published at the ITSC 2004, Osaka, J, May 10th - 12th Oxidation behaviour of disilicide coatings at 1500 °C

B. Wielage, G. Reisel, A. Wank, G. Fritsche, Chemnitz / D

Molybdenum disilicide (MoSi2) is a suitable material for high temperature applications especially because of its excellent high temperature oxidation resistance. For several high temperature applications MoSi2 shows high potential to be used as a protective coating. The oxidation behaviour of HVOF sprayed MoSi2 coatings is studied at 1500 °C. The oxidation tests are carried out in a simultaneous thermogravimetric device and the mass change is measured in dependence on the oxidation time. The microstructure of the coatings before and after oxidation is examined by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXS). The mass of the coating increases according to a parabolic function. During the oxidation test the microstructure changes significantly from a typical thermal spray coating microstructure with lamellae, pores and a phase mixture of MoSi2 and Mo5Si3 to a two phase system with sharply separated grain boundaries. On the surface of the coating a layer with a thickness of less than 10 µm is formed.

1 Introduction 1.0 MoSi2 0.9 Monolithic molybdenum disilicide (MoSi2) shows an 0.8 excellent resistance against high temperature 0.7 oxidation. Other good properties of this material are 0.6 -3 the relatively low density of 6.25 g·cm , the high 0.5 of 2030 °C and the high toughness 0.4 0.3 above the brittle-ductile transition at approximately Intensity fraction SiO2 800 - 1100 °C. So MoSi2 has a great application 0.2 potential in the temperature range between 1200 and 0.1 1800 °C [1-3]. 0.0 Often it is not useful to produce a component as a 0 2 4 6 8 10 12 14 16 Penetration depth [µm] bulk completely of molybdenum disilicide, but to apply a protective coating made of MoSi2 [4-6]. One suitable Fig. 1: Information depth of XRD (2 θ = 45°; Cu-kα- technique to produce such coatings is thermal radiation) in dependence on the investigated material spraying, especially high velocity oxy fuel spraying (HVOF) [7-9]. In the present paper the oxidation Caused by this disadvantage of XRD, it is necessary behaviour of HVOF-sprayed molybdenum disilicide to use further analysis techniques for the detection of coatings at a temperature of 1500 °C is examined. phases, which are positioned deeper inside the coating. In the present investigation, the micro- 2 Methods structure of the coatings before and after oxidation is characterised additionally to XRD by scanning The molybdenum disilicide coatings are produced by electron microscopy (SEM) and energy dispersive X- high velocity oxyfuel spraying on polished ray analysis (EDXS). SEM, which is required to get an substrates and then detached from it [8]. The HVOF optical impression of the coatings, is applied on system used was Sulzer Metco Diamond Jet. fracture surfaces and on polished cross sections, The oxidation tests are carried out with a Netzsch while EDXS only is used to investigate polished cross simultaneous thermogravimetric equipment STA409C sections, because the dispersion of the rays is too at 1500 °C. To accelerate the oxidation, compressed great in the case of examining fracture surfaces. Only air flows with a rate of 100 cm3·min-1 through the phases with an area larger than 1 µm2 and a depth furnace. The mass change is measured in situ in exceeding 1 µm can be ascertained by EDXS. dependence on the oxidation time. The phase composition of the coatings is determined 3 Results by X-ray diffraction analysis (XRD) before and after oxidation. The X-ray diffraction pattern gives infor- 3.1 MoSi2 coatings before oxidation test mation about the phase composition of the samples volume, which is incited by the X-rays. The penetra- SEM investigations of the molybdenum disilicide tion depth of the radiation into the surface layer coatings before oxidation show the typical lamellar depends on the extinction coefficient µ and on the microstructure of a thermal spray coating, Fig. 2. way of the radiation through the coating. However, the Some different phases and pores as well as the intensity fractions for molybdenum disilicide is surface roughness are visible, Fig. 3. The phases are -1 -1 µ = 0.074 µm and for silicon dioxide µ = 0.0077 µm , identified by EDXS as MoSi2 (dark appearing parts) Fig. 1. In the case of molybdenum disilicide, phases and Mo5Si3 (brighter appearing parts) with MoSi2 as with a depth of more than 5 µm inside the coating can the main phase. be detected with only 15 % of their maximum intensity.

published at the ITSC 2004, Osaka, J, May 10th - 12th

0.60

0.50

0.40

0.30

0.20 mass change [%] mass

0.10

0.00 0 300 600 900 1200 1500 1800 time [min]

Fig. 4: Mass change of the MoSi2 coating during oxidation at 1500 °C

Fig. 2: MoSi2 coating “as sprayed” before oxidation 3.2 MoSi2 coatings after oxidation at 1500 °C (polished cross section, SEM) The microstructure of the coating after oxidation is significantly different from the microstructure of the coating before oxidation, fig. 5 - 8. A layer with a thickness of less than 10 µm is grown on the coatings surface, fig. 5. Its composition is determined to silicon dioxide by EDXS. XRD identifies the layer as SiO2 in its cristobalite modification, but with this technique it is not possible to find amorphous amounts of SiO2, which are expected after oxidation at 1500 °C.

Fig. 3: MoSi2 coating “as sprayed” before oxidation (polished cross section, SEM)

In XRD analysis two modifications of MoSi2 are detected. First, the tetragonal modification (α-modi- fication) with a C11b structure is found as the greatest fraction of the coating. Furthermore, a second modification of MoSi2 with a hexagonal lattice and a C40 structure is detected. This phase is the high temperature (β-) modification of molybdenum disilicide Fig. 5: MoSi2 coating after oxidation at 1500 °C and is merely detectable above 1900 °C, but the rapid (polished cross section, SEM) cooling during and after the spraying process is responsible for the existence of this phase after The microstructure of the coating shows a two phase system with sharply separated grain boundaries, spraying. Mo5Si3 occurs in its modification with a hexagonal lattice structure. The XRD pattern of the fig. 6. EDXS analysis shows that the dark appearing coating before spraying is shown in fig. 9 at the phase consists of MoSi2 and the bright one consists of bottom. The microhardness of the coating, which was Mo5Si3. measured on the polished cross section with a The different grains, which have a blocky structure, Vickers indenter, is measured to 830 HV0.05. are also clearly visible on the fracture surface of the The mass change in dependence on the oxidation MoSi2 coating, fig. 7. The dark oxide layer on the time at a temperature of 1500 °C is shown in fig. 4. coating surface appears smooth and glassy. It seems The mass increases parabolically and is only a little to be dense and shows some inclusions, fig. 8. These higher than 0.5 % after 25 h oxidation time. inclusions consist of the crystalline silicon dioxide which is embedded in an amorphous silicion dioxide matrix.

published at the ITSC 2004, Osaka, J, May 10th - 12th SiO2 layer is also detectable by XRD, but in the case of molybdenum disilicide only to a depth of about 5 µm. The two phases inside the coating are identified

by XRD to MoSi2 in its α-modification and hexagonal Mo5Si3.

Intensity

Fig. 6: MoSi2 coating after oxidation at 1500 °C 10 30 50 70 90 (polished cross section, SEM) 2 theta [°]

Fig. 9: XRD of the MoSi2 coating before (bottom) and after (top) oxidation

The amount of Mo5Si3 as well as the crystallinity of the single phases, which is detectable by the smaller peaks in fig. 9, are higher compared to the coating before oxidation. The ratio of MoSi2 to Mo5Si3 is calculated by means of PowderCell 2.3 software [10], which uses the data won by the XRD measurements as basis. The MoSi2/Mo5Si3 ratio decreases from 10.5 for the as sprayed coating to 4.6 for the coating after the oxidation at 1500 °C. Based on this data, it can be concluded that the oxidation of the MoSi2 coating follows the reactions given in equations (1) and (2).

Fig. 7: MoSi coating after oxidation at 1500 °C 2 5MoSi (s) + 7O → Mo Si (s) + 7SiO (s) (1) (fracture surface, SEM) 2 2 5 3 2

2MoSi2 (s) + 7O2 → 2MoO3 (s, g) + 4SiO2 (s) (2)

MoO3 is volatile at temperatures higher than 800 °C. Caused by the formation of the silicon dioxide layer, the molybdenum oxide accumulates below it. SiO2 has a high Pilling-Bedworth value of 2.15 [11], which means that the volume of the formed SiO2 is much greater than the volume of the metal needed to form the oxide layer. However, high residual stresses arise. When these residual stresses are too high, the SiO2 layer cracks in vertical direction and the volatile MoO3 escapes. So the mass of the coating decreases for a short time. After this process the silicon dioxide layer heals by itself caused by forming of new SiO2 and the mass increases, until the residual stresses in the silicon Fig. 8: MoSi2 coating after oxidation at 1500 °C dioxide layer become too high again. These (fracture surface, SEM) processes are the reason for the intermittent run of the curse of the mass change in fig. 4. As visible in fig. 1, the intensity of the X-rays is The microhardness of the coatings is measured to decreased by only 33 %, when the rays penetrate 1210 HV0.05. One reason for the increased micro through a silicon dioxide layer with a thickness of hardness after the oxidation test could be the higher 10 µm. So, the microstructure of the coating under the amount of Mo5Si3 in the coating. Indentation tests with

published at the ITSC 2004, Osaka, J, May 10th - 12th a Fisherscope equipment should prove this sup- [5] Baik, K.H., P.S. Grant, A.R. Bhatti and position in further investigations. R.A. Shatwell: Fabrication of SiC Fibre Reinforced MoSi2 Based Composites by Low Pressure Plasma 4 Summary Spraying. Proc. 1st ITSC (2000), ASM Int. Materials Park, OH, USA, pp. 821-827 The oxidation behaviour of high velocity oxy fuel [6] Wielage, B., S. Steinhäuser, G. Reisel, I. Mor- sprayed molybdenum disilicide coatings at a genthal and R. Scholl: Vacuum Plasma Spraying of st temperature of 1500 °C is examined by four analysis prereacted MoSi2 and SiC reinforced MoSi2, Proc. 1 techniques: thermogravimetric measurements, ITSC (2000), ASM Int. Materials Park, OH, USA, scanning electron microscopy coupled with energy pp. 865-869 dispersive X-ray analysis and X-ray diffraction [7] Reisel, G., B. Wielage, S. Steinhäuser, I. Mor- analysis. genthal and R. Scholl: HVOF Spraying of Prereacted The microstructure of the coatings changes during Molybdenum Silicide-Powders Produced by HEM. oxidation to a crystalline two phase system with MoSi2 Proc. Materials Week 2000, (2000), in its α-modification as the main phase and hexagonal (http://www.materialsweek.org/proceedings/index.htm Mo5Si3 as the second phase. A dense protective layer ) of silicon dioxide in the modification of cristobalite was [8] Wielage, B., G. Reisel, S. Steinhäuser, I. Mor- formed on the surface of the coating. The cristobalite genthal and R. Scholl: Oxidationsverhalten von crystallites are embedded in an amorphous silicon HVOF-gespritzten unverstärkten und verstärkten dioxide matrix. Molybdändisilizid-Pulvern. Verbundwerkstoffe und Werkstoffverbunde (2001), Wiley-VCH, Weinheim, 5 References pp. 582-587 [9] Reisel, G., B. Wielage, S. Steinhäuser, I. Mor- [1] Schlichting, J.: Molybdändisilizid als Kompo- genthal, R. Scholl: High temperature oxidation beha- nente moderner Hochtemperaturwerkstoffe. High vior of HVOF-sprayed unreinforced and reinforced Temp. High Press. 10 (1978), pp. 241-269 molybdenum disilicide powders, Surf. Coat. Techn. [2] Yao, Z.. J. Stiglich and T.S. Sudarshan: 146-147 (2001), pp. 19-26 Molybdenum Silicide Based Materials and Their [10] N.N.: PowderCell 2.3, Software zur Erstellung Properties. J. Mat. Eng. Perf. 8 (1999), pp. 291-304 von Pulverdiffraktogrammen aus Einkristalldaten und [3] Friedrich, C., G. Berg, E. Broszeit and zur Anpassung experimenteller Beugungsaufnahmen C. Berger: Datensammlung zu Hartstoffeigenschaften. [11] Schütze, M.: Protective Oxide Scales and Mat.wiss. u. Werkstofftechnik 28 (1997), pp. 59-76 their Breakdown, John Wiley and Sons, Chichester [4] Newman, A., S. Sampath and H. Herman: und Institute of Corrosion (1997), pp. 17ff Processing and Properties of MoSi2-SiC and MoSi2- Al2O3. Mat. Sci. Eng. A 261 (1999), pp. 252-260