3, Solidification of Castings Chapter 3 SOLIDIFICATION OF CASTINGS © Introduction © Mechanism of solidification ‘crystallization and development of cast structure mucleation and grain growth dendritic growth solidification in pure metals and alloys Structure of castings - significance and practical control of east structure = grain shape, grain size and orientation ~ refinement and modification of cast stmeture * Concept of progressive and directional solidification, - methods to achieve directional solidification = factors affecting solidification = solidification time (Chvorinov’s equation) 3.1 INTRODUCTION The pouring of molten metal into a relatively cool mould initiates the process of solidification wherein the phase transformation from liquid to solid occurs. The mode of freezing has a twofold influence upon the final properties of the casting; the metallographic structure (grain shape. size and orientation) as well as the underlying erystal structure, besides strueture the soundness of the casting also depends upon the solidification mechanism. 3.2 MECHANISM OF SOLIDIFICATION 3.2.1 Crystallization of the melt Crystal lattice represents a more closely packed state of matter than the liquid, thns freezing is associated with volume contraction. Moreover, fieezing results in reduced molecular motion leading to liberation of energy in the form of latent heat of crystallization which affects the rate and mode of erystal growth, Crystallization from the melt involves suecessive stages of nucleation and grain growth. The location and relative rates of these two phenomena determines the final structure. Pruthvi Loy Serrao SUEC, Mangalore3._ Solidification of Castings Crystals which will form grains Grains Figure 3.1: Nucleation and grain growth At the melting point the thermal fluctuations result in the formation of tiny particles of the produet phase which grow further by the transfer of atoms across its interface. The process of formation of the first stable tiny particle is called nucleation and the process of increase in the size of these particles is called grain growth 3.2.2 Nucleation ‘Nucleation is the beginning of phase transformation. There can be two types of nucleation: ‘+ Homogeneous nucleation and ‘* Heterogeneous nucleation i) Homogeneous nucleation: This type of nucleation is observed when solids are formed within its own melt without the aid of any foreign particles. It occurs in perfectly homogenoeus materials such as pure metals. Homogeneous nucleation requires some amount of under cooling and the nucleation of super cooled grains depends on two factores, viz, volume fiee energy and surface free energy. a) Volume free energy (Afy): the free energy available fiom the solidifetion process. and it depends upon the volume of particle formed. Where, AFy— fice energy change per unit volume (the -ve sign indicates that the free energy decreases) Pruthvi Loy Serrao SUEC, MangaloreSolidification of Castings b) Surface free energy (Afs): the energy required to form a solid-liquid interface. Als = dtr? y Where, y— interfacial free energy per unit area Radius of particle, r -<0 44 Free energy change, Af SAF =f, + Of “unstable stable “embryo "~~ nucles Figure 3.2: Free energy changes in Homogeneous nucleation Therefore, the total energy change is, Af=— Sar? AFy + 4ar? y il) Heterogeneous Nucleation: It takes place due to the influence of foreign particles (container or insoulble impurities); the presence of impurites lower the liquid-solid interface energy and help in nucleation there by reducing the amount of super cooling needed to actuate nucleation, The basic requirements for hetergeneous nucleations are a) Nucleating agents: the presence of foreign particles so that nucleation takes place easily b) Low contact angle: a good wetting between the liquid metal and the foreign particles Pruthvi Loy Serrao. SIEC, Mangalore._ Solidification of Castings Figure 3.3: Contact angle for Heterogeneous nucleation (with small contact angles the interface has low surface energy and nucleation can occur at small amount of under cooling) Once the intial unclei are established two possiblities exist for fimther crystallization. ie., more solid may be deposited upon the first nuclei or fresh nucleation may occur, but growth might be expected to predominat over further nucleation. However there could be barriers to growth resulting fiom the evolution of latent heat of crystallization and in case of alloys fiom the change in compostion of the adjacent liquid through differential fieezing. Table 3.1: Comparison of Homogeneous and Heterogeneous nucleation Homogeneous nucleation Heterogeneous nucleation ‘Occurs in pure metals Occurs in alloys ‘Nucleation is by deposition of atoms from } Nucleation is by the influence of foreign its own melt particles Requires some amount of undercooling | Undereooling is less as compared to for nucleation. homogeneous nucleation. Starts below the equilibrium freezing Starts comparatively at much higher temperature temperature 3.2.3 Grain growth Growth follows nucleation and it determines the final crystallographic structure of the solid. The mode of growth depends upon the thermal conditions in the solidification zone and the coustitution of the alloy. Pruthvi Loy Serra SUEC, Mangalore3,_ Solidification of Castings Duing growth, the material is transferred by diffusion and the rate of transfer by diffusion can be analyzed by an equation of Arrhenius type, as shown below; Rate of transfer = constant xe °*7 Where, Q~ Activation energy R - Gas constant T — absolute temperature The growth is controlled by the rate of heat transfer from the casting. Since there is a temperature gradient towards the casting surface, the growth occurs in a direction opposite to heat flow. For growth to occnr more atoms must join the solid than leave it and for this to happen the temperature of the interface must be slightely below the equillibrium freezing temperature. This means some amount of wndercooling must exist if the interface is to advance. “+ atoms leaving the solid = atoms joining the solid Figure 3.4: Material transfer during growth In case of pure metals, the undercooling can be produced only by thermal means (thermal undercooling) but in alloys the undercooling may be produced by the changes in temperature as well as composition which is termed as constitutional undereooling. © Pure metals ~ thermal undercooling ‘© Alloys ~ constitutional undercooling The presence of undercooling alters the growth morphology (ie., the advance of solidification front); a faster advancing interface experiences a transition of the solidification frout from planar to cellular and to dendritic fom at even higher rates. Pruthvi Loy Serrao, SJEC, Mangalore3,_ Solidification of Castings Front Side Temperature regima Solid) Liquie Temp. Plane growth Tm Kedah sie gun’ pe dese Jb ee hl Pn, eee hth] await Figure 3.5: Transition of growth morphologies due to undercooling r = hala ln? i) Growth in pure metals: The heat wansfer from the casting to the cooler mould produces a positive temperature gradient, as a result the solid-liquid interface advances progressively as a flat plane under conditions of slow cooling and steep temperature gradients, Here the latent heat of erystallization is insuficient to reverse the direction of heat flow. Pruthvi Loy Serra. SUEC, Mangalore3,_ Solidification of Castings Interface Interface t - Tv t T g ef yh 5 E thermal é = undercooling e 2 SOLID uauIp Soup’ uiQuiD Distance > Distance > (a) Positive temperature gradient (b) Negative temperature gradient Figure 3.6: Temperature gradient If the evolution of latent heat is sufficient enough to reverse the temperature gradient at the interface ie., a negetive temperature gradient, then minimum temperature in the liquid will no longer be adjacent to the interface; hence growth by general advance of a smooth solidification front gives way to other modes of growth. ii) Growth in alloys: The growth structure in alloys depends on constitutional undercooling, Let ko — be the distribution coefficient. = concentration of solute inthesolid _ Cs Concentration of solutein the liquid — C, For ky < 1, ie., when the concentration of the solute in the solid is less than that of the liquid, there must be a rejection of the sokute into the liquid at solid-liquid interface and hence the liquid is enriched with the solute concentration and if sufficient time is not allowed for the solute to distribute itself throughout the liquid, a concentration gradient is developed which promotes constitutional undereooling. ‘Also for ky > 1, there is a depletion of solute concentration in the liquid adjacent to the interface which intum gives rise to constitutional undercooling if sufficient time is not allowed for solute redistribution. Pruthvi Loy Serrao. 'SIEC, MangaloreChe Composition 3,_ Solidification of Castings = Actual temp. Freezing emp. ndercooled one | Distance from interface | t 1 ’ I ' ! ! 1 Concentration of solute in the liquid atany distance fom the interface Actual tem, Freezing temp. ‘Composition 4 on é cela fase i mtn Coes ay (“tenes rd wh Figure 3.7b: Variation of solute concentration (when ko > 1) Pruthvi Loy Serra. SUEC, Mangalore3._ Solidification of Castings 3.2.4. Dendritic growth Pure metals solidifying with a negative temperature gradient may result in uneven projection of interface due to the thermal undercooling. The tip of the projection is at a region of greater undercooling than the remainder of the interface and will have a tendency to grow further into the liquid. The solids grow in a stem perpendicular to the surface. The latent heat evolved tends to lower the amount of undercooling at the main interface. The protrusion grows into a spike while the growth of main interface is somewhat retarded. The spike grows and branches develop on it, this branched structure is known as a dendrite. The rate of dendritic growth depends upon the amount of undercooling in the liquid ahead of the advancing dendrite. Figure 3.8: Dendritic growth structure In case of alloys as it solidifies, it tends to reject solute at the solid-liquid interface. The rejected sohute elements lower the melting point of the liquid adjacent to the freezing front and tend to inhibit further solidification, Freezing then continues by dendrites reaching out into the residual liquid, the dendrite is the result of the preferred growth at an edge or comer of an existing crystallite. Dendritic growth is most common in alloys (commercial casting alloys forming solid solution). Dendritic growth in a pure metal can only be detected by interrupted freezing and decantation, but is evident in alloys through the persistence of compositional differences, which can be revealed on etching. Pruthvi Loy Serrao SIEC, Mangalore3._ Solidification of Castings 3.2.5 Solidification curves A solidification curve (or cooling curve) is a record of material temperature vs time, as it cools down fiom its molten state to room temperature. It can be used to determine the phase transition temperatures of materials (pure metals or alloys). i) Solidification in pure metals Pure metals have a clearly defined melting or freezing point. ie. it solidifies at a constant temperature. The evolution of latent heat is associated with solidification and as a result temperature remains constant. An equilibrium cooling of pure metal maybe assumed as shown in figure 3.9. It is also seen that if a pure metal is cooled rapidly or otherwise when it is very pure it may cool with some amount of undercooling, ——= Pouring temperature _p— Hiauid cooling /- Solidification begins Solidification ends Temperature ~ Freezing temperature wt (AT-undercooting) J Sod cooting Local solidification time Total solidification time Figure3.9: Cooling curve for pure metals Skin formation in pure metal When pure metals are allowed to solidify in a mould, the portion of the molten metal next to the mould wall begins to solidify, this metal solidifies in the form of solid skin and then liquid metal tends to freeze on it. The solid skin progresses towards the center of the monld from mould walls and due to this progressive solidification, suecessive layers of molten metal buildup in the form of solid skin, As the solid metal wall thickness increases the liquid level in the mould falls because of solidification shrinkage. This canses pipe defects and hence use of risers becomes necessary. Pruthyi Loy Serrao SIEC, MangaloreSolidification of Castings ‘skin type solidification Mould Figure 3.10: Skin formation in pure metals Also pure metals have high melting temperature as compared to alloys due to which they exhibit difficulties in casting especially while pouring due to severe metal-mould reactions. Moreover it is prone to cracking and other defects due to their mode of solidification. ii) Solidification in alloys Solidification in solid solution alloys occurs over a range of temperature as shown in figure 3.11 below. In alloys the amount of undercooling required is less as compared to pure metals and hence the nucleation occurs with ease. A rapidly solidifying alloy may show considerable amount of undercooling owing to differential freezing. —— Pouring temperature Ui cooting _-— Solidification begins Temperature Solidification ends 5 (AT-undercooling) Solid cooling Ln Total solidification time Time Figure 3.11; Cooling curve for alloys Pruthvi Loy Serrao SUEC, Mangalore3._ Solidification of Castings loy solidifying with a mushy zon Figure 3.12: Mushy type solidification in alloys When an alloy solidifies by rejecting solute at the solid liquid interface, the rejected solute elements lower the melting point of the liquid adjacent to the interface. A mushy zone is thus formed due to several dendrites reaching out into the residual liquid. Pure metals will have a narrow mushy zone (steep temperature gradient), Chilling effect brings about steep temperature gradients thus a narrow mushy zone ean be achieved. 3.3 STRUCTURE OF CASTINGS 3.3.1 Significance and control of cast structure The metallographic structure of a casting consists of © Grain size, shape and orientation ‘* Distribution of alloying elements ‘© Underlying crystal structure and its imperfections The above stated attributes of a metallographic structure are acquired during solidification and they define the properties of a casting. These attributes are influenced by various factors such as the thermal conditions, alloy constitution, conditions for nucleation and growth, ete. Pruthvi Loy Serrao SIEC, Mangalore3,_ Solidification of Castings The principal factors governing the final metallographie structure are: 1. Casting alloy properties (alloy constitution and thermal properties) Mould properties (design and thermal properties) 3. Solidification process parameters (pouring and casting temperature, conditions for heterogeneous nucleation, mode of solidification, ete.) 4, Subsequent heat treatments such as annealing, normalizing, ete, Table 3.2: Influences of casting variables upon structure Variable Effect Structural tendency ing | Decreases fieezing rate and inhibits nucleation | Coarse columnar Increasing pouring temperature Increases temperature gradient Columnar Decreasing montd | Hnetewses freezing rate Fine equiaxed ‘Temperature Increases temperature gradient Columnar Decreasing pouring | leteases temperature gradient Columnar rate Increases mechanical disturbance Fine equiaxed 3.3.2 Grain structure The grain structure is defined by the grain size, grain shape and its orientation. Grain size is a very important factor in relation to strength, usefiuluess and other physical properties. A fine grained structure offers better strength over a coarse grained structure but suffers low ductility, The other advantages of a finer grained structure includes ‘+ increased impact toughness ‘© improved machining finishes ‘© mitigate cracks and quenching distortions The grain size in the final produet phase depends on the relative rates of nucleation and growth, ‘As each mucleating particle becomes a grain in the final product; a high nucleation rate means a large number of grains, moreover with low growth rate more time is available for further nucleation to take place in the parent phase. Thus with a high nucleation rate and low growth rate a fine grained structure can be obtained. Pruthvi Loy Serrao. 'SIEC, Mangalore3._ Solidification of Castings Ivica] grain structure A solidifying melt can assume any of the grain structures as shown in figure 3.13 below. In case of pure metals a columnar grain structure with the grains growing from the mould wall towards the casting is observed with a thin layer of equiaxed grains near the mould due to chilling effect. On the other hand alloys experience better ndercooling as compared pure metals and hence they usually solidify with a completely equiaxed structure. The metals with minor alloying constituents may solidify with a grain structure intermediate to pure metals and alloys. The solidification begins similar to pure metals with an equiaxed chill Zone near mould walls and then followed by a colummar zone; as the concentration of the solute in the remaining melt becomes richer the mode of solidification switches to that of an alloy type due to inereased undercooling and the remaining melt solidifies as equiaxed erystals. Chill zone Equiaxed ay /-Calumnar zone 0) structure an — Figure 3.13: Typical grain structures in (a) pure metals (b) metals with minor alloying constituents, and (c) alloys Pruthyi Loy Serrao SIEC, MangaloreSolidification of Castings 3.3.3 Grain refinement and modification Grain refinement is a process of refining the grain structure to impart better properties. It is simply a technique to coutvol the grain size of the cast structure, Grain refinement aims at reduction or elimination of columnar zone and increase in number of equiaxed grains ‘Mechanism of grain refinement and modification ‘Various practical measures employed for grain refinement and modification are {)_ variation of cooling rate ii) chemical treatment of melt iii) agitation during freezing iv) subsequent heat treatments i) Variation of cooling rate The association of rapid cooling with fine grain size arises from the influence of undetcooling on the comparative rates of nucleation and growth. Higher nucleation rate is observed due to better undereooling and less time is available for the grain growth. ii) Chemical treatment of the melt Effective grain refinement can be achieved by inoculation whieh involves the addition to the melt of small amount of substances designed to promote nucleation. The effectiveness of inoculants or refiners are determined by their structural affinity (ie., similarity of symmetry and lattice parameter) Example: Silica, Aluminium, titanium are used as refiners during casting of steel. iii) Agitation during freezing Nucleation can be brought about by physieal disturbance of undercooled liquid, for example by stirring or gas evolution, This may be attributed to a). the widespread distribution of nuclei originally produced at the surface b) the fragmentation of already growing crystals. Vibration too is a well-known method of structural refinement. Other practical possibilities include electromagnetic stirring with the aid of induction coils, iv) Subsequent heat treatment With the above teclmiques the grain size control can be achieved during the casting stage but if they are found ineffective then the cast specimens may be subjected to subsequent heat treatment operations such as annealing, normalizing, ete Pruthvi Loy Serrao. SSIEC, Mangalore3._ Solidification of Castings 3.4 PROGRESSIVE AND DIRECTIONAL SOLIDIFICATION The mode of solidification marked by the growth of a partially solid and partially liquid zone from the outside to the interior of the casting (as represented by B in figure 3.14) is termed as progressive solidification. It is the product of natural freezing mechanism. A steep temperature gradient promotes progressive solidification and the conditions favoring steep temperature gradient are, ‘© High conductivity mold material «Low conductivity of solidifying metal ‘© High solidification temperature ‘© Short liquidus to solidus range of solidifying metal (A) Riser (B) Progressive solidification (©) Directional solidification (D) Solid metal ) Liquid metal. Temperat distribution Figure 3.14: Progressive and Directional solidification 3.4.1 Directional solidification A progressive solidification which is controlled to progress in a particular direction by designing the gating system sueh that no portion of the casting is isolated fiom liquid metal feeding channel till the completion of solidification is refered to as directional solidification. The directional solidification is represented along C in figure 3.14 Pruthvi Loy Serrao. SUEC, Mangalore3._ Solidification of Castings ‘The conditions favoring directional solidification are, 34.2 direction of solidification from thin section towards heavier sections solidification must start in mold parts furthest from feeder heads feeder heads are last to solidify Methods to achieve directional solidification To obtain a sound casting free fiom shrinkage defects directional solidification is necessary and the various methods to achieve directional solidification are, 1 ye a 3.4.3 ‘Use of gating and risering ~ feeding Use of Padding - design modifications ‘Use of Chills ~ differential cooling Use of exothermic materials — differential heating Control of pouring rate and temperature Use of different thermal conduetivity mold materials for different parts of the mold Factors affecting sol Solidification time (t) Solidification rate (R) ‘Temperature gradient (G) The inherent properties of a casting depend on its solidification structure which is strongly influenced by the solidification time. The total solidification time depends on the casting design (ie., volume to surface area ratio) as explained by Chvorinov and is discussed in next section (seetion 3.4.4). caller Dende Temperature Indepardestuceaton R Distance trom interface Figure 3.15: Effect of temperature gradient and freezing rate on solidification structure Pruthvi Loy Serrao SIEC, Mangalore3,_ Solidification of Castings The effect of solidification rates as well as the temperature gradient on growth pattem has already been discussed earlier. With increasing solidification rates as well as decreasing temperature gradient there is an increased undercooling and hence the growth pattem switches from planar to cellular and then to dendtitie (figure 3.13). But dendritic growth with wider mushy zone is prone to shrinkage porosity and hence steep temperature gradients are favored Steep temperature gradients offers narrow mushy zone and hence results in a sound casting free from defects. 3.4.4 Solidification time - Chvorinov’s Equation Freezing is associated with shrinkage of metal which necessitates feeding and for the effective feeding of a casting it is essential to know the total freezing time. But the total freezing time is profoundly influenced by the casting geometry. Thus it is required to be able to predict the solidification time irrespective of the shape of the casting Chvorinov Rule postulates that the total freezing time of any casting is a direct function of the ratio of its volume to its surface area. Consider a semi-infinite mould, ‘Then, Heat flux (semi-infinite mold) is given as, qa Atma mat Heat loss, _ Ak (im=To) ptt. Q=qxA le ae Figure 3.16 semi-infinite mould 8 2A (Tm =To) Jt _k Latent heat evolved, Q= Vly On energy balance, 2Ak (Tm—T) Jt Fe = pV Hy Pruthvi Loy Serrao. 'SIEC, Mangalore3,_ Solidification of Castings Thus, the ratio of volume to surface area ratio is often used as a measure for designing the feeder heads by estimating the freezing times of feeder heads and the casting sections they are intended to feed, The overall solidification time for a given volume of metal is thus found to be greatest when the ratio V/A is a maximum, ie. in the case of a sphere, becoming progressively less for cylinders, bars and plates References: 1, A text book of Foundry Technology ~ O.P. Khanna 2. Castings - ASM Handbook, Volume 15 3. Foundry Technology ~ Peter Beeley Castings — John Campbell + Pruthvi Loy Serrao SIEC, Mangalore