Fig. 1 a) WC-12%Co Par. A, b) WC-17%Co Par. A, c) WC-25%Co Par. A, d) WC-12%Co Par. B, e) WC-17%Co Par. B, f) WC-25%Co Par. BA 3.2 Mechanical properties

Basic mechanical properties of WC-Co layer were measured on all samples and the average values are given in Tab. 2. The measurements clearly show that the cobalt binder has significant influence on resulting microhardness of the coating and deviations are in toleration. Hardness is increasing with decreasing porosity, which could be caused by higher boxing material content [5]. Surprisingly, the slightly higher microhardness shows the sample with 17% cobalt binder, which has already been reported in the studies [3] showing slight increase in microhardness with increased binder to 17%. This increase does not exceed the values of tolerance, which are generally similar to the values reported by other authors. [5]. The microhardness increase of WC-12%Co coating is significant with the change of spraying requirements. The increase in flame temperature can cause better coating properties in terms of internal stress and increase of oxides in coating structure. Higher oxide amount results in higher microhardness values, but on the other hand, in lower toughness and coating cohesion strength, which could result in worse wear resistance. Microhardness of remaining samples shows anticipated trend of decreasing values, which corresponds with the increase of cobalt matrix content.

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Tab. 2 Mechanical properties Deposition rate (Thickness per pass [m]) 56.5 67.9 44.12 50 52.1 Roughness [Ra] 3.79 0.47 3.55 0.35 2.88 0.14 Thickness [m] 509 9 476 23 353 17 415 18 521 12 398 19

Material WC-12%Co, Par. A WC-12%Co, Par. B WC-17%Co Par. A WC-17%Co, Par. B WC-25%Co Par. A WC-25%Co, Par. B 3.3

HV0,3 1052 148 1181 115 1148 62

HR15N 86.2 3.1 92.3 1.7 92.2 2.4 91.7 1,2 92 1.6

2.916 0.16
3.08 0.33

1190 134
1009 74 956 120

44.4

2.654 0.12

92.3 1

Abrasive wear resistance ASTM G-65

The results of abrasive wear resistance evaluated with ASTM G-65 (Dry Sand Rubber/Wheel Test) method are given in the graph in Fig. 2. Wear mechanism evaluated by ASTM G-65 test is characteristic for cermet coatings due to gradual matrix wear and subsequent carbide releasing. Based on the expectations, the wear resistance of 25%Co coating is lower. The abrasive wear resistance of this type is decreasing with increasing binding content [4, 7]. This phenomenon is considered to be a result of increasing WC solid particles in the coating [4, 9 and 10]. The difference between wear resistance of 12% and 17% coatings is insignificant. However, it is worth mentioning that 12%Co coating deposited under A parameters has lower resistance that 17%Co coating deposited under A parameters, whereas 12%Co coating deposited under B parameters has similar wear resistance as WC-17%Co coating. These measured results correspond with microhardness measurement results. The remaining two coatings deposited under B parameters (17% and 25%Co) shows remarkably higher wear. As it has already been mentioned before, this phenomenon is probably the result of higher oxide content in the structure, which lowers toughness and cohesive coating strength.

Fig. 2 Abrasive wear characteristics 3.4 Sliding wear properties ASTM G-99

The results of tribological characteristics gained by ASTM G-99 (Pin-on-disc test) method are shown in the graph on Fig. 3 and in Tab. 3. Values of COF (coefficient of friction) and COF progress of coatings deposited under A spraying parameters are similar for all variations (12, 17 and 25%Co). Whereas in the case of steel ball, the ball material is transferred on the coating surface, which influences COF values (steel-steel contact is approximately 0.7); the COF value of contact with Al2O3 is remarkably lower. Convenient properties are given by the wear

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mechanism. After the slight matrix wear, the carbide particles are in contact with Al2O3. The contact not only lowers COF values but also reduces wear. It is visible from lower wear rate values in contact with Al2O3 compared with steel counterpart. WC-12%Co coating deposited under B parameters has in both cases insignificantly lower friction coefficient for both two counterparts (steel and Al2O3). This COF reduction show all samples deposited under B conditions. The results also prove that new parameters with higher spraying temperature could support desirable tribofilm formation in higher extend.

Fig. 3 Tribological characteristics Tab. 3 Coefficient of fiction and wear rate values Wear rate ASTM G 99- Al2O3 3 [mm /m] -7 (3.94 0.47).10 (3.87 0.91).10 (3.69 0.65).10
-7 -7 -7 -7

Material WC-12%Co, Par. A WC-12%Co, Par. B WC-17%Co, Par. A WC-17%Co, Par. B WC-25%Co, Par. A WC-25%Co, Par. B

COF-Al2O3 0.431 0.004 0.308 0.014 0.419 0.053 0.349 0.036 0.431 0.020 0.309 0.067

COF-100Cr6 0.806 0.010 0.655 0.011 0.760 0.060 0.747 0.038 0.781 0.022 0.766 0.052

Wear rate ASTM G 99- 100Cr6 3 [mm /m] -7 (7.36 1.08).10 (34.9 2.84).10 (30.1 11.1).10
-7 -7 -7

(3.63 0.66).10

( 27.4 17.9).10

(4.34 0.92).10 -7 (4.64 0.88).10

(65.4 15.6).10 -7 (26.2 11.6).10

-7

Wear rate was evaluated by KLA-Tencor P-6 Profiler profilometr. It enables to determine the track cut space after wear. But the track cut space determination is considerable subjective (null plane determination poses the problematic question). The determined values relatively correspond with microhardness trend. On the contrary, lower wear occurs by harder ceramic Al2O3 counterpart. Mutual contact of WC grains and Al2O3 ball causes lower friction coefficient. The use of steel ball leads firstly to the ball wear as the ball material changes to abrasive medium inside the track. Mutual slide contact is changing to three body abrasive contact, which is more aggressive to the coating [10].

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4.

CONCLUSION

The research shows that the new parameters (par. B) exhibit lower porosity at the same level of cobalt content. Changing parameters has no significant effect on the measured macrohardness and all values are in the same range within tolerance. Microhardness has undergone some changes when the parameter B has been noticeable increased in comparison with the standard parameters. Only samples with 25% Co matrix underwent reduce in this value. Abrasive resistance of sprayed coatings parameters B shows a slight reduction in wear with WC-12% Co. However the remaining samples show significant deterioration in abrasive resistance due to the higher degree of oxidation. The results of tribological testing of the coating sprayed by parameters B have better properties. In all cases, there was a decrease in COF compared to parameters A. The wear rate of all coatings remained almost unchanged within tolerance even with the new parameters. ACKNOWLEDGEMENT The paper was prepared in the framework of the institutional support of research organization longterm conceptual development. LITERATURA
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