August 2011

Serial Report

Colour Metallography of Cast Iron

By Zhou Jiyang, Professor, Dalian University of Technology, China Translated by Ph.D Liu Jincheng, Fellow of Institute of Cast Metal Engineers, UK

Note: This book consists of five sections: Chapter 1 Introduction, Chapter 2 Grey Iron, Chapter 3 Spheroidal Graphite Cast Iron, Chapter 4 Vermicular Cast Iron, and Chapter 5 White Cast Iron. CHINA FOUNDRY publishes this book in several parts serially, starting from the first issue of 2009.

Chapter 5

White Cast Iron ()

White cast iron or white iron refers to the type of cast iron in which all of the carbon exists as carbide; there is no graphite in the as-cast structure and the fractured surface shows a white colour. White cast iron can be divided in three classes: Normal white cast iron this iron contains only C, Si, Mn, P and S, with no other alloying elements. Low-alloy white cast iron the total mass fraction of alloying elements is less than 5%. High-alloy white cast iron the total mass fraction of alloying elements is more than 5%. These three classes of white cast iron have similar crystallization rules and structures. The as-cast structure contains a large amount of carbides that make these irons very hard and brittle, and difficult to machine. These irons are wear resistant due to their high hardness and find wide applications for abrasion-resistant components.

5.1 Introduction
5.1.1 Normal white cast iron
Normal white cast iron, without any alloying elements, is used mainly in engineering for the following applications: (1) Abrasion resistant components without especially high wearresistant requirements. (2) White cast iron for the manufacture of malleable iron castings. The composition of normal white cast iron is listed in Table 5-1. The composition characteristics for abrasion resistant components are high carbon and low silicon contents, so as to increase the amount of carbides to improve wear resistance. However, the chemical composition of white cast iron for making malleable iron castings contains higher silicon and lower carbon, to accelerate graphitization during the annealing process and improve the morphology of the resultant graphite.

Table 5-1: Typical composition of normal white iron (mass %)

No 1 2 C 3.5 4.5 2.4 2.8 Si 0.4 1.2 1.2 1.8 Mn 0.2 1.0 0.3 0.6 P 0.1 0.3 0.1 S 0.1 0.2 Application Abrasion resistant castings Malleable iron castings

5.1.2 Low-alloy white cast iron

Low-alloy white cast iron occurs when alloying element(s) are deliberately added, but their total mass fraction is less than 5%. The functions of alloying elements are to increase the microhardness of carbides, strengthen the metal matrix and further improve wear resistance. Alloying elements normally used include chromium, nickel, molybdenum, copper, vanadium, titanium and boron. Normally, for low-alloy white cast iron, the silicon content is lower (generally w(Si) = 0.4% 1.2%) to ensure a white structure is obtained; in this case the range of carbon content is wider and is usually w(C) = 2.4% 3.6%. Low-alloy white cast iron is used mainly for abrasion resistant castings.

5.1.3 High-alloy white cast iron

According to the type of alloying elements used, high-alloy white cast irons can be sub-divided into four systems: (1) nickelchromium system; (2) chromium-molybdenum system; (3) high chromium system and (4) tungsten system. These systems, (except the tungsten system) are included in the Chinese National Standard for white cast irons; see Table 5-2. (1) Nickel-chromium system The irons within this system are known internationally as Nihard irons; generally the nickel content is w(Ni) = 3.3% -7.0%. The predominant characteristics of Ni-hard irons are that they have high strength and toughness and can be heat treated at a relatively low temperature, which is favourable for those large castings which are not suitable for heat treatment at high temperature and 337

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are prone to cracking. Table 5-3 lists the chemical composition of Ni-hard cast irons listed in the ASTM standard; types I, II and IV correspond to grades KmTBNi4Cr2-GT, KmTBNi4Cr2-

Vol.8 No.3 DT and KmTBCr9Ni5 respectively listed in the Chinese National Standard.

Table 5-2: Specification and composition of Chinese abrasion resistant white irons (GB/T8263-1999)
Specification KmTBNi4Cr2-DT KmTBNi4Cr2-GT KmTBCr9Ni5 KmTBCr2 KmTBCr8 KmTBCr12 KmTBCr15Mo KmTBCr20Mo KmTBCr26

Composition (mass %) C 2.4 3.0 3.0 3.6 2.5 3.6 2.1 3.6 2.1 3.2 2.0 3.3 2.0 3.3 2.0 3.3 2.0 3.3 Si 0.8 0.8 2.0 1.2 1.5 2.2 1.5 1.2 1.2 1.2 Mn 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Cr 1.5 3.0 1.5 3.0 7.0 11.0 1.5 3.0 7.0 11.0 11.0 14.0 14.0 18.0 18.0 23.0 23.0 30.0 Mo 1.0 1.0 1.0 1.0 1.5 3.0 3.0 3.0 3.0 Ni 3.3 5.0 3.3 5.0 4.5 7.0 1.0 1.0 2.5 2.5 2.5 2.5 Cu 1.2 1.2 1.2 1.2 1.2 2.0

Note: Ni-hard irons: w(S)0.15%, w(P)0.15%; KmTBCr2: w(S)0.1%, w(P)0.15%. All other specifications: w(S)0.06%, w(P)0.10%. DT means low carbon and GT means high carbon in Chinese Pinyin by initials. Normally, these grades should contain molybdenum.

Table 5-3: Chemical composition of American Ni-hard irons (ASTM A532M-93a) (mass%)
Types A B C D Specification Ni-hard Ni-hard Ni-hard Ni-hard C 2.8 3.6 2.4 3.0 2.5 3.7 2.5 3.6 Mn 2.0 2.0 2.0 2.0 Si 0.8 0.8 0.8 2.0 Ni 3.3 5.0 3.3 5.0 4.0 4.5 7.0 Cr 1.4 4.0 1.4 4.0 1.0 2.5 7.0 11.0 Mo 1.0 1.0 1.0 1.5 P 0.3 0.3 0.3 0.10 S 0.15 0.15 0.15 0.15

(2) Chromium-molybdenum system Cr-Mo high-alloy white cast irons contain w(Cr) = 7% - 23% and w(Mo) 3%. There are mainly four types of Cr-Mo highalloy white cast irons in the Chinese National Standard (their chemical compositions are shown in Table 5-2): KmTBCr8 KmTBCr12 KmTBCr15Mo KmTBCr20Mo Among these, the medium Cr white cast iron (KmTBCr8) is the wear resistant material with Chinese characteristics, especially the high Si/C ratio; medium Cr white cast iron and medium Cr-Si white cast iron (both belong to KmTBCr8) have been widely used in China. The main features of these irons are the alloying of C and Cr to give a ratio of Cr/C3 and the formed eutectic carbide is of the type M7C3, thus giving the irons excellent combination of properties and a higher performance/price ratio. KmTBCrl2 has limited hardenability, so it is not normally heat treated, except for stress relief. The as-cast matrix structure is pearlite (which has good impact fatigue strength) and type M7C3 eutectic carbide. KmTBCr15Mo is a type of high Cr white cast iron, which has been studied deeply and is widely used. It is normally air quenched 338

and tempered and has high hardness, strength and toughness, with excellent resistance to erosion and impact-abrasion. KmTBCr20Mo iron has a high Cr content and thus a higher Cr/C ratio; hence it has better hardenability, hardness, toughness and corrosion resistance. This iron is suitable for thick section components used under certain impact and wet abrasive-wear conditions. (3) High chromium system The irons under this heading have the highest Cr content within the high-alloy white cast iron family. High Cr gives these irons good wear resistance, corrosion resistance, impact toughness and hardenability, all better than the properties of KmTBCr20Mo white cast iron; the resistance to corrosive and abrasive wear, and wear at elevated temperature are also remarkably improved. In an acidic medium, white cast iron with w(Cr) = 28% has much better wear resistance and high-temperature oxidation resistance than a white cast iron with w(Cr) = 15%. The carbon content of this white cast iron can vary between w(C) = 2.0%-3.3%; increasing the Cr content and reducing the C content can improve its corrosion and abrasion resistance. Cr26 high Cr white iron castings are used mainly after quenching and tempering, but can also be used ascast.

August 2011 (4) Tungsten system White cast irons within the tungsten system represent a new type of abrasion resistant material, which has higher abrasion resistance; some casings made from the tungsten system have a service life close to or equal to the service life of Cr-Ni-Mo high-alloy white cast iron. According to the content of W and C, tungsten alloy white cast irons can be divided into three classes:

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hypo-eutectic, eutectic and hyper-eutectic (see Table 5-4). When the mass fraction of carbon is between 2.7% - 3.3%, with increasing tungsten, the carbon supersaturation of the iron changes from hypoeutectic to eutectic and then to hypereutectic: w(W) 18% Hypoeutectic w (W) = 18% 22% Eutectic w (W) 22% Hypereutectic

Table 5-4: Classification and as-cast structure of the tungsten system white cast irons

Type of white cast iron

w (W) (%)

w(C) (%)

W/C
2

As cast structure
Primary austenite + divorced network-like binary eutectic (M3C+) Primary austenite + divorced network ternary eutectic (M3C+) + ternary eutectic (M6C+M3C+) Binary eutectic (M3C+) + ternary eutectic (M6C+M3C+) Blocky primary M6C + fishbone-like binary eutectic (M6C+) + ternary eutectic (M6C+M23C6+) Dendritic primary M6C + fishbone-like binary eutectic (M6C+)

Hypoeutectic

18

2.7 3.3 26

18 22 Eutectic 23

2.7 3.3 2.5 2.7 3.3 >6

Hypereutectic

> 22 2.0 2.5 >6

High tungsten white cast irons have high hardness and good impact toughness due to the presence of hard, tough, primary carbide and binary eutectic. Thus, high W white cast iron often takes eutectic or hypereutectic composition: w(W) = 20% 30%, w (C) = 2.0% 2.5%.

5.1.4 Roles of alloying elements in white cast iron

Carbon: With increasing carbon content, the hardness and wear resistance of a white cast iron are increased. However, transverse fracture toughness is decreased and brittleness is increased. The higher the carbon content, the lower the impact toughness; the linear relationship is shown in Fig. 5-1. Increasing the carbon content increases the amount of hard and brittle eutectic carbides, and also decreases hardenability; thus when choosing the carbon content, comprehensive consideration should be taken.

Fig. 5-1: Relationship between impact toughness and carbon content of high Cr [w(Cr) = 15%] white cast iron

Chromium: The main roles of Cr in white cast iron are: forming carbides, improving corrosion resistance and stabilizing the structure at high temperature. Increasing both the carbon and chromium contents will increase the amount of carbides, and thus improve wear resistance, but will also decrease toughness. The amount of carbides can be estimated from the following equation: Mass fraction of carbides = w(C)12.33% + w(Cr)0.55% -15.2%. When calculating, if w(C) = 3.0%, then 3.0 is put into the equation to replace C, the same is for Cr. It can be seen from the equation that the effect of chromium in increasing carbide content is not as significant as that of carbon. Thus, to increase the amount of carbide present, it is normal to increase the carbon content. In the Cr-Mo system irons, the volume fraction of carbides is about 20% - 40%; part of the Cr forms carbides, whilst the remainder dissolves in the metal matrix to improve hardenability. The amount of Cr dissolved in the metal matrix [l] is: Mass fraction of Cr in metal matrix = 1.95 (Cr/C)% 2.47%. With increasing Cr content, the structure and properties of alloyed white cast iron change substantially; the carbide is changed from (Fe,Cr)3C to (Fe,Cr)7C3; the hardness of the carbide is markedly increased and at the same time, the toughness is improved. Therefore, in addition to higher wear resistance, high Cr white cast iron also has superior toughness and strength compared with low-alloy white cast iron. Figure 5-2 shows the relationship between the mechanical properties and Cr content for a series of white cast irons; it can be seen from the figure that with increasing Cr content, both the strength and the deflection vary significantly. When the mass fraction of Cr is lower than 7%, there exists a continuous network of M7C3 type carbides, which result in lower strength and deflection. When the mass fraction of Cr is above 9%, 339

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a discontinuous M7C3 type of carbide is formed, and the strength and the deflection are both improved. When the mass fraction of Cr is increased to 12% 19%, the properties reach their highest values. If the mass fraction of Cr exceeds 25%, hypereutectic carbide is formed; the fracture changes to a coarse needle-like appearance and the mechanical properties are decreased. In addition, a high Cr content will increase the corrosion resistance and high-temperature oxidation resistance. Most high Cr white cast irons have a Cr mass fraction between 11% - 23% and a Cr/C ratio between 4 - 8.

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Fig 5-3: Influence of Mo on the hardenability of high Cr white cast iron with different w(Cr)/w(C) ratios[3]

Fig. 5-2: Influence of Cr on strength and deflection of white iron [2]

Molybdenum: In white cast irons, approximately 50% of the mass fraction of Mo forms Mo2C, 25% enters other carbides and the remaining 25% dissolves in the metal matrix. The Mo which enters the metal matrix improves hardenability of the iron; with increasing Mo content, the hardenability also increases. The ability of Mo to improve the hardenability in white cast iron is related to the Cr/C ratio, as shown in Fig. 5-3. When added together with any one of Cu, Ni or Cr, or with Cr+Ni together, the effect of increasing hardenability is more significant. Also, in Ni-Cr type martensitic white cast iron, Mo has the ability to replace Ni. Nickel: Nickel is insoluble in carbides and all of it dissolves in the austenite, thus its only purpose is to improve the hardenability. The addition of 2.5% Ni to low Cr white cast iron can promote a fine and hard pearlitic structure. When w(Ni)4.5%, the formation of pearlite can be inhibited. With further increasing in Ni content [w(Ni)6.5%], austenite is stabilised and martensite transformation occurs at low temperature or in the as-cast state. For example, Ni-hard iron in the as-cast condition has a structure of martensite + M7C3 eutectic carbides. For thick section, high Cr white iron, the addition of w(Ni) = 0.2%-1.5% can inhibit the formation of pearlite; if Ni and Mo are added together, the inhibiting effect is more significant. Copper: In low Cr and high Cr martensitic white cast irons, copper has the effect of inhibiting the formation of pearlite. Because of limited solubility in austenite, too much Cu should not be added; a suitable amount is w(Cu) 2.5%, thus copper cannot replace Ni in Ni-hard irons. A combined addition of Cu and Mo can markedly improve the hardenability. However, excessive Cu 340

causes the percentage of retained austenite to increase and hence has an adverse effect on the wear resistance. Reducing the amount of C and Cr can decrease the stability of austenite, and at the same time decrease the amount of martensite, resulting in hardness to decrease. Vanadium: Vanadium is a strong carbide promoter and forms primary carbide or secondary carbide, and increases the degree of chilling. The strong chilling effect of vanadium can be balanced with Ni, Cu or by increasing the carbon and silicon contents. In addition, a small amount of vanadium, for example w(V) = 0.1% - 0.5% can refine coarse columnar crystals. Because it combines with carbon in the liquid iron, this reduces the carbon content in the metal matrix; vanadium increases the martensite transformation temperature and causes the microstructure to transform into martensite under casting conditions. Silicon: Silicon is a restricted element in white cast iron since it increases carbon activity and thus easily promotes graphite formation and retards the formation of carbides. In addition, silicon reduces the hardenability and promotes pearlite formation, therefore having an adverse effect on the wear resistance. In low alloy white cast iron, w(Si) is about 1%; in high Cr white iron, silicon is often controlled w(Si) = 0.4% 0.7%. Too low a silicon content (for example, w(Si) 0.4%) is unfavourable for deoxidation. Different from general conclusions, it was reported [4] that in medium Cr white cast iron, silicon has a tendency of increasing the amount of carbide (Fe,Cr)7C3.

5.2 Carbides in white cast iron

Carbide is an important constituent phase in white cast iron and its volume fraction can reach as high as 40%; its type, chemical composition, amount, size, shape and distribution all have an important influence on the properties of the iron. The elements which can form carbides are the transition

August 2011 elements in the periodic table, such as Fe, Mn, Cr, W, Pt, V, Nb, Ti, etc. The atoms of all these elements have an incompletely filled d-electron shell. The tendency to form carbides is related to the degree of incompleteness of their d-electron shell; the more unfilled vacancies in the d-electron shell the element has, the stronger the ability to form carbide and the more stable the carbide. The formation ability in descending order is as follows: Ti, Nb, Zr, V, Mo, W, Cr and Mn (Fe). Carbides have a close-packed structure or slightly distorted, close-packed structure arranged by interaction of these metal and carbon atoms, which form an interstitial structure consisting of a metal atom sub-lattice and a carbon atom sub-lattice. The sublattices of metal atoms are obviously different from the metal lattices from which they are formed, but they still belong to the typical face-centred, body-centred and close-packed hexagonal (or complex) structures. If the interstice in a metal sub-lattice is large enough to contain a carbon atom, a simple close-packed structure is formed. Therefore, the ratio of carbon atom radius rc to atom radius of transition metal rM, rc/rM, will determine the type of carbide formed.

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(2) Interstitial carbides with a complex hexagonal, close-packed structure. When rc/rM 0.59, carbon cannot form a simple, closepacked interstitial phase, but forms an interstitial compound with a very complex crystal lattice. The carbides of Cr, Mn and Fe belong to this complex close-packed structure. Among them, M23C6 and M6C are complex cubic, M7C3 is complex hexagonal and M3C has an orthorhombic lattice. Commonly observed carbides with a complex close-packed structure are: M3C type Fe3C, Mn3C or (Cr,Fe)3C, Kc for short; M7C3 type Cr7C3, Mn7C3 or (Cr,Fe)7C3, K2 for short; M23C6 type Cr23C6, Mn23C6, and ternary carbides Fe21W2C6, Fe21Mo2C6, (Cr, Fe)23C6, K1 for short. M6C type Fe3W3C, Fe4W2C, FeMo3C, Fe4Mo2C ternary carbides and so on. (a) M 3C type carbide: The carbide most commonly seen is cementite in normal un-alloyed white cast iron. The crystal structure of cementite is an orthogonal lattice, with lattice constants a = 0.45144 nm, b = 0.50787 nm, c = 0.67287 nm [5]. The crystal structure of cementite is illustrated in Fig. 5-5. Around each carbon atom there are six iron atoms which form an octahedron; all the axes of the octahedron are inclined at an angle to each other, to form a rhombohedral crystal. Because each octahedron has a carbon atom in it, and each iron atom is shared between two octahedrons, the atomic ratio of Fe and C in the molecular formula Fe3C is satisfied exactly. The projection of an octahedron of cementite is a rhombic, chain-like structure (see Fig.5-6). When observed as a whole, the rhombus planes are parallel, showing a lamellar arrangement. In each rhombohedral crystal unit, the Fe-C atoms are connected by a covalent bond, which is realized by the covalent electrons of four carbon atoms and 3d-electrons of the nearest iron atoms at the apexes of the rhombohedral unit. The other two iron atoms are situated in neighbouring rhombohedral units where the iron atoms are near to the next carbon atoms, therefore a strong connection is formed between the layers. In addition, the electronegative difference between iron and carbon strengthens the connection of Fe-C, thus the connective force of Fe-C is about twice as strong as that of Fe-Fe [6]. Whilst the layers are connected by a metallic bond between iron atoms, the connection is weak, thus resulting in the strong anisotropy of cementite. Addition of a third element into an iron-carbon binary alloy can change the connective strength of the Fe-C bond. The

5.2.1 Types of carbides

According to the structure of their crystal lattice, carbides fall into two types: (1) Interstitial carbide with a simple, close-packed structure. When rc/rM 0.59, carbon atoms are located at the interstices of the simple lattice, forming an interstitial phase, which is different from the original metal crystal lattice; the elements Mo, W, V, Ti, Nb and Zr belong to this type. The formed carbides include: MC type WC, VC, TiC, NbC, ZrC M2C type W2C, Mo2C If a variety of transition metals exist at the same time, complex carbides will form. If three conditions (lattice type, electrochemical factor and size factor) are satisfied, the metal atoms in the carbides can displace each other; for example, TiC-VC system forms (Ti,V)C; VC-NbC system forms (Nb,V)C; TiC-ZrC system forms (Ti, Zr)C, etc. The metal atom M in MC type carbide has a simple face centred cubic structure, the octahedral interstices all are occupied by carbon atoms, so M : C = 1 : 1, and the crystal structure type is that of NaCl, see Fig. 5-4.

Fig. 5-4: NaCl type structure

M 2C carbide possesses a hexagonal, close-packed structure and examples are W2C, Mo2C, V2C and Nb2C; carbon atoms are situated at the tetrahedral interstices.

Fig. 5-5: Crystal structure of cementite

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Fig. 5-6: Chain-like crystal structure of cementite[6]

Fig. 5-7: The structure of (Cr, Fe, W, Mo)23C6 crystal cell unit [8]

elements enhancing the Fe-C bond will further stabilize cementite; whilst the elements that weaken the Fe-C bond cause Fe-C to be broken-down easily, thus reducing the stability of cementite and promoting graphitization. Some elements have limited the solid-solubility in Fe3C and form alloyed cementite. The elements which can dissolve in Fe3C are[7]: w(Cr)28%, w(Mo)14%, w(W)2%, w(V)3%. The formed alloyed cementite, (Fe, M)3C, has a high valency, stronger coherent bond and is more stable [8]. (b) M7C3 type carbide: A typical representative of type M7C3 carbide is Cr7C3, which consists of 56 Cr atoms and 24 carbon atoms and has an even more complex crystal system than M3C. The three crystal systems of Cr7C3 are hexagonal, orthogonal and rhombohedral; their lattice constants are listed in Table 5-5.
Table 5-5: Crystal type of M7C3 carbide [9, 10]
Crystal system/type Hexagonal Lattice constant nm a = 0.688 b = 0.454 a = 0.454 b = 0.688 c = 1.194 a = 1.398 b = 0.452 6.92 Density gcm-3

on the edges of the large cube, and at the same time are located in between the cuboctahedron and small cube; hence each carbon atom has 8 neighbouring metal atoms, as shown in Fig. 5-8.

Fig. 5-8: The relationship of a C atom and neighbouring metal atoms in the Cr23C6 crystal cell unit [8] (nm)

Orthogonal Rhombohedral

The Cr in Cr7C3 can be partially replaced by Fe and Mn; if replaced above 60% by Fe, then the carbide changes to (Fe,Cr)7C3. (c) M23C6 type carbide: This is a cubic crystal lattice cell consisting of 92 atoms; the structure is shown in Fig. 5-7. The large crystal cell is divided into 8 small cubes; on the apexes of the small cubes, there alternatively exist atom groups which become cuboctahedron or cube. Normally, the M in the carbide is mainly Cr, forming M23C6; sometimes, the M is also mainly Mn. When containing more Mo and W, Fe21Mo2C6 carbide or Fe21W2C6 carbide is formed. In the structure of Cr23C6, the centre of each small cube also has an additional atom which can only be replaced by W. When replaced by W, the crystal type (Fe, W, Cr)23C6 is formed. The carbon atoms in the Cr23C6 crystal cell are situated 342

(d) M6C type carbide: This carbide is a complex interstitial, ternary compound consisting of W, Fe and C, which exists in high W cast iron and has a micro-hardness above 2,250 HV, and good strength and toughness properties. The carbides in as-cast, high W iron consist of M6C + M3C, or M6C + M23C6, or M6C + M7C, but the main phase is still M6C. This phase is a meta-stable structure; it will disappear after equilibrium treatment, to be replaced by WC. M6C has a face-centred cubic lattice consisting of 96 metal atoms and 16 carbon atoms, with 48 W atoms distributed at the apexes of octahedrons; the lattice structure is shown in Fig. 5-9. Among the 48 iron atoms, 32 are distributed on the apexes of 8 tetrahedrons; the centres of the tetrahedrons form a diamond lattice and the remaining16 Fe atoms are situated in free interstices. In a pure FeW-C system alloy, the composition of M6C is in between Fe4W2C and Fe3W3C, containing w(W) = 61% - 75%. M6C can dissolve a large amount of Si [8].

5.2.2 Characteristics of carbides

The characteristics of carbides are high hardness, high elastic modulus, high melting point, and they are very brittle. In addition, carbides possess obvious features of metals such as a metallic

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carbon, and hence carbides have the features of metals. A high melting point and high hardness are the important features of carbides; this is because when forming carbides, there exists a strong cohesive force from the covalent bond formed by a p-electron of the carbon atom and a d-electron in the metal atom. The more unfilled vacancies the d-shell has, the stronger the covalent bond is, and the higher the melting point and hardness are. The characteristic constants of various carbides are listed in Table 5-6. Among the carbides, the MC type has the highest hardness, M 7C 3 has the next highest and M 3C has the lowest, indicating that, as far as hardness is concerned, the connective force of the covalent bond is more important than the crystal type. In addition to high hardness (can reach as high as 2,300 2,700 HV), MC also has high oxidation resistance, hence, under high temperature and service wear conditions, this carbide is highly valued [10].

Fig. 5-9: The octahedron in M6C lattice

lustre, high heat conductivity, and their electrical resistance decreases with decreasing temperature. When forming carbides, the electrons of carbon are filled in the d-shell of the metallic element atoms, resulting in the metallization of non-metallic

Table 5-6: The characteristic parameters of carbides [7, 8, 10]

Carbide Crystal type Lattice constant nm a = 0.4514 b = 0.5087 c = 0.6728 a = 0.688 b = 0.454 a = 1.064 a = 0.30 c/a = 0.158 a = 0.298 c/a = 0.1578 a = 0.2901 a = 0.4130 a = 0.4458 a = 0.432 a = 0.4687 Melting point C 1,650 Hardness HV 860

Fe3C

Rhombic

Cr7C3 Cr23C6 Mo2C W2C WC VC NbC TiC ZrC

Hexagonal Complex cubic Hexagonal Hexagonal bcc fcc fcc fcc fcc

1,780 (decompose) 1,520 (decompose) 2,600 (decompose) 2,750 2,867 2,830 3,500 3,150 3,530

2,100 1,650 1,500 2,060 HM 2,400 2,800 2,400 3,200 2,890

Note: If a carbide dissolves another element, its hardness will change, for example if it dissolves Fe: (Fe,Cr)3C: 8401,100 HV; (Fe,Cr)7C3: 1,5001,800 HV; (Fe,Cr)23C6: 1,1401,500 HV

5.3 Crystallisation of primary carbide in white iron

When hypereutectic white cast iron solidifies under equilibrium conditions, the earliest formed primary phase is primary carbide.

5.3.1 Crystalline thermodynamics and kinetics of primary cementite Fe3C

For a hypereutectic white cast iron, the first precipitated phase is primary carbide. Figure 5-10 shows the free energy change of various phases for the Fe-C phase-diagram at temperature T1; the two inclined lines at the bottom of the figure represent the free energy of liquid-graphite mixture and of liquid-cementite

mixture, respectively. When liquid iron with a composition X is undercooled to T1, the carbon content of the liquid X, exceeds the equilibrium content under meta-stable conditions Xa, forming a supersaturation (X-Xa); thus a high carbon phase is precipitated. Whether the precipitated phase is graphite or cementite is dependent on the thermodynamic and kinetic conditions. Because G2 G1, this means that graphite precipitation will cause a larger decrease of system thermodynamic potential than cementite precipitation; therefore the condition is favourable for graphite precipitation. However, since the mass fraction of carbon in cementite is only 6.67% and that in graphite is 100%, the formation of graphite requires carbon atoms to migrate on a large scale. In addition, cementite is an interstitial compound and when 343

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GL Free energy of liquid phase; Gcm Free energy of cementite; Ggr Free energy of graphite; G1 Free energy change when precipitating cementite; G2 Free energy change when precipitating graphite

Fig. 5-11: Plate-flake shaped dendrites of primary cementite [11]

Fig. 5-10: Free energy change when precipiting cementite and graphite

forming carbide, iron atoms have no need to diffuse out from the crystal lattice; therefore, from a kinetic consideration, forming cementite is easier than forming graphite.

carbides are often observed. Because of high carbon, low silicon and fast cooling, the plate-flakes grow thin and long, displaying a long, fine, needlelike structure in a two-dimensional plane, as illustrated in Fig. 5-13. described the growth process of primary cementite, as . . shown in Fig. 5-14, as follows [5]:

5.3.2 Crystallization of primary cementite Fe3C

The growth characteristics and morphology of primary cementite are influenced by the anisotropy of bond energy between atoms in a crystalline structure. Although cementite is an interstitial compound, its growth mode is the same as a solid solution and follows the dendritic growth mode. Due to the obvious anisotropy of cementite, the growth velocities along different directions are very different; the growth velocity along the longitudinal direction (the forward direction of the dendrite) is much faster than that along the transverse direction (vertical to the dendritic plane). There are large numbers of unsaturated Fe-C coherent bonds on the edges of the rhombic plane, which cause cementite to grow preferentially on (010) plane along [100] direction and thus grow to a plateflake like dendrite as illustrated in Fig. 5-11. This is somewhat similar to austenite, but austenite has a three-dimensional dendritic structure, whilst cementite has a two-dimensional structure. The amount, size, appearance, degree of branching and crystalline orientation of plate-flake shaped dendritic cementite are related to the solidification conditions. Figure 5-12 shows the as-cast structure of a thin wall SG iron casting, formed in a water-cooled mould; on the edge adjacent to the mould wall, a large amount of primary, needle-like cementite (the transverse section of plateflake shaped cementite) was formed. Besides, when inverse chill occurs in grey and SG irons, primary 344

Fig. 5-12: Needle-like primary cementite formed under chilling conditions

Fig. 5-13: Primary cementite in an inverse chill structure

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Fig. 5-15: Morphology of primary carbide M7C3 (transverse section)

Fig 5-14: The growth process of primary carbide (Fe3C) [5]

(a) Protruding branches grow on the edge of a cementite germ; impurities gather at the front edges and cause undercooling. (b) New crystal layers grow on two-dimensional crystal nuclei. (c) Through a dislocation (mainly screw dislocation) mechanism, new layers grow on older layers; at the same time, grooves form between the gaps of protrusions. (d) The grooves between branches become deep and wide, and form micro-isolated melt pools. The increased impurities aggravate the branching tendency and cause zigzag growth. (e) The layers become thicker, but the velocity of thickening is far less than the forward velocity. On the surface of flake crystals, undulated contours of dendrites are formed; the transverse sections of dendrites are square or T-shaped.

5.3.3 Crystallization of primary carbide M7C3

For a hypereutectic, high Cr cast iron with w(Cr) 10%, the carbide formed changes from M3C to M7C3. There is no report in the literature about the nucleation mechanism of M7C3; research work has been more focused on the growth process. M7C3 has two growth morphologies rod and plate-flake like. When following the hexagonal crystal growth system, a rod-shaped morphology is obtained; if following the rhombic or rhombohedral growth system, then a plate-flake shaped morphology is easily formed. Most of the primary carbide in hypereutectic, high Cr white cast iron follows the hexagonal growth system; because of the obvious anisotropy of hexagonal crystals, which results in the main growth direction [0001], the crystal that is formed is a long rod-like crystal with a hexagonal shape on a transverse section, as shown

in Fig. 5-15. When primary M7C3 grows, there exists no influence of austenite around. Even greater undercooling does not cause twining, thus M7C3 does not branch, and grows along the [0001] direction, following a single crystal mode; the grain size of M7C3 is far coarser and larger than that of eutectic carbide. This feature is obviously different from that of flake graphite as primary graphite still shows a certain amount of branching. Each side plane of a rod hexagonal crystal of primary carbide M7C3 is very smooth; hence the growth is inwards as the crystal is enveloped by its sides. When the enclosed melt solidifies, a eutectic structure or a small amount of shrinkage is formed; hence the shrinkage holes are often observed inside a hexagonal single crystal, particularly in large, coarse primary M7C3 carbides. The size of M7C3 rods is closely related to cooling rate. When fast cooling occurs, primary carbides grow into fine rods and they are difficult to distinguish from the eutectic carbides surrounding them; when slow cooling occurs, large, coarse rods are formed, which are obviously different from the surrounding eutectic structure, thus they can be easily distinguished [10]. The size of hexagonal rods is related to the chromium content. For example, the primary M 7C 3 of hypereutectic white cast iron with w(Cr) = 15% is coarser than that of a hypereutectic white cast iron with w(Cr) = 26%. The reason may be due to the different Fe/Cr mass ratio [12]. The precipitation of primary M7C3 influences the solidification morphology; when the cooling rate is fast, isolated and disconnected M 7C 3 rods will solidify on a large scale, with a mushy solidification feature. Normal white cast iron or low Cr, hypoeutectic white cast iron solidifies from the surface towards the centre in a successive-layer solidification mode.

5.3.4 Crystallization of primary carbide M6C

For a W system white cast iron with Sc 1, the W content is as high as w(W) 25%, and there exists a large amount of tungstenenriched atom groups in the liquid phase. M 6C can nucleate without the need for long distance diffusion of tungsten atoms. Since M6C is a complex interstitial compound and has a facecentred cubic lattice, and (111) is an atom close packed plane, when primary phase M6C grows freely in liquid, the atom close345

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packed plane (111) is developed very quickly. Along [100] direction of the apex of polyhedron, M 6C crystal grows in a dendritic mode; at the same time, other planes also grow forward, and in the end form a regular and symmetrical octahedron (see Fig. 5-9). Therefore, primary M6C type carbide presents different morphological blocks. However, except for the effect of phase structure, the undercooling caused by compositional redistribution at the interface between crystal and liquid and the precipitation of a second phase, also have important influences on the growth of M6C. Besides, during the growth process, a stacking fault is easily formed due to atom misalignment, which causes an associated twin structure to form. Thus, if cutting a real, primary M6C crystal, which grows to a twin crystal, at different sections, various independent, regular and complex morphologies can be obtained [13, 14] . If a tungsten system white cast iron contains low carbon, the carbon depletion in the liquid in front of primary M6C is even more obvious, thus larger constitutional undercooling is formed. This causes M6C crystals to branch, resulting in a type of primary M6C carbide which has a primary or secondary axis that branches like a fork. Normally, this type of structure has high toughness. The growth of primary M6C is also related to the content of other elements. In a W-Cr system iron, chromium has a certain inhibiting effect on the formation of M6C, since with the increase of Cr, the solubility of W in M6C is increased [15]. The solubility of Cr in M6C is very low, so the existence of Cr causes M6C to branch in the [100] direction, making the primary M6C to crystallize in a dendritic shape, similar to the morphology of primary austenite.

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5.4.1 Morphology of primary austenite

Primary austenite dendrites in white cast iron fall into two types of morphologies, (see Fig. 5-16): Long, rod-like dendrites (called a spiking structure). This type of dendrite shows obvious orientation and a parallel arrangement as illustrated in Fig. 5-16(a); the dendrites form large, coarse austenite grains. Equiaxed dendrites. This type of dendrite is arranged randomly, without any orientation; the dendrites form fine austenite grains which are distributed randomly, as shown in Fig.5-16(b). The morphology of primary austenite is directly related to its solidification mode. For white iron castings which solidify in an exogenous mode (crystals nucleate and grow adjacent to the mould wall), the primary dendrites show mainly a spiking structure. For white cast iron castings which solidify in an endogenous mode (crystals nucleate and grow inside the melt), the solidified structure shows the second type of dendrite morphology. R. Dopp [17] divided the dendrite morphologies of white cast iron into six types, in a detailed way, see Fig. 5-17; each types own feature is listed in Table 5-7. White cast iron has mainly type I and II morphologies, whilst grey iron has mainly type V and VI. In white cast iron, the effect of austenite morphology is more important, whilst in grey iron, the amount of dendrites is more important.

5.4.2 Factors influencing the morphology of primary austenite

For a white cast iron with a low degree of carbon saturation (low carbon equivalent), or with the same carbon saturation, but high carbon and low silicon, a coarse Spiking structure is likely to be produced. Figure 5-18 shows the effect of carbon content on the morphology of austenite. The formation of Spiking dendrite morphology is related to the nucleation status of the iron melt; if the liquid iron has a low level of nucleation, a Spiking structure is easily produced. Compared to cupola melted iron, electric-furnace melted iron has a lower level of nucleation, thus its solidification is mainly in the exogenous mode [18]. When furnace charges have more scrap steel and less pig iron, coarse and orientated dendrites are increased significantly. High super-heating or long holding

5.4 Crystallisation of primary austenite in white cast iron

Hypoeutectic white cast iron first precipitates primary austenite. Basically, the crystalline rule of primary austenite in white cast iron is similar to that of grey iron (see sections 2 and 3 in chapter 2). However, white cast iron contains low carbon and silicon, high alloying elements and has a high chilling tendency, etc., all of which cause the primary austenite to have its own morphology features.

(a) Spiking structure

(b) Equiaxed grains

Fig. 5-16: Primary austenite dendrites of white cast iron

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I: Exogenous solidification; II-V: Transition solidification mode; VI: Endogenous solidification

Fig. 5-17: Six morphologies of austenite dendrites in white cast iron [17] Table 5-7: Types and features of dendrite morphologies Type
I II III IV V VI

Qualitative explanation
Exogenous crystal sheaves reach the centre On the periphery, exogenous crystal sheaves; in the centre, endogenous crystal sheaves On the periphery, exogenous crystal sheaves; in the centre, endogenous crystal sheaves On the periphery, exogenous crystal sheaves; in the centre endogenous crystal sheaves Over the whole section, endogenous crystal sheaves Over the whole section, endogenous, irregular crystal sheaves

Quantitative explanation
d=0 0dD/4 D/4dD/2 D/2dD d=D d=D

d is the diameter of central endogenous growth region; D is the diameter of sample.

time in an electric furnace will decrease the nucleation level of a liquid iron, encouraging the formation of long, coarse Spiking dendrites, as illustrated in Fig. 5-19. Inoculation has a remarkable effect on the dendrite morphology of white cast iron. The author found that inoculation with Fe-Ti or Fe-B alloy can increase the nucleation and produce small grain-shaped, equiaxed dendrites, thus strengthening endogenous solidification, see Fig. 5-20.

5.4.3 Influence of primary austenite morphology on the defects of white cast iron
Primary austenite morphology influences the feeding characteristics, volume shrinkage distribution and associated defects of white cast iron. When solidification is mainly exogenous, coarse and orientated dendritic structures are prone to form hot tears along the grain boundaries; this occurs because the inclusions around grain boundaries weaken the strength of the crystal boundaries. In addition, the boundary shrinkage porosities due to difficult feeding to boundary regions also contribute to the formation of tearing. Conversely, fine grain sizes significantly 347

1: Charge is w(pig iron) 20% + w(scrap steel) 80% 2: Charge is w(pig iron) = 25% -75%, balance of scrap steel

Fig. 5-18: The influence of carbon on primary austenite morphology [17]

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(a) 1,450C

(b) 1,550C

Fig. 5-19: The influence of superheating on austenite dendrite morphology

(a) Without inoculation (1,550C)

(b) Inoculated with Fe-Ti

reduce the sensitivity of forming hot tears. The relationship between dendrite morphology and hot tearing tendency is shown in Fig. 5-21. Spiking dendrite structures are prone to produce hot tearing defects. In addition, it is easy to form inter-dendritic shrinkage cavities or porosity in the hot spots; this is because the coarse dendritic network blocks the feeding channel and inhibits liquid flow. Small grain dendrites significantly decrease shrinkage cavities.

(c) Inoculated with Fe-B

Fig. 5-20: The influence of inoculation on austenite dendrite morphology

(a) Sensitive to hot tearing

(b) Not sensitive to hot tearing

Fig. 5-21: Relationship between dendrite morphology and hot tearing tendency [17]

Figure 5-22 illustrates the relationship between dendrite morphology and shrinkage cavities. For a grey iron, well-developed austenite dendrites (for example, Spiking structure) can improve the strength of the iron significantly. However, for a tempered malleable iron, with increasing coarse austenite dendrites, the mechanical properties show a trend of gradual decrease [18].

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(a) Spiking dendrites

(b) Small grain dendrites

Fig. 5-22: Relationship between dendrite morphology and shrinkage cavities

To be continued

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