This action might not be possible to undo. Are you sure you want to continue?
JOHN CAMPBELL The various microstructures of cast irons are reviewed, including carbidic and graphite forms (ﬂake, compacted, spheroidal, and undercooled, etc.), exploring whether the presence of externally introduced defects in the form of oxide double ﬁlms (biﬁlms) in suspension in melts seem to provide, for the ﬁrst time, a uniform explanation for all the structures and their properties. Silica-rich oxide biﬁlms provide the substrates on which oxysulﬁde particles form, nucleating graphite. The presence of the ﬁlm provides the favored substrate over which graphite grows, which leads to the development of ﬂake graphite. The addition of limited Mg to form compacted graphite destroys all but a remnant of the silica-rich biﬁlms. The oxide ﬁlm remnant is stabilized by the presence of the graphite nucleus, which causes the graphite to grow unidirectionally in a ﬁlamentary form. The addition of excess Mg destroys all traces of the oxide biﬁlms, leaving only the original nuclei, around which graphite is now free to entirely enclose, initiating the spherical growth mode. Undercooled graphite is the true coupled growth form, nucleated at even lower temperatures in the absence of favorable ﬁlm substrates in suspension; the graphite adopts a continuous growth mode in a matrix of austenite. Carbides in mottled and white irons form on the oxide biﬁlms that often lie along grain and interdendritic boundaries, which explains the apparent brittleness of these strong, hard phases. In most cases of nonspheroidal growth modes (ﬂake and misshaped spheroids), it is proposed that the impairment of the mechanical properties of irons is not strongly determined by graphite morphology but by the presence of oxide biﬁlms. Spheroidal graphite iron has the potential for high properties because of the absence of biﬁlms. DOI: 10.1007/s11663-009-9289-0 Ó The Minerals, Metals & Materials Society and ASM International 2009
THE forms of graphite in cast irons have been the subject of intense interest and huge research eﬀorts mainly since the 1950s, but a full understanding has been elusive. Readers are referred to the review by Loper for a wideranging synopsis covering many details not included in this study. Here, a diﬀerent review is made of the literature, exploring the possibility of a unifying approach based on the hypothesis that oxide ﬁlms (as doubled-over ‘‘biﬁlms’’) are present in liquid irons. Recently, a comprehensive understanding of the microstructure of Al-Si alloys has been proposed in terms of biﬁlms, explaining both the mechanism of modiﬁcation and the structures of hypoeutectic and hypereutectic alloys. Biﬁlms (double ﬁlms), usually oxides, are introduced into molten metals at every pour or stirring event. These surface ﬁlms, which are doubled up during the process of entrainment into the bulk, seem to be of major signiﬁcance for the development of solidiﬁcation structure.[3,4] Their outer surfaces seem to
JOHN CAMPBELL, Emeritus Professor, is with the Department of Materials and Metallurgy, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK. Contact e-mail: email@example.com. This article is based on a presentation given in the ‘‘3rd Shape Casting Symposium,’’ which occurred during the TMS Spring Meeting in San Francisco, CA, February 15–19, 2009, under the auspices of TMS, the TMS Light Metals Division, the TMS Solidiﬁcation Committee, and the TMS Aluminum Processing Committee. Article published online September 1, 2009.
786—VOLUME 40B, DECEMBER 2009
be favored substrates for the precipitation of many, if not all, second phases during solidiﬁcation, whereas the inner unbonded interface acts as a crack. The ﬁlms are generally so thin they are eﬀectively invisible to casual observation, which leads to a liquid that is invisibly cracked and, on solidiﬁcation, to a solid whose cracks may or may not be visible. Nakae and Shin, among many others, have drawn attention to the analogous features of Al-Si and Fe-C alloys. This article is an extension of the biﬁlm hypothesis, which is apparently valuable to an understanding of the Al-Si system as well as to a possible understanding of the various morphologies of carbon in the form of graphite and carbides in the Fe-C alloy system. Naturally, the presence of invisible defects in opaque liquids is not easily conﬁrmed directly, although it will not be impossible in the longer term. In the meantime, this article surveys the experimental evidence from the literature to ascertain whether indirect evidence is supportive of this hypothesis.
THE EVIDENCE FOR OXIDE BIFILMS IN CAST IRON
De Sy has shown that liquid cast iron generally contains signiﬁcant quantities of oxygen in solution in excess of its solubility. He concluded, on the basis of careful and rigorous experiments, that the undissolved fraction of oxygen was present as SiO2 particles. Interestingly, by heating to 1550 °C, he conﬁrmed the
METALLURGICAL AND MATERIALS TRANSACTIONS B
would increase this already large. Even so. FeO. A diﬀerent population of oxide biﬁlms deﬁnitely exists in ductile irons that have been cast turbulently. as well as the long periods during which irons are held molten in holding furnaces. and MnO among others. Both magnesium oxide and magnesium silicate are extremely stable and represent permanent damage folded into the liquid metal and subsequently transferred to the casting. Thus. in the surface ﬁlm. forms in a typical melt when cooling from 1480 °C to 1350 °C. especially during an extended time in holding furnaces or pouring systems. and this eﬀect has been widely accepted as the loss of nuclei (in agreement with proposals made in this article). but superheating and holding at high temperature eliminated many of these. Hartman and Stets report not only the presence of SiO2 in suspension but also olivine. DECEMBER 2009—787 . Also. In this case. but would most likely be in the form of ﬁlms. In any case. together with some FeO. cubes. For instance. such as pouring actions. Only ﬁlms would have a suﬃciently low Stokes velocity (one or two orders of magnitude lower than particles as a result of their greatly increased drag) to remain in suspension for long periods of time associated with these experiments. rods. and the oxide introduced from the surface of the charge (whether steel. at least two diﬀerent populations of oxide biﬁlms seem to exist in suspension in liquid iron. MgO. as discussed earlier by the author. In an elegant study of the thermodynamics. the ﬁlm morphology is to be expected. such as the growth of dendrites. the subsequent straightening of these biﬁlms by various natural processes.Fe)OÆSiO2 is found in those irons that contain Mg. thus forming a magnesium silicate MgOÆSiO2. it is well known that iron from electric furnaces is more liable to chill formation problems in thin sections than cupola iron. which METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. including SiO2. Mampaey and Beghyn show how mainly SiO2. 2—Optical micrograph through the fracture surface of ‘‘platefractured’’ ductile iron shows misshapen graphite nodules growing on biﬁlms straightened by dendrite growth. include the following: (1) the hypothesized silica-rich biﬁlms as a natural population in equilibrium with the melt. During melting in the cupola as droplets of iron rained down. stirring in induction furnaces. they will be expected to go into solution if the melt is held above approximately 1450 °C for any length of time. and (2) the known magnesia-rich biﬁlms in ductile irons are the result of mechanical accidents that involve the turbulent entrainment of the VOLUME 40B. natural population.expectation that the SiO2 solids dissolved because they became less stable than CO but reappeared on cooling once again. Additional treatments or handling. Fig. the amount of silica-rich phase being predictable by thermodynamics. of course. the presence of Mg stabilizes the magnesia. the natural enfolding of the surface ﬁlm of SiO2 of each droplet would ensure a natural population of SiO2-rich biﬁlms. which creates extensive planar cracks. pig. this process results in extraordinary structures (Figures 1 and 2) and the phenomenon of brittleness in so-called ductile iron in the form of plate fracture. Although the biﬁlms are known to have an initially compact morphology as a result of the turbulence during their formation and are relatively harmless as cracks. and their oxygen is removed as MgO when Mg is added to the melt. although Si might also contribute. 2(Mg. Silica-rich oxides in irons are not stable in some conditions. is common. or foundry returns). they are rapidly reduced to Si metal. Hoﬀman and Wolf ﬁnd a variety of oxides. etc. It seems reasonable to speculate that these oxides almost certainly would not be compact spheres. 1—A so-called ductile iron casting illustrating brittle fracture as a result of dendrite-straightened biﬁlms. which is equivalent to MgSiO3.
of the microprobe analyzer in 1974. while working on preconditioning treatments for gray irons (treatments involving small additions of elements such as Al prior to inoculation possibly to enhance the population of naturally occurring nuclei in uninoculated irons). but the subsequent growth of the graphite is aﬀected by the presence or absence of oxide biﬁlms of diﬀerent types. and its development continues to the present day (for instance Skaland and Hartung et al. In this article. but it has been studied by several others since (for instance Fredriksson). III. only oxide biﬁlms seem to have signiﬁcant roles. the particles take time to melt and time to disperse. and their ﬁnal composition consists of mixed oxides and sulﬁdes. Hurum[20. but their number and eﬀectiveness cannot be relied on. they ﬁnd that undercoolings below the liquidus of between 200 °C and 400 °C are required to trigger nucleation by austenite. Many authors have reported the beneﬁcial eﬀects of S. Warrick) composed of particles of complex oxides and sulﬁdes. The mechanisms proposed by Riposan[16. leading to the oxides consisting mainly of alumina or zirconia).17] ﬁnds that MnS shells with Mn/S high ratios are numerous in the matrix but do not seem to 788—VOLUME 40B. nucleate graphite. carbon biﬁlms exist in irons in those cases in which hydrocarbon gases from the mold disassociate on the hot surface of the melt.21] was the ﬁrst to draw attention to this phenomenon. The question therefore arises. This approach is the ﬁrst to suggest separate functions of the graphite nucleating particles and graphite growth substrates. show how this region is eﬀectively undercooled by several hundred degrees Celsius as a result of its constitution of nearly undiluted graphite promoter. so that if surface turbulence occurs. (b) Complex sulﬁdes (<5 lm diameter) nucleate on the oxides (mainly based on MnS with low Mn/S ratio but complicated by additions. Interestingly. What does nucleate graphite? This question is all the more intriguing following the work by Mampaey and Xu. have demonstrated that austenite is ineﬀective in nucleating graphite. thus providing a region in which a high driving force exists for the nucleation of graphite. Riposan[16. carbide precipitation is likely in places. Sr. Harding et al. Inoculation with graphite or SiC. with a reduced tendency to carbide formation and a consequent beneﬁt to the mechanical properties and machinability of the iron.surface ﬁlm into the bulk liquid. In passing. as will become clear during the progress of this account.K. Flakes occur but are relatively few in number and uncontrolled in size. Only those shells with low Mn/S ratio seem to act as nuclei. the resulting carbon ﬁlm can be folded in.17]) eﬀective for all types of graphite. giving a copious crop of graphite ﬂakes of good uniformity of size. of course. Thus. FLAKE GRAPHITE IRON (FGI) AND INOCULATION Mizoguchi et al. In fact. As an example of an excellent recent study. which contains perhaps 50 to 75 wt pct Si. which is below liquid iron casting temperatures. and therefore possibly constitute a favored substrate. The mechanical properties of the iron are generally poor. it seems that some nuclei exist prior to inoculation. usually containing Al and/or Zr. for instance Chisamera et al. in which they found that a single population of nuclei could explain both gray and ductile irons. which results in nonreversible damage. which suggests that the oxysulﬁde mix of the various elements will have a spectrum of lattice spacings ensuring that at least part of the compound will match graphite. Also. the melting point of such an inoculant is close to 1210 °C. However. This was the conclusion reached in the ﬁrst study after the development in the U. DECEMBER 2009 Uninoculated iron is characterized by poor control of the graphite morphology. In this review of the microstructures of cast irons. particularly Ca. Such lustrous carbon defects are not necessarily permanent because the carbon can slowly dissolve. In general. GRAPHITE NUCLEI IV. Riposan[16. if not identical. The inoculation process was found to increase greatly the number of nuclei available. it is worth drawing attention to the possibility that other nonoxide biﬁlms are to be expected in cast irons. There is a growing consensus that both ﬂake and spheroidal graphite nucleate on similar. and Ba). and so on. For instance. The gradual introduction of the inoculation process occurred from about 1920 onward. The relatively few opportunities for the carbon to precipitate lead to relatively large regions of the iron elsewhere being supersaturated with carbon. forming temporary supersaturated regions of liquid rich in silicon surrounding the melting and dissolving inoculant particles. The complex sulﬁdes form a shell around the central oxide. nuclei (for instance. Many conﬁrmations of this ﬁnding have since been made (for instance Skaland). the added particles melt. Thus.17] deﬁnes a three-stage model for the nucleation of graphite: (a) Small oxides (<2 lm diameter) are formed in the melt (from the preconditioner. (c) Graphite nucleates on parts of the sulﬁde shell. the mechanisms proposed to explain the various morphologies of graphite are based on the possibility of nucleating particles (probably based on oxysulﬁdes as described by Riposan[16. nitride biﬁlms probably form in cast irons giving rise to the ‘‘nitrogen ﬁssure’’ defects associated in the past with high nitrogen binders. which explains why such features are observed in only relatively thin section castings but not in thicker sections. usually in the range 1350 °C to 1400 °C.17] are highly convincing and are in agreement with the general consensus that few nuclei exist prior to inoculation but are enhanced in eﬀectiveness and number by preconditioning and inoculation. acts similarly to promote regions of METALLURGICAL AND MATERIALS TRANSACTIONS B . A more unfavorable nucleus would be diﬃcult to imagine.). The inoculation process is often carried out by addition to the melt of granules of a graphite promoter such as a ferrosilicon.
the graphite formed rapidly in these regions is slow to redissolve. which forces graphite to form around the nucleus. the MnS shells around the oxide centers are modiﬁed in these regions in which the additions are concentrated (prior to their dissipation and dilution in the melt). extending in the directions in its basal plane. Sr. high above the expected liquidus temperatures. the graphite extends across the biﬁlm. leading to the fairly ﬂat morphology of ﬂakes in gray iron. but it will subsequently dissolve in the open melt rather slowly because the graphite will ﬁnd itself only modestly above its equilibrium eutectic temperature. Feest et al. straightening the biﬁlm. above the general eutectic freezing temperatures) because of the energetically favored growth of graphite on the oxide substrates in suspension (Figure 5). would favor the straightening of the biﬁlm (Figure 3(d)). initiating a graphite ﬂake. The overwhelming driving force explains the wide variation of successful nuclei. and Ba).high-constitutional undercooling. Ca. graphite embryos on their nucleating particles will take time to go into solution. so although insuﬃciently favored to cause nucleation. eﬀectiveness. VOLUME 40B. All this is taking place in the region highly constitutionally undercooled with respect to graphite. which. would be expected to be of only mediocre. many will survive to reach the regime close to the freezing temperature where they will now start to regrow.. its minimal rigidity exerting negligible constraint of the advancing graphite crystal. in gray irons. nucleate from those nuclei already sitting on the oxide biﬁlms. of course. This is almost certainly the phenomenon known to all foundry personnel as ‘‘fade’’ of the inoculation eﬀect. point out that once nucleated in the regions of high driving force for initiation. (c) graphite nucleation on nuclei in regions of high eﬀective carbon supersaturation as in Figure 3(b). the nucleus experiences a massive driving force as a result of hundreds of degrees of eﬀective undercooling. However.e. all the inoculant particles will have melted and dispersed. On entering this region.17] indicates that only parts of the nucleant particles are active nucleation sites. it is suﬃciently favored to support the subsequent growth of the graphite. neither of which applies during the mechanism of inoculation of cast irons. not only on equilibrium behavior but also on the behavior of alloys of perfectly uniform composition. graphite would. (d) growth of graphite ﬂakes along the length of the biﬁlm. Thus. 3—The mechanism of inoculation: (a) a biﬁlm in suspension in the melt together with nuclei already attached from trace contaminants or preconditioners. Figure 3 schematically shows a graphite nucleus formed on an oxide biﬁlm approaching an undercooled region provided by a dissolving inoculant particle. Because of the additional trace alloying elements in the inoculant (particularly group IIA elements of the periodic table. The biﬁlm would be expected to be extremely thin. The observations by Loper and Heine conﬁrm that graphite can nucleate in both hypoeutectic and hypereutectic irons at 1400 °C. as observed experimentally by Loper and Heine. Mampaey conﬁrms that graphite forms in the melt prior to the appearance of austenite. it seems reasonable to assume that these new graphite nuclei would also preferentially nucleate on biﬁlm substrates. ﬁnd that although the Si-rich inoculant particles disperse relatively rapidly. (b) additional nuclei provided by inoculant. the graphite particles attached to their nuclei now will emerge from these regions into the general melt where they will become unstable and start to redissolve. The freedom from restraint would explain the development of relatively perfect crystals of graphite as observed growing ahead of the coupled eutectic graphite (Figure 5). The growth morphology of graphite. Bearing in mind that many (if not all) second phases precipitate on biﬁlms as preferred substrates. in other circumstances. thus naturally providing the driving force for nucleation of graphite in precisely the location needed for maximum eﬀectiveness. This is reasonable because the graphite initially grows quickly in the highly constitutionally undercooled region. in turn. well into the liquid range. The silica-rich biﬁlm will form a ‘‘next best’’ substrate for graphite.) Given suﬃcient time. Thus. possibly measure in nanometers. (These observations are contrary to expectations based on the equilibrium diagram based. The ﬂakes grow in regions ahead of the solidiﬁcation front (i. and all the embryonic particles of graphite nucleated in the undercooled regions will have re-dissolved. 4—(a) A biﬁlm with precipitated nucleus from natural contaminants or preconditioners. DECEMBER 2009—789 . including Mg. so that the matrix would be eﬀectively nearly saturated in carbon. if any. leaving no pockets of undercooling. which encourages graphite nucleation and growth on any suitable available substrates that happen to be in this region. Harding et al. with a consequent central planar crack in the graphite ﬂake. and (b) the biﬁlm ﬂoating into a region of high constitutional undercooling surrounding a dissolving inoculant particle. Fig. METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. so that if the melt is cast without undue delay. The newly forming graphite cannot grow completely around the nucleating particle because the particle itself has itself grown on the planar biﬁlm substrate so that at least one of its faces is inaccessible (Figure 4(c)) (work by Riposan[16. so that initial growth is rather irregular).
6—Two populations of ﬂakes: extrinsically formed on biﬁlms and intrinsically grown as a coupled (undercooled) eutectic. DECEMBER 2009 work of Enright et al. would regain its good solidiﬁed structure when cooled once again. It would be interesting to know whether the melt. For instance. it would be expected to be common to see gray irons with two separate populations of ﬂakes: (1) those formed by free growth in the liquid (primary ﬂakes) and (2) those formed by coupled growth at lower temperatures (eutectic ﬂakes). suggesting a similar origin and behavior in the melt. The more common Type A graphite ﬂakes are similar. it is not likely to be a good substrate for the development of a good ﬂake structure. the populations of primary and eutectic ﬂakes should be expected to be mixed in most. Primary ﬂakes seems to be a good name for these forms. particularly if the iron has been held in an acid-lined induction furnace. In agreement with the mechanism described in this article. which exhibit elegant hexagonal symmetry and are apparently largely free from defects. the ﬁnal pouring of the melt into the mold may provide suﬃcient turbulence to address this problem. operators commonly ﬁnd the iron has poor graphite structure.Fig.17] shows that this is at least partly the result of the gradual loss of the graphite nuclei. nor even a ﬁlm. displaying only minimal irregularity. on the Monday morning after the melt has been held for the weekend. 5—Extrinsic initiation of straight graphite ﬂakes in the liquid. with some branching. In terms of the biﬁlm substrate. messy structures. the form of the silica may not be a biﬁlm. they observed this result. Similarly. the advancing solidiﬁcation front will overtake those ﬂakes growing on biﬁlms ﬂoating freely in suspension in the liquid. this is straightforwardly understood from the irregular structure of the biﬁlms. Thus eventually. More usually in castings. Fig. As such. but instead they entrain as randomly folded. Particles that seem to be nuclei for the initiation of ﬂakes have often been observed. ﬂake graphite irons. the presence of a dense mesh of austenite dendrites constrains the size and shapes of ﬂakes and prevents any signiﬁcant buoyancy eﬀects. without some kind of surface turbulence. He calls these proeutectic ﬂakes. they tend not to entrain as nicely parallel double ﬁlms. straight ﬂakes. folds leading to parts of the double ﬁlm at irregular angles to the main biﬁlm fold are to be expected and would account for the branching of growing ﬂakes. For many other irons. after losing its silica-rich biﬁlms at high temperature. unencumbered by the presence of austenite. which makes the METALLURGICAL AND MATERIALS TRANSACTIONS B . The mechanism proposed above explains the growth of ﬂake graphite from nucleating particles introduced by inoculation. but it may be a compact particle. these freely ﬂoating ﬂakes will become incorporated into the solid (Figure 5). even though. as may be inferred from the 790—VOLUME 40B. Experience of variable performance is also to be expected. Thus. Thus. Riposan[16. Even so. A bimodal distribution of graphite ﬂakes is therefore to be expected in most gray iron microstructures. and it is clearly observed in Figure 6.17. Thus. Goodrich attributes the Type C iron (ASTM A247). of course. which is characterized by large.28] Eventually. iron heated to high temperature suﬀers a similar degradation of graphite structure. ahead of coupled growth of eutectic graphite and austenite. because although de Sy reports that the silica reappears in the melt on cooling. such mixtures may not always be obvious to casual observation. Less obvious but important bimodal distributions are almost certainly common. the graphite ﬂakes are seen to branch relatively frequently. Loper and Fang use deep etching to reveal what they call pre-eutectic ﬂakes. They originate in suspension in the melt and therefore can ﬂoat to the upper regions of a casting. to the result of the growth of the ﬂakes in the liquid. The coupled growth mode is discussed below.[16. almost certainly as a result of the dissolution of the biﬁlms because of the instability of SiO2 above approximately 1450 °C in the presence of carbon. and these particles seem likely to be a universal phenomenon in both ﬂake and nodular irons. Part of the eﬀect would also be expected to be loss of biﬁlm substrates. if not all. During their entrainment from the liquid surface into the bulk melt. unless this is an extraordinary coincidence. On the ﬁrst occasion that these authors used the highly sensitive fractal analysis technique to assess microstructures of cast irons.
 and Chisamera et al. The relatively poor mechanical properties of gray iron seems likely to be more to do with the presence of biﬁlm cracks down the centers of graphite ﬂakes (or the sides of graphite ﬂakes if graphite grows on only one side of the biﬁlm— the impression now is that the ﬂake has METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. evidence indicates that alumina-based. the carbon in solution will be unable to precipitate. in which austenite and graphite grow in a coupled mode. Only relatively few such nuclei will operate. the hollows in the fracture surfaces of spheroidal graphite matrix that had contained spheroids exhibit no oxygen. This behavior is exactly predicted by a biﬁlm hypothesis: If ﬂake graphite formed on one side of the oxide biﬁlms. or possibly Al-containing Si-based biﬁlms (for instance. then the fracture surface would necessarily reveal the oxide. below which SiO2 is stable. would develop diﬀerent qualities of precipitated graphite. It is right to question. Larger quantities of kish were formed at temperatures below 1400 °C. gray iron has a curious behavior in that nothing seems to attach to the graphite. Basdogan et al. The above discussion relates to those graphite ﬂakes growing freely in the melt giving rise to large. Carlberg and Fredriksson ﬁnd that cast irons based on Fe-C-Si exhibit ﬁne graphite structures. It seems possible that graphite is strong in tension perpendicular to its basal plane. the eﬀect of oxygen addition to the melt during the pouring of iron into the mold is demonstrated by several authors. the halves of the biﬁlm appear on both fracture surfaces. For most intermetallics precipitating on one side of a biﬁlm. we move the focus from ‘‘anomalous’’ to the truly regular. conﬁrms that conventional gray irons that contain Al develop coarse graphite ﬂakes. randomly oriented ﬂakes which tend to ﬂoat or settle irregularly. decohered from the matrix) rather than any intrinsic weakness of the graphite itself. 7—Graphite ﬂake exhibiting a central crack (the solid state precipitation of surrounding temper graphite is also fractured oﬀ). therefore. Thus. activating in those parts of the melt that are especially cool. Liu and Loper found that oxygen was necessary to nucleate kish graphite on the surface of gray iron melts. sulfur) are present on fracture surfaces of gray irons that were adjacent to a graphite ﬂake (fractured and observed in high vacuum). In the absence of suitable nuclei that have formed on oxide substrates in suspension in the melt. but oxides would be absent in the case of spheroidal graphite iron (as discussed below). which leads to the familiar easy shear in its free condition. whereas those based mainly on Fe-C-Al display coarse graphite ﬂakes. the melt will continue to undercool until the undercooling ﬁnally becomes suﬃcient to provoke precipitation on some other (less favorable) substrate. V. such as those regions close to VOLUME 40B. what role has the biﬁlm played in the fracture because its central unbonded interface has not seemed to act as the decohering surface on this occasion. based on mullite or other stable alumino-silicate compound) exist. ‘‘classic’’ eutectic form. therefore. Although all the above discussion relates to silicabased biﬁlms. creating what has been called in the past an ‘‘anomalous’’ eutectic. Johnson and Smart describe a critical experiment in which they use sophisticated Auger analysis to prove that two or three atomic layers of oxygen (and interestingly. In their studies of crack initiation and propagation in irons. Moreover. In fact. In agreement with the prediction that graphite grows on oxide biﬁlms. but the continuing decohering action seems to follow the graphite interface. It would be reasonable to expect that silica-rich and alumina-rich biﬁlms would have diﬀerent mechanical and chemical characteristics and. and kish was not observed in Si-free melts.problem essentially invisible to those attempting to study the eﬀect. because although the interplane bonding is not strong. it seems likely that the biﬁlm will have nucleated the decoherence. A crack down the center of a ﬂake is observed in Figure 7. found oxygen to be highly eﬀective in converting carbidic irons into beautifully ‘‘inoculated’’ ﬂake graphite irons. COUPLED EUTECTIC GROWTH OF GRAPHITE AND AUSTENITE In this section. Chisamera et al. This nonattachment (perhaps we should say ‘‘active detaching’’) phenomenon between graphite and other phases is observed elsewhere in bubble trails in gray irons as well as in lustrous carbon ﬁlms detached from the matrix and adhered to the sand mold. DECEMBER 2009—791 . However. Voigt and Holmgren report many centerline cracks in graphite ﬂakes plus some decoherence from the matrix. there are approximately 1015 bonds per mole in the graphite surface. In contrast. so that both halves of the biﬁlm seem to have attached to the matrix. For instance. The huge number of bonds will ensure high strength in tension in a situation in which the graphite is encapsulated. preventing easy failure by peeling or shear.
therefore. this explains the ‘‘coral’’ type of graphite morphology (to be discussed later). that ﬁne graphite morphologies. the graphite having nucleated. At modest undercoolings. In the case of silica-rich biﬁlms. On the other hand. Thus. whereas rosette (or cell) graphite would represent an intermediate case as a result of its larger spacing. would be highly faulted. Probably all coupled eutectic graphites experience this eﬀect. If sulfur is also present in the melt. VI. the coupled growth takes the form of rosettes. DECEMBER 2009 . will help to settle such questions. seems in general to have been avoided for general engineering castings. The disappearance of the biﬁlms and the initiation of spheroids are shown schematically in Figure 9. the silica will be reduced by magnesium to (1) silicon metal. augmenting these original particles. the addition of Mg. in general. will lose any graphite to their neighbors by a natural coarsening process. might also somehow METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. it seems likely that a single initiation event on a nucleus. These compact nuclei are now the only nucleation sites available for the precipitation of graphite. We would expect. it may be some kind of aggregate of biﬁlms that. would be expected to contain the least faults.the mold walls. Those biﬁlms present between ﬂakes. then the MgO is likely to contain a component of MgS. if such a behavior also exists for ductile iron. They are mainly inﬂuenced by the continuous growth process. ﬂakes have to realign their growth direction continually because of the intrusion of their neighbors into their growth space. All the coupled eutectic forms described below are therefore not especially inﬂuenced by the (rather rare) nucleation events. containing high defect densities. The cells are beautifully regular structures with interﬂake distances now strictly controlled by diﬀusion in the boundary layer immediately ahead of the advancing front. which is sometimes designated Type D or E according to ASTM speciﬁcation A247. but graphite forms preferentially on isolated regions of the particle. is not clear. possibly augmented by additional MgO. and so these biﬁlms become invisible. SPHEROIDAL GRAPHITE IRON (SGI) (DUCTILE IRON) When suﬃcient magnesium is added to the melt. A careful examination of graphite ﬂakes to determine whether they contain biﬁlms.17] on ﬂake graphite irons shows that the particulate nuclei do not seem. and an examination of interﬂake regions to check for biﬁlms. then this unpromising start to nodularity will emphasize the possible importance of plastic constraint of the surrounding austenite matrix as will be discussed below. The precipitating graphite grows over the compact nucleus. Whether the rosette form is a strictly coupled growth. expanding to form a cell (courtesy of Fras et al. On the one hand.[40. Because the growth direction of graphite is mainly parallel to the basal (0001) plane. limiting the strength of such irons. The ‘‘wrapping around’’ process (Figure 9(d)) may consist of renucleation of many separate microscopic grains of graphite on favorable fragments of the oxysulﬁde surface. 792—VOLUME 40B. expands the coupled growth front as a hemisphere to form the rosettes. this means that the crystal has to develop faults to allow it to change direction. as seems possible. subsequently develops along radially oriented biﬁlms to generate the appearance of a single growth phenomenon. as mentioned above. the oxide biﬁlms are completely eliminated. and (2) solid magnesium oxide that will precipitate probably on the pre-existing nuclei that originally sat on the ﬁlms. the radial structure of graphite nodules develops from the graphite grains growing radially out from the compact nucleus to form the familiar approximately spherical nodule (Figure 11). However.41]). wrapping completely around it so as to form a compact initiating morphology. In this way. For instance. The reaction is simply SiO2 þ 2Mg ¼ Si þ 2MgO The total loss of biﬁlms means that only solids remaining in suspension in the melt are the original particulate nuclei. types D and E graphite. which will dissipate into solution in the matrix. 8—A scanning electronic microscope (SEM) image of a deeply etched rosette of ﬂake graphite. The subsequent evolution of heat will inhibit other nuclei from becoming active. in particular. in addition to eliminating the silica-rich biﬁlms. At lower undercoolings. which is often sited on the mold wall. Primary ﬂake graphite.[40. to be completely wrapped around by graphite. This is possibly because the interﬂake diﬀusion distance is now so small that only ferrite can be formed. which are often called ‘‘cells’’ (Figure 8). not requiring the presence of biﬁlms. at less than a diﬀusion distance from neighbors. a clearly formed rosette structure may be capable of generating from a random morass of biﬁlms. During coupled growth.41] Thus. more highly undercooled eutectic. which is highly faulted. or cells (Figure 8). The growth mode is probably some kind of addition of carbon atoms to spiral growth steps generated by h0001i oriented screw dislocations (Figure 10). ﬁner. The careful study by Riposan[16.
(Some subsequent surface smoothing driven by surface energy would be expected to occur rapidly. The pressure developed in a thick spherical shell (Figure 13) expanding plastically because of internal pressure is quantitatively expressed by P ¼ 2Y ln b=a ½1 where P is the internal pressure. Subsequent research will clarify this point. (e) growth of spheroids. DECEMBER 2009—793 . a shell of austenite would be expected to wrap itself rapidly around the nodule. subsequently developing a shell of austenite. Many studies have clearly revealed the deformation of austenite dendrites by the growth of internal nodules (Figure 12). in which the graphite nodule does not grow a shell of austenite until it contacts an austenite dendrite. whatever the ﬁner details of the encapsulation process. Stefanescu concludes in his review that all the evidence points to nodules initially growing freely in the liquid. A minor modiﬁcation of this development may be envisaged. Fig. Anyway. Y is the yield stress. as the graphite grows. with their austenite shells and the austenite dendrites results in their mutual assimilation.Fig. the shell of austenite seems a key feature associated with the growth of spheroids. 11—Graphite nodules in an austempered iron indicating nucleation on a small central inclusion. (d) the nucleation of graphite. Later. and b and a are the external and internal radii of the shell. Painstaking metallography would be required to clarify this detail. It seems possible that the spherical morphology of the graphite nodules may be encouraged by the mechanical constraint provided by the nodule having to force its growth against the resistance provided by its surrounding shell of austenite. and Stefanescu assume the protrusions to be the natural growth shapes arising from cooperative growth of austenite and graphite by diﬀusion from the liquid. wrapping completely around existing nuclei (particularly if they happen to pass through constitutionally supercooled regions). (c) the survival of existing nuclei and additional nuclei from inoculation. to create a local bump on the dendrite. At that moment. as discussed below. locally expanding the surrounding solid to accommodate the increasing volume occupied by the graphite has to be important.) (c) Deformation of the dendrite by plastic ﬂow. VOLUME 40B. but it is important and worthy of examination. This eﬀect seems to have been generally overlooked. (b) the elimination of the silica-rich biﬁlms by addition of Mg. 9—(a) The melt with biﬁlms and sundry contaminant or preconditioned nuclei. all of which are likely to contribute to some degree. (b) Buhrig-Polackzed and Santos indicate in a schematic illustration that the contact between nodules METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. aﬀect the ability of the nuclei to work more eﬃciently. and ﬁnally contacting and becoming incorporated into an austenite dendrite. as follows: (a) Ruxanda et al. 10—The probable structure of a graphite nodule. so that a complete wrapping around eﬀect might be promoted. This lumpy morphology has been attributed to various mechanisms.
 leaving mainly argon. 13—A thick shell expanding plastically because of internal pressure. it may be signiﬁcant that on the addition of Mg causing dissolution of the silica-rich oxide biﬁlms. a biﬁlm of 100 lm square and an average gas gap of 1 lm would yield a pore of approximately 20 lm diameter. If we take Y to be approximately 6 MPa for austenite at the melting point of iron. the pressure to extend plastically the growth at this location would (according to Eq. Thus. P is of course unchanged. For instance. having a necessarily smaller radius r. a rounding eﬀect caused by mechanical smoothing of the forces to expand the austenite shell seems to be important. 12—The distortion of dendrites as a result of the internal growth of nodules (after Hillert). taking r = a/2 to a/10 locally increases P to approximately 35 to 60 MPa. followed by nitrogen that would react to form nitride. A small biﬁlm of 794—VOLUME 40B. The easier spherical growth mode. Even at values of a = 20 lm and b = 200 lm. DECEMBER 2009 METALLURGICAL AND MATERIALS TRANSACTIONS B . would therefore be encouraged. A similar area biﬁlm of an average 10-nm gas gap would form a pore approximately 5 lm in diameter. However. then the nodule developed as a sphere. that there is some qualitative justiﬁcation for believing that mechanical forces stabilize the spherical growth mode of the nodule. In general agreement with this conclusion. therefore. sphericity is encouraged. This leaves mechanical stabilization as a potential critical mechanism. after which the spherical form can no longer be stabilized. A perturbation radius r is not favored because a higher local pressure is required. it seems possible that clouds of ﬁne argon bubbles will be released into the melt. Clearly.Fig. and a = 2 nm and b = 20 nm. respectively. The logic is as follows: If a perturbation to the spherical graphite shape were to occur. It is not easy to deﬁne the sizes of such bubbles with any accuracy. used color etching to reveal the austenite shells around graphite. This conclusion is reinforced by the recent evidence[16. simply expanding the uniform radius a. it is useful to ascertain whether there is quantitative justiﬁcation for this mechanism. ) be increased (Figure 12(b)). The air trapped in a biﬁlm will be expected to lose its oxygen by continued oxidation of the matrix. Fig.17] that the early phases of growth of the graphite around the nucleus are anything but regular. Johnson and Smart use the sophisticated and respected perturbation analysis by Mullins and Sekerka to suggest that interfacial energies are of importance in spherodizing graphite nodules up to a diameter of perhaps 50 nm. more work is required to conﬁrm this preliminary indication. the above result can be relied on to give us an order-of-magnitude estimate of the eﬀect. much speculation by earlier authors that interfacial energies may be important in deﬁning the shape of spheroidal graphite seems irrelevant. respectively. any residual air trapped between the ﬁlms is expected to be released. Thus. Thus. growth of the extension of smaller radius would be discouraged because additional pressure would be required to stabilize the perturbation. In this way. a strong spherodizing eﬀect is needed that neither the nucleation mechanism nor surface energy can provide. It seems. It seems likely that some Mg vapor will also diﬀuse into the bubbles. In passing. With regard to the possible asymmetric eﬀect of a perturbation of radius r. which indicates that there is a substantial restraining pressure on the growth of the nodule during most of its life. whereas slow-developing or nonenveloping shells led to misshapen nodules. Thus. then we ﬁnd P = 30 MPa approximately. Clearly. Although a creep model rather than the above plastic model might give a somewhat more accurate result. They found that if the shell formed quickly and completely. Jiyang et al.
its distant ‘‘twin’’ half not enjoying the protective inﬂuence of the nucleus will dissolve and disappear. but a successful penetration of a particle into the bubble would depend critically on a reduction in interface energies. It is intriguing. it will have been energetically favorable for the nuclei to attach to the biﬁlm. but the observations by Riposan[16. in which ﬂake is converted into nodular iron by simply purging the melt with ﬁne bubbles of nitrogen. The subsequent nucleation of graphite on the nucleus will result in rapid spreading of growth around the nucleus. Thus.[54. will be well ‘‘wetted. COMPACTED GRAPHITE IRON (CGI) If the addition of magnesium is more carefully controlled to some level intermediate between spheroidal and ﬂake iron. VII. argon or carbon dioxide become explicable. as a result of the reduction in strain energy involved. The transformation of the planar cracks sandwiched inside the biﬁlms into clouds of ﬁne bubbles that may ﬂoat and escape from the alloy is the essence of the process by which apparently brittle gray iron becomes ductile.55] However. Originally. Clearly. that a theory proposes that nodules nucleate from Mg bubbles in suspension in the melt. Furthermore. In our biﬁlm model. will remain (Figure 15(b)).17] and others indicates that the nucleating particle is often not entirely surrounded in the case of Fig.e. compacted (‘‘vermicular’’ based on the Italian for ‘‘worm-like’’) graphite is the result (Figure 14). it seems that a fog of bubbles in the range of approximately 1 to 20 lm is to be expected. although a mechanism for the presence of extremely ﬁne bubbles may be provided by the current analysis. as noted below. From experience in the light metals industries. However. On arrival at the nonwetted interface of the residual patch of biﬁlm. the growth cannot now be a ﬂake because no biﬁlm is present. Thus. DECEMBER 2009—795 .. 14—CGI viewed by (a) SEM deep etching and (b) optical metallography. but not perhaps relevant.) Only half of the biﬁlm will be retained in this way. and the reduction of surface energy to encourage such precipitation in the liquid state seems negligible.’’ which is a necessary condition for the particle to be a nucleating agent).. (Naturally. Thus spherodization seems to be achievable via a purely mechanical route. it seems to be irrelevant to the formation of graphite nodules. the theory requires the incorporation of solid particulate oxide nuclei into the bubble.10 lm square and 10-nm average spacing would create a 1-lm-diameter pore. The subsequent growth of graphite is forced to occur not radially but in general unidirectionally away from the biﬁlm residue (Figure 15(d)). Such particles will be energetically rejected by bubbles. Another interesting aside can be noted. It does not oﬀer support to the gas bubble nucleation hypothesis. (Ductile iron only becomes embrittled once again. this spreading will be arrested (Figure 15(c)). curious observations. Only the small part of 1/2 of the biﬁlm together with its unbonded interface. METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 40B. This is unlikely for particles formed by precipitation in situ in the liquid. replicating the condition achieved chemically by the addition of Mg. it is known that purging with gases can eliminate biﬁlms from melts. small patches may remain if the Mg addition is not too high. such as that reported by Yamamoto et al. which will be in perfect atomic contact with the melt (i. attractive this hypothesis might be to explain graphite coatings inside pores in solidiﬁed castings. stabilizing the combination. the tiny patches on which the original nuclei sat will be resistant to dissolution because they will be stabilized by their attachment to the nuclei. so that the combination of nucleus and ﬁlm will enjoy a reduction in overall energy. it was thought that it could not be spherical because it could not encapsulate the complete nucleating particle.) Finally. any strain energy relief in the liquid state is zero. the remnants of the layer of air. if oxide biﬁlms are reintroduced by turbulence by handling of the melt or poor ﬁlling system design of the casting. it is clear that most of the oxide biﬁlms will be dissolved by the addition of Mg.
With regard to the microstructure of growth. Fig. (d) growth continues unidirectionally. References 60 and 61). as its name suggests. Naturally. and when the growth rate is suﬃciently high. and the last remaining patches of biﬁlm will be dissolved. 2009). ﬂake iron. It is tempting to consider that the resemblance reﬂects an underlying similarity. encouraging the growth of totally spherical grains. If the Mg level is too low. no silicarich oxide biﬁlms can be present. thus advancing subsequently on a substantially planar growth front away from the wall.Fig. to (b) eliminate most of the silica-rich biﬁlms. then the limited stability enjoyed by the residual biﬁlm patches will be overcome. MISSHAPEN SPHEROIDS The presence of ill-formed spheroids. ﬁbrous ﬁlamentary morphologies. neither ﬂakes nor spheroids can form. the subsequent growth form is not possible to predict and has to depend on completely diﬀerent factors. the growth of the eutectic is likely to be so fast that it will cover large undercooled regions at the mold wall. Because of the purity of the alloys. Clearly. They show the close similarity between the coral eutectic structures of Fe-C and Al-Si alloys. is widely known to be associated with the reduction in mechanical properties METALLURGICAL AND MATERIALS TRANSACTIONS B . This seems to be a coupled growth mode. formed in rather pure. or Ce is added. even though nowhere in their report do Nakae and Shin mention coral graphite. IX. Thus. then residual biﬁlms will encourage ﬂake graphite. Thus. but not the remnant of ﬁlm attached to the nuclei. several workers ﬁnd that the graphite seems to stay in contact with the liquid (for instance. As an important feature of the continued growth of CGI. CORAL GRAPHITE Coral graphite is. coral graphite occurs at high undercoolings (clearly at least one nucleation event is required. whereas if the Mg level is too high. The great sensitivity of the compacted graphite morphology to magnesium concentration is corroborated by the proposed biﬁlm mechanism. a ﬁbrous morphology of graphite. AFS. After initiation in undercooled regions. 16—An SEM image of deeply etched CGI closely resembling coupled eutectic coral structure. particularly if present in large numbers. noninoculated irons. they present micrographs that clearly illustrate coral growth when the iron is suﬃciently pure. It develops its continuous worm-like growth because of a continuous growth process. DECEMBER 2009 phenomenon is dominated by growth). unidirectional spiral structure similar to the worm-like growth mode clearly observed in Figure 14. expanding the casting and increasing feeding requirements. The purity and absence of inoculation also means that no oxysulﬁde nuclei are present. VIII. and this may also be true of nodular iron. and the fact that it can be grown in alloys containing Ce. illustrating the overall similarity of these structures (Courtesy of Thomas Prucha. 15—The formation of CGI by addition of just enough Mg to (a) melts with existing biﬁlms with attached nuclei. CGI and coral forms of graphite (Figure 16) are both ﬁne. the ﬁnal form of CGI is not strongly inﬂuenced by the inoculation and nucleation events. (c) Inoculation promotes graphite growth on the nuclei. in contrast to ductile iron in which the graphite transfers its expansion to its surrounding solidiﬁed shell. Cole had observed a ﬁne. but the 796—VOLUME 40B. thus transferring the expansion of the graphite to the liquid. reducing feeding requirements. Liu ﬁnds that the growth direction is along the C axis (0001 direction perpendicular to the basal planes) and seems to develop by a spiral dislocation mechanism as witnessed by the coarse and irregular spirals that they observe. For interested readers.
thereby folding in the oxide surface of the liquid to create entrained biﬁlms. This was almost certainly a result of adding the inoculants through the melt surface. on pouring into the mold. This seems most unlikely. then the uniform graphite would be expected to have a substantially uniform rate of dissolution. such as tensile strength and ductility.67] This undesirable morphology is not easily explained at this stage as a result of relatively little experimental work to clarify the problem. not all of these defects will ﬁnd their way into the castings to impair the structure and properties. Thus. as a crack. occupying a vastly greater cross sectional area than the spheroids. The 50 pct or so component of ﬂakes or other non-nodular shapes does not particularly aﬀect properties such as proof strength but greatly reduces those properties sensitive to failure. Thus. now containing a planar biﬁlm crack. the biﬁlm provides the unbonded interface. In this ﬁgure. Because exploded nodules appear exclusively in the ﬂotation region of hypereutectic irons two far more likely factors are as follows: (a) Nodules growing in a suﬃciently hypereutectic melt will experience an enhanced driving force for growth because of the carbon supersaturation that develops as the melt cools. on contact. in common with widely held belief. spheroids would be created in suspension. These planes. adding to the Mg-rich slag. should completely eliminate poor nodularity. given a reasonable time between Mg treatment and the pouring of the castings for separation of Mg-rich biﬁlms (an interesting and clearly important process variable that seems not well researched). Furthermore. who observe that nodules are converted from misshapes to spherical by the use of a ﬁlter to take out the ‘‘inclusions produced by inoculation. or (2) poor casting practice. so that large quantities of Mg oxide and/or Mg silicates are expected to be created by the turbulent jumping and splashing of the liquid surface.[66. graphite would be expected to grow on oxide biﬁlms. DECEMBER 2009—797 . This will encourage growth instabilities leading to ‘‘dendritic’’ rather than ‘‘planar’’ growth. (b) Austenite will be less likely to form in hypereutectic irons. in which an otherwise nicely inoculated and spherodised melt is recontaminated with oxides.of nodular irons. EXPLODED NODULAR GRAPHITE ‘‘Exploded’’ spheroids (Figure 17) are commonly observed in irons subject to graphite ﬂotation and especially if the composition of the iron is suﬃciently hypereutectic. leading to exploded rather than smooth spheroid surfaces. or counter-gravity ﬁlling system. This would not be true if graphite had high tensile strength perpendicular to its basal plane but is probably only true if the ﬂakes are formed on biﬁlms. solidiﬁcation and remelting would be expected to be reversible. the signiﬁcant reduction of properties associate with malformed spheroids cannot be the direct result of the shape of the spheroids. lead to disastrous brittleness known as plate fracture (Figure 1) described elsewhere by the author. The symmetrical spherical constraint previously provided by the surrounding austenite is also destroyed. These are expected to be lying on random areas of biﬁlm not straightened by dendrite growth. many Mg addition techniques are extremely turbulent. This eﬀect can be observed in Figure 2. of course. added ‘‘post inoculants. These new biﬁlms will be permanent defects formed from highly stable magnesia or magnesium silicate. the spheroid will grow to become signiﬁcantly misshapen. A step in the right direction is presented in the work of Takita et al. which would have also entrained the surface oxide to create Mg-rich oxide biﬁlms that. would generate nonspheroids. The appearance of poorly shaped spheroids is therefore predicted to be associated with the growth of nodules on METALLURGICAL AND MATERIALS TRANSACTIONS B biﬁlms as a result of either (1) insuﬃcient dwell time for the damage introduced during Mg addition to ﬂoat out. However. the silica-rich biﬁlm content of the melt would be eﬀectively eliminated. During the Mg treatment. after the Mg addition. Thus. In terms of the biﬁlm hypothesis.’’ These were highly successful to increase the nodule count but led to a disastrous fall in nodularity. These extensive biﬁlms simply act as cracks in the casting. It is interesting to predict that perhaps more time after the spherodizing treatment to allow the melt to clear. particularly if the mold ﬁlling system is a rather poor design. because if the nodule had grown uniformly in a compact morphology. Cole suggested they had suﬀered remelting as a result of being carried by convection in and out of hot zones of the liquid. aiding the nonspherical development. however. this belief presupposes that the ﬂakes act as cracks. additional large quantities of Mg-rich oxide biﬁlms are likely to be reintroduced. because they occupy such a small volume fraction of the alloy. especially in conditions of carbon enhancement by segregation during cooling in the liquid VOLUME 40B. Meanwhile.’’ This positive step contrasts with that taken by Liu et al. X. Unfortunately. some of these will fortunately ﬂoat out. Hughes. together with a properly designed ﬁlling system. who. On contact with an oxide biﬁlm. The loss of properties is predicted to be the result of the presence of the biﬁlms in the melt. signiﬁcantly reducing properties. the subsequent growth of the existing suspended spheroids will be redirected along the plane of the ﬁlm.. However. It is the presence of the crack provided by the biﬁlm that has to be viewed as the principal cause of failure. in a liquid now cleaned from transient silica-rich biﬁlms. Hughes describes how a good ductile iron can achieve at least 90 pct nodularity but less good irons can fall to as low as 50 pct or less and suﬀer reduced properties. Additional misshapen nodules are evident elsewhere in the structure. attributes this loss of fracture resistance to the sharp notches at the root of ﬂakes. the nodules attached to the biﬁlms are clearly poorly shaped. several oxide biﬁlms have been straightened by the growth of dendrites so as to lie along 100 planes. Prior to pouring.
The nodules may have nucleated early in the liquid phase and grown without the beneﬁt of the mechanical constraint of the austenite. phase. which slowly take on the growth forms of chunky graphite. DECEMBER 2009 Fig. and interconnected fragments (Figures 17(c) and 18).Fig. otherwise.[59. When not pressurized to remain spherical. chunky graphite in the thermal center of a 200-mm cube. Thus. Furthermore. branched. All these workers observe the characteristic form of chunky graphite. compacted. promoting the development of ferrite. (d) SEM iron image of an exploded spheroid. irregular. (c) chunky graphite (after Liu et al. (e) electron image. Once again. Evidence for mechanical restraint as a powerful eﬀect is presented in the section on nodular graphite above. and chunky graphites. Liu et al. Its ‘‘chunkiness’’ is only apparent under the microscope at high magniﬁcation. they conclude that chunky graphite is a degenerate form of spheroidal graphite. but only METALLURGICAL AND MATERIALS TRANSACTIONS B . it simply appears to be ﬁne. developing instabilities that grow into projections to its growth front. Itofugi and Uchikawa conﬁrm the identical growth orientations of spheroidal. XI. the nodule will be free to grow more like a dendrite. they report observations on spheroids that exhibit gradual degeneration. The individual chunk sections are composed of layers parallel to the basal plane. 17—(a) Spheroid and (b) malformed spheroid. ﬁnally developing the characteristic exploded forms.65] ﬁnd evidence that chunky graphite grows along the C-axis direction. However. as does nodular graphite. 798—VOLUME 40B. and their work implies that chunky graphite grows out from spheroids.). ‘‘Chunky’’ is not a particularly helpful descriptive adjective for this variety of graphite. as an apparently ‘‘stop/start’’ growth in the C-direction consisting of nearly separate pyramidal ‘‘chunks’’ linked by a narrow neck. like beads on a branching string. CHUNKY GRAPHITE Chunky graphite is often observed concentrated in the centers of heavy sections of nodular iron castings. 18—Graphite nodules and areas of ﬁne. it seems the loss of properties is possibly more associated with the short diﬀusion distances between branches of the graphite ﬁlaments. the properties of nodular iron are reduced.
both originating from spheroids. spheroids cannot form. If the above mechanism is correct. branching growth. Biﬁlms would segregate to grain boundaries and possibly actually constitute the boundary. corroborate the absence of nuclei in these regions. Because the growth will constitute an extension of the spheroid. and (4) from the graphite ﬂakes sitting in the boundary (called by the authors. is not clear at this time. then exploded spheroids can be viewed to be a similar growth mode to chunky graphite. The key word here is ‘‘careful. therefore. why continued growth should not occur in all directions as in the exploded variety. followed by the development of a rod type of eutectic at right angles. and so on. The presence of the central unbonded region (including the pores) between the ﬁlms. accelerating the next phase of growth of the graphite until the local carbon concentration is depleted once again. such as the temperature and solidiﬁcation rates. forming the nearly pinched-oﬀ neck of the graphite. DECEMBER 2009—799 . constituting the crack through the interiors of the carbides. it will continue to grow. It is tempting to consider that the original planar expansion would have been facilitated by growth across the surface of a biﬁlm. the runners were not designed to be pressurized and ﬁll on a single pass. are all similar. perhaps happening to ﬂoat into this region. the ‘‘ﬁlms’’ would have been ‘‘biﬁlms’’ (it seems impossible to devise a mechanism by which a single thickness of ﬁlm can be introduced into a matrix). Both graphite and carbides are expected to form on the wetted. The biﬁlm would originally have been randomly crumpled but would have been straightened by the progress of the carbide across its face.nanometers thick. They conclude that a collaboration among Mg. In the absence of nuclei. have studied carbides in heavysection austenitic ductile iron (ADI). much greater sophistication of melting and casting will be required for experiments designed to clarify the solidiﬁcation mechanisms for cast irons. the spheroidal mechanism of growth along the C-axis is likely to be continued. they ﬁnd degradation of properties more serious than they would have expected from the carbides themselves. It is hoped that in the near future. ‘‘degenerate’’ graphite). However. Faubert et al.’’ For instance. and all the cast METALLURGICAL AND MATERIALS TRANSACTIONS B material would have suﬀered from turbulence and air entrainment. unﬂatteringly. This is a clue to their biﬁlm associations. extending along the C-axis direction. These intermetallic compounds would otherwise be expected to be strong and resistant to failure by cracking at the modest stresses that can be induced by solidiﬁcation and cooling. which are much larger than cells of other types of graphite. XII. the experiment by Asenjo et al. outer surfaces of the biﬁlms. the whole region will ﬁll with a variety of continuous. S. with the austenite advancing to grow nearly over the top of the graphite. if a graphite nodule can be initiated somewhere in or near this region. In the absence of signiﬁcant numbers of nuclei. These features are almost certainly sheets of oxides decorated with graphite nodules that have been nucleated on the oxide (analogously to those observed in Figure 2). However. Thus. They suspected that the real impairment was caused by the presence of ﬁlms that had ﬂoated into this region. but only in a few select directions (possibly one direction) in chunky graphite. because the austenite forming during solidiﬁcation also possesses a closely similar facecentered-cubic structure. and other conditions. Thus. IRON CARBIDE (CEMENTITE) Work by Rashid and Campbell has demonstrated the nucleation and growth of carbides on oxide biﬁlms in vacuum-cast Ni-base super-alloys. so that its growth mechanism seems likely to be asymmetrical. The presence of the biﬁlm is not only inferred from (1) the cracked carbides but also (2) from the linear rows of nodules viewed in micrographs from this work. therefore containing unknown quantities of oxide biﬁlms. The extended size of chunky graphite regions. in which the growth of iron carbide eutectic (ledeburite) occurs by the spreading of carbide (cementite) across a plane. explains the apparent brittleness of the carbides. Carbides in irons seem to form preferentially at grain boundaries and often seem to be associated both with residual graphite (sometimes as nodules. This is because so much time is available for particles in suspension to ﬂoat out from the centers of heavy sections where chunky graphite is commonly found. it will not enjoy the beneﬁt of the presence of an austenite shell in a region of higher temperature and enhanced segregation. a reverse ﬂow is likely to have contaminated the mold cavities. it seems possible that at the same time there is likely to be an absence of nuclei. Stefanescu quotes the work of Hillert and Steinhauser. (3) from the pores as the residues of air bubbles trapped between the ﬁlms. that an analogous reaction would occur in Fe-C alloys. in common with most iron casting. only to be overtaken again because the carbon in solution will now build up in the liquid ahead of the front. This characteristically lumpy growth may be the result of a pulsating or irregular advance of the growth front. Clearly. Almost certainly. and O is important for chunky graphite formation. or ﬂakes aligned with the boundary) and pores all forming on the same boundaries. seem consistent with an origin associated with biﬁlms. Observations by Kallbom et al. This was because. thus creating an essentially planar crack that would constitute a serious defect in the VOLUME 40B. in the future. malformed nodules. Toward the top of their castings. They observe the chunky graphite to be concentrated in the center of heavy sections. which is explained by the growth of the freezing front pushing biﬁlms ahead by their observations of ‘‘stringers’’ of graphite nodules. the correct explanation for the origin of chunky graphite might be elucidated by subsequent careful experiments. that involves the placement of inoculants in diﬀerent branches of a runner system to diﬀerent sized cavities in a mold to compare the eﬀects of mold inoculation in diﬀerent heavy castings was a clever concept but regrettably ﬂawed in execution. It would be expected. Although the above authors provide evidence that suggests the presence of biﬁlms.
ACKNOWLEDGMENTS The author is grateful to those who have assisted with the micrographs. chunky. Barton: Foundry Trade J. subsequently growing along the biﬁlm and losing sphericity (Figure 2). 114. vol.R. 3. 6. Cast iron melts normally contain double ﬁlms (biﬁlms) in suspension. 25. expanding to form cells of coupled growth with austenite. the absence of biﬁlms explains the high mechanical properties. 5. fairly continuous forms of coral.. or disprove these proposals. 10. F. undercooled coral and chunky graphites. Carbides form at low temperatures on oxide biﬁlms. GENERAL Overall. de Sy: AFS Trans. 11 (5). both nucleation and growth mechanisms inﬂuence graphite morphology. 4. J. Compacted graphite forms on oxysulﬁde nuclei that occupy biﬁlm residues. The formation mechanism is not clear at this time. pp. trapped inside or alongside graphite ﬂakes accounts for the poor tensile properties of ﬂake irons. In addition. Misshaped spheroids seem to be spheroids that have encountered a Mg-rich biﬁlm. vol. Hoﬀman and G. It is hoped that improved control and improved castings will result from these eﬀorts. 158–60. Hartmann and W.. UK. 2006. D. straightening the biﬁlms. A. pp. pp. Spheroids form in the absence of silica-rich biﬁlms. 2. pp. METALLURGICAL AND MATERIALS TRANSACTIONS B . 10. Associated branching cracks would have arisen from irregular folds in the biﬁlm. XIV. Chunky graphite occurs in heavy-section ductile iron regions. advancing together with the austenite. Beghyn: AFS Trans. vol. with castings at times even failing disastrously by the brittle ‘‘plate fracture’’ mechanism. 2006. 2006. pp. consisting of highly faulted continuous branching ﬁlaments of graphite in the austenite matrix. pp. 999–1008. Graphite nucleates on the oxysulﬁde particles and grows.. as cracks. Mampaey and K. 2009. as proposed here.. vol. 345–49.. but when oxide biﬁlms (mainly magnesia-rich) are entrained by poor casting technology. 131–51. 6. last but not least. The presence of biﬁlms in the carbides explains the brittle behavior of these strong intermetallics and their common association with both pores and residual graphite fragments. 2. 2001. Oxford. Naturally. and its ‘‘beads on a branching string’’ morphology may result from an unstably advancing growth front. Furthermore. growth morphology may be natural but is additionally encouraged by the mechanical constraint of the austenite matrix. 114. vol. biﬁlms play no part in this growth mode. it may be a coupled eutectic form. They do seem similar in the sense that they all appear to be more-or-less coupled growth forms. vol. Elsevier. vol. 22 (2). 75. without the beneﬁt of the mechanical constraint of an austenite shell. this short account presents only an outline of a new approach to the structures of cast irons. The spherical 800—VOLUME 40B. Ductile iron is ductile because of the absence of oxide biﬁlms. pp. spreading over the biﬁlms. Loper: AFS Trans. 178–81. not because of its spherical graphite morphology. Inoculation produces oxysulﬁde particles that nucleate on silica-rich oxide biﬁlms. 5. R. 7. Wolf: Giessereiforschung. C. Shin: Int. Technol. Much more research is needed to prove. 3. DECEMBER 2009 REFERENCES 1. Campbell: Mater. 1999. 2003. and forming ﬂakes of crystallographically near-perfect graphite. CONCLUSIONS A hypothesis is proposed as follows: 1. nucleation dominates the formation of spheroids and deformed spheroids. 1999. This seems typical of biﬁlm phenomena. Sci. 8. The presence of the biﬁlms. 1985. the various forms of graphite are signiﬁcantly inﬂuenced by the presence or absence of biﬁlms. vol. 9. Coral morphology nucleates on unknown nuclei at low temperatures. nucleation occurs once to initiate each cell. 9. For instance. 7. 127–45. both nucleation and growth are inﬂuential. 4. the presence of the biﬁlm destroys the symmetrical mechanical constraint of the austenite that favors sphericity. 53 (4). Nakae and H. Sci. leaving regions nearly devoid of nuclei and creating graphite akin to coral morphology. pp. 117–26. pp. the ﬁner. Campbell: Castings. 1967. assiduous. H. XIII. E. Exploded spheroids may be the result of growth in the liquid. and doubtful reviewer of this article from whom I learned much. (8). and. Campbell: Mater. Res. For compacted. 8. 161–62.. it seems likely that the principle cause of reduced mechanical properties in all cases of nonspheroidal forms of cast irons is the presence of various kinds of oxide biﬁlms that act as cracks. whereas for ﬂake graphite.. and compacted graphites are so similar that they often seem to be confused in the casting literature..carbide. 523–28. after which continuous growth leads to developing continuous branching morphologies. 1055– 58. ductile iron can be seriously reduced in ductility. 125–26. As such. Technol. The central regions comprise either (1) regions containing Mg-rich biﬁlms as a result of poor casting techniques or (2) regions from which nuclei have ﬂoated out. enhance. J. J. 161–72. If. pp. although these mechanisms dominate to diﬀerent extents in diﬀerent circumstances. Cast Met. J. then it would explain the historical resistance of the phenomenon to explanation so far. Indeed. 637– 56. to the painstaking. to Carl Loper and Riposan and colleagues for inspiring research. Stets: AFS Trans. 107. nucleating on oxysulﬁde particles.
98. 2008. 1996.. A. S. 144. Liu. vol. Bennett. Schmidt. and M.C. 1991. 313–30. pp. M. and D. Hurum: AFS Trans. pp. 31. ASM.. UK. Stan. Hummer. Kondic: Proc. D. I..C..X. 28. 47. S. Y. I. Oxford. and R. Chadwick: Int. 125–30. 1999. 1999. Sci. Karsay: Ductile Iron II. 2008. Harrogate. H. 425–32. vol. and C. G. 138–42. 29. vol. Gorny. White: Mater. 157–62. P. 26. 298–303. pp. 98. Toboc. and D. 8. 105. 104. Stefanescu: Metall. and H.J. 52. Altstetter and R. Barstow: AFS Trans. J. 73. 56. 647–66. 1980. Stefanescu: Metals Handbook. 38A (7). 60. 59.D. L. and H. Larranaga. Chaput: AFS Trans.K.. Fras. Y. World Foundry Congr. 357–62. 45. Oxford.S. A. 1977. Lu. S. 2000. J. J. Mater. H. Mampaey and Z. 2007.. Rao: Proc. 317–29.. and L. Fras. Nowicki: AFS Trans. Sci. 25. H. L. 61. Warwick University Conf. 91. 3. 1964. 15. pp. I. ´ ´ 70..F. paper 08-065(05). Riposan. vol. P.. and D. 108. 50. M. and S. 90. A. M.D. 39B. 11–17. Trans. vol. Mampaey: AFS Trans. F. vol. Ecob. pp.. P. 722–33. A. Loper. Gorshov: Russ. 213–25. 22. J. and K..P. pp. Druschitz and W. Mater. Goodrich: Metals Handbook.J. Sheﬃeld Conf. 447–58. pp. 14. 1990. Harding. Warwick University Conf. Trans. Basdogan.M.M. 12. Metalcast. 11 (5). Gomez. vol. pp. Trans. F. Hartung. 583– 600. 1983. Loper: AFS Trans. M. Chow. Riposan. Raiszadeh and W. pp. 1980. J. M. pp..-M. and H. S. 18. A. Campbell: Trans. 667–77.R. pp. 1985. B. K. Stowell: Met. 71. McHugh. R. Asenjo. 88. 783–86. R. E. Li. 1971. 119–26. Enright. 34. and N. pp.J. 98. Ferrer. METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 40B. H. vol. vol. 1980. Trans. Su. J. I.. NY. W. 101–27.A. and J. and Y. 16. 77–88. J. 105. B. and V. 1972. Nomura: Int. OH. Stan. Kallbom. Uchikawa: AFS Trans. 1968. Mater.. 1990. 581–88. 1967. Mater.X. Heine: AFS Trans. E. Prod.F. Liu. and T. pp. 2007. 2001. Wallace: AFS Trans. 1975.R.K. pp. Stefanescu: AFS Trans. Chisamera. Hillert and H. 1997. pp. M.J.C. D.. 36..S. OH. 1990. R. Beltran-Sanchez.M. Lopez: AFS Trans. Merchant. Voigt and S. 1 (11). 69. M. pp. pp. 53–64. vol. vol. Sun and C. pp. 18–21. Loper: AFS Trans. Res. OH. pp.R. Roviglione and J.J.R.. pp. 5. White: Mater. I. Hughes: Metals Handbook. Chisamera. vol. Chang. pp. 63. 1990. vol. 7–20. 58. 65. 2008. Res. TMS-AIME. pp. Law.. 959–70. vol. 17. 66.W. Liu and C. pp. p. ASM. 2007. 33. M. vol. 101.H. D. C. B.. 24. 98. Hurum: AFS Trans. 83. 1990. 34. Lopez: Metall. 68. pp. pp. Steinhauser: Jernkontorets Ann. Yamamoto. 319–24. 42. Mizoguchi. 239.-E.. vol. D. pp. Liu. 1996. Loper: AFS Trans. Fredriksson: Mater. Rundman: AFS Trans.. C.. Gordon and Breach. Zhu. R... D. Wilkinson: Casting Plant Technol. 72. vol. pp. 105.H. in press. Technol. vol. J. vol.Z. Ecob. Sertucha. 338–40. 335–48. Cook: Proc. Oxford. 37–48. Warrick: AFS Trans. 1977.11.H. R. Hellawell. G. S. Hermida: Metall. Rashid and J. 115.R.R. vol. G. vol. Moore. 520–22. D. 13. 2001. and C.H. Liu.. 57. M. 65.J.. Wu. vol. and M.. 15. R. vol. 55.. T. 2007. Sheﬃeld. 483–88.. vol. Cast Met. 108. 1997. 579–84. Li: Proc. 1974. 20. 232–39. 35B. and E. W. Hartung. 1965. and I. vol. Cast Met. A. S.D. 785–811. 95–103. pp. M. pp..R. Welch.H. R.. 15. vol. Hillert and S. ASM. 32. 30. 1990. Perepezko. 53. vol. Li. vol. pp. Sci. pp. Campbell. Buhrig-Polackzek and A.T. pp. T. Oxford.P. 2008. Lacaze: Int. vol. Sha.D. 23. ASM. C. Takita. Mampaey: AFS Trans. 1984. Melford. I. 49. P. 1966.M. Cast. 489–93.. Pilling: AFS Trans. vol. D. J. Brighton Conf. 100. Loper: AFS Trans. 217–26. E. 834–48. pp. vol.M. 2006. Res. 1 (1).W. vol.. Holmgren: AFS Trans. 1960. vol. A. Fredriksson: Proc. Z.M.H. 707–12. G. L. 48. Engineering Design Properties Applications. 2004. 19. 1982. Y.A. 40. 20 (6).. pp. pp. 240–47. vol. 24 (5). paper 184/1-10. pp. J. 62. 43. 565–74. C. Feest. 79–87. New York. J. Mater. P. 99. 899–906.F. DECEMBER 2009—801 . 97–118. vol. vol. J.C. 1988. 115–24. Loper and R. pp. 2008. Yang. pp. Carlberg and H. vol. pp. Massone. 38A. Stefanescu. 44. C. 1–17. 2. Fang: AFS Trans. 1993. 2063–71.. 429–48. 15.J.F.. Witter: AFS Trans. vol. Ruxanda. 168–81. 109. G.. 37. Xiang: AFS Trans. T.. and H.. vol. B. 64. vol. 90. 21. T. Y. Sci. Kawano. de Santos: Metals Handbook.O Morton.A. 385–95. Eng. Smart: Proc. Park: AFS Trans. N. Loper and K. vol. pp. 385–94.. 1982. M. Skaland: AFS Trans. pp. Cole: AFS Trans. vol..A. 2008. pp. 27. pp. vol. vol.. A.. 490–500. Canada. Trans. Loper: AFS Trans. Oxford.N.R. De Rong and Y.. ed. Mater. 2007. 69. Technol. Bjorkegren: Proc. C. 204–12. 54.A. pp.D. 165–82. Nechtelberger: Metals Handbook. p. Jiyang. F.C.Y. 46. pp.R.. Saunders: Solidiﬁcation Processing 97. Suarez. R. Hillert: in Recent Research on Cast Iron. 1988. Chisamera. 98. Itofugi: AFS Trans.. and J. P. vol. 39. Mech. and J. 1952. 2004. 2000. Gorny. Jacobs. Technol.B.. 35. and D. 74. Hamberg. 841–54. Itofugi and H. vol.C. 15. 73. vol. Campbell: Metall. 1967. C. 1997.L.. vol. Faubert. 41.A. Solidiﬁcation and Casting of Metals Conf. F. and C. vol. C. 1992. G. J.M. pp. OH. vol. pp. Ozaki: AFS Trans. T. Campbell: Int. Soc. 831–45. Engler: AFS Trans.I. pp. pp. pp. 1433–47. 1983. 1988.B. OH. 107. 104. pp.. 35A (7). E. 1963. UK. 38. 98. R. A. 67. 60. pp. 51. pp. pp. Johnson and H. Murakami. C. pp. Riposan. vol. pp. Griﬃths: Metall. 89–94. 1961. pp. pp. F.L. Kimura. Quebec Iron & Titanium Corporation. 80.B. 137–44. 91. 15. Loper.. S. Xu: AFS Trans.
This action might not be possible to undo. Are you sure you want to continue?