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HOT TOPICS

Issue #1 2007 Molybdenum in Ductile Iron


Molybdenum can be harmful and beneficial to Ductile Iron depending on the grade of iron. Basic Elemental Information Molybdenum ( Moly) Element Atomic Symbol Mo Atomic number 42 Atomic mass Density Melting point Boiling point Discovered by 95.94 g.mol -1 10.2 g.cm at 20C 2610 C 4825 C
-3

from the molten bath but can be diluted using clean scrap steel or pig iron. Depending on the level of moly, castings can be annealed to bring the casting back into specification. Beneficial effects of Mo Various levels of molybdenum are used in grey and ductile iron castings. In ADI moly is used for hardenability as needed up to a max of 0.3%. Beyond that level, segregation and excessive carbide formation in the grain boundary, lowers the ductility and toughness of ADI. The ausferrite matrix in ADI is much more sensitive to any defects present, hence the recommended limitation on the addition of Mo. In the Carbidic ADI or CADI grade, 0.5% Mo is added and carbides are stabilized through an ADI heat treatment. A majority of moly grade ductile irons are used in high temperature cyclical load conditions such as engine exhaust components (manifolds and turbocharger housings). Most of these are classified as SiMo grades of Ductile Irons with silicon (3.5 to 5%) addition to resist oxidation as well as increasing the AC1 temperature and moly levels between 0.4 to 1.2% are added for improved thermal fatigue and creep properties. On slow cooling the presence of Mo allows pearlite to transform into a secondary phase, commonly referred as Mo Rich Phase. This phase is more stable at the grain boundaries. Commercial grades of moly are typically available as a Ferro Alloy (FeMo with 60-75% Moly content) which is the most commonly used in the foundry industry. Microstructure Moly segregates to the last to freeze volumes of the casting. This moly rich carbide phase located typically at the grain boundries, at low magnification can be mistaken for a fine pearlite. (Fig2). At higher magnification (Fig3) moly rich phase is readily recognizable and SEM with EDAX analysis (fig4 and 5) clearly identifies the phase being rich in moly. Mechanical Properties In addition to the room temperature mechanical properties already mentioned, moly aids in improved

Carl Wilhelm Scheele in 1778 Molybdenum is a transition metal. The pure metal is silvery white, fairly soft, and has one of the highest melting points of all pure elements See Appendix B for production information.

Methods of Introduction As a tramp element, Molybdenum is typically introduced to the foundry process through scrap steel. Many HSLA and stainless grades of steel have Molybdenum added to them to promote the following: a) Raise austenite coarsening temperature b) Contribute to deep hardening c) Raise high temperature strength and creep resistance d) Enhance corrosion resistance Molybdenum can also be introduced into the foundry process by mixing alloyed iron returns of molybdenum bearing grades of cast iron. It is important to be able to segregate raw materials, scrap castings and sprue in the foundry process. Negative effects of Mo In normal grades of ductile Iron molybdenum should be kept to a minimum as it is a carbide former during solidification. Increased strength and reduced elongation (Fig1) is usually experienced along with reduced impact properties at sub zero temperatures. The effect on a particular iron grade or casting is dependent on factors such as Carbon Equivalent and section thickness. Moly cannot be readily removed

Tony Thoma, Wescast Industries, Brantford, Canada

mechanical properties at elevated temperatures. As moly level increases the creep rupture strength also increases while there is a reduction in the creep rate (Fig6, 7 and 8). The effective range of this improved performance appears to be in the range of 0.5 to 1.9% moly Alternatives to Mo As the market price of moly products have increased significantly over the last few years, many foundries have tried to mitigate these costs. Attempts to replace moly with other elements surrounding it in the periodic table (Vanadium, niobium, chromium, tungsten etc.) have been partially successful but may not generate the same results in performance. The reasoning behind this is that compared to Mo, these elements do not come out of solution at the same time during solidification, nor do they form the same phases in the matrix. Iron alloyed with Mo forms Mo rich phases at the grain boundary. Nb forms NbC scattered randomly throughout the structure. W forms carbides that locate closer to the grain boundary similar to Mo. Cr forms carbides and promotes pearlite. Appendix A

Fig 3

Fig 4

Fig 5

Fig 1

Fig 2

Fig 6

Molybdenum Market Review: Estimated Production by Region

145 126 123

146

100
2004 2005est

80

22 23

North America
12

South America

Asia (incl. China)

Others

Source: IMOA, Climax Molybdenum

January 1, 2007

Includes recycle catalyst

Fig 7
Molybdenum Production History

450 400 Million lbs. Molybdenum 350 300 250 200 150 100 50 0 1920 1930 1940 1950 1960 1970 1980 1990 2000 2005e
Source: IMOA, Climax Molybdenum estimates
11 January 1, 2007

CIS-Mongolia China Western By-Product Western Primary


By-product and Chinese production increases significantly

Climax mine started: 1917

By-product production as a source of molybdenum commences

Molybdenum Market Consumption Sectors

Fig 8 Appendix B World statistics of alloy


Furnace

Tool & High Speed Steels 5% Cast Iron 10%

Petrona Twin Towers, High-Speed Drill Kuala Lumpur, Malaysia 316 Stainless Steel

Stainless Steels & Super Alloys 33%

Catalyst & Chemicals 20%


Catalysts for Petrol & Fibers

Source: IMOA, Climax Molybdenum


13 January 1, 2007

Low Alloy Steels 32%

Low Alloy Pipeline

World Molybdenum Metallurgical Consumption


5-Year CAGR ~ 3.4%

300 250 Million lbs Mo 200 150 100 50 0

10 Year CAGR ~ 2.9% 15 Year CAGR ~ 3%

Global Molybdenum Reserves 2004: 19,000,000 mt

Source: US Bureau of Mines

14

19 90 19 91 19 92 19 93 19 94 19 95 19 96 19 97 19 98 19 99 20 00 20 01 20 02 20 03 20 04 20 05

Actuals
Source: IISI, Climax Molybdenum
January 1, 2007

Trend Line

Molybdenum Prices Rise to Record Levels


($/lb)

40 35 30 25 20 15 10 5 0
Ja n86 Ja n8 Ja 7 n8 Ja 8 n8 Ja 9 n9 Ja 0 n91 Ja n9 Ja 2 n9 Ja 3 n9 Ja 4 n9 Ja 5 n96 Ja n97 Ja n9 Ja 8 n9 Ja 9 n0 Ja 0 n0 Ja 1 n02 Ja n0 Ja 3 n0 Ja 4 n05 Ja n06
Source: Metals Week
15 January 1, 2007

Record High: $36.63/lb.

May 2005

20 year Average Price

$5.57/lb.

High: Jan 1995 $16.13/lb.

Production process of Molybdenum Mining Molybdenum has been found in various minerals. Only molybdenite (MoS2) is suitable for the industrial production of marketable molybdenum products. The Mo content of viable ore bodies ranges between 0.01 and 0.25%, often associated with the sulphide minerals of other metals, notably copper. Ore bodies and mines are classified in three types: Primary mines, where the recovery of molybdenite is the sole objective; ? ? By-product mines, which separate molybdenite during copper recovery; ? ? Co-product mines, where commercial viability is dependent upon the extraction of both molybdenite and copper-bearing minerals. Mining techniques used are:
?? ?? ??

Thompson

Creek

Open

Pit

Molybdenum

Molybdenum Ore

Open cast pits; or Underground block caving, wherein large blocks of ore are undercut and allowed to collapse under their own weight.

Molybdenum Processing

FeMo typically contains: Mo Cu 65 0.5% max. 75%

Sizes ranges are usually falling between:


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Smelting Ferromolybdenum

0 and 10 mm, and 10 mm on the low side and several maximum size limits between 20 and 100 mm

Between 30 and 40% of the production of roasted molybdenite concentrate is further processed into Ferromolybdenum (FeMo). The roasted concentrate is mixed with iron oxide and reduced by aluminum in a thermite reaction, producing an ingot of several hundred kilograms of ferromolybdenum grading between 60 and 75% molybdenum, balance essentially iron. After air cooling the ingot is crushed and screened to meet specified Ferromolybdenum product size ranges.

FeMo is also available as powder for special applications such as welding electrodes FeMo is packaged in steel drums or big bags. FeMo standards:
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ASTM A132-04 Standard Specification for Ferromolybdenum ? ? DIN 17561, 2004-02, Ferromolybdn
References 1) Bain E., Paxton H., Alloying Elements in Steel, Second Edition, American Society for Metals, 1966 2) Walton C, Opar T., Iron Castings Handbook Iron Castings Society, Inc, 1981 3) Hayrynen K, Applied Process Inc 4) SAE J2582, Automotive Ductile Iron Castings for High Temperature Applications 5) Black B, Burger G, Logan R. - Microstructure and Dimensional Stability in Si-Mo Ductile Irons for Elevated Temperature Applications. SAE 2002-012115. 6) Logan R., Presentation to DIS T&O June 2005 SiMo Ductile for Elevated Temperature 7) International Molybdenum Association Web Site 8) Allison J, Climax Molybdenum Co Molybdenum Market Overview, Oct 2006

Ferromolybdenum (FeMo)

Ferromolybdenum

FeMo can be used in any melting or refining unit to produce Mo containing steel or cast iron. It is especially used as ladle addition to achieve accurate final analysis adjustment. In steels with low Mo content such as High Strength Low Alloy (HSLA) steel with usually no more than 0.2% Mo, 100% of the Mo is added as FeMo.