MECHANISM FOR SOLIDIFICATION OF GRAY CAST IRON & CONDITION FOR OBTAINING DIFFERENT TYPES AND SIZES OF GRAPHITE: Gray

iron refers to a broad class of ferrous casting alloys which are defined as an iron having a chemical composition such that after solidification, a large portion of its carbon is distributed throughout the casting as free or graphite carbon in “flake form” In other words, iron which is normally characterized by a micro structure of flake graphite in a ferrous matrix. Gray irons are in essence iron carbon silicon alloys containing small quantities of other elements. Gray iron always leaves a sooty surface when fractured. For purpose of clarity and simplicity the chemical analysis of gray iron can be broken down into 3 categories. Major elements - the 3 major elements are iron, silicon, and carbon. Both carbon and silicon influence the nature of the castings, so their impact on the solidification is attributed for by introducing a factor CARBON EQUIVALENCE, CE. CE = % C + [% Si / 3] If we take the effect of phosphorus in account, CE = % C + [% Si + % P / 3] Irons with a CE of 4.3 are considered to be of eutectic composition. Most gray irons are hypoeutectic. Nearly all of the properties of gray iron are closely related to CE value. Minor elements - these are phosphorus and the two inter related elements like manganese and sulphur. Phosphorus increases the fluidity of iron, by forming a low melting phosphide called steadite. At high levels it can promote shrinkage

porosity while very low levels can increase metal penetration into the mold. Its concentration is 0.02 – 0.10 %. Sulphur plays a significant role in nucleation of graphite in gray iron. Sulphur levels should be in the range of 0.05 – 0.12 %. Sulphur content should be balanced with the manganese to promote the formation of manganese sulphides. This is achieved by % Mn >= 1.7% S + 0.3% Trace elements – trace elements like antimony, arsenic, bismuth, boron, chromium, nickel can be present or can be added in the gray iron to induce some properties. All the elements normally present in gray iron exert some influence on the microstructure of the iron. The effects of different elements on the properties are discussed below: Carbon: Carbon in gray iron is present from about 2.5 to 4.5 per cent by weight. Carbon occurs in two different forms. Elemental carbon in form of graphite flakes and combined carbon as Fe3C. The degree of graphitization may be assessed by the following relationship % total carbon = % graphitic carbon + % combined carbon If graphitization is complete the percentage of total carbon and percentage of graphitic carbon is equal. If no graphitization has occurred, the percentage of graphitic carbon is zero. If about 0.5 to 0.8 % combined carbon exists in a gray iron, it generally indicates that the microstructure is largely pearlitic since pearlite in gray iron having about 0.2 % silicon forms from the austenite eutectoid containing about 0.60 per cent carbon. For sufficient graphitization to develop during solidification of a true gray iron, certain minimum total carbon content necessary, which is

under 0. As such it hardens and strengthens the ferrite. MnS or complex manganese iron sulphides.20 %. but it will cause nucleation and graphitization in the solid state at high temperatures. Sulphur : sulphur which may be present up to about 0. are found. partly white and partly gray results. Silicon promotes the graphitization.0 to 3. silicon occurs dissolved in the ferrite of gray iron. but this value depends on Silicon percentage in the iron. The manganese sulphides begins to precipitated early. and .25 percent. High sulphur percentage favors the retention of a completely pearlitic microstructure in a gray iron.around 2. Silicon : silicon is present in gray iron about 1.010% S will graphitize most completely.50 per cent by weight. whereas 2% Silicon in a ferritic iron raises the hardness to about 120 t 130 BHN. The eutectic shift is described by the following relationshipEutectic Carbon % ( in Fe-C-Si) = 4. Low percentages are not sufficient to cause graphitization during solidification. is on of the important modifying elements present in gray irons.30 – 1/3 X %Si (in iron) Microstructurally. depending on the manganese content. Increasing silicon percentage shift the eutectic point of the iron carbon diagram to the left. A low sulphur iron-sillicon-carbon alloy. and a mottled iron. This effect is causes sulphur to be known as an element restriciting graphitization (carbide stabilizing) Manganese: when manganese is present. Certain silicon percentages will cause limited graphitization during solidification. Ferrite in pure iron will measure 80 to 90 BHN.

continue to do so during the entire freezing process. following rule offers a favorable combination of manganese and sulphur percentages: 3 X % S + 0. Because of the segregation the steadite usually adopts a cellular pattern characteristic of the eutectic cell size developed during the solidification process. The Excessive phosphorus content percentage of steadite present in the final stricture may amount to ten times the percentage of phosphorus. Therefore manganese above that is necessary to react with the sulophur will assisit in retaining the pearlitic microstructure. Because it forms a eutectic as it segregates. phosphorus is often looked upon as increasing the tendency for a particular iron composition to be eutectic type alloy. and are therefore randomly distributed. formed. For commercial gray irons in which a pearlitic microstructure is desired.35 = % Mn Phosphorus: Phosphorus results in formation of steadite. For this reason the Carbon Equivalent is sometimes modified to include a factor fpr phosphorus as follows: CE = % C + [% Si + % P / 3] raises the hardness and brittleness of gray iron because of the steadite . The effect of Mn alone as an alloying element is to promote resistance to graphitization.

.carbon.silicon ternary phase diagram taken at 2% Si.SOLIDIFICATION OF GRAY CAST IRON: Most gray irons are hypo eutectic in nature. The sequence of events associated with the solidification of hypo eutectic irons can be studied with simplified version of the iron.

primarily freezing begins with the formation of pro eutectic austenite dendrites.Figure 1: Simplified iron-carbon-silicon phase diagram at 2% Si At temperatures above point 1 the iron is entirely molten. These dendrites grow and new dendrites form as the . As the temperature is decreased and the liquidus line is crossed.

carbon is rejected into the remaining liquid. The type of solid formed depends on whether the solidification is following the metastable or stable eutectic reaction. This takes place between points 2 and 3. When eutectic solidification is complete. which is marked by the points 1 and 2.temperature drops through the primary freezing range. At eutectic temperature solidification of eutectic occurs by certain amount of under cooling. Iron carbide plus austenite forms during the metastable reaction. Graphite plus austenite forms during the stable reaction. rapid cooling promotes a fin grain size. the liquid transform in two solids. Once this composition is achieved. During the formation of the austenite dendrites. Lower CE produces large dendrites because the temperature interval between the liquidus and eutectic lines is greater for those irons than those with a greater CE. As expected. In the temperature interval between the eutectic and eutectoid transformations. and any further reaction takes place in the solid state. the high carbon austenite rejects the carbon. no liquid metal remains. Dendrite size is governed by the CE of the iron and solidification rate. The nucleus which subsequently grows to form eutectoid solid may be attached to the tip of the austenite dendrite (endogenous solidification) or may form an independent nuclei. which . The degree of under cooling determines the mode of solidification of the eutectic.3 %. The carbon content of the liquid increase until it reaches the eutectic composition of 4.

Condition for obtaining different types and sizes of graphite: The following discussion is for ASTM A 247 Type A – this type of flakes are randomly distributed and oriented throughout the iron matrix. A certain amount of under cooling is necessary fro nucleation to occur. At the end of eutectic solidification the low melting point contents of the liquid namely p. no significant changes in micro structure occur below the eutectoid transformation line. . In unalloyed gray irons. which under equilibrium conditions takes place between points 4 and 5. This allows the austenite to acquire the composition needed for the eutectoid transformation. This type of graphite is found in irons that solidify with a minimum amount of under cooling. and is suitable if mechanical properties are to be optimized.diffuses to the graphitic flakes. Increased cooling rate and nucleation affects the solidification characteristics of the gray cast iron.constituents will form an envelope in the eutectic and solidifies as a layer separating the neighboring eutectic grains. depending on such factors as the cooling rate and alloy content of the iron. This transformation involves the decomposition of austenite into pearlite or pearlite plus ferrite.

Type B – it is found in irons of near eutectic composition that solidify with a grater amount of under cooling than that associated with type A. random orientation CE is 3. CE is 4.0 %.3 %. This is formed when graphite precipitates in the primary freezing of irons. . Type C.4 – 4. rosettes containing fine graphite that are characteristics of type B.Figure 2: uniform distribution. Figure 3: rosette grouping CE is approximately 4. precipitate at the start of eutectic solidification. The heat of fusion associated with their formation increase the temperature of the surrounding liquid.5 %. This is obtained when hypo eutectoid iron are cooled at faster rate.superimposed flake sizes with random orientation. thus decreasing the under cooling and resulting in the formation of type A graphite.

It greatly reduces the mechanical properties of the iron and produces a rough surface finish when machined.Figure 4: superimposed flake sizes. Type E – in this the graphite has inter dendritic segregation with preferred orientation of graphite flakes. It is however desired in application requiring a high degree of surface finish. random orientation Both types are found in the inter dendritic regions.this is formed when the amount of under cooling is high but it is not sufficient to cause carbide formation. This type of graphite is randomly distributed. Figure 5: inter dentritic segregation. Type D. random orientation It appears as coarse plates. . This is obtained with low CE and with rapid cooling.

Figure 6: interdentritic segregation. short flakes. Small flakes because they disrupt the matrix to lesser extent. are desired when maximum tensile properties and a fine smooth surface finish is to be obtained. Strongly hypoeutectic irons and irons subjected to rapid solidification generally exhibits small. The large flakes are suitable for applications requiring high thermal capacity and thermal conductivity. preferred orientation Large flakes are associated with irons having high CE and slow cooling rates. .

It is recognized that 2 irons with the same apparent composition can have dramatically different micro structures and properties if one is inoculated and the other is not. The purpose of inoculation is to increase the number of nuclei in molten iron and decrease in the eutectic cell size. improvements in mechanical properties. It is considered that . Control accomplished by the addition is defined as inoculation. and a reduction of chilling tendency that are not explainable on basis of composition changes with respect to silicon.INOCULATION AND ITS INFLUENCE ON THE STRUCTURE AND PROPERTIES OF GRAY CAST IRON: Inoculation is defined as the late addition of an element or elements to the molten iron to produce changes in graphite distribution. As the amount of inoculants is increased. until a point of diminishing returns is reached. a reduction in chill is realized.

75 - - - 1.75 0. Instead. Intermediate.this increase in number of cells is accomplished by nucleation of eutectic solidification and the graphite phase. It is convenient to group inoculants into 4 performance categories. The calcium when mixed with barium falls in the intermediate group.90 1. When undercooling is minimized. which has the greatest tendency for chill reduction.25 0.25 0.2 - - .75 -1.60 Ba C e TRE Ti Mn Sr Others - 0. a more uniform microstructure consisting of small type A graphite flakes is produced. Strontium or calcium plus cerium alloys are the high potency inoculants.5 - - - - - - - 1. Due to inoculation graphite precipitation can start with minimum amount of under cooling.0 11.25 Ca 0. The calcium bearing alloys fall into the standard category.50 max 0.51. there is a corresponding reduction in the tendency to form eutectic carbide or white iron.5 -1. Stabilizing inoculants normally employ chromium as the major element. High potency and Stabilizing. Standard. These micro structural changes can result in improved machinability and mechanical properties. Performanc e category Standard Si 46 50 74 79 74 Intermedi 79 46 Al 0. which is referred to as chill.

515 - - - - 0.81.50 0.5 0.5 - - - - - - - - - 91 1 - 10.6 1.N .53 0.5 1.ate 50 60 65 70 74 max - - 5 ma x 712 - 1.25 0.H.25 5-7 4-6 - - - 42 44 50 55 50 High 55 36 40 73 Stabilizin g 78 611 - - - 91 1 91 1 91 1 - - - - - - - - 0.75 1.25 1.81.10 max max - - - 0.0 - - 0.5 0.3 0.25 0.50 0.51.71.75 1.81.50 max max - - - - - 48-52 chromiu m Table 1:Composition of ferro silicon inoculants for gray iorn Ioculant Tensile Impact B.

7 20. Al 0.5” inch-s/g Table 3: Comparison of properties of regular Gray Cast Iron and Inoculated Gray Cast Iron. Mg 2% Fe-Si 80%.6%.5 16. .Si (1. 70% Si 0.8 17 24.1 Strength 21.4% Al.5 17.2 29. Al 1% Fe-Si 70%.1 222 220 21. Zn 2% 20.5 17.4” inch-s/g 20.4%.9 20.3% Al.1 22. 70% Si Normal – commercial Ferro. Al0. Ca 2%. Al0.8 16.4 18.4% Al. Ca 2%. Al0.9 18.9 27.9 25 224 205 208 216 215 220 Table 2: Comparison of mechanical properties of various inoculated Cast Irons Type of Iron Gray Fe Inoculated Gray Cst Iron Shrinkage 3/16” ft/ft 1/4” ft/ft Fluidity 3.3% Fe-Si 75%. 7% Ca) Fe-Si 75%. Al 2.strength Commercial low Alferrous 0.3% Fe-Si 60%.8 17.1% Fe-Si 75%.8 26.

. and they help to eliminate ferrite in heavy sections.Stabilizing inoculants are designed to promote pearlite and at the same time provide graphitization during solidification. Because these alloys an be difficult to dissolve. They are useful in producing high strength castings with a minimum of chill. the are not suggested for mould addition.

. Careful addition and relatively higher temperatures are needed to ensure its complete solution.0 Graphite or ferro .silicon based alloys can also be used as an inoculants. Property changes –  graphite has been found to promote extremely high eutectic cell counts. The graphite used must be highly crystalline. But graphite is rarely used by itself and most often mixed with crushed ferro silicon.Figure 6: general classification of inoculants showing chill reduction in iron with carbon equivalence of 4.

the effect of time can be greatly reduced. . the alloy is added to the metal stream as it flows from the transfer ladle in to the pouring ladle. it helps to distribute the reactive elements throughout the melt  The reactive elements in addition to reacting with iron. Stream inoculation requires that the alloy be added to the stream of metal flowing from the pouring ladle in to the mold. A small heel of metal should be allowed to accumulate in the bottom of ladle prior to inoculation. By adding inoculant late in the process. Inoculation methods: Ladle inoculation is a common method for inoculation. react readily with sulphur and oxygen. In this method. their addition may therefore lead to dross formation. Addition of alloys to bottom of an empty ladle may cause sintering and reduction in inoculant effectiveness. Because ferrosilicon dissolves readily. Problems may also arise if the alloy is added to a full ladle because the material can become entrapped in the slag layer that forms on the surface. Thos allows the inoculant to be mixed and evenly distributed. Stream and mold inoculation are two latest methods of inoculation that ar believed to promote more uniform quality from casting to casting.

Inoculants fir this method can be crushed material. alloy dissolution rate is an important factor. As in stream inoculation. powder bonded into a pellet. at the base of the sprue or in suitable chambers in the runner system. The same inoculants used to treat iron in the ladle can be used for stream inoculation. such a sin pouring basins.Figure 7: schematic showing the principle of stream inoculation One of the electro pneumatic devices used to sense when the metal flow starts and stops is shown in figure 7. but less of a performance distinction is has been observed amongst them. or pre-cast slugs or blocks. Mold inoculation involves placement of the alloy in the mold. Too large a size can cause plugging of the equipment and incomplete dissolution. . The pre-cast and bonded alloys are designed to dissolve at a controlled rate throughout the entire pouring cycle. An uniform and consistent size is an important factor in stream inoculation. This device ensures that that the alloy is dispensed in such a manner that the last metal entering the mold is treated similarly to first metal.

and because the castings are inoculated to the same extent. thus eliminating heat treatment. .There are several advantages of late inoculation over ladle inoculation. It has also been observed that the late inoculation is more successful in preventing carbide formation in thin sections. there is greater consistency in structure form casting to casting. Fading is virtually eliminated.

Carl.W. Loper 3.J. 2.Heine. www. pg 629-645.Craig.K. www.htm retrieved on 5-10-2010 at 3:50 pm .htm.C. M. “Ferrous Casting Alloys”. . pg 575-611. Richard . D.mifco.com/search=gray+cast+iron+metallurgy.REFERENCES 1. Philip .com/inoculation.McCluhan. R. 30th reprint 2005. “Principles of Metal Casting” Tata Mc Gram Hill Publications. retrieved on 5-10-2010 at 3:30 pm 4. Hornung and T.B. ASTM Handbook.wikipedia. Rosenthal.

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