OXIDATION OF WI-52, A COBALT-BASE SUPERALLOY C a r l E.

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.

MATERIALS AND PREPARATION

The following shows the nominal composition of WI-52:

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.

PROCEDURE AND RESULTS

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.

High Temperature X-Ray Diffraction

If, instead of suspending the sample in a furnace from the end of a balance, we heat the sample while it is positioned in an X-ray diffractometer, we get the results shown in figure 20-3. Here the relative X-ray intensity of phases in the oxide is plotted a s a function of time. These data were taken from X-ray diffractometer scans made a t frequent intervals while the sample oxidized. The major phase was COO initially. Also present a r e Cr203, Co4Cb209, and some spinel, CoCr204. With time the COO and C r 2 0 3 react to form CoCr20q causing a marked lessening of the amounts of the simple oxides. The spinel intensity continues to increase a t the expense of the other oxides until the end of the test (100 hr).

High Temperature Microscopy

Figure 20-4 shows the layout of the high temperature microscope. The sample is heated on a strip of platinum through which current is passed. Normal incident illumination is provided by a xenon lamp. The quartz plate prevents volatiles from the sample from coating the lens. The beam splitter allows focusing while the time lapse camera i s in operation. This equipment is used to photograph the changing morphology of the surface of an oxidizing sample. In the sequence shown, the time scale has been reduced by adjusting both the frame interval and the temperature. As oxidation begins, we first s e e the reaction of the grain boundary carbides with the matrix and oxygen to form Co4Cb209 (see fig. 20-5(a)). Next, the matrix begins to oxidize to COO with probably C r 2 0 3 underneath (fig. 20-5(b)). A change in color is noted due to interference film thickening a s the oxide layer grows. Also Cr2Q3 is formed over the Cr6C a t the grain boundaries. Now, in the middle of the COO layer nodules of CoCr2Q4, the reaction product of COO and Cr203, begin to form (fig. 20-5(c)). These nodules s t a r t the final stage of the process which is their growth upwards and laterally until they cover all but the a r e a s of Cr2 O3 which formed over the Cr6C and the Co4Cb209 which formed over the (W, Cb)Co (fig. 20-5(d)).

Post Mortem Analysis

After oxidation the samples were scraped f o r room temperature X-ray diffraction and sectioned for metallography. Room temperature diffraction confirmed the high temperature diffraction data a s to the oxides present. Figure 20-6 is the microstructure of WI-52 after oxidation for 100 hours a t 1800' F. The surface oxide appears to be single phase, CoCr204, and continuous but of varying thickness. Notice the rather extensive subscale corrosion along grain boundaries caused by the oxidation of the grain boundary carbides.

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.

X500.

HR

CS-52382

F i g u r e 20-2. - Parabolic weight gain of WI-52 in a i r ( 1 8 0 0 ~ F).

RELATIVE INTENSITY X-RAY

I
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A
1 1 0 10 0
CS-52381

HR
Figure 20-3.

- Composition

changes in oxide layer on WI-52 (1800' F).

BEAM SPLlllER

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VIEW AND FOCUSING

@LIGHT SOURCE
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LENS

THERMOCOUPLE
Figure 20-4.

cs-52573

- High temperature

microscope.

(a) Oxidation of (Cs,W)C to Co4Cb2Oy

(b) Oxidation of matrix to COO and C r 2 0 3

Figure 20-5.

- High temperature

microscopy of oxidizing WI-52.

(c) Initiation of CoCr204 formation.

(d) Growth of CoCr204. Figure 20-5. - Concluded.

Figure 20-6. - Structure of corrosion zone on WI-52 (100 h r ; 1800' F). X750.

PRIOR TO OXIDATION

GRAIN BOUNDARY ATTACK ON CARBIDES

111

GROWTH OF OXIDE FILMS ON MATRIX INITIATION OF CoCr204 OXIDATION AFTER 100 HR

CS-52383

Figure 20-7.

- Sequential oxidation of WI-52.