Oxidation of Wi-52, A Cobalt-Base Superalloy C A R L E. Lowell
Oxidation of Wi-52, A Cobalt-Base Superalloy C A R L E. Lowell
Oxidation of Wi-52, A Cobalt-Base Superalloy C A R L E. Lowell
Lowell
The oxidation of WI-52 was studied by combining weight gain, high temperature X-ray diffraction, and high temperature microscopy exF periments. All experiments were carried out a t 1 8 0 0 ~ in static air. The weight gain data followed a parabolic curve, implying a simple diffusion controlled reaction. High temperature X-ray diffraction, however, revealed a complex oxide growth pattern. The strongest phase initially was COOwith C r 2 0 3 and Co4Cb205 a s minor phases. As the oxidation progressed, the COOand CrZ03 reacted to form a spinel, CoCr204. At the end of 100 hours, CoCr204 was by far the major oxide. High temperature microscopy showed complex oxide morphology changes. Initially, the grain boundary carbides, (Cb, W)C, oxidized rapidly. As this reaction slowed, the matrix oxidized uniformly, giving the color appearance of a thickening interference film. Finally, a nodular oxide nucleated in the middle of the matrix. This oxide spread laterally and in thickness until it covered all but the grain boundary oxide. Combining the results of all experiments led to a three-stage model of oxidation, The first was the oxidation of the grain boundary CbC and the nearby matrix to form Co4Cb209. The succeeding matrix oxidation consisted of COO formation with Cr203 formed between the Coo and the metal. The final stage was the reaction of COO and Cr20g to form CoCr204 and its subsequent growth over all of the surface except for parts of the grain boundary oxide.
The preceding paper shows that the use of superalloys in jet engines is currently limited by a lack of oxidation resistance a t operating temperatures hoped for in future designs. One approach to an oxidation resistance improvement of these alloys is through an understanding of their oxidation processes. This paper is an attempt at such an understanding. The oxidation of a superalloy is, however, a complex process which cannot rely on the use of a single experimental technique, such a s the weight change experiments described in the previous paper. This work is a synthesis of the results obtained from several techniques to form a comprehensive view of the oxidation of a superalloy. The f i r s t technique whose results a r e described is the standard oxidation t e s t weight change experiments. This technique is used to determine an overall rate of oxidation. To supplement this information with a knowledge of what oxides a r e being formed and their changes in relative abundance with time, high temperature X-ray
diffraction is employed. High temperature microscopy is used to obtain information concerning the change of morphology of the oxide with time. Finally, these results a r e combined with a conventional post mortem analysis by room temperature X-ray diffraction and metallography. This paper presents the results of the use of this approach on WI-52. This cobalt-base alloy is currently used in jet engines a t temperatures lower than those dictated by its strength potential.
While individual heats show slight variations, a l l samples in this work came from the same heat, thus making comparisons more reliable. The important elements from an oxidation standpoint a r e the first four, which a r e the major oxide f o r m e r s (Co, C r , W, and Cb). Figure 20-1 is the microstructure of as-cast WI-52. The matrix phase is basically a solid solution of C r , W , Fe, and probably Mn and Si in Co. At the grain boundaries a r e two kinds of carbides. Most of the carbides a r e needlelike (Cb, W)C. The r e s t a r e irregularly shaped particles of Cr6C. All samples were prepared by cutting to size followed by polishing t o a 0.5 diamond finish to remove surface roughness and s t r e s s . No heat treatment was given to the samples prior to oxidation.
Weight Gain
Figure 20-2 shows the results of the weight gain experiment, which was outlined in Dr. Probst's paper. The data a r e obtained by suspending the sample from a balance into a hot furnace and recording its change in weight a s a function of time. In this case the weight change per unit a r e a was squared and plotted against time. This is a commonly used technique to determine whether o r not the data fit a para-
bola. It is commonly assumed that if the weight change is parabolic then the oxidation process is simply a diffusion controlled layer growth. Although our data do fit such a parabola, the following shows that the usual conclusions do not apply.
Synthesis
Combining all of the previous sources of information gives the model for the oxidation of WI-52 shown in figure 20-7. The top line represents the unoxidized metal a s it reaches temperature. The dark vertical lines represent the (W, Cb)C, the triangle represents Cr6C, and the shaded a r e a represents the cobalt solid solution. As oxidation starts on the second line, the (Cb, W)C have begun t o oxidize to Co4Cb209 with the evolution of CO gas. The fact that one of the products of this reaction is a gas undoubtedly helps keep open a path for oxygen down the grain boundaries. This results in the subscale oxidation shown earlier. As the grain boundary attack slows, the matrix begins to oxidize to form a thin film of COO overlaying C r 2 0 3 . However, over the s m a l l Cr6C particles only C r 2 0 3 forms. Shortly after the COO film formation, the COO begins to react with the underlying C r 2 0 g to form CoCr204. The final stage shown on the bottom line shows how the CoCr204 has grown both in thickness and laterally to almost completely cover the surface. Note that the oxides over the carbides a r e the last to be covered and therefore the thinnest CoCr20q layers a r e a t that point.
CONCLUDING REMARKS
As a result of this investigation, we have gained an understanding of the intrinsic oxidation of WI-52. This understanding alone does not, however, solve the oxidation problems of this material f o r use in engines where thermal cycling, high gas velocity, and sulphidation a r e complicating effects. These factors were clearly defined by D r . Probst in his paper. This work, however, can be used for finding directions in which to proceed for improvement of oxidation resistance. It may also be used to predict the effect of variables such a s s t r e s s and microstructural changes on the ox-
dation process. For example, the microstructure might be altered to minimize subscale penetration of the oxide. Another possibility might be the use of surface s t r e s s to promote C r 2 0 3 formation and inhibit CoCr20q. This could be useful inasmuch a s C r 2 0 3 scales a r e more stable during thermal cycling than spinel scales. Even though we cannot solve all the problems associated with the corrosion of this alloy, we have established a base of information on which to build.
CS-52378
F ' 4 H
F i g u r e 20-1.
- Microstructure
of a s - c a s t WI-52.
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A
1 1 0 10 0
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Figure 20-3.
- Composition
BEAM SPLlllER
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@LIGHT SOURCE
pMTE $BJECTlVE QUARTZ
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LENS
THERMOCOUPLE
Figure 20-4.
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- High temperature
microscope.
Figure 20-5.
- High temperature
Figure 20-6. - Structure of corrosion zone on WI-52 (100 h r ; 1800' F). X750.
PRIOR TO OXIDATION
111
Figure 20-7.