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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: firstname.lastname@example.org. 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
as well as the long periods during which irons are held molten in holding furnaces. thus forming a magnesium silicate MgOÆSiO2. although Si might also contribute. the natural enfolding of the surface ﬁlm of SiO2 of each droplet would ensure a natural population of SiO2-rich biﬁlms. MgO. they are rapidly reduced to Si metal. 2—Optical micrograph through the fracture surface of ‘‘platefractured’’ ductile iron shows misshapen graphite nodules growing on biﬁlms straightened by dendrite growth. 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. It seems reasonable to speculate that these oxides almost certainly would not be compact spheres. Even so. rods. Both magnesium oxide and magnesium silicate are extremely stable and represent permanent damage folded into the liquid metal and subsequently transferred to the casting. the presence of Mg stabilizes the magnesia. 2(Mg. is common. the subsequent straightening of these biﬁlms by various natural processes. Hartman and Stets report not only the presence of SiO2 in suspension but also olivine. especially during an extended time in holding furnaces or pouring systems. FeO. In this case. and their oxygen is removed as MgO when Mg is added to the melt. Thus. forms in a typical melt when cooling from 1480 °C to 1350 °C. Hoﬀman and Wolf ﬁnd a variety of oxides. the amount of silica-rich phase being predictable by thermodynamics. Fig. which creates extensive planar cracks. and the oxide introduced from the surface of the charge (whether steel. but superheating and holding at high temperature eliminated many of these. stirring in induction furnaces.Fe)OÆSiO2 is found in those irons that contain Mg. would increase this already large.expectation that the SiO2 solids dissolved because they became less stable than CO but reappeared on cooling once again. Mampaey and Beghyn show how mainly SiO2. and this eﬀect has been widely accepted as the loss of nuclei (in agreement with proposals made in this article). Also. Silica-rich oxides in irons are not stable in some conditions. such as pouring actions. they will be expected to go into solution if the melt is held above approximately 1450 °C for any length of time. and MnO among others. such as the growth of dendrites. include the following: (1) the hypothesized silica-rich biﬁlms as a natural population in equilibrium with the melt. together with some FeO. etc. 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. pig. 1—A so-called ductile iron casting illustrating brittle fracture as a result of dendrite-straightened biﬁlms. of course. the ﬁlm morphology is to be expected. or foundry returns). at least two diﬀerent populations of oxide biﬁlms seem to exist in suspension in liquid iron. A diﬀerent population of oxide biﬁlms deﬁnitely exists in ductile irons that have been cast turbulently. Additional treatments or handling. it is well known that iron from electric furnaces is more liable to chill formation problems in thin sections than cupola iron. During melting in the cupola as droplets of iron rained down. 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. which METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. In an elegant study of the thermodynamics. natural population. DECEMBER 2009—787 . cubes. but would most likely be in the form of ﬁlms. in the surface ﬁlm. In any case. 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. which is equivalent to MgSiO3. as discussed earlier by the author. For instance. including SiO2.
nucleate graphite. A more unfavorable nucleus would be diﬃcult to imagine. but it has been studied by several others since (for instance Fredriksson). Riposan[16. Also. nitride biﬁlms probably form in cast irons giving rise to the ‘‘nitrogen ﬁssure’’ defects associated in the past with high nitrogen binders. thus providing a region in which a high driving force exists for the nucleation of graphite. particularly Ca. Warrick) composed of particles of complex oxides and sulﬁdes. In this article. as will become clear during the progress of this account. GRAPHITE NUCLEI IV. The inoculation process is often carried out by addition to the melt of granules of a graphite promoter such as a ferrosilicon. The relatively few opportunities for the carbon to precipitate lead to relatively large regions of the iron elsewhere being supersaturated with carbon. There is a growing consensus that both ﬂake and spheroidal graphite nucleate on similar. III.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. DECEMBER 2009 Uninoculated iron is characterized by poor control of the graphite morphology. for instance Chisamera et al. acts similarly to promote regions of METALLURGICAL AND MATERIALS TRANSACTIONS B . In fact. Thus. in which they found that a single population of nuclei could explain both gray and ductile irons. the melting point of such an inoculant is close to 1210 °C. the particles take time to melt and time to disperse. it is worth drawing attention to the possibility that other nonoxide biﬁlms are to be expected in cast irons. The question therefore arises. of the microprobe analyzer in 1974. if not identical. Many authors have reported the beneﬁcial eﬀects of S. only oxide biﬁlms seem to have signiﬁcant roles. which contains perhaps 50 to 75 wt pct Si. it seems that some nuclei exist prior to inoculation. In general. However. nuclei (for instance. Only those shells with low Mn/S ratio seem to act as nuclei. As an example of an excellent recent study. and their ﬁnal composition consists of mixed oxides and sulﬁdes. carbide precipitation is likely in places. 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. with a reduced tendency to carbide formation and a consequent beneﬁt to the mechanical properties and machinability of the iron. Hurum[20. the resulting carbon ﬁlm can be folded in. Flakes occur but are relatively few in number and uncontrolled in size.). usually in the range 1350 °C to 1400 °C. and Ba). Inoculation with graphite or SiC. Many conﬁrmations of this ﬁnding have since been made (for instance Skaland). 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). show how this region is eﬀectively undercooled by several hundred degrees Celsius as a result of its constitution of nearly undiluted graphite promoter. The gradual introduction of the inoculation process occurred from about 1920 onward.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. and so on. Riposan[16. In passing. The mechanical properties of the iron are generally poor. the added particles melt. (b) Complex sulﬁdes (<5 lm diameter) nucleate on the oxides (mainly based on MnS with low Mn/S ratio but complicated by additions.surface ﬁlm into the bulk liquid.21] was the ﬁrst to draw attention to this phenomenon. they ﬁnd that undercoolings below the liquidus of between 200 °C and 400 °C are required to trigger nucleation by austenite. FLAKE GRAPHITE IRON (FGI) AND INOCULATION Mizoguchi et al. of course. and its development continues to the present day (for instance Skaland and Hartung et al. but their number and eﬀectiveness cannot be relied on. Thus. 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. giving a copious crop of graphite ﬂakes of good uniformity of size. but the subsequent growth of the graphite is aﬀected by the presence or absence of oxide biﬁlms of diﬀerent types.17] ﬁnds that MnS shells with Mn/S high ratios are numerous in the matrix but do not seem to 788—VOLUME 40B. so that if surface turbulence occurs. have demonstrated that austenite is ineﬀective in nucleating graphite. and therefore possibly constitute a favored substrate. The mechanisms proposed by Riposan[16. forming temporary supersaturated regions of liquid rich in silicon surrounding the melting and dissolving inoculant particles. which is below liquid iron casting temperatures. Harding et al.17]) eﬀective for all types of graphite. What does nucleate graphite? This question is all the more intriguing following the work by Mampaey and Xu. Such lustrous carbon defects are not necessarily permanent because the carbon can slowly dissolve. This approach is the ﬁrst to suggest separate functions of the graphite nucleating particles and graphite growth substrates. which explains why such features are observed in only relatively thin section castings but not in thicker sections. For instance. leading to the oxides consisting mainly of alumina or zirconia). (c) Graphite nucleates on parts of the sulﬁde shell. Interestingly. usually containing Al and/or Zr. which results in nonreversible damage.K. In this review of the microstructures of cast irons. This was the conclusion reached in the ﬁrst study after the development in the U. The inoculation process was found to increase greatly the number of nuclei available. Sr. carbon biﬁlms exist in irons in those cases in which hydrocarbon gases from the mold disassociate on the hot surface of the melt. The complex sulﬁdes form a shell around the central oxide.
(b) additional nuclei provided by inoculant. point out that once nucleated in the regions of high driving force for initiation. eﬀectiveness. which encourages graphite nucleation and growth on any suitable available substrates that happen to be in this region. Mampaey conﬁrms that graphite forms in the melt prior to the appearance of austenite. thus naturally providing the driving force for nucleation of graphite in precisely the location needed for maximum eﬀectiveness. high above the expected liquidus temperatures. 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. (These observations are contrary to expectations based on the equilibrium diagram based. it is suﬃciently favored to support the subsequent growth of the graphite. Thus. Feest et al. 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). extending in the directions in its basal plane. This is almost certainly the phenomenon known to all foundry personnel as ‘‘fade’’ of the inoculation eﬀect. leaving no pockets of undercooling. The growth morphology of graphite.e. initiating a graphite ﬂake. 4—(a) A biﬁlm with precipitated nucleus from natural contaminants or preconditioners. the graphite formed rapidly in these regions is slow to redissolve. straightening the biﬁlm. including Mg. The ﬂakes grow in regions ahead of the solidiﬁcation front (i. Because of the additional trace alloying elements in the inoculant (particularly group IIA elements of the periodic table. in gray irons. However. graphite embryos on their nucleating particles will take time to go into solution. well into the liquid range. neither of which applies during the mechanism of inoculation of cast irons. On entering this region. the graphite extends across the biﬁlm.high-constitutional undercooling. in other circumstances. The overwhelming driving force explains the wide variation of successful nuclei. Figure 3 schematically shows a graphite nucleus formed on an oxide biﬁlm approaching an undercooled region provided by a dissolving inoculant particle. if any. of course. so although insuﬃciently favored to cause nucleation. and all the embryonic particles of graphite nucleated in the undercooled regions will have re-dissolved. possibly measure in nanometers. above the general eutectic freezing temperatures) because of the energetically favored growth of graphite on the oxide substrates in suspension (Figure 5). 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). The silica-rich biﬁlm will form a ‘‘next best’’ substrate for graphite. DECEMBER 2009—789 . all the inoculant particles will have melted and dispersed. ﬁnd that although the Si-rich inoculant particles disperse relatively rapidly. would favor the straightening of the biﬁlm (Figure 3(d)). which forces graphite to form around the nucleus. not only on equilibrium behavior but also on the behavior of alloys of perfectly uniform composition. Ca. (d) growth of graphite ﬂakes along the length of the biﬁlm. The observations by Loper and Heine conﬁrm that graphite can nucleate in both hypoeutectic and hypereutectic irons at 1400 °C.17] indicates that only parts of the nucleant particles are active nucleation sites. nucleate from those nuclei already sitting on the oxide biﬁlms. so that initial growth is rather irregular). (c) graphite nucleation on nuclei in regions of high eﬀective carbon supersaturation as in Figure 3(b). 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. Harding et al. METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. so that the matrix would be eﬀectively nearly saturated in carbon. so that if the melt is cast without undue delay. Bearing in mind that many (if not all) second phases precipitate on biﬁlms as preferred substrates. and (b) the biﬁlm ﬂoating into a region of high constitutional undercooling surrounding a dissolving inoculant particle. Thus. and Ba). All this is taking place in the region highly constitutionally undercooled with respect to graphite. Fig. VOLUME 40B. but it will subsequently dissolve in the open melt rather slowly because the graphite will ﬁnd itself only modestly above its equilibrium eutectic temperature. it seems reasonable to assume that these new graphite nuclei would also preferentially nucleate on biﬁlm substrates. the nucleus experiences a massive driving force as a result of hundreds of degrees of eﬀective undercooling.) Given suﬃcient time. The biﬁlm would be expected to be extremely thin. graphite would. as observed experimentally by Loper and Heine. in turn. with a consequent central planar crack in the graphite ﬂake. would be expected to be of only mediocre.. This is reasonable because the graphite initially grows quickly in the highly constitutionally undercooled region. Sr. 3—The mechanism of inoculation: (a) a biﬁlm in suspension in the melt together with nuclei already attached from trace contaminants or preconditioners. which. leading to the fairly ﬂat morphology of ﬂakes in gray iron. 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.
nor even a ﬁlm. particularly if the iron has been held in an acid-lined induction furnace. messy structures. this is straightforwardly understood from the irregular structure of the biﬁlms. which exhibit elegant hexagonal symmetry and are apparently largely free from defects. As such. to the result of the growth of the ﬂakes in the liquid. 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. Less obvious but important bimodal distributions are almost certainly common. For instance.[16. ﬂake graphite irons. the graphite ﬂakes are seen to branch relatively frequently. Thus eventually. they tend not to entrain as nicely parallel double ﬁlms. these freely ﬂoating ﬂakes will become incorporated into the solid (Figure 5). 6—Two populations of ﬂakes: extrinsically formed on biﬁlms and intrinsically grown as a coupled (undercooled) eutectic.28] Eventually. Thus. Similarly. such mixtures may not always be obvious to casual observation. They originate in suspension in the melt and therefore can ﬂoat to the upper regions of a casting. For many other irons.17] shows that this is at least partly the result of the gradual loss of the graphite nuclei. On the ﬁrst occasion that these authors used the highly sensitive fractal analysis technique to assess microstructures of cast irons. Thus. Fig. the ﬁnal pouring of the melt into the mold may provide suﬃcient turbulence to address this problem. the form of the silica may not be a biﬁlm. suggesting a similar origin and behavior in the melt. it is not likely to be a good substrate for the development of a good ﬂake structure. During their entrainment from the liquid surface into the bulk melt. unencumbered by the presence of austenite. operators commonly ﬁnd the iron has poor graphite structure. It would be interesting to know whether the melt. The more common Type A graphite ﬂakes are similar. The mechanism proposed above explains the growth of ﬂake graphite from nucleating particles introduced by inoculation. 5—Extrinsic initiation of straight graphite ﬂakes in the liquid. He calls these proeutectic ﬂakes.Fig. In terms of the biﬁlm substrate. In agreement with the mechanism described in this article. which makes the METALLURGICAL AND MATERIALS TRANSACTIONS B . Experience of variable performance is also to be expected. but it may be a compact particle. Goodrich attributes the Type C iron (ASTM A247). of course. straight ﬂakes. they observed this result. and these particles seem likely to be a universal phenomenon in both ﬂake and nodular irons. Riposan[16. 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. if not all. 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). DECEMBER 2009 work of Enright et al. with some branching. Part of the eﬀect would also be expected to be loss of biﬁlm substrates. the advancing solidiﬁcation front will overtake those ﬂakes growing on biﬁlms ﬂoating freely in suspension in the liquid. on the Monday morning after the melt has been held for the weekend. as may be inferred from the 790—VOLUME 40B. the presence of a dense mesh of austenite dendrites constrains the size and shapes of ﬂakes and prevents any signiﬁcant buoyancy eﬀects. ahead of coupled growth of eutectic graphite and austenite. iron heated to high temperature suﬀers a similar degradation of graphite structure.17. A bimodal distribution of graphite ﬂakes is therefore to be expected in most gray iron microstructures. because although de Sy reports that the silica reappears in the melt on cooling. without some kind of surface turbulence. Primary ﬂakes seems to be a good name for these forms. Even so. the populations of primary and eutectic ﬂakes should be expected to be mixed in most. and it is clearly observed in Figure 6. even though. but instead they entrain as randomly folded. Thus. unless this is an extraordinary coincidence. which is characterized by large. displaying only minimal irregularity. after losing its silica-rich biﬁlms at high temperature. More usually in castings. Loper and Fang use deep etching to reveal what they call pre-eutectic ﬂakes. would regain its good solidiﬁed structure when cooled once again. Particles that seem to be nuclei for the initiation of ﬂakes have often been observed. The coupled growth mode is discussed below.
 conﬁrms that conventional gray irons that contain Al develop coarse graphite ﬂakes. In their studies of crack initiation and propagation in irons. sulfur) are present on fracture surfaces of gray irons that were adjacent to a graphite ﬂake (fractured and observed in high vacuum). COUPLED EUTECTIC GROWTH OF GRAPHITE AND AUSTENITE In this section. randomly oriented ﬂakes which tend to ﬂoat or settle irregularly. activating in those parts of the melt that are especially cool. 7—Graphite ﬂake exhibiting a central crack (the solid state precipitation of surrounding temper graphite is also fractured oﬀ). In contrast. we move the focus from ‘‘anomalous’’ to the truly regular. therefore. it seems likely that the biﬁlm will have nucleated the decoherence. decohered from the matrix) rather than any intrinsic weakness of the graphite itself. because although the interplane bonding is not strong. In the absence of suitable nuclei that have formed on oxide substrates in suspension in the melt. Carlberg and Fredriksson ﬁnd that cast irons based on Fe-C-Si exhibit ﬁne graphite structures. evidence indicates that alumina-based. would develop diﬀerent qualities of precipitated graphite. but the continuing decohering action seems to follow the graphite interface. For instance. preventing easy failure by peeling or shear. the hollows in the fracture surfaces of spheroidal graphite matrix that had contained spheroids exhibit no oxygen. Moreover. Basdogan et al. Only relatively few such nuclei will operate. In fact. This behavior is exactly predicted by a biﬁlm hypothesis: If ﬂake graphite formed on one side of the oxide biﬁlms. 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. the melt will continue to undercool until the undercooling ﬁnally becomes suﬃcient to provoke precipitation on some other (less favorable) substrate. below which SiO2 is stable. Liu and Loper found that oxygen was necessary to nucleate kish graphite on the surface of gray iron melts. found oxygen to be highly eﬀective in converting carbidic irons into beautifully ‘‘inoculated’’ ﬂake graphite irons. Chisamera et al. It would be reasonable to expect that silica-rich and alumina-rich biﬁlms would have diﬀerent mechanical and chemical characteristics and. in which austenite and graphite grow in a coupled mode. gray iron has a curious behavior in that nothing seems to attach to the graphite. Voigt and Holmgren report many centerline cracks in graphite ﬂakes plus some decoherence from the matrix. based on mullite or other stable alumino-silicate compound) exist. which leads to the familiar easy shear in its free condition. V. It seems possible that graphite is strong in tension perpendicular to its basal plane. Although all the above discussion relates to silicabased biﬁlms. The huge number of bonds will ensure high strength in tension in a situation in which the graphite is encapsulated. 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. then the fracture surface would necessarily reveal the oxide. so that both halves of the biﬁlm seem to have attached to the matrix. or possibly Al-containing Si-based biﬁlms (for instance. 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. there are approximately 1015 bonds per mole in the graphite surface. It is right to question. A crack down the center of a ﬂake is observed in Figure 7. therefore. 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 agreement with the prediction that graphite grows on oxide biﬁlms. For most intermetallics precipitating on one side of a biﬁlm. the carbon in solution will be unable to precipitate. such as those regions close to VOLUME 40B.problem essentially invisible to those attempting to study the eﬀect. the halves of the biﬁlm appear on both fracture surfaces. Larger quantities of kish were formed at temperatures below 1400 °C. The above discussion relates to those graphite ﬂakes growing freely in the melt giving rise to large. creating what has been called in the past an ‘‘anomalous’’ eutectic. However. whereas those based mainly on Fe-C-Al display coarse graphite ﬂakes. Thus. but oxides would be absent in the case of spheroidal graphite iron (as discussed below). and kish was not observed in Si-free melts. ‘‘classic’’ eutectic form. the eﬀect of oxygen addition to the melt during the pouring of iron into the mold is demonstrated by several authors. DECEMBER 2009—791 .
17] on ﬂake graphite irons shows that the particulate nuclei do not seem. Those biﬁlms present between ﬂakes. 8—A scanning electronic microscope (SEM) image of a deeply etched rosette of ﬂake graphite. SPHEROIDAL GRAPHITE IRON (SGI) (DUCTILE IRON) When suﬃcient magnesium is added to the melt. The careful study by Riposan[16. However. DECEMBER 2009 . more highly undercooled eutectic. These compact nuclei are now the only nucleation sites available for the precipitation of graphite. this means that the crystal has to develop faults to allow it to change direction. it may be some kind of aggregate of biﬁlms that. containing high defect densities. not requiring the presence of biﬁlms. and so these biﬁlms become invisible. VI. seems in general to have been avoided for general engineering castings. At lower undercoolings. if such a behavior also exists for ductile iron. In this way. Thus. The disappearance of the biﬁlms and the initiation of spheroids are shown schematically in Figure 9. Whether the rosette form is a strictly coupled growth.the mold walls. Probably all coupled eutectic graphites experience this eﬀect. 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. the oxide biﬁlms are completely eliminated. as mentioned above. The growth mode is probably some kind of addition of carbon atoms to spiral growth steps generated by h0001i oriented screw dislocations (Figure 10). in particular. in general. which is often sited on the mold wall.41]). In the case of silica-rich biﬁlms. will help to settle such questions. which will dissipate into solution in the matrix. would be highly faulted.41] Thus. it seems likely that a single initiation event on a nucleus. the graphite having nucleated. We would expect. 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. which are often called ‘‘cells’’ (Figure 8). which is highly faulted. A careful examination of graphite ﬂakes to determine whether they contain biﬁlms. 792—VOLUME 40B. expands the coupled growth front as a hemisphere to form the rosettes. The cells are beautifully regular structures with interﬂake distances now strictly controlled by diﬀusion in the boundary layer immediately ahead of the advancing front. Primary ﬂake graphite. that ﬁne graphite morphologies. which is sometimes designated Type D or E according to ASTM speciﬁcation A247. expanding to form a cell (courtesy of Fras et al. might also somehow METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. Because the growth direction of graphite is mainly parallel to the basal (0001) plane. 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). ﬂakes have to realign their growth direction continually because of the intrusion of their neighbors into their growth space. and (2) solid magnesium oxide that will precipitate probably on the pre-existing nuclei that originally sat on the ﬁlms. then this unpromising start to nodularity will emphasize the possible importance of plastic constraint of the surrounding austenite matrix as will be discussed below. They are mainly inﬂuenced by the continuous growth process.[40. the silica will be reduced by magnesium to (1) silicon metal. this explains the ‘‘coral’’ type of graphite morphology (to be discussed later). will lose any graphite to their neighbors by a natural coarsening process. The subsequent evolution of heat will inhibit other nuclei from becoming active. If sulfur is also present in the melt. subsequently develops along radially oriented biﬁlms to generate the appearance of a single growth phenomenon. All the coupled eutectic forms described below are therefore not especially inﬂuenced by the (rather rare) nucleation events. but graphite forms preferentially on isolated regions of the particle. then the MgO is likely to contain a component of MgS. On the one hand. to be completely wrapped around by graphite. At modest undercoolings. the addition of Mg. the coupled growth takes the form of rosettes. For instance. would be expected to contain the least faults. as seems possible. During coupled growth.[40. types D and E graphite. The precipitating graphite grows over the compact nucleus. whereas rosette (or cell) graphite would represent an intermediate case as a result of its larger spacing. possibly augmented by additional MgO. is not clear. On the other hand. or cells (Figure 8). and an examination of interﬂake regions to check for biﬁlms. therefore. This is possibly because the interﬂake diﬀusion distance is now so small that only ferrite can be formed. wrapping completely around it so as to form a compact initiating morphology. augmenting these original particles. in addition to eliminating the silica-rich biﬁlms. limiting the strength of such irons. at less than a diﬀusion distance from neighbors. ﬁner. a clearly formed rosette structure may be capable of generating from a random morass of biﬁlms.
Y is the yield stress. and b and a are the external and internal radii of the shell. and ﬁnally contacting and becoming incorporated into an austenite dendrite. DECEMBER 2009—793 . VOLUME 40B. (b) the elimination of the silica-rich biﬁlms by addition of Mg. (c) the survival of existing nuclei and additional nuclei from inoculation. wrapping completely around existing nuclei (particularly if they happen to pass through constitutionally supercooled regions). Many studies have clearly revealed the deformation of austenite dendrites by the growth of internal nodules (Figure 12).Fig. 10—The probable structure of a graphite nodule. with their austenite shells and the austenite dendrites results in their mutual assimilation. but it is important and worthy of examination. A minor modiﬁcation of this development may be envisaged. and Stefanescu assume the protrusions to be the natural growth shapes arising from cooperative growth of austenite and graphite by diﬀusion from the liquid. as the graphite grows. 9—(a) The melt with biﬁlms and sundry contaminant or preconditioned nuclei. 11—Graphite nodules in an austempered iron indicating nucleation on a small central inclusion. subsequently developing a shell of austenite. (b) Buhrig-Polackzed and Santos indicate in a schematic illustration that the contact between nodules METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. Subsequent research will clarify this point. 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. to create a local bump on the dendrite. in which the graphite nodule does not grow a shell of austenite until it contacts an austenite dendrite. aﬀect the ability of the nuclei to work more eﬃciently. This lumpy morphology has been attributed to various mechanisms. so that a complete wrapping around eﬀect might be promoted. 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. the shell of austenite seems a key feature associated with the growth of spheroids. (Some subsequent surface smoothing driven by surface energy would be expected to occur rapidly. This eﬀect seems to have been generally overlooked. as follows: (a) Ruxanda et al. (e) growth of spheroids. whatever the ﬁner details of the encapsulation process. as discussed below. Anyway. (d) the nucleation of graphite. all of which are likely to contribute to some degree. At that moment. a shell of austenite would be expected to wrap itself rapidly around the nodule.) (c) Deformation of the dendrite by plastic ﬂow. Painstaking metallography would be required to clarify this detail. Fig. Later. Stefanescu concludes in his review that all the evidence points to nodules initially growing freely in the liquid. locally expanding the surrounding solid to accommodate the increasing volume occupied by the graphite has to be important.
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. Thus. This leaves mechanical stabilization as a potential critical mechanism. 12—The distortion of dendrites as a result of the internal growth of nodules (after Hillert).17] that the early phases of growth of the graphite around the nucleus are anything but regular. Although a creep model rather than the above plastic model might give a somewhat more accurate result. A similar area biﬁlm of an average 10-nm gas gap would form a pore approximately 5 lm in diameter. This conclusion is reinforced by the recent evidence[16. much speculation by earlier authors that interfacial energies may be important in deﬁning the shape of spheroidal graphite seems irrelevant. a rounding eﬀect caused by mechanical smoothing of the forces to expand the austenite shell seems to be important. the above result can be relied on to give us an order-of-magnitude estimate of the eﬀect. The easier spherical growth mode. then the nodule developed as a sphere. whereas slow-developing or nonenveloping shells led to misshapen nodules. then we ﬁnd P = 30 MPa approximately. In passing. A perturbation radius r is not favored because a higher local pressure is required. leaving mainly argon. ) be increased (Figure 12(b)). They found that if the shell formed quickly and completely. In this way. it seems possible that clouds of ﬁne argon bubbles will be released into the melt. Thus. With regard to the possible asymmetric eﬀect of a perturbation of radius r. simply expanding the uniform radius a. that there is some qualitative justiﬁcation for believing that mechanical forces stabilize the spherical growth mode of the nodule. Thus. taking r = a/2 to a/10 locally increases P to approximately 35 to 60 MPa. a biﬁlm of 100 lm square and an average gas gap of 1 lm would yield a pore of approximately 20 lm diameter. growth of the extension of smaller radius would be discouraged because additional pressure would be required to stabilize the perturbation. A small biﬁlm of 794—VOLUME 40B. therefore. it is useful to ascertain whether there is quantitative justiﬁcation for this mechanism. respectively. after which the spherical form can no longer be stabilized. followed by nitrogen that would react to form nitride. the pressure to extend plastically the growth at this location would (according to Eq. For instance. any residual air trapped between the ﬁlms is expected to be released. Thus. In general agreement with this conclusion. However. would therefore be encouraged. a strong spherodizing eﬀect is needed that neither the nucleation mechanism nor surface energy can provide. which indicates that there is a substantial restraining pressure on the growth of the nodule during most of its life. Jiyang et al. Even at values of a = 20 lm and b = 200 lm. it may be signiﬁcant that on the addition of Mg causing dissolution of the silica-rich oxide biﬁlms. It is not easy to deﬁne the sizes of such bubbles with any accuracy. having a necessarily smaller radius r. sphericity is encouraged. DECEMBER 2009 METALLURGICAL AND MATERIALS TRANSACTIONS B . P is of course unchanged. It seems. If we take Y to be approximately 6 MPa for austenite at the melting point of iron. used color etching to reveal the austenite shells around graphite. and a = 2 nm and b = 20 nm. respectively. It seems likely that some Mg vapor will also diﬀuse into the bubbles. 13—A thick shell expanding plastically because of internal pressure. The logic is as follows: If a perturbation to the spherical graphite shape were to occur.Fig. Clearly. The air trapped in a biﬁlm will be expected to lose its oxygen by continued oxidation of the matrix. more work is required to conﬁrm this preliminary indication. Clearly. Fig.
such as that reported by Yamamoto et al. it will have been energetically favorable for the nuclei to attach to the biﬁlm. stabilizing the combination. Thus spherodization seems to be achievable via a purely mechanical route. 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. curious observations. 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. Thus. Clearly. 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. Furthermore. as noted below.e. VII. METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 40B. the remnants of the layer of air. COMPACTED GRAPHITE IRON (CGI) If the addition of magnesium is more carefully controlled to some level intermediate between spheroidal and ﬂake iron. it was thought that it could not be spherical because it could not encapsulate the complete nucleating particle.. will be well ‘‘wetted. (Ductile iron only becomes embrittled once again. any strain energy relief in the liquid state is zero.17] and others indicates that the nucleating particle is often not entirely surrounded in the case of Fig. The subsequent growth of graphite is forced to occur not radially but in general unidirectionally away from the biﬁlm residue (Figure 15(d)). in which ﬂake is converted into nodular iron by simply purging the melt with ﬁne bubbles of nitrogen. small patches may remain if the Mg addition is not too high.) Finally. but a successful penetration of a particle into the bubble would depend critically on a reduction in interface energies.’’ which is a necessary condition for the particle to be a nucleating agent). argon or carbon dioxide become explicable. attractive this hypothesis might be to explain graphite coatings inside pores in solidiﬁed castings. it seems that a fog of bubbles in the range of approximately 1 to 20 lm is to be expected. Originally. The subsequent nucleation of graphite on the nucleus will result in rapid spreading of growth around the nucleus. and the reduction of surface energy to encourage such precipitation in the liquid state seems negligible.[54. this spreading will be arrested (Figure 15(c)). replicating the condition achieved chemically by the addition of Mg. it is known that purging with gases can eliminate biﬁlms from melts. so that the combination of nucleus and ﬁlm will enjoy a reduction in overall energy. if oxide biﬁlms are reintroduced by turbulence by handling of the melt or poor ﬁlling system design of the casting. Another interesting aside can be noted. Only the small part of 1/2 of the biﬁlm together with its unbonded interface. it seems to be irrelevant to the formation of graphite nodules.. as a result of the reduction in strain energy involved. It does not oﬀer support to the gas bubble nucleation hypothesis. it is clear that most of the oxide biﬁlms will be dissolved by the addition of Mg. 14—CGI viewed by (a) SEM deep etching and (b) optical metallography. but the observations by Riposan[16. its distant ‘‘twin’’ half not enjoying the protective inﬂuence of the nucleus will dissolve and disappear. In our biﬁlm model. From experience in the light metals industries. compacted (‘‘vermicular’’ based on the Italian for ‘‘worm-like’’) graphite is the result (Figure 14). the theory requires the incorporation of solid particulate oxide nuclei into the bubble. This is unlikely for particles formed by precipitation in situ in the liquid.) Only half of the biﬁlm will be retained in this way.55] However. which will be in perfect atomic contact with the melt (i.10 lm square and 10-nm average spacing would create a 1-lm-diameter pore. that a theory proposes that nodules nucleate from Mg bubbles in suspension in the melt. although a mechanism for the presence of extremely ﬁne bubbles may be provided by the current analysis. (Naturally. will remain (Figure 15(b)). Such particles will be energetically rejected by bubbles. but not perhaps relevant. DECEMBER 2009—795 . It is intriguing.
illustrating the overall similarity of these structures (Courtesy of Thomas Prucha. and the fact that it can be grown in alloys containing Ce. a ﬁbrous morphology of graphite. Because of the purity of the alloys. Naturally.Fig. References 60 and 61). The purity and absence of inoculation also means that no oxysulﬁde nuclei are present. is widely known to be associated with the reduction in mechanical properties METALLURGICAL AND MATERIALS TRANSACTIONS B . then residual biﬁlms will encourage ﬂake graphite. thus transferring the expansion of the graphite to the liquid. noninoculated irons. the subsequent growth form is not possible to predict and has to depend on completely diﬀerent factors. 2009). MISSHAPEN SPHEROIDS The presence of ill-formed spheroids. Thus. AFS. For interested readers. then the limited stability enjoyed by the residual biﬁlm patches will be overcome. If the Mg level is too low. This seems to be a coupled growth mode. but the 796—VOLUME 40B. unidirectional spiral structure similar to the worm-like growth mode clearly observed in Figure 14. the growth of the eutectic is likely to be so fast that it will cover large undercooled regions at the mold wall. CGI and coral forms of graphite (Figure 16) are both ﬁne. as its name suggests. they present micrographs that clearly illustrate coral growth when the iron is suﬃciently pure. whereas if the Mg level is too high. to (b) eliminate most of the silica-rich biﬁlms. 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. and when the growth rate is suﬃciently high. VIII. ﬂake iron. Fig. coral graphite occurs at high undercoolings (clearly at least one nucleation event is required. reducing feeding requirements. Cole had observed a ﬁne. in contrast to ductile iron in which the graphite transfers its expansion to its surrounding solidiﬁed shell. Clearly. The great sensitivity of the compacted graphite morphology to magnesium concentration is corroborated by the proposed biﬁlm mechanism. neither ﬂakes nor spheroids can form. DECEMBER 2009 phenomenon is dominated by growth). formed in rather pure. (d) growth continues unidirectionally. thus advancing subsequently on a substantially planar growth front away from the wall. 15—The formation of CGI by addition of just enough Mg to (a) melts with existing biﬁlms with attached nuclei. the ﬁnal form of CGI is not strongly inﬂuenced by the inoculation and nucleation events. expanding the casting and increasing feeding requirements. 16—An SEM image of deeply etched CGI closely resembling coupled eutectic coral structure. Thus. but not the remnant of ﬁlm attached to the nuclei. no silicarich oxide biﬁlms can be present. (c) Inoculation promotes graphite growth on the nuclei. encouraging the growth of totally spherical grains. As an important feature of the continued growth of CGI. After initiation in undercooled regions. even though nowhere in their report do Nakae and Shin mention coral graphite. ﬁbrous ﬁlamentary morphologies. They show the close similarity between the coral eutectic structures of Fe-C and Al-Si alloys. It develops its continuous worm-like growth because of a continuous growth process. IX. several workers ﬁnd that the graphite seems to stay in contact with the liquid (for instance. and this may also be true of nodular iron. particularly if present in large numbers. It is tempting to consider that the resemblance reﬂects an underlying similarity. and the last remaining patches of biﬁlm will be dissolved. CORAL GRAPHITE Coral graphite is. With regard to the microstructure of growth. or Ce is added.
additional large quantities of Mg-rich oxide biﬁlms are likely to be reintroduced. The symmetrical spherical constraint previously provided by the surrounding austenite is also destroyed. in which an otherwise nicely inoculated and spherodised melt is recontaminated with oxides. after the Mg addition. However. this belief presupposes that the ﬂakes act as cracks. in common with widely held belief. occupying a vastly greater cross sectional area than the spheroids. Meanwhile. who observe that nodules are converted from misshapes to spherical by the use of a ﬁlter to take out the ‘‘inclusions produced by inoculation. During the Mg treatment. attributes this loss of fracture resistance to the sharp notches at the root of ﬂakes. 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. on contact. 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. It is interesting to predict that perhaps more time after the spherodizing treatment to allow the melt to clear. This seems most unlikely.’’ These were highly successful to increase the nodule count but led to a disastrous fall in nodularity. On contact with an oxide biﬁlm. many Mg addition techniques are extremely turbulent. the nodules attached to the biﬁlms are clearly poorly shaped. Thus. which would have also entrained the surface oxide to create Mg-rich oxide biﬁlms that. because they occupy such a small volume fraction of the alloy. such as tensile strength and ductility. 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.of nodular irons. adding to the Mg-rich slag. the silica-rich biﬁlm content of the melt would be eﬀectively eliminated. Thus. Additional misshapen nodules are evident elsewhere in the structure. It is the presence of the crack provided by the biﬁlm that has to be viewed as the principal cause of failure.67] This undesirable morphology is not easily explained at this stage as a result of relatively little experimental work to clarify the problem. should completely eliminate poor nodularity. would generate nonspheroids. leading to exploded rather than smooth spheroid surfaces. the biﬁlm provides the unbonded interface. because if the nodule had grown uniformly in a compact morphology. These are expected to be lying on random areas of biﬁlm not straightened by dendrite growth. thereby folding in the oxide surface of the liquid to create entrained biﬁlms. These planes. on pouring into the mold. X. DECEMBER 2009—797 . In this ﬁgure. in a liquid now cleaned from transient silica-rich biﬁlms. now containing a planar biﬁlm crack. This was almost certainly a result of adding the inoculants through the melt surface. These extensive biﬁlms simply act as cracks in the casting. however. 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. the subsequent growth of the existing suspended spheroids will be redirected along the plane of the ﬁlm. A step in the right direction is presented in the work of Takita et al. In terms of the biﬁlm hypothesis. Hughes.’’ This positive step contrasts with that taken by Liu et al. or counter-gravity ﬁlling system. Unfortunately. Thus. the spheroid will grow to become signiﬁcantly misshapen. This eﬀect can be observed in Figure 2. the signiﬁcant reduction of properties associate with malformed spheroids cannot be the direct result of the shape of the spheroids. aiding the nonspherical development. 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. 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). solidiﬁcation and remelting would be expected to be reversible. graphite would be expected to grow on oxide biﬁlms. lead to disastrous brittleness known as plate fracture (Figure 1) described elsewhere by the author. This will encourage growth instabilities leading to ‘‘dendritic’’ rather than ‘‘planar’’ growth. However.. 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. The loss of properties is predicted to be the result of the presence of the biﬁlms in the melt. some of these will fortunately ﬂoat out. several oxide biﬁlms have been straightened by the growth of dendrites so as to lie along 100 planes. 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. of course. Furthermore. (b) Austenite will be less likely to form in hypereutectic irons. Cole suggested they had suﬀered remelting as a result of being carried by convection in and out of hot zones of the liquid. not all of these defects will ﬁnd their way into the castings to impair the structure and properties. spheroids would be created in suspension. together with a properly designed ﬁlling system. signiﬁcantly reducing properties. as a crack. These new biﬁlms will be permanent defects formed from highly stable magnesia or magnesium silicate. particularly if the mold ﬁlling system is a rather poor design. Prior to pouring. added ‘‘post inoculants. especially in conditions of carbon enhancement by segregation during cooling in the liquid VOLUME 40B. or (2) poor casting practice.[66. then the uniform graphite would be expected to have a substantially uniform rate of dissolution. who.
and their work implies that chunky graphite grows out from spheroids. and interconnected fragments (Figures 17(c) and 18). the nodule will be free to grow more like a dendrite.65] ﬁnd evidence that chunky graphite grows along the C-axis direction. it simply appears to be ﬁne. (c) chunky graphite (after Liu et al. (d) SEM iron image of an exploded spheroid. irregular. 798—VOLUME 40B. it seems the loss of properties is possibly more associated with the short diﬀusion distances between branches of the graphite ﬁlaments. Furthermore. Once again. the properties of nodular iron are reduced. (e) electron image. as an apparently ‘‘stop/start’’ growth in the C-direction consisting of nearly separate pyramidal ‘‘chunks’’ linked by a narrow neck. and chunky graphites. XI. When not pressurized to remain spherical. they report observations on spheroids that exhibit gradual degeneration.Fig. branched.[59. 17—(a) Spheroid and (b) malformed spheroid. All these workers observe the characteristic form of chunky graphite. ﬁnally developing the characteristic exploded forms. Evidence for mechanical restraint as a powerful eﬀect is presented in the section on nodular graphite above. as does nodular graphite. Itofugi and Uchikawa conﬁrm the identical growth orientations of spheroidal. promoting the development of ferrite. compacted. 18—Graphite nodules and areas of ﬁne. ‘‘Chunky’’ is not a particularly helpful descriptive adjective for this variety of graphite. developing instabilities that grow into projections to its growth front. chunky graphite in the thermal center of a 200-mm cube. like beads on a branching string. but only METALLURGICAL AND MATERIALS TRANSACTIONS B .). Its ‘‘chunkiness’’ is only apparent under the microscope at high magniﬁcation. Liu et al. they conclude that chunky graphite is a degenerate form of spheroidal graphite. However. phase. CHUNKY GRAPHITE Chunky graphite is often observed concentrated in the centers of heavy sections of nodular iron castings. which slowly take on the growth forms of chunky graphite. The individual chunk sections are composed of layers parallel to the basal plane. The nodules may have nucleated early in the liquid phase and grown without the beneﬁt of the mechanical constraint of the austenite. DECEMBER 2009 Fig. otherwise. Thus.
It would be expected. outer surfaces of the biﬁlms. corroborate the absence of nuclei in these regions. have studied carbides in heavysection austenitic ductile iron (ADI). However. 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. In the absence of signiﬁcant numbers of nuclei. The biﬁlm would originally have been randomly crumpled but would have been straightened by the progress of the carbide across its face. that an analogous reaction would occur in Fe-C alloys.nanometers thick. therefore containing unknown quantities of oxide biﬁlms. in the future. which is explained by the growth of the freezing front pushing biﬁlms ahead by their observations of ‘‘stringers’’ of graphite nodules. so that its growth mechanism seems likely to be asymmetrical. If the above mechanism is correct. or ﬂakes aligned with the boundary) and pores all forming on the same boundaries. are all similar. they ﬁnd degradation of properties more serious than they would have expected from the carbides themselves. the whole region will ﬁll with a variety of continuous. therefore. They suspected that the real impairment was caused by the presence of ﬁlms that had ﬂoated into this region. The extended size of chunky graphite regions. is not clear at this time. 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. because the austenite forming during solidiﬁcation also possesses a closely similar facecentered-cubic structure. 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. in which the growth of iron carbide eutectic (ledeburite) occurs by the spreading of carbide (cementite) across a plane. which are much larger than cells of other types of graphite. Thus. it seems possible that at the same time there is likely to be an absence of nuclei. the runners were not designed to be pressurized and ﬁll on a single pass. then exploded spheroids can be viewed to be a similar growth mode to chunky graphite. The presence of the central unbonded region (including the pores) between the ﬁlms. explains the apparent brittleness of the carbides. the spheroidal mechanism of growth along the C-axis is likely to be continued. 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). perhaps happening to ﬂoat into this region. and so on. Although the above authors provide evidence that suggests the presence of biﬁlms. This was because. Clearly. if a graphite nodule can be initiated somewhere in or near this region. and (4) from the graphite ﬂakes sitting in the boundary (called by the authors. and all the cast METALLURGICAL AND MATERIALS TRANSACTIONS B material would have suﬀered from turbulence and air entrainment. both originating from spheroids. 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. a reverse ﬂow is likely to have contaminated the mold cavities. only to be overtaken again because the carbon in solution will now build up in the liquid ahead of the front. The key word here is ‘‘careful. Toward the top of their castings. followed by the development of a rod type of eutectic at right angles. (3) from the pores as the residues of air bubbles trapped between the ﬁlms. and other conditions. Carbides in irons seem to form preferentially at grain boundaries and often seem to be associated both with residual graphite (sometimes as nodules. the experiment by Asenjo et al. In the absence of nuclei. spheroids cannot form.’’ For instance. This is a clue to their biﬁlm associations. much greater sophistication of melting and casting will be required for experiments designed to clarify the solidiﬁcation mechanisms for cast irons. but only in a few select directions (possibly one direction) in chunky graphite. it will not enjoy the beneﬁt of the presence of an austenite shell in a region of higher temperature and enhanced segregation. XII. extending along the C-axis direction. unﬂatteringly. Observations by Kallbom et al. thus creating an essentially planar crack that would constitute a serious defect in the VOLUME 40B. Faubert et al. S. why continued growth should not occur in all directions as in the exploded variety. 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. with the austenite advancing to grow nearly over the top of the graphite. and O is important for chunky graphite formation. They observe the chunky graphite to be concentrated in the center of heavy sections. They conclude that a collaboration among Mg. the correct explanation for the origin of chunky graphite might be elucidated by subsequent careful experiments. ‘‘degenerate’’ graphite). constituting the crack through the interiors of the carbides. It is hoped that in the near future. Because the growth will constitute an extension of the spheroid. This characteristically lumpy growth may be the result of a pulsating or irregular advance of the growth front. malformed nodules. 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). forming the nearly pinched-oﬀ neck of the graphite. Biﬁlms would segregate to grain boundaries and possibly actually constitute the boundary. such as the temperature and solidiﬁcation rates. However. It is tempting to consider that the original planar expansion would have been facilitated by growth across the surface of a biﬁlm. it will continue to grow. accelerating the next phase of growth of the graphite until the local carbon concentration is depleted once again. branching growth. DECEMBER 2009—799 . in common with most iron casting. Both graphite and carbides are expected to form on the wetted. Stefanescu quotes the work of Hillert and Steinhauser. seem consistent with an origin associated with biﬁlms. Almost certainly. Thus.
161–62. vol. 127–45. 6. Chunky graphite occurs in heavy-section ductile iron regions. vol. J. Oxford. 114. 345–49. 75. Ductile iron is ductile because of the absence of oxide biﬁlms. the various forms of graphite are signiﬁcantly inﬂuenced by the presence or absence of biﬁlms. expanding to form cells of coupled growth with austenite. spreading over the biﬁlms. pp. A. 11 (5). 9. Associated branching cracks would have arisen from irregular folds in the biﬁlm. pp.. Shin: Int. Sci. CONCLUSIONS A hypothesis is proposed as follows: 1. 53 (4). 131–51. 25. 2009. vol. vol. the ﬁner.. trapped inside or alongside graphite ﬂakes accounts for the poor tensile properties of ﬂake irons. J. 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. and compacted graphites are so similar that they often seem to be confused in the casting literature. 1999. 4. 1967. both nucleation and growth mechanisms inﬂuence graphite morphology. ductile iron can be seriously reduced in ductility. R. nucleation dominates the formation of spheroids and deformed spheroids. 8. pp. H. 7. 3. this short account presents only an outline of a new approach to the structures of cast irons. nucleation occurs once to initiate each cell. after which continuous growth leads to developing continuous branching morphologies. Mampaey and K. vol. undercooled coral and chunky graphites. assiduous. it may be a coupled eutectic form.R. 2006. Res. XIV.. chunky. 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. DECEMBER 2009 REFERENCES 1. The formation mechanism is not clear at this time.. the absence of biﬁlms explains the high mechanical properties. Campbell: Mater... biﬁlms play no part in this growth mode. 1985. and its ‘‘beads on a branching string’’ morphology may result from an unstably advancing growth front. Cast Met. growth morphology may be natural but is additionally encouraged by the mechanical constraint of the austenite matrix. 10. Sci. pp. or disprove these proposals. although these mechanisms dominate to diﬀerent extents in diﬀerent circumstances. pp. both nucleation and growth are inﬂuential. then it would explain the historical resistance of the phenomenon to explanation so far. UK. 9. de Sy: AFS Trans. pp. leaving regions nearly devoid of nuclei and creating graphite akin to coral morphology.. C. 2001. Coral morphology nucleates on unknown nuclei at low temperatures. and forming ﬂakes of crystallographically near-perfect graphite. 4. E. J. and. nucleating on oxysulﬁde particles. but when oxide biﬁlms (mainly magnesia-rich) are entrained by poor casting technology. 114. consisting of highly faulted continuous branching ﬁlaments of graphite in the austenite matrix. 117–26. Wolf: Giessereiforschung. Spheroids form in the absence of silica-rich biﬁlms. The presence of the biﬁlms. as proposed here. last but not least. pp. 637– 56. 2. The spherical 800—VOLUME 40B. 107. Much more research is needed to prove. to the painstaking. As such. Hartmann and W.carbide. Stets: AFS Trans. Naturally. Technol. fairly continuous forms of coral. In addition. Barton: Foundry Trade J. pp. pp. (8). XIII. 5. vol. 158–60. J. Cast iron melts normally contain double ﬁlms (biﬁlms) in suspension. Graphite nucleates on the oxysulﬁde particles and grows. whereas for ﬂake graphite. 22 (2).. with castings at times even failing disastrously by the brittle ‘‘plate fracture’’ mechanism. not because of its spherical graphite morphology. 2006. Compacted graphite forms on oxysulﬁde nuclei that occupy biﬁlm residues. pp. Indeed. vol. Carbides form at low temperatures on oxide biﬁlms. 178–81. 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. GENERAL Overall. Hoﬀman and G. 3. Beghyn: AFS Trans. Inoculation produces oxysulﬁde particles that nucleate on silica-rich oxide biﬁlms. 8. Elsevier. This seems typical of biﬁlm phenomena. F. Misshaped spheroids seem to be spheroids that have encountered a Mg-rich biﬁlm. 2006. 10. Nakae and H. 2003. D. Technol. 1999. 7. For compacted. 523–28. and doubtful reviewer of this article from whom I learned much. 1055– 58. the presence of the biﬁlm destroys the symmetrical mechanical constraint of the austenite that favors sphericity. to Carl Loper and Riposan and colleagues for inspiring research. enhance. 999–1008. Exploded spheroids may be the result of growth in the liquid. Furthermore. vol. 6. 5. 2. straightening the biﬁlms. For instance. advancing together with the austenite. 161–72. Campbell: Castings. as cracks. They do seem similar in the sense that they all appear to be more-or-less coupled growth forms. METALLURGICAL AND MATERIALS TRANSACTIONS B . If. ACKNOWLEDGMENTS The author is grateful to those who have assisted with the micrographs. Loper: AFS Trans. subsequently growing along the biﬁlm and losing sphericity (Figure 2). 125–26. It is hoped that improved control and improved castings will result from these eﬀorts. without the beneﬁt of the mechanical constraint of an austenite shell. 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