5 International Advanced Technologies Symposium (IATS09), May 13-15, 2009, Karabuk, Turkey

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HIGH PURITY PIG IRON PRODUCTION BY USING STEEL SCRAP AND COMPARISON WITH SORELMETAL EL K HURDALARI KULLANILARAK YKSEK SAFLIKTA P K DEM R RET M VE SORELMETAL LE KIYASLANMASI
a

Gkhan ZER , Nilfer EVC MEN , Ahmet EKER M * Yldz Teknik niversitesi Kimya-Metalrji Fakltesi Metalrji ve Malzeme Mhendislii Blm 34210 Esenler/ stanbul, Trkiye, E-posta: gozer@ yildiz.edu.tr, nevci@ yildiz.edu.tr, ekerim@ yildiz.edu.tr

ABSTRACT
Sorelmetal (high purity iron ingots produced by QIT - Fer et Titane Inc); is the most common charge material of ductile iron production used in worldwide range. In this study, high purity pig irons with different compositions were produced from steel scrap instead of iron ore by using electrical arc furnace. These products were compared with Sorelmetal , according to their chemical compositions and microstructure observation. Experimental studies were performed on pig irons to examine the similarities to Sorelmetal . For chemical analyses optical emission spectrometry, for microstructural observation optical light microscope have been used. In addition, graphite sizes of the ductile iron were measured by using image analyzer. Depending on the obtained results, both structure and size distribution of graphites resemblances to Sorelmetal. Therefore this method can be used as a promising of Sorelmetal Key words: Pig iron, Sorelmetal, steel scrap, electrical arc furnace.

metot Sorelmetal e alternatif olarak gelecek vadeden bir metottur. Anahtar Kelimeler: Pik demir, Sorelmetal , elik hurdas, elektrik ark frn.

1. Introduction
The first iron castings to be made were cast directly from the blast furnace. Foseco 23 Blast furnaces do not produce steel, they produce pig iron. Primary, Iron produced in the blast furnace is converted into the following commercial products as steel, cast iron and pure iron. Table 1.1. shows typical analysis of these products. [1] Table 1.1 Typical analysis of ferrous materials. Pig Iron(%) 3.5 4.25 1.25 0.9 2.5 0.04 0.06 3.0 Cast Iron(%) 2.5 3.75 0.5 3.0 0.40 1.0 0.01 0.18 0.12 1.1 White Cast Iron(%) 1.75 2.7 0.8 1.2 < 0.4 0.07 -0.15 < 0.02 Steel(%) 0.10 0.02 0.40 0.03 0.03

C Si Mn S P

ZET
Sorelmetal (QIT Fer et Titane Inc.de tarafndan retilen yksek saflktaki demir ingotlar); kresel grafitli dkme demir retiminde dnya apnda en yaygn kullanm alanna sahip arj malzemesidir. Bu almada yksek saflktaki farkl kompozisyonlara sahip pik demir, demir cevheri yerine elik hurda kullanlarak elektrik ark frnnda retilmitir. retilen pik demirler kimyasal kompozisyon ve mikro yap incelemeleri bakmndan Sorelmetalle kyaslanmtr. Deneysel almalar, pik demirler ile Sorelmetal arasndaki benzerlikleri gzlemlemek amacyla gerekletirilmitir. Kimyasal analizler iin, optik emisyon spektrometresi, mikro yap incelemeleri iin ise optik k mikroskobu kullanlmtr. Buna ek olarak grafit boyutlar imaj analiz cihaz kullanlarak tespit edilmitir. Elde edilen sonular dorultusunda kresel grafitli dkme demirin hem yapsal hem de grafit boyut dalmlar Sorelmetal e uyum salamaktadr. Buna bal olarak bu

Liquid iron from a blast furnace contains around 4 %C and up to 2 %Si, together with other chemical elements derived from the ore and other constituents of the furnace charge. The presence of so much dissolved carbon etc. lowers the melt point of the iron from 1536 (pure iron) to a eutectic C temperature of about 1150 (Fig. 1.1) so that blast C furnace iron is fully liquid and highly fluid at temperatures around 1200 C.

IATS09, Karabk niversitesi, Karabk, Trkiye

zer ,G., Evcimen, N. and Ekerim, A.

Figure 1.3 Nodular graphite, X100. [4] The spheroidal form of graphite that characterizes ductile iron is usually produced by a magnesium content of about 0.04 to 0.06%. Magnesium is a highly reactive element at molten iron temperatures, combining readily with oxygen and sulfur. For magnesium economy and metal cleanliness, the sulfur content of the iron to be treated should be low (preferably <0.02%); this is readily achieved in an electric furnace by melting charges based on steel scrap or special-quality pig iron supplied for ductile iron production, together with ductile iron returned scrap. The contents of elements that affect the formation of nodular graphite and promote the formation of carbide are low according to the application of the grade concerned. Higher-strength grades of ductile iron can be made with common grades of constructional steel scrap, pig iron, and foundry returns, but certain trace elements, notably, lead, antimony, and titanium, are usually kept as low as possible to achieve good graphite structure. Titanium in trace amounts is beneficial to gray iron flake graphite, but is detrimental to the nodular graphite forms needed in ductile iron. [3] Pig iron production from ilmenite, FeTiO3, process starts with the mixing of is a certain amount of carbon which is just enough to reduce the iron oxide component of the ore. Then charged in an electrical furnace at 1650 where C iron oxide is reduced to metal while titanium is separated as a slag. The high purity iron ingots produced at the metallurgical complexes of QIT - Fer et Titane Inc. (Sorel, Canada) and Richards Bay Minerals (Richards Bay, South Africa). Rio Tinto Iron & Titanium which markets Sorelmetal, guarantees the quality of this product as well as the consistency, lot after lot, of its chemical composition. Figure 1.4 represents the selective reduction of ilmenite process. A small amount of TiO2 is reduced to Ti2O3 and will be found in the slag. The slag is mainly titanates of iron, magnesium and calcium together with some calcium and aluminum silicates. Its titanium dioxide content varies between 72 and 98 %.

A B C D

Iron Graphite ( - ) Carbon Temperature Content ( C) (%C) 2.09 1154 4.25 1154 0.68 739

Iron- Carbide ( - - - ) Carbon Temperature Content ( C) (% C) 2.12 1148 4.31 1148 6.68 1226 0.76 727

Figure 1.1 The ironcarbon phase diagram. [2] While the solidification of the iron, most of the carbon is thrown out of solution in the form either of graphite or of iron carbide, depending on the composition of the iron, the rate of cooling from liquid to solid and the presence of nucleate. When the carbon is precipitated as flake graphite, the casting is called grey iron. (Fig. 1.2) if as carbide, the casting is said to be white iron. [3]

Figure 1.2 Random flake graphite, X100. [4] Ductile iron has been known only since the late 1940s, but it has grown in relative importance and currently represents about 20 to 30% of the cast iron production of most industrial countries. [5] Ductile iron, also known as spheroidal graphite (s.g.) iron or nodular iron is made by treating liquid iron of suitable composition with magnesium before casting. This promotes the precipitation of graphite in the form of discrete nodules instead of interconnected flakes (Fig. 1.3). The nodular iron so formed has high ductility, allowing castings to be used in critical applications such as: Crankshafts, steering knuckles, differential carriers, brake calipers, hubs, brackets, valves, water pipes, pipe fittings and many others. [3]

zer ,G., Evcimen, N. and Ekerim, A.

tenor of graphite powder is % 99.5. Furthermore, pressing process was applied on both graphite powders and steel scrap to obtain convenient samples for melting operations. Additional carbon content amount was determined by using Equation 2.1 [9]
( B C ) xM G A= Amount of charge C (kg) A =

(Equation 2.1) E=Percentage of experimental C (%) M= Mass of steel scraps (kg)

B= Percentage of exist C (%) G=Percentage of graphite tenor (%)

Melting process was realized on atmosphere controlled, single electrode, direct current electrical arc furnace as laboratory scale. Picture and schematic illustration of vacuum arc furnace has shown in Figure 2.1 a and b. Figure 1.4 Selective reduction of ilmenite. [6] The analysis of iron produced at Sorel also known as Sorelmetal is given in Table 1.2. The slag is high in titanium and low in iron and is therefore preferable to ilmenite in manufacturing TiO2 pigment or titanium metal. [6] Table 1.2 Analysis of iron produced from Qebec ilmenite at Sorel. C 1.8-2.5 V2O5 0 S 0.11 Cr 0.05 P2O5 0.025 Si 0.08 MnO Trace TiO2 Trace (a) (b) Figure 2.1 Vacuum arc furnace (a) Picture (b) Schematic illustration [10] After melting process both chemical composition and metallographic analyses were done on prepared samples. The specimens were grinded and then polished with Al2O3 paste. 2% nital was used to etch the samples. The microstructures of the samples were observed up to the magnification of 1000X in a light microscope with LEICA DFC280 Image Analyzer.

As the primary sources of metal, natural ores deplete consistently, there is an obvious recognition that the total supply of any metal on Earth is finite. It is evident that the metals have to be recycled from "scrap" to maintain a steady supply to meet the demands of industry and wherever else metals are used., recycling of metal from secondary sources (scrap of relatively abundant metals like iron, steel and aluminum) is an established industry, motivated by both economic as well as environmental factors. [7] According to this approach, improvements on iron- steel industry in process steps are accelerated. [8] In this study, experiments were carried out by bringing a new, different point of view on high purity pig iron production. An alternative method of production was investigated by using steel scrap instead of iron ore.

3. RESULTS and DISCUSSION

3.1. Chemical Analysis of Steel Scrap Acquirement of high purity pig iron, choosing the convenient steel scrap according to its chemical composition has great importance. The amount of Sulfur (S), Titanium (Ti), Magnesium (Mn) and Silicon (Si) must be as lower as possible. Chemical composition of selected steel scrap is shown in Table 3.1.

2. EXPERIMENTAL METHODS
Experimental studies started with selecting the conformable steel scrap. Chemical composition of the scrap was determined by optical emission spectroscopy on a HILGER Analytical. According to the determination of steel scraps, sawdust was prepared from them as small as possible in laboratory conditions. Graphite powders were used as a carbon source for transforming steel scrap to pig iron. Carbon

zer ,G., Evcimen, N. and Ekerim, A.

Table 3.1 Chemical composition of selected steel scrap. Fe 98.70 As 0.006 Mo 0.00 C 0.13 B 0.00 Ni 0.02 Si 0.250 Co 0.004 Ti 0.00 Mn 0.476 Cu 0.040 V 0.00 P 0.007 Nb 0.006 Al 0.052 S 0.18 Pb 0.00 W 0.04 Cr 0.027 Sn 0.024 Fe 95.5 Cr 0.02 B -

Table 3.3 Chemical analysis of Sample 1. C 4.32 Cu 0.04 V 0.00 Mn 0.038 Mo 0.005 Nb 0.006 S 0.010 Al 0.021 Ti 0.003 P 0.005 Sn Si 0.007 Ni 0.00 As W 0.013

The results as shown in Table 3.1, suitability of selected steel scrap that would be used in experimental study. 3.2. Determination of Charge Amount Mass of charge steel scrap was determinate as 20 g according to melting furnace conditions. Additionally, amount of charge carbon was measured by using Equation 2.1. Percentage of exist carbon content was taken as 4.00 and experimental was 0.134 (from Table 3.1). As mentioned before carbon tenor of graphite powder was taken as % 99.5. By placing, these dates in Equation 2.1, Equation 3.1 was achieved.
A=

Table 3.4 Chemical analysis of Sample 2. Fe 95.5 Cr 0.00 B C 4.09 Cu 0.00 V 0.00 Mn 0.146 Mo 0.002 Nb 0.007 S 0.031 Al 0.025 Ti 0.00 P 0.007 Sn Si 0.066 Ni 0.00 As W 0.001

Table 3.5 Chemical analysis of Sample 3. Fe 94.5 Cr 0.075 B C 4.13 Cu 0.00 V 0.00 Mn 0.293 Mo 0.003 Nb 0.010 S 0.031 Al 0.031 Ti 0.00 P 0.007 Sn Si 0.22 Ni 0.008 As W 0.099

(4 .00 0. 134 ) (20 g ) 0 .780 g (99 .5 )

( 3.1)

According to Equation 3.1 amount of charge carbon was determinate as 0.78g. After pressing the samples with pressing mold (Figure 3.1.(a)), shapes of samples became like Figure 3.1(b).

Table 3.6 Chemical analysis of Sample 4. Fe 95.4 Cr 0.00 B C 4.18 Cu 0.025 V 0.00 Mn 0.054 Mo 0.002 Nb 0.006 S 0.028 Al 0.054 Ti 0.001 P 0.08 Sn Si 0.07 Ni 0.00 As W 0.017

Table 3.7 Chemical analysis of Sample 5. (a) (b) Figure 3.1 View of (a) pressing mold, (b) pressed sample. 3.3. Chemical Analysis of Samples Firstly, chemical analysis of Sorel pig was done as shown in Table 3.2. Table 3.2 Chemical analysis of Sorel pig. Fe 95.1 Cr 0.00 B C 3.72 Cu 0.01 V 0.05 Mn 0.03 Mo 0.005 Nb 0.007 S 0.025 Al 0.005 Ti 0.003 P 0.023 Sn Si 0.032 Ni 0.05 As W 0.00 Fe 95.1 Cr 0.036 B C 4.20 Cu 0.044 V 0.00 Mn 0.124 Mo 0.002 Nb 0.015 S 0.026 Al 0.043 Ti 0.00 P 0.018 Sn Si 0.331 Ni 0.00 As W 0.048

3.4. Microstructure Analysis Microstructure analyses with magnification of 100X are shown in Figure 3.2.

Chemical analysis results of five samples are given in Table 3.3, 3.4, 3.5, 3.6 and 3.7.

zer ,G., Evcimen, N. and Ekerim, A.

References
[1] F. Habashi, Hanbook of extractive metallurgy, Vol.1, The Metal Industry Ferrous Metals, Wiley-VHC, 1997. [2] Elliott, R., Cast Iron Technology, ButterworthHeinemann, reproduced by permission of the publishers, 1988. [3] J. R. Brown, Foseco Ferrous Foundrymans Handbook, Butterworth Heinemann, 2000. [4] T. SJOGREN and I. L. SVENSSON, The Effect of Graphite Fraction and Morphology on the Plastic Deformation Behavior of Cast Irons ,Metallurgcal And Materials Transactions A, Vol. 38A, 840-847, 2007 [5] ASM Metal Handbooks, Vol.15, ASM International, 1988. [6] www.sorelmetal.com [7] S. R. Rao, Resource Recovery and Recycling from Metallurgical Wastes, Elsevier, 2006. [8] M. Yanmaz, klim Deiiklii ve AB Uyum Yaklamnn Demir elik Sektrne Etkileri, Erdemir Srdrlebilir evre Grubu, Kasm 2005. [9] N. Aras, Kresel Grafitli Demir Dkm, MMO, Yayn No:45, 1970. [10] A. C. Parlak, Titanyum Tetraklorrn Redklenmesi ve Titanyum retim Koullarnn Termodinamik Esaslarnn ncelenmesi, Y.T. Metalurji ve Malzeme Mh. Blm Lisans Bitirme Tezi, stanbul, 2004.

(a)

(b)

(c)

(d)

(e)

(f)

Figure 3.2 (a) Sorelmetal , (b) Sample 1, (c) Sample 2, (d) Sample 3 ,(e) Sample 4 ,(f) Sample 5 microstructures. The microstructures of the samples shown in Figure 3.2 could be compared with sorel pig (Figure 3.2 (a)). However, structures were changed according to sample chemical compositions, they pointed similarities with Sorelmetal pig structure.

4.

CONCLUSION

In this study, an alternative material, in comparison with sorel pig (most commonly used in production of spherical graphite cast iron known as ductile iron) has been investigated. During production process instead of using iron ore, high quality steel scrap has been employed. High quality pig iron production has been obtained by adding extra carbon into the steel scrap and melting in electrical arc furnace with repeating the operation three times. After melting process, completed similar results between samples and sorel pig were obtained in both chemical compositions and microstructures. According to this achievement, the pig irons produced by this alternative method could be used as an alternative of sorel metal pig. Furthermore, this method improves the recycling of steel scrap that provides environmental and economical benefits.