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Analyses of Possible Nucleation Sites in Ca/Sr Over-inoculated Gray Irons

I. Riposan, M. Chisamera, S. Stan


Politehnica University of Bucharest, Romania

T. Skaland
Elkem, Norway

M.I. Onsoien
SINTEF, Norway Copyright2001 American Foundry Society

ABSTRACT The main objective of the present paper is to study the conditions for heterogeneous graphite nucleation in gray irons. Experimental gray irons with low silicon concentration (0.4-0.5 % Si) were overinoculated by the addition of 2.0 wt % High Purity (HP)-FeSi, CaFeSi or SrFeSi inoculants. The cast irons have a slightly hypoeutectic chemical composition (CE=3.83-3.96 %). Inclusions found in the matrix and in superficial contact with graphite flakes as well as inclusions partially and totally encapsulated in graphite flakes were analyzed using SEM, EPMA and TEM. Important elements such as Ca and Sr was found to distribute differently in the inclusion volume, Ca was distributed evenly throughout the inclusion volume while Sr was found mainly in the core of the inclusions. The Mn/S ratio is affected by inoculant type and cooling rate. The particles which are associated with graphite have a lower Mn/S ratio than the matrix embedded particles, and Ca-FeSi and Sr-FeSi inoculated irons have a lower Mn/S ratio than HP-FeSi treated irons. The presence of aluminum and oxygen in the inclusions core in all cases is a peculiar conclusion of this work. It was found that polygonal or rounded (Mn,X)S particles (where X = Fe, Al, O, Ca, Si, Sr, Ti etc.) nucleated on Al2 O3 -based sites, and sometimes covered with a thin layer of silicate, are the major nucleation sites for graphite flakes in the produced experimental gray irons. INTRODUCTION A number of inclusions have been evaluated as possible sites for heterogeneous nucleation of graphite in gray iron. Two types of particles were retained for a more thorough examination, namely sulfides and oxides/silicates. Both of these types of particles may, according to the thermodynamics, be formed in industrial gray iron melts as simple or complex compounds during melting, holding or handling.(Chisamera 2000, Loper 1998, Skaland 1993, Stefanescu 1998, Chisamera 1998, Jianzhong 1989, Guoging 1982) At a first glance nucleation of graphite at silicate particles look more feasible, especially due to good crystallographic compatibility with graphite, favorable wetting relationships, a sufficient lattice disregistry acceptance and relatively high stability of the compounds. However, the low oxygen content in the iron melt and the coagulation of silicates may prevent graphite nucleation at this group of particles. The ability of sulfides to nucleate graphite can also be very well promoted, especially by the capacity of the main inoculating elements (Ca, RE, Sr, Ba) to transform MnS to complex sulfides (Mn, X)S, which might have very good lattice match with graphite, a low coagulation capacity, good stability and adequate interfacial energy relationships. There are, however, still many problems that remains unsolved concerning inoculation of gray iron, e.g., crystallographic features of both graphite and the possible substrates, an understanding of complex sulfide structures, importance of interfacial energy relationships, difficulties to inoculate gray iron with less than 250 ppm S and the effect of sulfur additions on the iron melt behavior. To further the understanding of the nature of possible nucleation sites for graphite in gray irons the present investigation concerns a thorough analysis of a large number of inclusions that may act as possible nucleation sites for graphite in overinoculated gray irons. The analyses includes using state-of-the-art electron microscopy including both SEM- and TEManalyses as well as electron probe micro analyses.

EXPERIMENTAL PROCEDURE PRODUCTION OF OVER-INOCULATED GRAY IRONS The experimental gray cast irons were produced in batches of 10kg using a graphite crucible in an induction furnace. The charges were based on pig iron (25%), steel scrap (50%), iron flakes (10%), carbon electrode scrap, FeMn80, FeP26 and FeS2 . The irons was over-inoculated with a 2.0 wt.% addition of experimental inoculant. Three different inoculants were used HP-FeSi, Ca-FeSi and Sr-FeSi and two heats of each treatment were produced. Cylindrical samples with a diameter of 15mm were cast in dry sand moulds, giving a cooling rate of 4.3C/s, and cylindrical samples with a diameter of 5mm were cast in metal moulds, giving a cooling rate of 542C/s. The experimental conditions are summarized in Table 1. The chemical composition of the inoculated irons was thoroughly controlled and slightly hypoeutectic (CE=3.83-3.96 % , Sc=0.881-0.915). Very narrow Mn and S concentration ranges were obtained (Mn=0.50-0.53% and S=0.071-0.083 %), giving a Mn/S ratio in the 6-7 range. The oxygen content of the over-inoculated cast irons is much lower than the initial one (0.0025-0.0035 % O), due to the deoxidizing effect of inoculants. A nitrogen concentration in the range from 32 to 42 ppm was obtained, which indicates a constant influence of this element. Minor elements are regarded to be present in such concentrations that they do not affect the solidification the experimental irons. Significant levels of the main active (inoculating) elements Ca and Sr was introduced by over-inoculation, resulting in 20-29 ppm Ca in the Ca-FeSi treated irons and 19-28 ppm Sr, in the Sr-FeSi treated irons. Table 2 summarizes the chemical composition and characteristic ratios of the produced experimental gray irons. Table 1. Summary of experimental conditions for production of over-inoculated gray irons. Parameters Characteristics Crucible melting furnace Graphite crucible, 10kg, 8000 Hz Charge materials Pig iron (25%), Steel scrap (50%), Iron flakes (10%), Carbon electrode scrap, FeMn80, FeP26, FeS2 Base iron composition (before inoculation) 3.51% C, 0.43% Si, 0.51% Mn, 0.139% P, 0.084% S CE=3.71% Inoculation technique Ladle inoculation Inoculant addition 2.0 wt.% Inoculants (78-80%Si) HP-FeSi 0.038% Ca, 0.06% Al, 0.0023% Sr Ca-FeSi 0.755% Ca, 0.90% Al, 0.021% Sr Sr-FeSi 0.092% Ca, 0.407% Al, 0.92% Sr Thermal conditions: Superheating temperature Ts = 1460 1480 0 C Inoculation temperature Tin = 1430 1450 0 C Pouring temperature Tp = 1400 1420 0 C Cylindrical samples 15mm diameter, Sand Mould 5mm diameter, Metal Mould Table 2. Chemical composition of over-inoculated experimental gray irons. Heat Inoculant Chemical composition (in wt.%)1 Active elements (ppm) Characteristic ratios no. C Si Mn P S O N CE Ca Sr Mn/S Mn/O Mn/ (S+O) 10 HP-FeSi 3.23 1.80 0.50 0.133 0.082 0.0035 0.0035 3.85 7 0.5 6.10 142.9 5.85 11 HP-FeSi 3.23 2.14 0.51 0.146 0.083 0.0025 0.0038 3.96 0.1 0.1 6.14 200 5.96 20 Ca-FeSi 3.21 1.79 0.52 0.138 0.076 0.0030 0.0032 3.83 22.5, 27.0 0.3 6.84 173.3 6.6 21 Ca-FeSi 3.26 1.97 0.53 0.147 0.078 0.0025 0.0039 3.94 20.5, 29 1.8 6.80 212 6.6 30 Sr-FeSi 3.18 1.97 0.51 0.136 0.071 0.0030 0.0037 3.85 8.5 25; 27; 28 7.18 170 6.9 31 Sr-FeSi 3.21 2.05 0.51 0.141 0.083 0.0036 0.0042 3.91 5.5 19; 22; 19 6.14 141.7 5.9 1 0.09-0.10%Cr, 0.06%Ni, 0.14-0.21%Cu, 0.016-0.020%Mo, 0.005-0.007%Ti, 0.009-0.01%V, 0.009-0.011%W, 0.005%Co, 0.003-0.01%Al, 0.009-0.01%As, 0.006-0.007%Sn, < 0.003%Sb, < 0.001%Nb, 0.002%Pb, 0.0011%Bi, 0.002-0.0022%B. ANALYTICAL TECHNIQUES The chemical composition in different regions of the inclusions, such as the nucleus (n), compound body (Cm), compound/graphite interface (ic-g) and compound/matrix interface (ic-m), was found by the use of SEM (Philips SEM-515). The general appearance and element distribution (X-ray mapping) were recorded for representative inclusions. A total of 120 inclusions were analyzed on the prepared cross-section of each specimen produced form the 15mm diameter cylindrical bars using the SEM. On the prepared cross-sectional samples from the 5mm diameter cylindrical bars a total of 20 inclusions were analyzed on each specimen. 2

The compactness factor and roundness of the inclusions were found by analyzing gray scale images from the SEM using an automated image analyzer (ImagePro). The compactness factor is defined as K = 4 SA / D2 max where SA is the inclusion area in the metallographic plane and D max is the maximum diameter of the inclusion. The roundness is defined as = 3.54 SA 1/2/Pr where SA is the inclusion area in the metallographic plane and Pr is the perimeter of the inclusion in the metallographic plane. Several inclusions from the 15mm diameter cast iron cylinders were analyzed using an electron probe micro analyzer (EPMA) (JEOL EPMA JXA8900R WDS/EDS combined system). Carbon extraction replicas were prepared from the 5mm diameter cast bars and ion-thinned foils were prepared from the 15mm diameter cast bars and examined using TEMs (Philips CM30 for thin foils and JEOL 2010 for carbon extraction replicas) in order to: i) identify the complex (Mn,X)S particles expected to be possible site for graphite nucleation, ii) identify nuclei for the (Mn,X)S particles and possible compounds on the surface of the particles and iii) perform a spectral analysis of complex sulfides and their surroundings. RESULTS AND DISCUSSION The inclusions in the gray iron samples (15mm diameter cylindrical bars cast in sand mould) are either associated with graphite or are embedded in matrix, while almost all inclusions seen in specimens from the 5mm diameter cylinders are embedded in matrix because of the high cooling rate in these samples, Figure 1. Depending on the degree of contact between the inclusions and the graphite the following four relative positions were recorded: i) no visible contact with graphite (particle embedded in matrix), ii) superficial contact between inclusion and graphite, iii) partially encapsulated by graphite and iv) totally encapsulated by graphite. Chemical composition and morphological features of selected inclusions based on the SEM analyses and image analyses are given in Table 3, while Table 4 gives some representative results from the TEM analyses.

Figure 1. Examples of morphology of inclusions in Ca-FeSi inoculated cast irons. G dry sand mold, 15mm diameter samples; S metal mold, 5mm diameter samples.

Table 3. Chemical composition and morphological features based on SEM analyses of selected inclusions extracted from the inoculated 15mm diameter samples. Inoculant Compound1 Zone2 Chemical composition (at.%) No. 5G3 Pos. M Dmax (m) 3.8 Geometry K 0.68 0.87 Fe Mn S Ca Sr Si Al Ti O Others

n 15.49 40.93 28.40 - 1.33 5.54 8.31 Cm 21.86 43.18 34.03 0.93 HP-FeSi ic-m 47.85 25.24 23.83 0.57 P=2.5 5G4 G 3.3 0.93 0.87 n 50.45 24.52 21.39 3.64 + Cm 46.01 28.63 25.36 -ic-g 48.18 28.69 23.13 2G7 M 3.8 0.88 0.92 n 12.58 28.81 18.27 0.46 - 15.95 - 23.93 Cm 19.52 43.74 35.97 0.77 Ca-FeSi ic-m 48.64 24.97 26.05 0.34 2G8 G 4.0 0.86 0.89 n 17.46 29.27 29.51 0.70 9.23 - 13.83 Cm 14.86 42.33 41.71 1.10 ic-g 26.76 35.06 37.29 0.88 4G15 G 3.4 0.92 0.83 n 18.13 34.49 34.07 3.91 9.39 + Cm 26.69 38.42 34.89 Sr-FeSi ic-g 35.65 31.62 32.73 4G18 M 3.7 0.90 0.92 n 19.99 35.10 33.35 3.31 3.30 4.96 Cm 26.40 40.44 31.76 - 1.39 ic-m 58.17 23.44 16.56 - 1.83 1 G - in graphite, M - in matrix, D max= maximum diameter of inclusion in m, K=Compactness factor, =roundness factor 2 n nucleus; Cm -compound mass; ic-m compound/matrix interface; ic-g compound/graphite interface Table 4. Chemical composition based on TEM analyses of selected inclusions extracted from over-inoculated gray irons. Inoculant Inclusion Zone1 Chemical composition, at.% Mn/S C Si S Mn Fe Ca Sr Ti Al P HP-FeSi 1 Cm 54.47 45.53 0.84 ic-g 31.33 37.23 31.43 0.84 ic-g 12.83 47.47 39.71 0.84 ic-g 56.69 15.77 12.83 14.71 0.81 g 97.41 2.59 Ca-FeSi 1 Cm 52.28 46.04 1.38 0.88 ic-g 27.28 21.27 46.42 5.03 2.18 ic-g 38.75 4.76 10.62 41.35 2.39 0.53 1.59 2.23 ic-g 60.79 4.66 29.59 4.96 6.34 ic-g 85.44 4.84 9.73 ic-g 37.87 9.18 31.16 20.34 1.45 3.39 Sr-FeSi 2 Cm 50.45 45.22 4.33 0.90 n 42.62 37.21 1.69 19.39 0.87 ic-g 48.38 27.30 23.88 0.87 ic-g 48.56 27.35 24.09 0.88 ic-g 21.45 4.54 36.25 36.25 37.77 1.00 ic-g 21.03 1.85 15.78 12.83 48.51 0.81 1 Cm =Compound mass, ic-g =Compound/graphite interface; g =graphite. Over 90 % of the inclusions which were assumed to play a role in graphite nucleation were identified as (Mn,X)S compounds, where X = Fe, Al, O, Si, Ca or Ti. EPMA analysis showed that in HP-FeSi treated iron the chemical composition of inclusions associated with graphite flakes contained 80 wt.% (Mn+S), 5 wt.% Fe and small amounts of Al, Si, O, Ca and Ti (Al - only in the core of the inclusions). Complex (Mn,X)S compounds were also identified in the Sr-FeSi over inoculated iron. It should be noted that Sr was found only in the core of the inclusions in the Sr-FeSi treated irons. Calcium was found in almost all analyzed (Mn,X)S particles in the samples from the Ca-FeSi over-inoculated gray iron. Ca was present in amounts from 0.15 to 6.5 at.% in inclusions in the 15mm diameter samples and from 0 to 16.7 at.% in inclusions in the 5mm diameter 4

samples. Ca was also found in some inclusions in the Sr-FeSi over-inoculated iron and even in the HP-FeSi treated cast irons. Ca and Sr showed a different distribution pattern within the (Mn,X)S compound. X-ray composition maps showed a quasihomogeneous distribution of Ca over the whole particle surface, including the core (Figure 2), Sr was present only in the particle core (Figure 3). The latter finding does not, however, exclude the possibility of Sr to be present in a small (undetectable) amount as solid solution in the (Mn,X)S compound body. A more thorough analysis using the EPMA revealed a difference between the shell and core Ca concentrations (Figure 4). The Ca level is highest in the shell and much lower in the core, which suggests that CaS dissolves more readily in the inclusion body than in the core. The chemical composition along a line through the core of an inclusion illustrates the presence of fairly well defined zones within the inclusion (Figure 4). The core has high levels of aluminum and oxygen and lower level of Mn, S, Fe, and Ca. The inclusion body has high levels of Mn, S and Ca and low Fe concentration and no Al and O. The core and body parts of the inclusions can thus be easily separated in terms of chemical composition. In some cases, however, a transition zone at both the inclusion core/inclusion body and inclusion body/iron matrix is found.

(a)

(b)

(c)

(d)

Figure 2. Typical example of element distribution in an inclusion in the Ca-FeSi treated iron. a) compo image; b) CaK ; c) MnK; d) SK.

The Mn/S ratio of the inclusions is affected both by inoculant type and cooling rate. In addition the Mn/S ratio changes with position within the inclusion, such as nucleus (n), compound mass (c m) and compound/graphite interface (ic g ) (Figure 5). Ca-FeSi inoculated cast irons had a lower Mn/S ratio than the HP-FeSi treated iron, the lowest value, however, was found for the Sr-FeSi inoculated iron. The highest values of the Mn/S ratio was found in the compound body (c m) of particles embedded in matrix while the lowest Mn/S ratios was found on the compound/graphite interface (ic g ). The particles which are associated with graphite have a lower Mn/S ratio than the matrix embedded particles in all examined specimens. After inoculation, much sulfur is retained in the (Mn,X)S compounds because of the presence of elements, such as Ca, Al, Sr, Ba, etc, such that the Mn/S ratio is reduced. When the Mn/S ratio is decreased, more complex sulfides having a more compatible crystallographic system for graphite nucleation can be formed. The Mn/S ratio of (Mn, X)S compounds is determined by the quantity of sulfur active element addition (Ca, Sr, Ba) and the cast iron Mn/S ratio, so the manganese and sulfur contents in iron melt are also important. In addition MnS compounds can contain more Mn that the stoichiometric balance requires because of some solubility of Mn in MnS and in the FeMnFeSMnS system. Thus, the higher Mn concentration in the iron melt the higher Mn/S ratio in the (Mn,X)S particles, Table 5. An increase of the Ca content in the (Mn,X)S compounds leads to an increase in their Mn/S ratio, Table 5. Therefore it can be concluded that inoculation efficiency is controlled not only by the level of inoculant addition but also by the Mn and S contents or Mn/S ratio in the inoculated gray iron melt.

Independent of inoculant type (HP-FeSi, Ca-FeSi or Sr-FeSi) the cores in all examined inclusions (about 40 cores were analyzed by SEM and TEM) contained Al (from 1.2 to 46 at. %, more frequently between 3.0. and 20 at. %). In almost all cases the core also gave oxygen signals.

Figure 3. Typical example of element distrubution in an inclusion in the Sr-FeSi treated iron. a) compo image; b) AlK ; c) SrK; d) CaK; e) MnK; f) SK; g) CuK; h) CK

Table 5. Influence of Mn content in cast iron on the Mn/S ratio in (Mn,X)S compounds Iron composition, % Inoculant Mn/S ratio Mn S Inoculant addition Cast iron Compound mass Compound-graphite (wt.%) (Cm) interface (ic-g) 0.23 0.075 Ca-FeSi 0.2 3.05 0.88 0.88 0.52 0.076 Ca-FeSi 2.0 6.84 1.11 1.02 0.23 0.090 Sr-FeSi 0.2 2.57 0.52 0.55 0.51 0.083 Sr-FeSi 2.0 6.14 1.01 0.83 0.51 0.083 HP-FeSi 2.0 6.14 1.22 1.09 In steel metallurgy, small particles of Al2 03 have been identified as nucleation sites for precipitation of MnS particles although the planar disregistry between MnS (111) and A12 03 (111) is relatively large (28.8%).(Wakoh 1996) In a steel melt, the behavior of MnS precipitation on oxides particles (1 wt. % Mn in the steel) was characterized according to sulfur content (Figure 6): a) at S<0.002 wt.%, the number of MnS particles precipitated on oxides was low, b) at 0.002<S<0.01 wt.% the precipitation rate of MnS was high on some types of oxides, c) at S>0.01 wt.% the precipitation rate was high on many kinds of oxides, which means that they worked as precipitation sites for MnS. The strong deoxidizers (such as Al, Ti and Zr) bring about a powerful increase in oxide density and the precipitation rate of MnS is higher when the sulfur concentration increases.(Sano 1994, Yuki 1998, Dub 1991, Oikawa 1997, Sawai 1990 ) On this basis the sulfide core was considered to be a pure Al2 03 compound but, as evidenced by micro-analyses, the composition of the cores were much more complex. In addition to Al and O, the core almost always contains Mn, S, Fe, Si, Ca, Sr and possible many other elements in small quantities.

S 100 80
Matrix

Mn

Fe

Al

Ca 0.14 0.12

Fe, Mn, S, Al, O, at.%

Shell

Core

Shell

0.10 0.08 0.06 0.04 Ca, at.%

60 40 20

0.02 0 0 2 4 Distance, m
Figure 4. Change of chemical composition along a line through the core of a sectioned (Mn,X)S particle ( at. % ).

0.00 6 8

2.5

2.0 Mn/S ratio

Compound placed on graphite G (15mm dia sample)

Compound placed on matrix-M (15mm dia sample)

Compound placed on matrix-M (5mm dia sample)

1.5

1.0

0.5

Cm (a)

ic-g n

Cm

ic-m

Cm

0.0 Position of analyzed point

2.5

2.0

Compound placed on graphite G (15mm dia sample)

Compound placed Compound placed on on matrix-M matrix-M (15mm dia sample) (5mm dia sample)

Mn/S ratio

1.5

1.0

0.5

Cm (b)

ic-g

Cm

ic-m n

Cm

0.0

Position of analyzed point

2.5

2.0

Compound placed on graphite G (15mm dia sample)

Compound placed Compound placed on on matrix-M matrix-M (15mm dia sample) (5mm dia sample)

Mn/S ratio

1.5

1.0

0.5

Cm (c)
0.0

ic-g

Cm ic-m

Cm

Position of analyzed point


Figure 5. Influence of inoculant on the Mn/S ratio distribution in gray cast iron treated with: a) HP-FeSi, b) Ca-FeSi and c)Sr-FeSi. (Cm-Compound mass, i c-g-interface compound/graphite, i c-m-interface compound/matrix, n-nucleus)

Figure 6. Change in the precipitation ratio of MnS with S content and with the kind of deoxidization elements.(Wakoh 1996)

In the Sr-FeSi over-inoculated cast iron, around 50% of the analyzed cores belong to the Al-O system and a similar amount to the Al-Si-O system. An interesting observation is that Sr was found out only in the cores belonging to Al-O system, and not in the cores belonging to Al-Si-O system. It could thus be suggested that in Sr inoculated iron the core of the (Mn,X)S compounds belong to the Al-Sr-O system, perhaps in a SrO-Al2 O3 form which could have more favorable lattice parameters for nucleation of the (Mn,X)S compound. The SEM analyses showed that the amount of silicon present in the (Mn,X)S compounds depends on the inoculant type (see Table 3). In the 15mm diameter samples Si was present in 35% of the analyzed particles in the HP-FeSi inoculated iron and in 45% of the particles in the Sr-FeSi over-inoculated iron, but only in a few particles in the Ca-FeSi inoculated iron. In the Sr-FeSi over-inoculated cast iron Si was found in the core and to a lesser degree in the compound body, while in the HP-FeSi over-treated iron the Si concentration was much higher in the compound than in the core. As known from the steel metallurgy calcium exerts its strong deoxidation effect before it reacts with the sulfur present in the melt. From its chemical affinity to oxygen and sulfur it could be assumed that calcium may convert the existing inclusions (Al2 O3 , MnS, SiO2 , MnO, FeO) to calcium compounds containing sulfur. By its action on the (Mn,X)S compounds calcium exerts an important effect on the morphology of these particles. In Ca-FeSi over-inoculated cast iron samples, the (Mn,X)S inclusions have a ovoid form while the inclusions in the HP-FeSi treated irons which have an irregular polygonal form and the inclusions in the Sr-FeSi over-inoculated iron have a regular polygonal (hexagonal) form. This effect is reflected by the increase of the roundness factor with increasing Ca content, see Table 3. The size of the (Mn,X)S particles also showed a systematic change when changing inoculant. Ca-FeSi over-inoculated cast iron had the largest average inclusion size (Davg=5.24m ) while the smallest average inclusion size was found in the HP-FeSi treated iron (Davg=2.99m). The Sr-FeSi over-inoculated iron had an average inclusion size (Davg=4.15m) just below that of the Ca-FeSi treated iron. The amount of sulfides, which could be formed in the melt after inoculation treatment, was calculated taking into account the following assumptions: i) the main elements, which can react with sulfur (in present experiment), are Ca, Al, Sr, Ti, Ba, Ce, and Zr, ii) the entire amount of element reacts in principle with S neglecting the reaction with O (the oxygen level in cast iron melt is much lower than the sulfur level), and iii) the rate of inoculant assimilation in the melt is 100 %. It is assumed that the error induced by neglecting oxygen in this estimation could be minimized if the stoichiometric equivalence between sulfides and oxides of these elements ( CaS CaO; Al2 S3 Al2 O3 ; SrS SrO) are accounted for. After the interaction between the melt and the inoculant ExSy sulfides are formed (E = Ca, Al, Sr, Ti, Mg, Ba, Ce, Zr). The amount of sulfides can then be calculated using the general relation:

q Ex Sy = q i
Where :

Ei M E x S y 100 M Ex

q ExSy - is the amount of sulfide in g/100g metal q i - is the inoculant addition in wt. % Ei is the content of element E in inoculant in wt. % MExSy , MEx is the molar mass of compound and element Ex, respectively. Taking into account the specific mass of the sulfides, the theoretical volume of sulfides, Vt , can be calculated using the following equation:

Vt =

q Ex Sy q CaS q Al2 O3 + + ..... + CaS Al2 O3 Ex Sy


q ExSy - is the amount of Ex Sy compound in g / 100g metal. ExSy - is the specific mass of the ExSy compound in g / cm3

Where :

The total theoretical volume of sulfides in the melt after inoculation of the iron with Ca-FeSi or Sr-FeSi is much higher than the theoretical volume of sulfides in the iron inoculated with HP-FeSi, Table 6. However, the number density of inclusions was higher in the iron inoculated using HP-FeSi than in the irons inoculated with Ca-FeSi or Sr-FeSi, see Table 6. This finding leads to the conclusion that the inoculation effect is in principle not a result of creation of new particles in the melt, but a result of activation of inclusion already present in the melt. This conclusion is also supported by the fact that most of the observed inclusions (over 90%) are complex manganese sulfide compounds. Table 6. Theoretical amount and Surface density of sulfides in over-inoculated cast irons Inoculant Theoretical volume of sulfides, Vt Surface density of inclusions (1/mm2 ) 3 [cm /100g metal] 15mm diameter 5mm diameter sample sample [Gray Iron] [White Iron] HP-FeSi 0.313x10-2 1153 5011 Ca-FeSi 3.953x10-2 630 5225 Sr-FeSi 2.239x10-2 944 3333 A controversial subject in graphite nucleation research in cast iron is the existence of an intermediate silicate layer on the compound/melt interface having better crystallographic compatibility to graphite than the compound it self. This layer would be very thin and very difficult to detect. Nevertheless the Al and O distribution on the compound/graphite interface suggests the existence of such a layer with a high crystallographic compatibility towards graphite. The Al and O distribution also emphasizes the important role played by Al both with respect to the nucleation of the (Mn,X)S compounds and nucleation of graphite on the (Mn,X)S compound. Both SEM and EPMA analyses revealed that Al and O were localized in the sulfide core and at the sulfide/graphite interface, the TEM analyses have verified this observation. Based on the above analyses of a large number of inclusions the following three-stage model for graphite nucleation in both un-inoculated and inoculated gray irons is proposed: Stage 1) Micro-inclusions based on strong deoxidizing elements such as Mn, Si, Al, Ti and Zr are formed in the melt. Stage 2) Nucleation of (Mn,X)S compounds on the micro-inclusions in the melt. In un-inoculated irons X=Fe (mainly) and to a lesser extent X=Ca, Al or Ti, in addition the Mn level and Mn/S ratio in the compounds is high. In inoculated irons X=Ca, Sr, Ba, Al, RE etc., in addition the Mn level and Mn/S ratio in the compound is lower. A thin layer of silicate may form at the surface of the (Mn,X)S compound in the inoculated iron. Stage 3) Graphite nucleates on the (Mn,X)S compound. In un-inoculated iron the (Mn,X)S compound is simple and the crystallographic misfit between the graphite and the compound is relative large. In inoculated iron the (Mn,X)S compound is more complex and the crystallographic misfit between the graphite and the compound is lower. CONCLUSIONS Micro-inclusions that may act as possible nucleation sites for graphite in gray cast irons inoculated with either high purity ferrosilicon, calcium-ferrosilicon or strontium-ferrosilicon have been examined using scanning electron microscopy,

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transmission electron microscopy and electron probe micro analyses. Based on this work the following main conclusions can be drawn: (Mn,X)S compounds (where X= Fe, Al, O, Si, Ca, Sr, Ti, etc.) are major sites for graphite nucleation in gray irons. The inoculation effect is not a result of the creation of new particles in the melt but by activation of the inclusion already present in the melt. Inoculation efficiency is controlled not only by the level of inoculant addition, but also of the Mn and S contents or Mn/S ratio in the iron melt. Ca was found in almost all (Mn,X)S inclusions independent of inoculant type. Ca was found in all inclusions examined in Ca-FeSi inoculated irons. Ca and Sr have different distribution patterns in the inclusion volume. Ca is found throughout the inclusion, but higher concentrations is found in the inclusion body. Sr was found, with few exceptions, only in the core of the inclusions. The Ca/Sr inoculants exert an important effect on the (Mn,X)S compound morphology and size. In the HP-FeSi treated iron the inclusions have an irregular polygonal shape, in the Ca-FeSi treated iron the inclusions have an ovoid shape and in the Sr-FeSi treated iron the inclusions have a regular polygonal (hexagonal) shape. Inclusions in the Ca-FeSi and SrFeSi inoculated irons are larger than the inclusions in the HP-FeSi inoculated irons. Al and O was found to be present in the core of the inclusions in all cases. In addition Al and O was found at the interface between the inclusion and the graphite, which may indicate the presence of an interface layer between the inclusion and the graphite. Thus Al plays an important role in both the nucleation of the (Mn,X)S compounds and in the nucleation of graphite on (Mn,X)S. A three-stage model for the nucleation of graphite in both un-inoculated and inoculated gray irons is proposed. REFERENCES Chisamera, M., Riposan, I., Barstow, M., The Importance of Sulphur to Control Graphite Nucleation in Cast Iron, AFS Int. Inoculation Conference, April 68, Chicago, USA, paper no. 3 (1998). Chisamera, M.,Riposan, I., Stan, S., Skaland, T., Effects of Calcium and Strontium Inoculation on Undercooling, Chill and Microstructure in Gray Irons of Varying Sulphur and Oxygen Contents, 64th World Foundry Congress, Paris, 1014. Sept. (2000). Dub, A.V., Tsukihasi, F. and Sano, N., Solubilities of Al2 O3 , SiO2 and Cr2 O3 in the FeS containing systems, ISIJ Int., vol. 31, no.12, pp 1438-1440 (1991). Guoging, X., Zongsen, Y., Mobley, C.E., Solidification and structures in rare earth-inoculated gray irons, AFS Transactions, vol. 90, pp 943-958 (1982). Jianzhong, L., Inoculation mechanism of ReSiFe for gray cast iron, AFS Transactions, vol. 97, pp 31-34 (1989). Loper, C.R. Jr., Gundlach, R.B., Inoculation what is it and how does inoculation work? AFS Int. Inoculation Conference, April 68, Chicago, USA, paper no 1 (1998). Oikawa, K., Ishida, K., and Nishizawa, T., Effect of titanium addition on the formation and distribution of MnS inclusions in steel during solidification ISIJ Int. (Japan), vol. 37, no. 4, pp 332-338 (1997). Sano, N., Proc. of the Second Canada Japon Symposium on Modern Steelmaking and Casting Technology, Toronto, Canada, Aug., pp 19-28 (1994). Sawai, T., Wakoh, M., Ueshima, Y., and Mizoguchi, S., Metallurgy of oxides in steels. III. Effects of zirconium on the precipitation of MnS in low carbon steels, Proceedings of the Sixth International Iron and Steel Congress, Nagoya, ISIJ, pp 605-611 (1990). Skaland, T. , Grong, ., Grong, T., A Model for the Graphite Formation in Ductile Cast Iron: Part I. Inoculation Mechanisms, Met. Trans A, vol 24A, pp2321-2345 (1993). Stefanescu, D.M., Inoculation of Thin Wall Castings, AFS Int. Inoculation Conference, April 68, Chicago, USA, paper no 16 (1998). Wakoh, M., Sawai, T., and Mizoguchi, S.,- ISIJ Int., vol. 36, no.8, pp.1014-1021 (1996). Yuki, N., Shibata, F., and Emi, T., Solubility of MnS in Fe-Ni alloys as determined by in situ observation of precipitation of MnS with a confocal scanning laser microscope ISIJ Int. (Japan)., vol. 38, no.4, pp 317323 (1998).

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