JOURNAL OF NUCLEAR MATERIALS 12, 2 (1964) 208-215, NORTH-HOLLANDPUBLISHING CO.

, AMSTERDAM

"PEST" DEGRADATION IN BERYLLIDES, SILICIDES, ALUMINIDES, AND R E L A T E D COMPOUNDS

J. I-I. W E S T B R O O K and D. L. WOOD

General Electric Research Laboratory, Schenectady, .N.Y., USA

Received 10 April 1963 and in revised form 24 J a n u a r y 1964

Many intermetallic compounds, although possessed of good oxidation resistance at low and high temperature, fail catastrophically in some intermediate range b y degradation to p o w d e r - - t h e so-called pest phenomenon. The present study shows t h a t grain boundary hardening, arising from local concentrations of oxygen or nitrogen and developed b y heating the compounds in air, is an indicator of susceptibility to the pest. Among the observations made on MoSi2, NiA1, various beryllides, and TiB2 are the effects of stoichiometry and heat treatment. On the basis of experimental observations, a model is proposed in which such degradation results from preferential intergramflar diffusion of a gaseous element, coupled with a temperature dependent hardening reaction. De nombreux composds intermdtalliques, bien qu'ils poss~dent une bonne rdsistance k l'oxydation aux temp6ratures faibles ou dlev6es tombent de manibre catastrophique en poussibre par tree sorte de d6gradation. C'est le ph6nombne appel6 "peste" des composds. L'dtude pr(~sente montre qu'un durcissement aux contours de grains provenant de concentrations locales en oxyg~ne ou azote et favorisd par le chauffage de ces composds darts Fair est un test de cette suseeptibilitd au phdnom~ne de "peste". P a r m i les observations faites sur MoSie, NiA1, diffdrents composds du bdryllium et TiB2, on a consid6rd les effets

de la stoeehiomgtrie et du traitement thermique. En se basant sur les observations expdrimentales, on propose a n module duns lequel une telle ddgradation rdsulte de la diffusion intergranulaire prdfdrentielle d ' a n dldment gazeux combin6e k une rdaction de durcissement d6pendant de la temp6rature. Viele intermetallisehe Verbindtmgen zeigen in bestimmten Bereichen einen katastrophalen Zerfall zu Pulver, obwohl sic im allgemeinen tiber eine gute Oxydationsbestiindigkeit bei niedrigen und hohen Temperaturen verfiigen. Man neimt diese Erscheinungen "Pestph/~nomen". Die vorliegenden Untersuchungen zeigen, dass die Korngrenzenh~rtungen ein Indikator fiir die Empfiinglichkeit dieser " P e s t " sind. Die Korngrenzenh/~rtungen gehen yon lokalen Sauerstoff- oder Stickstoffkonzentrationen aus, welche durch Erhitzen der intermetallischen Phasen in Luft entstehen, g e l den Beobachtungen, die an MoSi2. NiA1, verschiedenen Berylliden lind TiB2 gemacht wurden, spielen die Effekte der St6chiometrie und ~V/~rmebehandlung eine Rolle. Auf der Grtmdlage dieser experimentellen Ergebnisse wird ein Modell entwickelt, in welchem der Zerfall zu Pulver aus einer vorherigen intergranularen Diffusion eines gasf6rmigen Elementes erkl~trt wird. Diese intergranulare Diffusion ist gekoppelt mit einer temperaturabhi~ngigen H/irtungsreaktion. integral bar to a mass of powder. By superficial analogy to the well known low temperature disintegration of tin, the so-called "tin pest", t h e p h e n o m e n o n w a s n a m e d b y F i t z e r 1) t h e m o l y b d e n u m d i s i l i c i d e " p e s t " . U n l i k e t h e case of tin, however, the catastrophic disintegration of molybdenum disilicide could not be linked to a crystallographic transformation. Rather, it s e e m e d t o b e a u n i q u e f o r m o f o x i d a t i o n since

1.

Introduction

Molybdenum disilicide has long been known for its excellent oxidation resistance at very h i g h t e m p e r a t u r e s (of t h e o r d e r o f 1500 C). Early investigators, therefore, were startled to discover that at much lower temperatures the material exhibited a dramatic degradation. Exposure in air for even a few minutes at temperatures near 700C could convert an 208

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it could be prevented if the sample was heated in an inert atmosphere. Unfortunately, the term "pest" seems now to be well established as a descriptor for the effect. For some time the pest effect was thought to be unique to MoSi2. Review of the literature discloses, however, that the effect is quite common among intermetallic compounds and that the experimental record dates back at least to 1899 with the observations of Sperry 2) on certain nickel aluminides. Thirty five years later, Tamman and Ruhenbeck 3) (in a paper which has apparently been lost sight of in recent years) summarized previous observations of the disintegration of intermetallics and added many new observations of their own. Table 1 lists all the presently known instances of occurrence of the pest effect t. Eight different classes of compounds and m a n y different crystal structure types are included. Among the common, but not universally observed, features of the phenomenon are the following : (1) Attack is predominently intergranular (although a considerably moderated form of disintegration has been observed in single crystals) 5). (2) Attack does not occur in inert atmospheres 1,3,8,9,17). (3) Disintegration will occur under either isothermal conditions or thermal cycling conditions as long as there is some exposure in the critical range 17). (4) Disintegration occurs at a time and place where the volume fraction of oxide formed is negligible 1,3,5,7). (5) The temperature range for the effect is specific to a given compound.
t All c o m p o u n d s a p p e a r i n g i n t h e T a m m a n a n d R u h e n b e c k article a) a r e so referenced. T h e r e a d e r is r e f e r r e d t o t h a t p a p e r for c i t a t i o n of t h e earlier l i t e r a t u r e . I n s o m e cases, t h e f o r m u l a t i o n of t h e compound has been changed to conform to present day designation.

(6) The period of rapid oxidation during which the powdering reaction occurs is preceded by an incubation period 5). (7) The effect can be aggravated by the presence of moisture in the atmosphere 3,8,14,18). (8) The effect can be aggravated by the presence of minor amounts of impurities in the compound, e.g., P in FeSi2 3,s), Zr in CbA13 5). (9) The effect can be moderated by high temperature preoxidation or by appropriate alloying 19). Although m a n y speculations have been advanced to account for the phenomenon, no detailed model yet exists which accounts for all the experimental observations. Recently, Westbrook and Wood 2o) discovered t h a t segregation of solutes at grain boundaries in a wide variety of materials could be revealed by a simple microhardness test. Grain boundary hardness values up to 50 % above that of the grain interior were observed in phase-pure material. Not only indentations centered on the boundary itself but also those some tens of microns away were found to be affected. On the other hand, no difference in grain boundary and bulk hardness could be detected in cases where segregation was known to be absent. Subsequently, Westbrook and Wood 21) made a detailed study of segregation in a variety of intermetallic compounds using the microhardness technique. I t was found t h a t in these materials the segregating solutes were oxygen and/or nitrogen which were either present in the starting material or absorbed during processing of the solid compounds. One of the strong evidences for this conclusion was the occurrence of marked hardness gradients along grain boundary paths perpendicular to the gas/metal interface. Concentration of the gaseous solutes along grain boundaries resulted in accentuated grain boundary embrittlement as evidenced by the completely intercrystalline fracture and a sharp increase in the ductile-

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brittle transition temperature. It was further observed that the local hardening produced by such concentrations was dependent both upon heat treatment and upon stoichiometry as illustrated in fig. 1 for a series of NiA1 compositions, all of which are within the phase field of this CsC1 structure. Grain boundary hardening only occurred in slowly cooled samples containing an excess of the more electropositive element. Finally, oxygen and/or nitrogen induced grain boundary hardening was found to be highly sensitive to the presence of small quantities of metallic solutes in the compounds.
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diffusion rates become comparable but also because the hardening reaction itself is sharply temperature dependent. The lower temperature limit of the pest effect is thus the temperature at which appreciable intergranular gaseous diffusion occurs during the time of the experiment ; the upper temperature limit, the temperature at which grain boundary hardening decreases abruptly.
3. Experiments

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Results are presented here which, in the authors' opinion, strongly support the above model and afford a basis for formulating a more definitive program of research on the problem. The majority of the specimens tested were arc-melted samples which were on hand in the authors' laboratory, residue from previous investigations. Beryllide samples, prepared by hot pressing, were obtained from E. A. Aitken, of NMPO Staff, G. E., Evendale, Ohio. Details of the experimental techniques are given in an earlier publication 21).
TABLE 2 Incidence of g r a i n b o u n d a r y h a r d e n i n g in selected in~rmetallic compounds some

Fig. 1.

Effects of h e a t t r e a t m e n t and stoichiometry on grain b o u n d a r y h a r d e n i n g in NiA1.

2.

A Proposed Model
Compound

The general parallelism between many of the above observations on solute induced grain boundary hardening and those previously reviewed for the pest phenomenon leads to the following model for the pest effect. At low temperatures where oxygen diffusion rates are low, reactions are confined to regions near the external surface of the sample. Over some intermediate temperature range oxygen diffuses rapidly through the sample along grain boundary paths but volume diffusion of oxygen is still very limited. Oxygen so confined to the grain boundary region embrittles the material by virtue of the sharp hardness increase, and internal stresses arising by one mechanism or another then fragment the specimen along the grain boundaries. At high temperatures the local hardening and embrittlement are relieved, not only because the grain boundary and bulk

Relative grain boundary hardening

AHIH(%)
MoSi2 . . . . . . . . . TiB2 . . . . . . . . . ZrBeza . . . . . . . . . Zr2Bez7 . . . . . . . . TaBez2 . . . . . . . . AgMg (Mg-rich) . . . . NiA1 (Al-rich) . . . . . . . . . . . .

35
18

20-50 30 55 20-50 25-60

A number of polycrystalline samples of compounds for which pest effects were known or suggested, were examined for incidence of grain boundary hardening with the results given in table 2. Values for AgMg and NiA1 from previous studies are included for comparison. It must be emphasized that the samples tested were not necessarily in equivalent condition. All that can be said is that all specimens had been exposed while hot to an oxygen bearing

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Fig. 2. Separated grains of an AgMg sample disintegrated by action of nitrogen at 700 C. atmosphere and all had been slowly cooled from a high homologous temperature. Although no studies were made of the powdering reaction as such, the inference is strong, in light of the previously reviewed literature, that grain boundary hardening is an indicator of susceptibility to the pest effect. The results obtained, however, prompted inspection of a series of coarse grained AgMg compositions which had been exposed to room temperature laboratory atmosphere for a period of years. Samples containing a stoichiometric excess of magnesium were found to have disintegrated completely to powder. Study of the individual powder particles revealed that they were for the most part single crystals of a size comparable to the grains of the original specimens; that the amount of oxide at the surface of these particles was slight; and that although, as described above, the sample had spontancously disintegrated the individual particles were still malleable. A similar magnesium-rich AgMg specimen prepared for another study was intentionally subjected to a nitrogen atmosphere at 700C and slowly cooled. Following this treatment the sample separated readily into individual grains having clean bright surfaces as shown in fig. 2. Some experiments were done to measure the extent of grain boundary hardening in com-

pounds which exhibit the pest effect. A typical example is shown for aluminum rich NiAI in fig. 3. The curve with the open points is for indentations made on grain boundaries where they intersected a random metallographic section. To establish whether or not the apparent breadth of the hardened region is affected by the mechanical constraint of the contiguous grains, another experiment was performed on the same specimen. The embrittled sample was separated and the hardness of a relatively planar grain boundary surface was measured. To obtain data as a function of distance from the boundary surface, the load on the indenter was varied to obtain different degrees of penetration. The effective depth of indentation was then calculated from the indenter geometry and the measured width of the indentation. These results are shown by the curve with the filled points in fig. 3. It is apparent that the effects of the contaminated grain boundary region can be sensed some 20# or so from the boundary itself and t h a t this distance is not substantially altered by the removal of constraints imposed by neighboring grains. It was previously cited, and illustrated in

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Good correspondence is observed between the temperature of disappearance of the boundary hardening and disappearance of the pest effect as reported in the literature cited in table 1. An exact correspondence with literature results is perhaps not to be expected in view of the reported variation in temperature range of sensitivity. In view of the model and the findings of this study such variation could result from differences in stoichiometry, purity, and composition of the atmosphere.

TEMPERATUREC OF

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Fig. 4. Grain boundary hardening as a function of quenching temperature in MoSi2, NiA1 and ZrBe13. fig. 1, that grain boundary hardening induced by oxygen penetration is affected by a quenching heat treatment. It remained to establish a connection between the critical temperature for solute-induced hardening and the disappearance of the pest phenomenon. It was shown previously 21) for the case of AgMg that specimens quenched from above the critical temperature and then aged at temperatures near room temperature show a progressive increase in the relative grain boundary hardening with time until an equilibrium hardness level is reached typical of that aging temperature. For refractory materials like NiA1 it was also shown that no significant aging takes place at room temperature. Therefore, relative hardness values at room temperature on samples given an aging treatment at an elevated temperature and again quenched are characteristic of the aging temperature. Three compounds were selected for study representing each of the principal classes exhibiting the pest effect : MoSi2, ZrBe13 and NiA1. A preliminary set of experiments established that a quenching temperature of 1000 C was adequate to prevent grain boundary hardening in all three cases. A new set of samples was then prepared to which, following the 1000 quench, 1 hour aging treatments at a series of temperatures were given and the samples again quenched. The relative grain boundary hardening curves for these samples are shown in fig. 4.

4.

Discussion

The results of this study reinforce the concept of the pest phenomenon as one embodying preferential intergranular diffusion of oxygen but with the important new feature of a temperature dependent hardening reaction. It cannot be said that heat treatment will prevent pest type powdering, but a significant increase in impact strength has been observed 21) in NiA1 samples given an appropriate quenching treatment. The moderated form of disintegration observed by Rausch 5) in single crystals of MoSi2 is probably a result of diffusion alon~ subgrain boundaries. The rate of penetration of oxygen along such surfaces would be expected to be lower than along high angle grain boundaries. It is obvious why the pest effect is not observed in a truly inert atmosphere. The present study adds nitrogen as a possible pest agent. Undoubtedly, other gases can play a similar role in specific instances. Russian workers s) have speculated on a possible action of water vapor to produce phosphene in phosphorus containing FeSi2. The effect of stoichiometry is believed to be general, although difficult, if not impossible, to verify in the cases of compounds of discrete composition such as the majority of beryllides and silicides. The incubation period noted b y Rausch 5) is at least partially explained as the time required for complete boundary penetration b y the diffusing gas. Since complete grain boundary hardening is observed when the increase in gas

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content is relatively small, it is reasonable that powdering is frequently obtained before oxide phase can be detected by either light or electron microscopy. In fact, since the hardening reaction is not yet defined 20,21) it may be questioned whether any oxide formation takes place prior to the disintegration process and the formation of additional free surface. It is not clear whether gas induced grain boundary hardening and pest effects will still occur in specimens which have been thoroughly equilibrated at high temperatures. This experimental ambiguity results from lack of knowledge of the diffusion rates and solubilities of oxygen and nitrogen in intermetallics as well as from the very low levels of gas concentration apparently necessary for the effect. Experimental achievement of a truly inert homogenization atmosphere is thus very difficult. "Equilibrium" segregation of one or more solute s])ccies, may also possibly exist as suggested earlier 20,21). Specific mechanisms for the various observed effects of impurities on the pest-phenomenon cannot be ascribed without much more information o~ the systems in question. There is no lack of potential mechanisms, however. Effects of diffusion rates, segregation coefficients, internal stresses, effective stoichiometry, etc. can all be imagined. Many more basic problems remain unsolved, for example : 1. Why is the effect particularly prevalent in intermetallics ? 2. Why is the marked ? effect of stoichiometry so

ature, stoichiometry and atmosphere. One such study has been carried out in the authors' laboratory on the model compound NiGa 23). This study supports the general model outlined herein and confirms the previously observed phenomenology.

Conclusions
1. A model for pest degradation is proposed, based upon preferential grain boundary diffusion of a gaseous element together with a temperature dependent hardening process caused by concentrations of that element in in the grain boundary region. 2. Microhardness measurements are shown to be capable of following the early stages of grain boundary contamination. 3. Nitrogen as well as oxygen can be a pest agent. 4. Pest degradation is dependent on stoichiometry. 5. Grain boundary hardening, a precursor of pest degradation, has a temperature dependence such that this dependence may be used to predict roughly the temperature range of pest susceptibility for a given compound.

Acknowledgements
The authors express their gratitude to Mr. A. J. Peat, who carried out much of the experimental work reported herein. This work was supported in part by the U. S. Air Force, Wright Air Development Division, under Contract No. AF-33(616)-7714.

3. What is the origin of the sharp temperature dependence of grain boundary hardening? 4. Is grain boundary segregation a necessary condition for the pest effect? A valuable initial contribution in attacking these and other problems would be a kinetic study of the grain boundary diffusion and hardening processes together with a more detailed examination of the effects of temper-

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2)

3)

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