Eur. Phys. J.

AP 5, 1931 (1999)

THE EUROPEAN PHYSICAL JOURNAL

APPLIED PHYSICS
c EDP Sciences 1999

Liquid metal embrittlement: A state-of-the-art appraisal

B. Joseph, M. Picat, and F. Barbiera
CEA-CEREM/SCECF, BP 6, 92265 Fontenay-aux-Roses Cedex, France Received: 18 June 1998 / Revised: 29 September 1998 / Accepted: 22 October 1998 Abstract. Although the risk of embrittlement of materials exposed to liquid metals has been recognized for many years, its prediction remains problematical insofar as the knowledge of the mechanisms involved in the phenomenon is limited. However, Liquid Metal Embrittlement (LME) is of prime interest because the risk of damage exists wherever the handling of liquid metals is required in various industrial or scientical elds (chemical plants, power-producing systems, soldering process, ...). The interest for this phenomenon needs thus to be pursued. The present paper reviews experimental results about the occurrence of LME and the inuence of dierent parameters, and presents a number of mechanisms which have been proposed to explain LME. PACS. 81.90.+c Other topics in materials science

1 Introduction
The phenomenon of Liquid Metal Embrittlement (LME) may be dened as the brittle fracture, or loss in ductility, of a usually ductile material in presence of liquid metal. Some authors add to this denition the necessary inuence of an external load or the presence of internal residual stresses: actually, it has long been known that LME, during a tension test, results in a signicant reduction in elongation to failure and fracture strength [1]. However, it is also possible for some ductile materials to become brittle without any stress, the best example being the Alsolid Galiquid system [2]. Embrittlement in liquid metal environments has been the subject of many reviews describing the phenomenological features of the LME, the prerequisites for its occurrence, the eects of variables including grain size, strain rate, temperature, metallurgical state... (Rostoker et al. in 1960 [3], Stolo in 1968 [4], Nicholas et al. in 1979 [5], Old in 1980 [6], Kamdar in 1973, 1983 and 1987 [79]). Actually, a qualitative explanation of LME has not yet emerged and its prediction is still missing, despite decades of research. Empirical predictions of LME susceptibility have been proposed, such as embrittled systems usually have a low mutual solubility and a lack of intermetallic compounds, but this tentative correlation is not completely reliable. It is therefore appropriate to review LME in the light of more recent work, to provide a current assessment of this phenomenon. In the second section of this review, we will make a summary of the experimental results reported in the literature in order to compare the basic characteristics of LME
a

and the inuence of parameters, to the predictions of models. In the third section, we will focus on the most important models which have been advanced so far to describe the LME. We will underline the elementary mechanisms involved in each model, and propose a diagram that recapitulates the links between those mechanisms. Then, we will do an analysis of each model based on experimental results and on comments found in the literature.

2 Experimental results on LME

The main purpose of this section is to present experimental facts about LME, in order to compare these with the results of the models that will be detailed further. After a characterization of the phenomenon, we will analyse the inuence of the dierent parameters involved. Experimental data depend a lot on the systems studied, and for a given system, diers sometimes from one author to another.

2.1 Description of the occurrence of LME Under certain experimental conditions, LME can be quite dramatic and one of the peculiarities of this phenomenon is the crack propagation rate which is reported to be very high. Other striking results are the drastic reduction of strain to rupture and the modication of stress-strain curves in presence of liquid metal. These rst experimental results have allowed the characterization of the LME phenomenon by simply studying some parameters that have been modied from an inert medium to a liquid metal environment.

e-mail: barbier@cyborg.cea.fr

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Fig. 1. Dependence of zinc monocrystals fracture strain on temperature and environment : (a) air, (b) mercury (after Rozhanskii et al. [12]).

2.1.1 Rate of crack propagation The most striking characteristic of LME is a very high propagation rate, in comparison with the rate in air or vacuum. Dierent results can be found in the literature, but they are all in the range of one centimeter to several meters per second [7,10]. This dierence in propagation rate is mainly due to important dierences in the characteristics of LME that exist from one solid metal-liquid metal system to another. According to some authors, the propagation is not the controlling stage: by instance, Glickman [11] asserts the existence of a slow precritical crack propagation stage, which is the controlling stage of failure. During this stage, the propagation rate is 107 to 103 cm s1 . In fact, the controlling stage, whose rate is quite low, induces a delayed failure that is not observed in every system. 2.1.2 Strain to rupture In almost every tension test in liquid metal reported in the literature, strain to rupture is drastically reduced in comparison to the same test in vacuum or in air. For example, Rozhanskii et al. [12] showed (Fig. 1) that in a dened range of temperature the strain to rupture is largly reduced by the presence of liquid metal. This limited range of temperature is called ductility trough, because it corresponds to the range of temperature where the solid metal shows a loss of ductility. For example, in Figure 1, under 150 C fracture strain is drastically reduced, and above 150 C, it is equal in air and in liquid metal. The lower limit of this trough is a temperature close to the melting temperature of the liquid metal. At a higher temperature, we can observe a recovery of ductility. We will study the inuence of the temperature (cf. Sect. 2.4.1). 2.1.3 Stress-strain curves When we compare the stress-strain curves obtained by several authors, two main trends are emerging. The rst one, sustained by Westwood [13] and Stolo [14], claims that until fracture occurs, the stress-strain behaviour of the solid metal is the same as that in the unwetted conditions (Fig. 2). The second one, sustained by Popovich [15], asserts that there is an initial promotion of plastic ow, and consequently, a dierent behaviour of the metal in presence of liquid metal before rupture (Fig. 3). In the two cases, the elastic domain is unchanged in presence of a liquid metal: the yield stress is not modied by an embrittling environment. However we can point out that in Popovich experiments, a part of the plastic zone is the same in vacuum and liquid metal.
Fig. 2. Embrittlement of polycrystalline aluminium: comparison between the behavior of aluminium in vacuum and in various mercury solutions (after Westwood et al. [13]).

Fig. 3. Stress-strain curves of Armco iron specimens tested in bismuth (continuous lines) and in vacuum (dashed lines) at 350 C, 400 C and 550 C (after Popovich [15]).

2.2 Analysis of the inuence of the liquid and solid metals compositions Compositions of solid and liquid metals are reported to inuence LME, that is to modify propagation rate, strain to rupture... In this subsection, experimental results about this inuence on the severity and the domain of application of LME, are presented.

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2.2.1 Composition of the liquid metal The eects of the liquid metal composition are often signicant. If we consider the eects of additions to the embrittling metal, the result can be either a decrease of the embrittlement or an increase of it. Sometimes, it may also have no inuence on the phenomenon. Besides this inuence on the degree of the embrittlement, the composition of the liquid metal can even modify the range of manifestation of LME. By instance, Preece and Westwood [16] have shown that the brittle to ductile transition temperature of aluminium (which corresponds to the upper limit of the ductility trough) is increased by gradually adding gallium to a mercury environment. Composition of the liquid metal also modies several physico-chemical parameters of the solid metal-liquid metal system (interfacial energy, mutual solubilities, ...) which are supposed, by many authors, to inuence the mechanism of LME, as we will examine in the next subsection.

Fig. 4. Interfacial energy between copper and bismuth-lead melts at 350 C as a function of lead concentration in melt [20], and grain-boundary energy at 950 C as a function of antimony concentration in copper [21] (after Glickman [11]).

2.3 Analysis of the inuence of the physico-chemical properties of solid and liquid metals 2.2.2 Composition of the solid metal The eect of alloying (additions to initial composition of the solid metal) has been widely studied in the literature, and the results are dierent from one author to another. Some additions can increase the eect of LME, some others can prevent the solid metal from it. However, the fact that the main inuence of an alloying element takes place at the level of grain-boundaries is commonly accepted. A study of the deformation at fracture, as a function of the composition of the solid metal has shown that the maximum eect on LME corresponds to a concentration of alloying additions in solid solution which ensures adsorption saturation at grain boundary [11]. In this section, we examine the physico-chemical interactions between the two metals (formation of intermetallics, wettability, mutual solubilities and penetration of liquid metal atoms in the solid metal), which are directly inuenced by their composition and microstructure. Many authors have tried to classify all the systems by considering their physico-chemical properties. The number of properties that are relevant for several systems is important, but very few of them seems to be appropriate for all the systems. Here is the analysis of the most important of these properties; others, as electronegativity, could have been presented, but they do not lead to a better classication nor explanation of the phenomenon. 2.3.1 Interfacial and grain-boundary energies 2.2.3 Microstructure of the solid metal The hardness and deformation behaviour of the stressed solid can aect its susceptibility to LME, the hardest materials normally being more severely embrittled. Thus, the microstructure of the solid metal inuences its susceptibility to LME. However, this increase in the severity may be oset if it is achieved by cold-working, since this can decrease the grain size [17]. Actually, the average size of the grains is pointed out by many authors to have two distinct eects on LME: in the rst place, LME is enhanced by an increase in grain size and there is a linear relation between the true tensile strength and d1/2 , where d is the average grain size, i.e. LME follows the Cottrell-Petch relationship of grain-size dependence on fracture stress [18]; in the second place, the brittle to ductile transition temperature is increased by an increase in grain size and there is a linear relation between this temperature and log(d) [19]. Among the physico-chemical parameters of the solid metal-liquid metal system, the interfacial energy SL (for the crystal-melt interface) and the grain-boundary energy b , are of rst importance, and they are considered in almost every LME model (Sect. 3), and thus, their variation is very likely to inuence the characteristics of LME. As an example, we can see in Figure 4 that on the one side, the composition of liquid metal modies the interfacial energy [20], and on the other side, the composition of the solid metal induces a variation of the grain-boundary energy [21]. 2.3.2 Formation of intermetallics Some authors (Kamdar [7], Shunk and Warke [22], ...) have introduced the notion of specicity of the LME phenomenon, that is the fact that only certain liquid metals embrittle certain solid metals.

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For this purpose, they have proposed an empirical law which claims that a system of a solid metal and a liquid metal that forms intermetallics can not undergo LME. However, Chaevski and Popovich [23] noticed that this empirical law is followed by some systems (gallium reacts with Armco iron to form intermetallics and no LME is observed) but not for all (tin forms intermetallics with iron and it produces LME).

2.4.1 Temperature As it has been pointed out in Section 2.1.2, LME occurs in a certain temperature range, called ductility trough. This domain is generally considered as depending on. The compositions of both solid and liquid metals, the structure of the solid metal and the external conditions. Inside this domain, the susceptibility of embrittlement may, in most cases, remain unchanged with temperature. The lower temperature of the ductility trough corresponds in many systems, to the melting point of the embrittling metal, but some embrittling metals have been reported to induce embrittlement in a solid state. This phenomenon has been called Solid Metal Embrittlement (SME). Anyway, this lower limit of the temperature domain of occurrence of LME is supposed to depend only on the nature of the embrittling metal. The higher temperature seems to depend mainly on the strain rate, as explained in the next subsection. Beyond this inuence on the domain of existence of LME, temperature has been reported to inuence the kinetics of LME. According to Glickman, the ratecontrolling stage is a slow subcritical growth, which is thermally activated. For the solid copper-equiatomic bismuth-lead bath system, the eective activation energy is Q = 0, 38 eV [11]. 2.4.2 Strain-rate According to Glickman, the relation between the strain rate and the crack propagation rate is nearly linear for the bismuth-copper system [11]. For Popovich, at slow strain rates, thus in conditions favorable for intense stress relaxation, the only eect of adsorption-active media is to ease plastic ow, i.e. to inhibit LME. With a decrease in strain-rate, the upper temperature of the ductility trough drops, which leads to narrowing of the temperature range of brittleness or to its disappearance. 2.4.3 Stress In some denitions of LME [7], an applied or residual stress () is a necessary prerequesite. In this context, the embrittlement of aluminium by liquid gallium, which can occur without any stress, is dened as another phenomenon than LME. In fact, the main problem about the presence of stress is to know whether the metal studied is free of stress or is containing high stress concentrations. Actually, grain-boundaries and other obstacle may serve as a stress concentrator. LME would occur only with stresses exceeding a threshold stress. The latter is not reported by all the authors, because some of them may have worked on a system for which the threshold stress is very low. Moreover, there are experimental results about stress dependence during creep tests: according to Glickman, the time to rupture c is a linear function of 2 [11], and for Popovich, the stress dependence of creep rate, plotted in logarithmic coordinates, is linear [25].

2.3.3 Mutual solubilities Another aspect of the specicity of LME is the requirement of low mutual solubilities. According to Kamdar [7], it could be related to diculty of propaging a brittle crack in a solvent environment because dissolution processes will tend to blunt the crack. However, it is sometimes stated that a very limited amount of solubility of a liquid metal in a solid metal is required to facilitate wetting [3]. Once more this criterion of low mutual solubilities knows exception such as the copper-bismuth or the aluminiumgalium systems and thus cannot be used as permanent rule.

2.3.4 Wetting Wetting is often considered as a necessary condition for LME to occur. If the contact between the solid metal and the liquid metal is interrupted by the presence of an oxide lm, or by removal of the liquid metal after preliminary contact, LME does not occur. It has to be noticed that the conditions for this specicity, that is low mutual solubilities and no formation of intermetallics, are in conict with the condition of good wetting since many studies associated good wetting with some degree of mutual solubility [3]. This discrepancy led Stolo [4] to regard parameters derived from wetting data as being irrelevant to the interpretation of LME. However, Old [5,6] reports that this view must be revised in the light of advances made in surface study techniques. In fact, wetting studies can now be conducted on clean surfaces and excellent wetting can be achieved even with systems having negligible solubilities. Consequently, these notions have no longer to be opposed. Anyway, the contact has to be good to produce LME, and the growth of cracks can be stopped if the supply in liquid metal is limited or interrupted. The issue of the supply of liquid metal has been extensively studied by Gordon [24] (Sect. 3.7.2).

2.4 Analysis of the inuence of the external parameters Many improvements have been done in the eld of the inuence of external parameters. Lots of experimental results have given a strong basis to compare to LME models. This list of parameters is not complete, but it corresponds to the most commonly studied.

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Fig. 5. Diagram illustrating all the elementary steps involved in the dierent LME models.

2.4.4 Time of exposure before testing In many studies, it was proved that preliminary contact of the solid metal in the embrittling medium did not enhance brittleness. By example, some systems such as aluminiummercury and (zinc-copper) alloy-mercury seem not to be sensitive to the time of exposure before testing, since the fracture stress is not inuenced by it [26].

to make a quick comparison between the dierent models and to see whether they use common elementary mechanisms or not. Furthermore, if we make this hypothesis that several mechanisms can occur at the same time to produce LME, as it has been proposed, this diagram gives a general overview of all the mechanisms that could be involved.

3 Mechanisms of LME
Here are presented dierent models that have been proposed so far to explain the LME phenomenon. This list is not complete, but the main purpose is to present the most outstanding models. For each of them, we recall the elementary mechanisms which are involved and we give its description. Then we report an analysis showing its limits or/and its possible improvements compared to other models. The models are summarized in Figure 5. This diagram describes, for each model, the sequence of the elementary mechanisms leading to the propagation of cracks in presence of stress and liquid metal. They are represented by arrows, which are numbered in order to link the following description of the models to the diagram. It allows

3.1 Summary of the dierent approaches of LME There are six dierent models of LME mechanism: the dissolution-diusion based models of Robertson (Sect. 3.2) and Glickman (Sect. 3.3); the brittle fracture theory based model, denominated SJWK (Sect. 3.4), proposed by Stolo, Johnson, Westwood and Kamdar; the ductile failure based models of Lynch (Sect. 3.5) and Popovich (Sect. 3.6); the liquid metal atoms penetration based model of Gordon (Sect. 3.7). The concept of the adsorption-induced surface energy lowering is the central point of all these models, excepted for Robertson who does not mention the occurrence of

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The magnitude of the stress at the crack tip, due to the applied stress a is given, for a long narrow crack, by the relation: L (1) r The concentration of the solute in the liquid, C , is equal to the equilibrium concentration in the presence of an unstressed at surface, C0 , plus the excess concentration due to the stress at the crack tip, C (), plus the excess concentration due to capillarity, C ( ). After calculations, the excess concentrations are given by: = 2a
Fig. 6. Crack of length 2L, thickness 2r, and tip radius r, subject to an applied stress a [30].
2 C0 2La (2) ErkT C0 C ( ) = (3) kT r with , the atomic volume of the solid, E the Youngs modulus of the solid metal, k the Boltzmann constant, T the temperature and the solid-liquid interfacial energy. Consequently, the concentration in the vicinity of the stressed crack tip is:

C () =

adsorption. This concept has rst been introduced by Rebinder and it is known as the Rebinder eect (RE). The RE is one of the eects exerted by a liquid or a gaseous medium on the mechanical properties of solids [2729]. It appears as a plastic ow increase and a strength reduction. The origin of the RE is the surface free energy reduction caused by adsorption which is a localized physicochemical interaction between a solid and the medium at the interphase boundary. The main problem in using the Rebinder eect to describe LME is that it has a pure thermodynamic character. That is the reason why many authors have improved his work by adding molecular mechanisms and/or by adding kinetic modelization of the phenomenon. 3.2 Robertson model Robertson [30] has presented his dissolution-diusion based model in 1966. The main purpose of his theory is to give an expression for the crack propagation rate. There is no reference to a crack initiation stage, consequently the nal expression concerns only the propagation rate. This model uses only macroscopic, thermodynamic and elastic concepts. 3.2.1 Elementary Mechanisms The presence of liquid metal at the crack tip results in a dissolution of the solid metal (Fig. 5, arrow 1) which is enhanced by stress and capillarity eects (Fig. 5, arrow 2). The dissolved atoms diuse then through the liquid metal and the crack propagates (Fig. 5, arrow 3). 3.2.2 Description Let us consider a crack (Fig. 6) of length 2 L, of thickness 2r and of tip radius r, subject to an applied stress a . The stress distribution around the crack tip establishes a gradient in the chemical potential at the tip, which causes a diusion ux through the liquid away from the tip.

C = C0 +

C0 kT r

2 2La E

(4)

The ux, J , of solute atoms away from the crack tip is given by Ficks rst law: J = D C x (5)
x=0

where D is the diusion coecient of the solute in the liquid. The velocity of the crack is dened by: v = J . Finally, the expression for the tip velocity is: v= C0 D 2 kT 1 r2
2 2La 1 E

(6)

(7)

The eect of capillarity, as expressed by the (1) in equation (7), provides a threshold stress for crack propagation. Setting v equal to zero gives the classical Grith criterion for the critical stress to obtain propagation: E (8) 2L We can deduce the maximum velocity from equation (7): the tip radius cannot be less than about d, the atomic diameter of the lattice atoms, and cannot be greater than E . If /r is small compared to E/2, then the maximum velocity is given by the product of the three terms: c = vmax = 1 2 E C0 D 2k d T
2

(9)

E where 21 k is a numerical constant, d is determined solely 0D by the properties of the solid, and CT depends on the interaction of the solid and the liquid and contains most of the temperature dependence of the crack velocity.

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3.2.3 Analysis Equation (9) gives vmax 15 cm s1 for copper in mercury which is of the same order as those observed by Rhines et al. [10] that were in the range of 1 to 10 cm s1 . Consequently, the present dissolution-diusion model predicts measurably high crack velocities. Popovich [15,25,31] notices that, in agreement with the model, the degree of embrittlement must increase with an increase in the solubility of the solid metal in the liquid metal, which does not agree with practical observation. Moreover, according to him, when the solution process becomes important, the crack tip is blunted and brittleness is suppressed. Futhermore, Glickman [32] notes that this model is certainly oversimplied: it does not take into account the possibility of relaxation of those elastic stresses during blunt2 ing of the crack, giving here the relation L/t a L. This equation is inconsistent with test data reported by Glickman: L/t = (a ). Concerning temperature, it aects the expression for the crack velocity directly through the factor C0 D/T , as noted earlier. This product increases as the temperature increases, predicting that the crack velocity will increase with increasing temperature. But Kamdar [7] underlines that the increased velocity with increasing temperature is opposed to the observed behavior of most embrittlement couples. Moreover, Gordon [24,33] says that this theory predicts an abrupt and substantial change in temperature dependence of crack propagation rate at the embrittler melting point, since its main temperature dependence derives from the activation energy for the diusion of the base metal atoms in the embrittler. He has shown that it was not true for indium embrittlement of steel. Anyway, contradictory results exist in litterature: for Rhines et al. [10], crack propagation rate increases with increasing temperature, but for Westwood [34], embrittlement is independent of temperature over a considerable temperature range. Finally, Robertson remarks that in all of the discussion, the crack-tip radius r has been left as an unspecied parameter. The tip-radius will depend on the dierential rates of dissolution at the tip and on the dynamic yielding behavior around the tip. This yielding behavior can vary markedly with composition, heat treatment and temperature. But it appears dicult to predict the dependence of r on T , and hence, it is not all clear how the crack velocity varies with temperature.

3.3.1 Elementary mechanisms For Glickman, the nucleation and subcritical growth of cracks which take place along grain boundaries are associated with selective dissolution in the melt of solid metal atoms at the crack tip (Fig. 5, arrow 1). This dissolution is enhanced by the adsorption of liquid metal atoms (Fig. 5, arrow 4), which favours the nucleation of dislocations (Fig. 5, arrow 5). These dislocations are creating an atomic roughness at the solid-liquid interface (Fig. 5, arrow 6) which enhance dissolution of solid metal atoms (Fig. 5, arrow 7). This is followed by rapid diusion of solid metal atoms from the crack tip and crack propagation (Fig. 5, arrow 3).

3.3.2 Description Glickman asserts that failure kinetics need to be known to understand the mechanism of LME. However these failure kinetics have to coincide with the rate at which the interatomic bonds at the crack tip are broken and reorganized boundary kinetics and not with the the rate of melt ow along the crack transport kinetics. Since the rate v of melt ow along a capillary crack of length l is v 1/l, it is dicult to obtain such data for macroscopic cracks (in this case, it is only possible to study transport kinetics), and consequently the rate of development of microscopic cracks has to be studied. According to Glickman, there are three kinetic stages for microcracks failure: Crack initiation, which results from selective dissolution of the grain boundaries in the melt. The melt-lled grooves are formed where boundaries exit to the surface. The basic outlines of the mechanism of this process are described by the well-known theory of the growth of thermal-etching grooves by Mullins [35]. For the copperbismuth system, the cracks switch from initiation to propagation at a length of approximately 10 m. Crack precritical propagation, which is the controlling stage of failure. It is a slow crack propagation whose duration, which determines the time-to-rupture c , depends on the crack rate during this stage and on the critical length lc at the moment of transition from subcritical to hypercritical growth. The rate of subcritical growth of cracks does not depend on their length, and its variation with the applied stress is approximately described by the linear function: v= L ( ) (10)

3.3 Glickman model According to Glickman [32], LME is a clear manifestation of the Rebinder eect (cf. Sect. 3.1). He adds to this approach, a mechanism based on dissolution and diusion of solid metal atoms. Glickman worked mainly with solid copper and lead-bismuth melt. His model of the phenomenon is mainly kinetic, but also thermodynamic because it is based on Rebinder eect.

where L the crack length, the crack mobility, the applied stress, the threshold stress of subcritical growth and the time. Crack supercritical propagation, which is due to the achievement of a certain critical deformation level in the plastic deformed region near the crack tip, according to data obtained by Glickman.

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Measurements of lc and stress c at the moment of fracture showed that regardless of the conditions of deformation (air or any liquid metal, creep or active tension), the transition from the subcritical to the hypercritical fracture stage occurs at a constant value of the product c lc . Glickman has developed a possible mechanism to explain the kinetics of precritical stage: the mechanism of dissolution-precipitation. According to this author, atoms of the solid at the crack tip dissolve in the melt, diuse in it, and become precipitated on the crack walls at a distance approximately equal to the crack opening . Both the dissolution and the reverse process of crystallization out of the melt take place at discontinuities on elemental steps formed on solid surface, the concentration of discontinuities Cj corresponding to its thermal equilibrium level: Cj exp Uj kT (11)

the exceptionally high diusional permeability of the melt lling the crack cavity, which ensures fast diusional removal of dissolved atoms from the crack tip; the high degree of atomic roughness of the metal-melt interfaces which is related to the low specic surface energy at these interfaces and which ensures a high dissolution rate. 3.3.3 Analysis In the equation (10), and are independent of and , but is much more sensitive to the physicochemical conditions of deformation than . Glickman has compared these theorical results of the variations of to its experiments for the copper-bismuth and copper-mercury systems and has found a good accordance. In comparison with the Robertson model, the analysis proposed by Glickman presents some improvements (difference between nucleation and propagation, better interpretation of the inuence of temperature). However, his model still faces the issue of the solubility of the solid metal which is supposed, contrary to experimental data, to enhance the embrittlement. He denies this allegation and claims that his mechanism still operates when the solubility tends to zero: such systems often contain impurities which react with the solid metal to form compounds soluble in the melt. He also proposes another possible explanation, with the mass transfer from crack tip to the metal bulk by volume or grain boundary diusion or even along the melt-metal interface: in the absence of solubility, the mechanisms of crack growth are analogous to those operating in vacuum, and the part played by the melt is limited to increasing the eectiveness of the metal surface in its role of the source of point defects taking part in the diusional mass transfer from the crack tip. At last, the contradiction with Gordon [24,33] about the abrupt transition in temperature dependence at the embrittler melting point is still under consideration. 3.4 SJWK model This model described in [7], is based on the weakening of interatomic bond mechanism (Fig. 7), which is a particular case of the brittle fracture theory. It manages to rationalize the eects of many experimental variables: temperature, strain rate, grain size, slip character, but it is not capable of predicting susceptibility of a new substrate-environment system. 3.4.1 Elementary mechanisms

The higher the value Cj , the faster the rate of dissolution and crack growth v : v Cj vj (w1/3 /h). (12)

Here, h denotes the average distance between dislocation steps at the crack front, is the atomic volume and vj is the rate of displacement of the discontinuities along the step, which is determined by the density of the diusional ow of solid atoms from the discontinuity into the melt and which increases with increasing stress , diusion coecient DL , and solubility of solid metal in the melt C0 . The role of SL in the framework of this model is associated with the variation in energy of formation of discontinuities Uj : Uj SSL SL SGB b (13)

where SSL is the increase in the area of the metal-melt interface due to the formation of discontinuities, and SGB is the accompanying decrease in the grain-boundary area. The decrease in SL and the increase in b produce an exponential increase in the crack growth rate as a result of the increase in the concentration of nuclei of dissolution, i.e. discontinuities at the crack tip. In the framework of this model, it was possible to derive a formula for crack growth rate v in a form similar to equation (10) and to express the crack mobility (T ) and the threshold stress in terms of the parameters of the metal-melt system: C0 4/3 exp v with = (2SL b ) E l (15) SSL SL Sb b kT RhkT DL ( ) (14)

Thus, in the case of LME, the accelerated fracture under the inuence of surface-active melts is associated with the simultaneous inuence of two factors:

A liquid metal atom B at the crack tip A A0 reduces the surface energy (Fig. 5, arrow 4), and consequently the strength of interatomic bonds (Fig. 5, arrow 8). As the stress s is applied, the stress acting on interatomic bond A A0 eventually exceeds its now reduced breaking stress, so that the bond breaks, the crack propagates to the next

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a result, the ratio / will decrease and according to the brittle fracture theory, the crack will develop by cleavage. Concerning crack initiation at the surface, it will also be facilitated by the adsorption of liquid metal atoms, and if chemisorption is strain activated, it will occur preferentially at sites of stress concentration, such as in the vicinity of piled-up groups of dislocations at high angle grain-boundaries. 3.4.3 Analysis As the ratio / represents the tendancy to cleavage, Kamdar explains the LME phenomenon by a reduction in , with unaected. Nevertheless, according to Popovich [31], the liquid metal increases the activity of dislocations, which should result in a change in the value of . Moreover, he asserts that LME is a ductile phenomenon at a microlevel: the use of brittle fracture theory may not consequently be used here. Consequently, Kamdar acknowledged in recent year [9], that some models based on plastic ow, like Lynchs one were relevant, but only in few cases. Nevertheless, Dimel [39], taking for granted the presence of plastic ow in LME, asserts that the the weakening of interatomic bond model is not contradictory with plastic ow. According to him, in usual ductile material, local elastic strains are not sucient to break atomic bonds until the bulk material undergoes signicant plastic ow. The work-hardening aspect of plastic strain allows an accompanying increment of elastic strain and hence allows sucient elastic strains for bond breaking and crack propagation. The presence of plastic ow is then consistent with SJWK model, and such an explanation allows to explain the inuence of cold work, strain rate and temperature. According to Glickman, all indicates that surfaceactive liquids role in LME consists only in accelerating the subcritical growth and crack nucleation and not in taking part in the decrease of the fracture thoughness, disputing here SJWK model. Moreover, he also contests the straightforward proportional relationship between surface energy and interatomic bonds energy. 3.5 Lynch model Lynchs model [4043], which is also based on the decrease of the strength of the interatomic bonds, diers from SJWKs model, because it assumes that crack propagation does not occur by atom rupture of the bonds. This model gives an explanation for the presence of ductility at a microlevel. It is mainly based on metallographic investigations on many dierent systems. 3.5.1 Elementary mechanisms Adsorption of liquid metal atoms (Fig. 5, arrow 4) is lowering the strength of interatomic bonds at the crack tip

Fig. 7. Displacement of atoms at the tip of a crack. The bond A A0 constitutes the crack tip, and B is a liquid metal atom [7].

solid atoms A1 (Fig. 5, arrow 9) and the liquid metal atom becomes stably chemisorbed on the freshly created surface. This procedure is then repeated until the specimen fails. The cracking process is limited by the arrival of liquid metal atoms at the crack tip and it is assumed that liquid is able to keep up with the propagating crack tip. 3.4.2 Description Stolo and Johnston [36] and Westwood and Kamdar [37], working independently, postulated that a perfectly straightforward proportional relationship must exist between surface energy and interatomic bonds energy. Their model, denoted SJWK, utilized a relation rst derived from Gilman [38], to show that cracking facilitated by the lowering of elastic surface energy must inevitably lead to a lowering of plastic work. This relationship between surface energy and interatomic bonds energy is as follows: for a crack radius , submited to a normal stress and a shear stress , the work associated with fracture is proportional to /a0 where is the elastic surface energy and a0 is the radius of an elastic crack. Any factor that facilitates crack blunting at the tip of a growing crack increases , resulting in high energy absorption or even crack arrest. If the work done in breaking interatomic bonds is then equated to the surface-free energy of the subsequently created fracture surface , we obtain the maximum stress m to break A A0 bonds: m = E a0
1 2

(16)

Consequently, the adsorption of liquid metal atoms, which reduces the surface energy, decreases the strength of interatomic bonds . This adsorption can also cause reductions in the shear strength of atomic bonds at the crack tip, but these eects will be localized at the surfaces of the crack tip and will not be felt at distances greater than several atomic spacings due to electronic screening eects. As

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do not intersect crack tips. Thus, relatively large strains are required to produce coalescence cracks with voids, so that larger and deeper dimples are observed on fracture surfaces, when dislocations egress rather than dislocation injection predominates. 3.5.3 Analysis The most important aspect of this model is that the delayed failure is not explained, as Gordon [24,33] underlined it in his study about delayed failure. However, Lynch is totally aware of that fact and explains it as follows: crack initiation sometimes involves the slow development of a notch of critical depth and acuity, by injection of dislocations facilitated by adsorption. Moreover, Kamdar [7] notices that adsorption eects on dislocations will be limited to several atomic spacings due to electronic screening eects, and will not be felt at larger distance in the bulk of the solid ahead or in the vicinity of the crack tip. According to him, these eects will be secondary in importance when compared to breaking of bonds where liquid is continuously adsorbed at the tip of a propaging crack. 3.6 Popovich model Popovich [15,25,31] presents a mechanism for LME, based on the Rebinder eect (cf. Sect. 3.1) and on enhanced plastic ow. At the thermodynamic aspect developed by Rebinder, he adds an atomistic approach. His model is only qualitative and give no quantitative expression for the time to rupture or for the crack propagation rate. 3.6.1 Elementary mechanisms This mechanism is based on the fact that, adsorbed liquid metal atoms (Fig. 5, arrow 4) enhance the outlet of dislocations to the surface (Fig. 5, arrow 5). These dislocations could lead to pile-ups at grain boundaries (Fig. 5, arrow 14) which result in rapid work hardening (Fig. 5, arrow 15) and crack propagation (Fig. 5, arrow 16). 3.6.2 Description Popovich proposes that adsorbed liquid metal atoms promote plastic ow in specic solid metals, which results in a more important dislocations activity (Fig. 9). He assumes that this easing of plastic ow is caused by the reduction of the shear stress , under the action of the liquid metal. Then, the increased dislocation activity can rapidly lead to enhanced work hardening in a localized region and, consequently, premature failure. He also proposes that adsorbed species can activate new slip planes, which results in enhanced plastic ow and work hardening. Alternatively, if the large number of dislocations is able to transfer the strain to neighboring grains by crossing grain boundaries,

Fig. 8. Diagram illustrating mechanisms of crack growth in D6ac steel in inert and liquid mercury environment [40].

(Fig. 5, arrow 8), which eases the nucleation of dislocations (Fig. 5, arrow 10) and promotes intensive slip of them, which lead to the occurence of voids (Fig. 5, arrow 11) and coalescence of them with the propagating crack (Fig. 5, arrows 12 and 13).

3.5.2 Description The consequence of the adsorption of liquid metal atoms at the crack tip is the weakening of interatomic bonds, thereby facilitating the nucleation of dislocations (Fig. 8). These dislocations, injected from crack tips on suitably inclined slip planes, produce crack advance (as well as opening) and, when extensive adsorption-induced dislocation injection occurs from crack tips, only small strains are required to link up crack tips with voids formed in a plastic zone ahead of cracks. These voids are nucleated at small particles, dislocation cell boundaries, or slip-band intersections ahead of cracks, and serve to resharpen cracks so that crack-tipopening angles are smaller than the angle between the two slip planes. This process produces fracture surfaces that are microscopically dimpled but macroscopically parallel to low-index crystallographic planes bisecting the two active slip planes, with crack fronts parallel to the line of intersection of crack planes with slip planes. In inert environments, dislocations are not injected from crack tips to any extents, so that coalescence of cracks and voids involves predominantly egress of dislocations nucleated from near crack-tip sources. Only a small portion of such dislocations emerges exactly at crack tip to produce an increment of crack advance: most dislocations either egress behind crack tips producing only blunting or

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Gordon, the present approach must allow to explain the delayed fracture, often observed in experimental studies.

3.7.1 Elementary mechanisms During this incubation period, embrittler atoms are absorbed (Fig. 5, arrow 4) and then penetrate (Fig. 5, arrow 17) by stress-aided diusion (Fig. 5, arrow 18) a short distance into base metal grain boundaries. In the penetration zones the presence of the embrittler atoms lowers the crack resistance and increase the diculty of slip. When a sucient concentration of embrittler atoms has been built up to some critical depth in one penetration zone, cracks nucleation takes place (Fig. 5, arrow 19), probably at the head of already existing dislocation pile-ups where the stress has become supercritical for the lowered crack resistance, and then the crack propagates (Fig. 5, arrow 20).

Fig. 9. Diagram explaining the Popovich model.

then overall ductility could actually be increased by the adsorption. Adsorption-LME manifests itself at lower temperatures where relaxation processes are limited, because at elevated temperature, relaxation is easier and therefore ductility is restored. Furthermore, at rapid strain rates, relaxation processes are slow so that rapid work hardening would also be expected to cause embrittlement. Concerning grain size, Popovich explains the experimental results (Sect. 2.2.3) by the fact that coarsed-grain structures are more strain hardened and less relaxed when the average grain size is increased. Actually, decreased strain hardening in ne-grain structures is explained by the easier movement of dislocations in ne-grain structure as a result of the presence of a multitude of boundaries with a high energy of disorientation. Thus, adsorption-LME would be expected to be more severe at high strain rates, at elevated temperatures and with high average grain size. 3.6.3 Analysis This model by Popovich has a number of similarities with Lynchs one. Most of the comments that have been done about Lynchs model are still relevant here. Consequently, we will concentrate our analysis on the main dierences between the two models based on ductile failure. Actually, Popovich proposes that the adsorbed liquid metal, besides the nucleation of dislocations, promotes new slip planes and work hardening, the latter being not developed in Lynchs model. Moreover, the inuence of the dislocations, for Popovich, can be felt at a great distance, which is impossible according to Kamdar, because of electronic screening eects. 3.7 Gordon model This model is based on the penetration of liquid metal atoms along the grain boundaries. The concept proposed by Gordon and An [24,33], is that the actual crack nucleation event is not the rate-controlling step in the crack initiation, but rather than during an incubation period there is a preparation process which is rate-controlling. For

3.7.2 Description Initiation stage The embrittler atoms penetration consists of two steps, namely: 1. change of the embrittler atoms from the adsorbed to the dissolved state on the surface; 2. subsequent diusion and penetration along preferential paths-usually grain boundaries. The rate of both steps is accelerated by increased stress. The corresponding nucleation time depends on the two steps as follows: tn exp GS RT exp Gd RT (17)

where GS and Gd are the activation free energies for steps 1 and 2, respectively. Gordon does not give atomic details of the nucleation process itself, but reports that once the crack is nucleated, it grows extremely rapidly. Moreover, he proposes a schematic diagram (Fig. 10) that represents the eect of stress and temperature on the total time to produce penetration zones during the crack initiation stage. Superimposed on the diagram is a dotted line marked threshold stress, th , which gives th versus temperature (not a function of time). If a sample preheated to T4 is tested at any xed level between i4 (for which the loading time equals the penetration zone formation time) and th (which is the stress below which no LME failure takes place), such as, for example, 1 (Fig. 10), delayed crack initiation will occur. The initiation time will be equal to t1 t1 , where t1 is the time to load to 1 and t1 is the time to form penetration zones at T4 and stress level 1 .

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3.7.3 Analysis Gordon manages to explain many phenomenological characteristics of LME and SME with this model, such as delayed failure, strain rate eects, solute eects, grain size eects and eects of cold work. However, according to Popovich [31], this model does not explain the dierence in the incubation period in SME and LME, since the rate of penetration will not depend on the solid or liquid nature of the coating. At last, according to Gordon, the main weak point of this model is that the existence of a threshold stress is not explained.

4 Conclusion
The survey has been concerned with the most outstanding models that have been proposed so far in the literature to describe liquid metal embrittlement. Unfortunately, the review does not allow an easy comparison between them. In fact, we cannot conclude that one model is more appropriate than another one for a specic solid metal-liquid metal couple. Attempts to apply these models in a system have often been carried out taking into account experimental results obtained in specic conditions. Therefore, we think it is dicult to draw general conclusions via such limited data. Some models have been developed to be in agreement with the behavior of large number of systems. In spite of some advances, the diculty still remains to understand and to predict why a particular embrittling species attacks a particular metal and how the embrittled metal will crack. As a consequence, the approach which consists in comparing the results obtained in two dierent systems is not relevant, since the elementary mechanisms which simultaneously work in one system may not be the same as those involved in the other. For example, diusionpenetration mechanism should not be eliminated because it is not involved in some systems. In fact, it takes place in the embrittlement of copper-bismuth system [44,45], like other elementary mechanisms such as adsorption. For this reason, studying the elementary processes that occur in the embrittlement of a specic solid-liquid couple may lead to improved understanding. The chemisorption process, which is assumed in most of the models, should be studied. Liquid penetration at sites of high stress concentrations (e.g., grain boundaries) and its eect on embrittlement should be also more investigated in the future. For example, in a recent paper, a mechanism of grain boundary penetration via the development of a macroscopic amorphous layer has been proposed to explain the loss of ductility in the aluminum-gallium system [46]. Such a mechanism could be expanded to other systems. It is necessary therefore to investigate new experimental work in that eld including microstructural and mechanical studies.
This work has been supported by the European Union in the frame of the fusion technology programme (task UT-SM&CLME).

Fig. 10. Schematic diagram showing time to develop penetration zones as a function of stress and temperature of test, and relationship to crack initiation time. T 9 > T 8 > . . . > T 1 [33].

Propagation stage Concerning the propagation stage, it is well established that the propagation of LME cracks cannot proceed without the continual supply of embrittler to the crack tip. It is nevertheless possible that the embrittler transport process may not be the rate-determining step in the propagation. Repeated renucleation along the crack path could sometimes be necessary, and this process could be slower than the embrittler transport. The posssible embrittler transport mechanisms that have been suggested for LME are: vapor transport; bulk liquid ow; grain-boudary diusion; heterogeneous diusion of a couple of layers of the embrittler over the crack surface; surface self-diusion of the embrittler. In Gordons analysis, it appears clearly that the embrittler transport mechanism for SME consists of a surface diusion of embrittler atoms over a layer of embrittler thick enough so that the moving of the embrittler atoms in the top atom layer is essentially self-diusing. The transport mechanism in LME is bulk liquid ow; liquid metals which wet the base metal can penetrate to the tips of even very sharp cracks under the impetus of surface tension, contrary to some statements in the literature. For a few high-vapor pressure embrittlers, such as Zn, Cd and possibly Hg, vapor transport could play a role. For all the other embrittlers, the rate of evaporation from the solid or liquid embrittler makes vapor transport too slow.

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