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LI CHONGMOt and MATS HILLERT Division of Physical Metallurgy. Royal Institute of Technology. 10044 Stockholm, Sweden

Abstrsct-Diffusion-induced grain boundary migration has been studied by zinci~~tio~ of pure iron. The temperature dependence of the rate was measured at 460~65o’C. A change in morphology was observed between 460 and 650 C and may explain the fact that the phenomenon changed character at higher temperatures. The temperature dependence of r’D”r5may be decisive. I‘ being the rate of migratton. D’ the gram boundary diffusivity and i, the thickness of grain boundaries. The concentration behind the migrating boundaries was studied as function of the distance from the surface by microprobe measurements and allowed the grain boundary diffusrvity to be evaluated as function of temperature. Fine zinc-rich grains of ferrite sometimes nucleate on the surface a form and complete fine-grained surface layer. After a while it disappears by abnormal grain growth but the increased zinc content remains. R6sumtLNous avons etudii la migratton de joints de grains provoquie par la diffusion de zinc dans le fer pur. lvous avons mesure la variation de la vitesse en fonction de la temperature entre 460 et 650 C et observe un changement de morphologie entre ces temperatures: il pourrait exphquer le changement de caractere du phenomene aux temperatures eievees. La variation de t/f?*6 en fonction de la temperature peut itre decisive. 1 itant fa viresse de migration. D” la diffusivit~ intergranulaire et d Tepaisseur des joints de grains. Nous avons etudie la concentration derriere les joints de grains en migration en fonction de la distance a la surface. par microsonde. et nous avons pu evaluer la diffusivite intergranulair, en fonction de la temperature. Des petits grains de ferrite riches en zmc germent parfois a la surface et forment une couche superficielle complete a petits grains. Au bout d’un certain temps. elle disparatt par croissance anormale de grains, mais I’augmentation de la teneur en zmc reste. Zu~rn~nfa~~-Die di~usionsIndu~ierte Korngren~enwanderung wurde mittels Verzinken von Reineisen untersucht. Die Temperaturabhlngigkeit der Geschwindigkeit wurde zwischen 460 und.G.t_YC gemessen. In diesem Temperaturintervall anderte sich die Morphologie. welches die beobachtete Anderung im Charakter der Erscheinung bei hoherer Temperatur erkllren kann. Die Temperaturabhangigkeit von I’ D”8 kann ausschlaggebend sein: r bedeutet die Wanderungsgeschwindigkeit. Dh die Korngrenzdiffusivitat und ci die Dicke der Korngrenzen. Die Konzentration hinter der wandernden Korngrenze wurde mittels Mikrosonde~messungen m Ab~n~igkeit von der Tiefenlage unter der Oberflache ermittelt. Diese Messungen ermoglichen. dte Korngre~zdiffus~vit~t als Funktion der Temperatur auszuwerten. Kleme zinkreiche Ferritkorner entstehen manchmal an der Oberflache und bilden eine vollstandige. femkornige Oberflachenschicht. Nach einer Weile verschwindet diese durch aul3ergewohniiches Kornwachstum. wobei der erhijhte Zinkgehalt erhalten bleibt.


The gain boundaries in the matrix phase migrate together with the advancing tips of the precipitate particles in so-called discontinuous precipitation (cellular precipitation). As a grain boundary passes. there is a discontinuous change of the alloy content in the matrix. This migration was long befieved to be due to a pulling effect of the precipitate particles [l]. Another mechanism was suggested by Sulonen [2] who pointed out that the difference in atomic size
would give rise to strain energy in the concentration

gradient in front of the migrating grain boundary. Later on. Hiilert [3] suggested that the driving force for the grain boundary migration originates from the t On leave from Beijing Institute of Aeronautics
Astronautics. and

in chemical potentials in the matrix phase on the two sides of the boundary. caused by the discontinuous change in alloy content. He also showed that Sulonen’s mechanism can be included in his thermodynamic treatment [4]. Even though the exact nature of the driving force is still under debate, it now seems to be generally agreed that it is caused by the change in alloy content and is thus dependent upon diffusion. The first observation of diffusion-induced grain boundary migration in an experiment without any precipitation was made by den Broeder [S] when studying Cr-W diffusion couples. In order to test that the grain boundary migration during discontinuous precipitation in Fe-Zn afloys is actually caused by the diffusion of zinc and not by the growth of the zincrich phase, Hillert and Purdy [6] reacted Fe--& alloys with a vapour phase which was in intimate contact with an Fe-Zn alloy of a different compodifferences


0~~0. a new phenomenon was observed.9989. The specimens were cut from an iron foil of purity 99. At 500 and 550-C. migrate during the experiment. [7] who studied the. In addition. The temperature did not seem to have any effect on the morphology of the grain boundary migration ciose to the surface. the grain boundaries were observed to continue migrating across the surface of the specimen until the whole surface has been swept and has thus increased its zinc content. the composition changes discontinuously. Figure 2 shows an example where the boundary ap~rently can form facets of low mobility. Most of the specimens were mounted in bakelite and prepared metaIiographically by a very light polishing of the original surface of the foil. Such precipitation did not seem to affect the processes inside the iron specimens. The migrating boundaries seem to stop before complete reaction and may then even start to move back. One important factor is the angle between the grain boundary and the surface. Zn) were prepared by powder metallurgy and turnings were produced by machining.80. in some of the experiments there seemed to be an impurity of carbon which caused the precipitation of an Fe-Zn carbide on the specimen surface. As a demonstration. In order to obtain a representative value. However. B and C (33. Interesting features were marked by microhardness indentations for identification and then repolished before microprobe measurements.127 mm. were in a two-phase state. The distance of the grain boundary migration as shown on these specimens varied from one grain boundary to another due to a number of reasons.1950 LI AND HILLERT: GRAIN BOUNDARY MIGRATION IN Fe-Zn sition. Cu-Zn. for alloy A up to 72o’C. The U-shape ensured that the specimen and Fe-Zn alloy were in the same temperature zone of the heat-treatment furnace during zinc&cation. EXPERIMENTAL Three different Fe-Zn alloys.. Zn and 9. it should usually be close to a right angle because of the initial annealing at 850 C. MICROSCOPIC OBSERVATIONS source.1-0. This boundary has initially moved upwards in the picture. 18. The capsules were U-shaped. The rate of migration is thus coupled to the rate of grain boundary diffusion.Zn. Experiments were carried out for different temperatues from 350-8OO’C. The pure iron specimen was put in one leg and the Fe-Zn alloy in the other. which were used as a zinc Fig. Xtwas removed by light polishing and the migration of the grain boundaries in the ferritic material was then studied as close as possible to the initial specimen surface. it has then stopped its uniform motion and instead made small The three Fe-Zn alloys. Other boundaries split up in several segments which move in opposite directions and some boundaries seem to have a special tendency For this. The specimens were mainly examined in a light microscope and an electron microprobe. The experimental technique. No incubation time was found and the rate of migration was constant within the experimental uncertainty. 1. The connecting part was made very thin in order to prevent direct contact. Grain boundary migration was observed down to 46OC. Magnification 500 x . An example is shown in Fig. which have contact with the surface.y/. Grain boundary migration close to the surface in an experiment with alloy B for 2900 min at 500 C. Similar experiments were later carried out by Cahn et al. Fe and thickness 0. the volume diffusion being negligibly small at the temperature of their experiment. Fig. in most of the experiments. the very largest values were excluded and an average -was taken between the next Iargest values. for alloy B up to 660°C and for alloy C up to 55OC. z + f. called A. Even a very small temperature difference between the iron specimen and the alloy powder may thus cause a precipitation of f on the specimen surface.5 h. introduced by Hillert and Purdy. is very simple and may thus be a valuable tool for a further study of diffusion-induct grain boundary migration. As they migrate through the volume of the material. 1 shows that a very long segment of a grain boundary can move in the same direction at 500°C and this even happens at the low temperature of 460°C.00/i. Each specimen was then sealed in a new capsule with 0.015 g and was sealed in an evacuated silica capsule and recrystallized at 8SO’C for 2. Each specimen weighed 0. It is interesting to note that the same facets form on both sides. They were etched for the microscopic examination. It was employed in the present work in order to study how this phenomenon is affected by temperature.3 g of turnings or powder of an Fe-Zn alloy. 3. They observed how the grain boundaries. At 600°C. Cu-Au and Ag-Au systems.

Magnification 1000 x . Magnification 200 x The grain boundaries seem to have migrated a long distance and then returned to their original positions.Q. 5 and the straight Iines obey the following relations I. = RT. The migrating boundary seems to have stopped and has started oscillating.\I. At 65o’C and higher. Grain boundary migration close to the surface in an experiment with alloy B for 120min at 600-C. assuming that all the total available chemical driving force can act on the boundaries. the grain boundaries showed signs of having stopped in all the experiments and no reliable rate values were obtained. to the positions of the diffuse lines and then back to their original positions. some bright and some dark because of the action of oblique illumination. (21 when the specimens are initially pure iron. IO” m’s.. The solubility varies with temperature [83. it is not known what part of the experimental time was spent on the first motion but it is interesting to note that a rate which was evaluated by dividing the distance between the two kinds of lines and the totaLexperimental time agreed fairly well with the rate evaluated from shorttime experiments. Mapniticabon 1000x. This assumption will now be used and the resulting values for the mobility ma! thus be regarded as a lower limit. and with QI = 287 kJ:mole Me = 0. close to the original surface of the specimens. The boundary has moved m both directions and formed the same type of facets.. Grain boundary migration close to the surface in an experiment with alloy B for 990min at 600 C. However. 4. is very close to the solubility of zinc in r-iron. as shown in Table I. Alloy B was used for this purpose but experiments with the other alloys indicated that the results where AC. which is also the composition of the 2 phase in the alloy powder used. show d&continuities in composition The geometric arrangement of the diffuse lines does not represent a natural grain boundary net-work in an annealed specimen whereas the sharp lines do. most of the values for the rate of migration were taken from short-time specimens. 2. Microprobe measurements. 3. An extrapolation to temperatures below 460 C demonstrates that the experimental times applied in the present study should be too short to produce a visible grain boundary migration at such low temperatures. Qw = 130kJ:mole. The experimental growth rate data are presented in Table 1. For low zinc contents one may use the approximation AG.are independent of the alloy composition as long as the alloy is inside the 2 + r two-phase field.Y~. In a few long-time specimens a related phenomenon was observed. Fig. = r. These values were used in the evaluation of the mobility.001 m4 J s.An Arrhenius plot of the velocity and the mobility is presented in Fig.4.exp . Fig. sz.Q. The quantity AC.:RT AI = . .. In view of this phenomenon. This process will be further discussed later on. . The sharp lines show the present positions of the grain boundaries and more diffuse lines. . adjustments in both directions. indicated that. to be discussed later. can be evaluated from the change in composition at the grain boundaries. is the driving force per mole and i& is the molar volume. 4. a value was taken from a short-time experiment at 650-C. Fig. It may thus seem that the grain boundaries have moved by a rather uniform motion from their initial positions. An ambitious evaluation of the total chemical driving force was presented in Ref. Of course.Q+RT (Jai t?b) r0 = 3. This assumption will be further discussed later on and an alternative will be considered. [6]. The mobility can be defined by Fig. represents the final composition.exp . Grain boundary migration close to the surface in an expertment with alloy B for 5910min at $20 C.

lo.I7 Fig. Under the present ex~r~mentaj conditions new grains sometimes nucleated on the surface.3 Inverse tempemture 1/T IK’I Fig.10-B 0.7.” 8.t *to-= 6.Table 1. 1o-9 5. Etching suggests that after lang times at 650°C the grain boundaries have been moving back and forth several times in a zinc-rich region surrounding the original position of the boundary and it has a very irregular Fig. to. Fig. Data for alloy A were very similar. 7. Kinetic data for d~~u~jon-induced grain boundary migration as function of temperature.10-” 5. observed cfose to the surface in an experiment with alloy A far 1000min at 6.1*10-” 1. A finegrained surface layer could thus form and it gradually grew into the material. Magnification 500 x . Growth rate and mobility of migrating boundaries in experiments with alloy B 460 480 500 520 550 600 620 650 t. Usciliation of a grain boundary around its original position. Figure 9 shows an example where the grain size is considerabiy liarger than in the shorter experiments from the same temperature. This nucleation seems to be promoted by a surface roughness.03037 0.9~10-‘@ 2.10-19 1.127 0. Figure f0 shows that the growth of such grains may stop and the grain boundary may start to osStillate. Magni~cation IO00 x .7*10-‘3 7.8.092 . At even higher temperatures the boundaries are less irregular and the etching suggests that they have moved by a jerky motion. leaving ghost fines in previous positions.3*10-‘z 2.0.7. some segments con- 1.047 0. This is demonstrated in Fig. as well. Oscillation of grain boundaries by a jerky motion observed close to the surface in an experiment with alloy A for 15min at 780-C. Rather c&mpfete fine-grained surface layers were observed in some specimens at 520°C and more ~requentIy at.higher t~m~rature. shape at the end of such an experiment. r is tire rate of migration observed close to the surface.7.4.2 1. 600°C. Some data for alloy 3 are presented in Table 2.8. 7.8*10_” 1. 6. The etching effects suggest that the grain boundaries have moved in a complicated fashion. 5.058 0.10-‘0 2.07 i 0.50X. The grain size within the surface layer seems to vary rather gradually with its thickness I at WC and probably at lower temperatures.2*10-1’ 3. 6. In many cases there were only a Few new grainoand they grew to a considerabIe size. Their thickness was studied as function of time.185 4. 8 which was taken on sectioned specimens. M is the mobility evaluated from r using equation (t).6~10-9 1. It occurred less frequently on electropolished specimens. t>/Dh& is a quantity evaluated from concentration profiles in sectioned specimens and D*a was evaluated by combination with the rate values _ close to the surface.5. .145 0. The grain diameter is approximately half the thickness of the surface layer. Fig.7*10-‘” 2.

I1 where the specimen was poiished down not quite enough to remove the surface layer completely. This is very similar to the phenomenon shown in Fig. This micrograph shows that the grain boundary has started to move back on the lower side. Ic) 990 min.. This is demonstrated by Fig. at 600°C it was observed that the migration was much more rapid along the surface and a surface layer of rather unifo~ thickness may thus form. --L ‘. 15. Evidentiy. 13. 3 and to the phenomenon which has probably given rise to the structure shown in Fig. However. This is very similar to the phenomenon shown in Fig. Magnification 500 x . Fig. -. Figure 14. The thickness of the surface layer formed by the process illustrated in Fig. fai @tImin. tinuing and other segments moving back. 12. Magnification 500x . Growth of fine-pined surface layer in experiments with alioy B 7CC) 500 520 550 580 1953 I fmin) 14640 5190 { 460 IiS0 I330 80 120 i 150 470 990 1200 15 30 60 120 i I50 470 loo0 1170 8430 I5 30 60 15 I @ml 5 18 5 3&s 12-15 20-22 22-27 22-24 50 50 _s7 7-9 lo-11 17-20 7-20 lo-15 10 15-f-I 10 7 6 6 2 600 . Grain growth in tRe fine-grained surface Iayer observed in a sectioned specimen from an experiment with aIIoy A for 1200min at 600°C. varies with temperature. At even higher temperatures. At 650 f a new phenomenon occurs in the’ finegrained surface layer.‘. 3. large grains grow back to the surface and the fine grains disappear completely. possibfy while the boundary is still advancing along the surface. 6.LI AND HILLERT: GRAIN BOUNDARY MIGRATION IN Fe-& fable 2. Fig. presumably due to volume diffusion which starts to become significant. Some specimens were sectioned perpendicular to the surface of the original foil. the zinc-rich layers at the surface and at the grain boundaries obtain a more uniform composition. 650 700 720 1w Fig. At the lower temperatures they showed that the grain finery migration occurred very uniformly through the whole thickness of the specimen. At the higher temperatures this reaction competes with the ordinary grain boundary migration and it may even dominate completely. at temperatures above 720-C this reaction was so rapid that the fine grains were never observed. 8. 15. The one-grainy surface layer usua~iy advances into the interior of the material with a slightly higher rate along the initial grain boundaries. Fig. the presence of a zincrich surface layer with a non-uniform distribution of zinc is an indication that there has been a tine-grained iayer. A kind of abnormai grain growth takes place by which the initial. Formation and growth of a fine-grained zinc-rich surface layer observed in sectioned specimens from experimen& with alloy B at 600-C. 9. Fig. @) f50min. On the other hand.

MagFig 13. Magnification 200 x Fig. 15. Favoured migration of a grain boundary aiong the surface observed in a sectioned specimen from an experiment with alloy C for 12OOmin at 600 C. . 11. On the lower side.1954 LI AND HILLERT: GRAfN BOUNDARY MIGRATION IN Fe-Zn Fig. 14. Fig.OOQ min at 460-C. The cessation of growth of a formed on the surface in an experiment 480min at 600°C. Magnification 200 x Fig. Magnification 200 x Fig. Favoured growth of fine-grained surface layer along grain boundaries observed at some distance from the surface in an experiment with alloy B for 280min at 600% Magnification 200 x . Magnification 1000x. The disappearance of the fine grains by abnormal grain growth of the original large grains observed at some distance below the surface in an experiment with alloy B for 470 min at 65O’C. few new grains with alloy B for boundaries then directions. Uniform migration of a grain boundary observed in a sectioned specimen from an experiment with ahoy 3 for I19. the migration seems to have stopped and the boundary has started to oscillate. 12. The zinc-rich layer remaining after the disappearance of the fine grains and some volume diffusion observed at some distance below the surface in an experiment with alloy C for 8430 min at 650°C. 10. Segments of the grain seem to have started to move in different ni~cation 1000 x .

is roughly equal to the value for lattice diffusion in s-iron. where they are both in the 1 + f two-phase state. which may be illustrated by Figs 3. In view of this result we should not expect the driving force for the migration to decrease towards higher temperatures. On the other hand. the so-called spike. can be estimated as d = D’:r where D’ is the ordinary. as i. The concentration in regions passed by a grain boundary was also measured as a function of the distance from the surface on sectioned specimens. illustrated by Fig. The primary one may be the local growth close to the surface. m 100 Fig. 16. heat treated from 480 to 580-C. It was about IO pm at 600-C and 2-6 vrn at 650‘C. Fig. there were large variations. if d is much smaller than the atomic dimensions. we should look for another explanation why the diffusion-induced boundary migration has not been observed at higher temperatures. It may be significant that the upper temperature limit of the experimental range coincides with some new phenomena. 230 kJ/mole. At d values close to the atomic dimensions the discontinuity will be smaller and one would need some model in order to evaluate the size of the chemical driving force. It may be interesting to examine this argument in detail. one would expect a very steep concentration gradlent just in front of the migration boundary and the width of the zone with a variable composition. There should be no real discontinuity in composition at the boundary if d is much larger than the atomic dimensions. 15. MICROPROBE MEASUREMENTS By microprobe measurements on specimens. which had only been polished very slightly. This is contrary to previous belief [7] which was based upon the increasing role of volume diffusion at higher temperatures. like the one shown in Fig. As already mentioned. Some concentration profiles were measured through the finegrained surface layer formed at 600-C. the composition was uniform in the regions swept by a grain boundary once. 240 kJimoIe [9]. 6. 17. At 70&C it was difficult to observe but there was an indication of a layer of less than 1 pm. The curves represent an attempt to fit the data to an approximate solution of the equation of diffusion. evaluated from the experimental rate of migration.r E5 \ Cl i 0 10 20 30 LO 50 Depth (pm1 60 Figure 5 shows the mobility. 4. In view of these considerations it should be interesting to evaluate D’:r from the experimental rates. 10 and 15. Normally. The curve is tentatively drawn. using equations 1 and 2. the experimental time was not sufficient for the surface layer to develop or the thickness of the specimens was not enough (127 pm). The concentration profile through a fine-grained surface layer. Instead. it was confirmed that the composition behind the migrating grain boundaries was close to the equilibrium solubility in the experiments with alloys A and B up to 650°C. It shows a rapid increase with temperature and there is no indication that the experimental rate of Fig.L1 4x1) HILLERT: ’ I GRAIN BOCNDARI’ MIGRATION IN Fe-Zn 1955 . In regions swept several times. In this kind of section. it has been suggested [3] that the driving force is related to the discontinuity in composition at the grain boundary. This evaluation gave a value of 2A at 600°C and an extrapolation to higher temperatures would give approximately the same value since the activation energy for the mobility. 16. At lower temperatures. 50 Dlstonce. lattice diffusion coefficient in the z phase and I‘ is the rate of migration. DISCUSSlON Ordinar_v grain houndarj~ miyrutim migration would not continue to increase at temperatures above the experimental range. . then the spike does not exist and instead there is a discontinuous change of the composition from the initial value of the specimen to the value of growing grain. Fig. 17. Measurements of the concentration behind the migrating boundaries as function of the distance from the surface.

The data can be represented by an equation cO/DbG= 10” exp . L’. IO” 8.D”6 (‘0 480 520 550 580 (rn-‘) 1. The final thickness of this layer./@‘& In this equation . We must conclude that the motion.K. By fitting the data to the simple solution given by Cahn [lo] x -= % cosh(z. that the diffusivity in a migrating boundary is several orders of magnitude larger than the values reported from experiments with stationary boundaries. lo8 2. Some quantitative information can actually be extracted from the experimental concentration profiles presented in Fig.Q/RT me2 (6) with Q = 100 kJ/mole... this criterion yields 1 = y’l. It is thus evident that Db6 has a smaller activation energy than the rate of migration c.0. This may explain how it is possible that a very large segment of a grain boundary starts to migrate in one direction even at the low temperature of MC. cO/Db6) w (5) where Q = 187 kJ/mole. 10s cosh(+ \ c. In order to understand Fig.3. Fig.9..10-” 1. Once there is a successful nucleation at some point. vary with temperature. This type of calculation was carried out by Hillert and Purdy. 15 it is important to realize that zinc must diffuse into the material in order to allow a zinc-rich grain to grow. [ll]. it was observed in this study that I decreases with increasing temperature. 18. The data are listed in Table 3 and plotted in Fig.Q/RT m’/s (7) where c’~ is the rate close to the surface.4DbSiro (4) By combining the data for ~+. illustrated by Fig. Their results were confirmed by Smidoda et al. who obtained values several orders of magnitude higher than for stationary boundaries.1.‘Db6) 2. illustrated by Fig.8. It may thus swallow other nuclei which have not yet developed fully and have not yet been able to make use of the high difl’usivity.7. who also observed an abnormally large activation energy which fell between the normal values for boundary diffusion and lattice diffusion. Their calculated concentration profiles are shown in Fig. the reaction may spread rapidly along the boundary in view of the increased diffusivity. lo-l9 3. The activation energy for r0 is thus 100 kJ/mole larger than for Db6 and the decreasing value of I with increasing temperature is explained.. The grain boundary diffusioity different from the uniform growth in the whole material.. 5. 14.8. According to the calculation by Hillert and Purdy. As already mentioned.‘O 1. Evaluation of the grain boundary constant diffusion Db6 (I& (m’is) rO. where Table 3. is only approximately uniform and in a very thick specimen one should see that the migration is slower in the center. The result is shown in Table 3 and can be described by Db6 = 3. It is thus impossible to predict the temperature dependence of I without knowing how DbS and c.1956 LI AND HILLERT: GRAIN BOUNDARY it was MIGRATION IN Fe-Zn -v \ possible to estimate a. It is still not understood how the migration starts but some kind of a nucleation process must be involved because a dislocation wall seems to form and remain at the position of the initial boundary [6].10-l exp . in a thick specimen. which is given as c in Table 1. The present result indicates some tendency for this but may not be reliable enough for a safe conclusion. The activation energy for normal grain boundary diffusion in iron is 155 kJ/ mole and for lattice diffusion 240 kJ/mole.10-” 5. lo8 4.4.0...4DbWJMRTx0 = \‘1. The concentration profile should thus be calculated together with the migration of the boundary.0. This leads to a decrease of the driving force for the grain boundary migration and of the rate of migration..10-‘8 . As a consequence.7. z. the zinc concentration must decrease along the grain boundary. It is thus evident that. 18.7. 16. is the composition at the surface. we can evaluate #‘a./@b in Table 3 with information on the rate of grain boundary migration close to the surface. 1o-9 2. is particularly interesting in connection with the start of the grain boundary migration. 12 of their report [6] and the rate of migration was predicted to be approximately proportional to the zinc concentration. These values of the grain boundary diffusivity confirm the result of Hillert and Purdy.. may be estimated as the distance below the surface. 1.6. is half the thickness of the specimen and z is the distance for any point from the center line. The observation. measured along the boundary. 1O-‘9 1. where the concentration is hali the value at the surface. IO-“’ 1. lo. the grain boundary will lag behind considerably below a certain depth and the shape of the migrating grain boundary will develop as illustrated in Fig. Development of a uniform zinc-rich surface layer by favoured migration close to the surface. 14.

The data for 520 and 550°C onfy concern the initial linear part of the curve. 19.LI I” AND HILLERT: GRAIN BOLJNDARY MIGRATION IN Fe-Zn 1957 I . . it seems probable that Fig. (81 where x. The grain boundary on the bottom side of the zinc-rich grain has started to move back. thus allowing another segment to continue into the pure iron region and increase its zinc content. I7 and the mobility could then be evaluated from equations (1) and (2) assuming that all the chemicaf driving force can be applied on the boundary. It seems that something happened to the specimen at a certain moment and that the boundaries coufd not move further. the values are almost constant. because of the surface tension effect. which must spread along the boundary.g. For the corresponding depth it was then possible to read the zinc content from Fig. Fig. During the oscillation of the grain boundary in the zinc-rich region. 3 was taken in such a way. It seems probable that Fig. minutes the grain boundaries seem to have moved back to their initial positions. At and above 650°C the growth seems to come to a standstill and the final thickness seems to decrease at increasing temperature. signs of a very similar oscillation was observed at the end of a discontinuous precipitation in a ternary system after a long time when the supersaturation had probably vanished [ 121. we cannot explain why the grain boundaries did not continue to migrate across the whole surface of the specimen. should be too slow to prevent many independent nuclei from forming. the zinc content of the surface layer wilI spread over a larger volume. 4 where The formation of a fme-grained surface layer resembles a kind of discontinuous precipitation observed by Tu [13]. It should then be stuck to the surface and. One may thus expect an oscillation to start once the supply of zinc is interrupted. the growth rate was evaluated at four times by reading the slope of the curve in Fig. The decreasing rate of 600°C should be intimately related to the decreasing zinc content with the distance from the surface according to the microprobe data in Fig. 19. equations (1) and (2) df & = MRTx$fV. The thrckening of the fine-pained surface layer formed during zincification of iron specimens with a rough surface. 18. Furthermore. a right angle. In fact. IO show5 another exampIe of the same phenomenon. In this way. is too long to allow the zinc supply to be maintained. one might have expected that the information. o 750 *C Alloy A Y? f 2o 5 10 0 0 500 lime. If a specimen of this kind is polished down to just below the zinc-rich surface layer. 19. e. it should eventually come into contact with the surface and there establish some contact angle. The Gibbs energy of the system can be decreased further if one segment moves back into the zinc-rich region and picks up some of the zinc. In order to estimate the rate of supply of zinc to the migrating boundary a very simple geometry was adopted. It thus seemed natural to develop a mathematical treatment from the basic relations of the rate of grain boundary migration. The initial linear part seems to be in essential agreement with the rate of ordinary migration of grain boundaries. is the zinc content just behind the migrating boundary. Oscillarions qf grain boundaries Figure 15 shows another interesting feature. 20. Model for the thickening of a fine-grained surface layer. 1500 1000 Fine-grui~ed swface layer Fig. 17. However. it is easy to see that the boundary will not be stable if it simply stops when the supply is interrupted. In order to test this relation. It is easy to understand that its growth has more or less stopped because the diffusional distance from the surface. and it was assumed that Fig. Furthermore. The information obtained for alloy B is shown graphically in Fig. This mechanism may provide part of the explanation of the diffuse lines in Fig. The reason for the standstill at high temperatures and the shape of the curve for 6OO’Cshould now be discussed. as measured along the boundary. it should drag the rest of the grain boundary out to the surface. The grain boundary would thus disappear from the zinc-rich region and only be found in the neighbourhood of the initial position of the boundary where it is stabilized by the presence of the boundary inside the material. Except for the result obtained close to the surface. The data presented in Table 2 indicate that the rate of growth of the layer into the material decreases with time. 20. The results are shown in Table 4. This is evident from Fig. one should still see a zinc-rich region close to the initial position of the grain boundaries..

Ii. In this connection it is of interest to compare the magnitude of the driving forces for the two reactions.~. As already mentioned we may use s = i/2 as a rough estimate after the fine grains have impinged upon each other and formed a complete surface layer. respectiveiy. 12. in principle there is always a driving force for abnormal grain growth if a large grain is in contact Sqwre mot of time. The factoi) was introduced because the flow is shared with the nei~bouring grains. 10e20 m’is../DbiSvm)’ . although there are strong variations even within a single specimen. In order to solve the equation for larger 1 we must know how the grain diameter. This flow supplies zinc for the growth of . and thus t/t = MR T. The flow of diffusion down the grain boundary of a circular. are normalized coordinates defined as T = 4~. = xi. one may use the fact that the curve of i. which do not extend to very large I.$“.Y$.. 19 and it is possible to evaluate the diffusivity in the vertical boundaries by fitting the two curves.0. 19 thus yielded a value of Db6 = 1. varies during the growth of the surface layer. T Fig. For large i we obtain t = i2 and thus The thickness E. abnormal grain growth was observed to occur after about t5Omin at 650°C. 19..2 (14) (1% 2 For smali 1 we obtain r = Ji.YgJY.2. .‘r approaches the straight line very early. (11) For small t we see that . is the composition at equilibrium with the vapour phase. vs r has a reasonable similarity with the curve for 600°C in Fig. is presented in Fig. i. It is possible that the cessation of growth is caused by the start of abno~ai grain growth. This assumption is supported by the observation that the horizontal boundaries are more or less flat. 9.. equations (16) and f 17) show that the Anneolmg time.the zinc-rich grain. vs . See for instance Fig. It is also supported by the microprobe m~surements which show that the zinc content is approximately constant at each depth. One may thus use a point at the Iongest time available and another point at a fairly short time.2~b~V~~~~RTls. columnar grain is (9) In order to evaluate (Iqit’h..’ f + i.rlCcifrom the data in Fig. the result of which was illustrated in Fig. This abnormal grain growth may be regarded as the reverse of the growth of the fine-grained surface layer. and T are defined by equations (14) and 115). In fact. /. = rqMJm~. The cessation of growth of the surface layer after some time at and above 650°C coincides rather well with the occurrence of abnormal grain growth. On the other hand. E where r and i. The explanation may be that the vertical boundaries between the fine grains have not been quite stationary but have been moving around because of the grain growth that has been observed to occur in the surface layer.1958 LI ANDHILLERT: GRAIN BOUNDARY MIGRA~IGN iN Fe-Zn difhtsivity can be evafuated from the di&sivity in the migrating boundary is so rapid that one only needs to evaluate the diffusion along the stationary vertical boundaries..(L)b(j)I.(~~R~~~“~~~) 3. As an example. + i. s. it is also possible that the growth stops by a different reason and abnormal grain growth can then start. The thickening of the fine-grained surface layer according to a simple mathematical analysis.’ + In(i. It is surprising to fmd that this value is three orders of magnitude larger than the value expected for stationary boundari~ f9J and only one order of magnitude smaller than the value obtained for migrating boundaries.The shape of the curve of i. where s is the grain diameter and I&. as a function of r and . 2 1. With this value we obtain By inserting this expression in equation (8) and solving the resulting differential equation we find 5 = 2. t. + t 1 + 2’) (13) The curve for 6GO’Cin Fig. By ~mbination with equation (8) we thus find t&If2 = c&l . which is self-evident.

or xg.127) would thus yield a driving force of 160 J zmole which is about l/6 of the total driving force according to equation (8).10-‘” 6. .051 25. will only vary bt a factor of 2 instead of 4. 16. ~~lirtc~l~I~. The driving force supphed by the surface energy may be estimated as 201’*. deduced from Table 1. it should be emphasized that AG. B. ‘50 500 1000 IO-‘& 9. 3. lo.x. If it is proportional to .value.d!. In future work it should be important to examine if the rate of migration is proportional to rr. A typical value of s at 6oO. equation (21 k shows a parabolic relationship and the driving force is thus predicted to decrease rapidly as the zinc concentration is decreased. Of course.. R. Clark. It does not seem probable that the increasing role of lattice diffusion is responsible for the lack of observations of diffusion-induced grain boundary migration at htgh temperatures. It would reach the value of 1 J/mole at . in equation (I) should be identified with the difference in driving force for the two reactions. Sulonen. 748 (1964). 2.10”“0 0 29 38 48 0. the maximum value of rzn (0.010. with a region A lower limit jior the driciny jiorce It has been suggested by Cahn er al.c~?~~.110 0. 2757 (1971). However. 7ran. and they are presented mainly in order to stimulate further work. then equation (111 t should replace equation (21 and result in many modifications of details in the present discussion. At the same time it was pointed out that the driving force should never be smaller than the contribution due to coherency strains in the thin zinc-rich layer which may form in front of the migrating boundary. [7] that there is no mechanism by which the decrease of the Gibbs energy due to the increase of positional entropy can act as a driving force for the boundary. This is a quarter of the value at the front after 90 min at 600-C according to Fig. This is still very much larger than the value of 1J/mole. Finally.t. was estimated to &c”h m = (20). These explanations should be regarded as first attempts. For the present experimental conditions. Primarily one should test whether the rate of migratjon is proportional to . The strain energy of a thin layer of composition s. M.070 0. It seems more probable that an increase of the rate of migration.086 0. It seems most probable that the growth reverses due to some fluctuation which may occur as the growth rate has decreased to a IOU. further measurements are required in order to test whether the driving force is only due to the coherency energy and whether the reaction stops when the driving forces for the two reactions balance each other. The theoretical treatment would thus be even more complicated.xzn = 0. it is evident that there must be a drastic decrease of this driving force before the driving force for the reverse reaction can stop the further growth. it has been questioned that all of the chemical driving force can act as a force for the grain boundary migration and one cannot rule out the possibility that the two forces may balance each other when the surface layer has reached a critical thickness. Fournelle and J. (20) This expression can also be used as an estimate of the driving force as long as the composition of the coherent layer at the contact with the migrating boundary is approximately equal to the composition of the growing grain. A. M. In that case. 12. 16. As the growth rate decreases.” of fine grains.4crtr rnrrall.oooOl3m”. relative to the grain boundary diffusivity.&. CONCLLSlONS Many nevv phenomena were observed in the present work and some attempts have been made to explain them. (2 . It is approximately lO. The parameter K is defined by equation .10-‘0 1. IO. At the start of the reaction one has .12 at 600 C and the total chemicai driving force for the growth of the fine zincrich grains is 900 J/mole according to equation (2). the reaction has not yet stopped and it thus seems quite possible that there will be a further decrease. which is coherent with a thick grain of composition .OtXl J/mole. Hillert. where the starting material is pure iron. deduced from Table 4. IO‘ ” 6.~~/.‘O 3.LI WD HILLERT: GRAIN BOUNDARY MIGRATION IN Fe-& 1959 Table 4. It has also been pointed out that a considerable part of the driving force may be lost due to diffusion of zinc into a thin layer of the iron grain in front of the migrating boundary [4]. However.10-‘” 8. (21) REFERENCES I. 7%r Mrc-ltorlis~t 01 Pku.. At 6WC. is responsible. One will for instance find that the mobility.x)‘.x’. or ~z~. we would thus have AG$’ = Xx. the effect of the diffusion will be stronger and the concentration at the front may not decrease-as rapidly as Indicated by an extrapolation of the curve in Fig.s where (T is the specific surface energy and s is the average grain diameter in the fine-grained region [ 143.~ Trutlsfornlarrons irt where x7” is the composition behind the migrating boundary.C is 1Ob. The grain boundary mobility evaluated from the rate of thickening of the fine-grained surface layer at 600 C in experiments with alloy B 0 3.Y?”= 0.. _~ 3..m and it yields a drivmg force of about 1 J:mole.~-~ Stimulating discussions with Drs Paul Shewmon and John W. S.J s and Q = 185 kJlmole and the mobihties. only. should be described by &lo = O. Cahn are gratefully acknowledged.. Mrrcrlf.

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