MANGANESE: FRIEND OR ENNEMY GRAY IRON

Manganese is one of the most popular alloying elements in gray iron, even that much that it is mostly not considered as an alloy. But it is because it does increase the pearlite content and as a consequence the tensile strength of gray iron. How did it become so popular? First it is a cheap element with a high availability. It is mostly added as a ferro-alloy with about 5 to 7 % of carbon. This alloy has a low melting point and this is an advantage when it was used in the cupola melting in earlier days. It also did show a tensile and hardness increase and additions even up to 1,00 % became common, especially when surface hardening (flame hardening) was locally required (slides of a tool bed casting). Let s systematically examine all influence of these element.

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009

MANGANESE: FRIEND OR ENNEMY GRAY IRON

1. Segregation It is known that manganese has a fairly high segregation behaviour, which means that the real manganese content at the surface layer is less than the content of the core of a section. The segregation tendency is ranked as follows (segregation factor), stating that a figure < 1,00 indicates an element that stays maximum in the first freezing liquid and a figure > 1,00 indicates an element that segregates to the last freezing liquid. Element Factor Mo Ti 25,3 25,0 V 13,2 Cr 11,6 Mn 1,7 3,5 P 2,0

Element Si Co Ni Cu Factor 0,7 0,4 0,3 0,1 The higher the factor, the more important the cooling time. A slow cooling (up to solidification), will increase the segregation.

The segregation effect is shown in next figure.

If the casting has small thickness (less than 25 mm), the segregation cannot cause a noticeable difference but if the sections are large or there is a hot spot (section thickness over 75 mm), the difference is measurable. So the foundries, pouring large castings did start getting porosity problems due to the fact that higher manganese content does increase the volume shrinkage during solidification.

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009

MANGANESE: FRIEND OR ENNEMY GRAY IRON

2. Increase pearlite content and strength The second influence is the increase of the pearlite content. The ranking for the pearlite promoting effect is as follows:
Element Effectiveness Sn 39 Mo 7,9 P 5,6 Cu 4,9 Ti 4,4 Mn 0,44 Ni 0,37 Cr 0,37

Increasing the pearlite content has the consequence that tensile strength and hardness should increase. This was not always achieved, unless the content was very high. What is the reason? In the absence of manganese, sulfur in iron forms iron sulfide which has a low melting point of 1193 C and thus will segregate to the eutectic ceIl boundaries, where the last areas to solidify are located. Manganese reacts with sulfur to form manganese sulfides. The ratio is 1,7 as shown in next formula. % Mn = 1,7 x % S So this amount of manganese is bounded and cannot increase the pearlite. On the contrary, it also removes sulfur from the matrix, which also is a pearlite promoter. So the real effect is, as shown in next figure, that first the tensile strength and hardness are decreasing and increasing with higher contents. The bottom point is obtained with about: % Mn = 1,7 x %S + 0,3 The effect of manganese is largely dependent on the sulfur content and it is clear that cupola iron will require much higher manganese content than electrical melted iron, due to its higher sulfur content (introduced by the cokes). This leads to the following formula and picture for calculating the expected tensile strength and hardness.
Rm = 1120 MPa + 2865 / D 150 (% C) 422 (% Si) 73 (% Mn 1,7 % S) - 181 (% Cu)2 164 (% Mo) 2 + 95 (% Cr) + 14 (% Ni) + 211 (% Cu) + 275 (% Mo) + 98 (% Si)2 D is the diameter of the test coupon in mm

It is clear that the effect of manganese on tensile is not very high.

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009

MANGANESE: FRIEND OR ENNEMY GRAY IRON

For the hardness, there is the following formula and graph.

HB = 444 71,2 (% C) 13,9 (% Si) + 170 (% S) - 61 {(% Mn) 2 + 58 {(% Mn) 1,7 (% S) -0,3} 1,7 (% S) -0,3}

HB = 444

71,2 (% C) 13,9 (% Si) + 170 (% S) - 61 {(% Mn) 1,7 (% S) -0,3} 2 +58 {(% Mn) 1,7 (% S) -0,3} + 20,5 (% Cr + % Cu) + 7 (% Ni) + 22 (% Mo)

The effect of manganese on the hardness is complex and first decrease strongly, after it will increase. To use this formula the following limitations are valid (in plus to the above limitations for C, Si, Mn, P and S):
%C % Si % Mn % Cr % Mo % Ni 2,90 1,00 0,25 0,20 0,20 0,60 4,00 3,30 1,00 0,60 1,00 1,00 % % % % % % %P %S % Cu %V % Sn 0,05 0,03 0,50 0,10 0,04 1,00 % 0,18 % 1,50 % 0,20 % 0,08 %

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009

MANGANESE: FRIEND OR ENNEMY GRAY IRON

3. Lining wear and slag Another problem occurred, especially with electrical melting, that the manganese was reacting heavily with the silicon of the ladle lining, causing a lot of slag and quick wearing of the lining. The slag consists of manganese-silicide compounds with a high melting point and is difficult to remove. This caused that, electrical melted iron that is supposed to be clean, was not the clean at all and more slag inclusions appeared in the castings. The slag also appeared in cupola melted iron but the foundries were aware of it and had mostly a much better slag removing procedure. 4. Blowholes The last problem that occurred was an increase in blowhole presence and frequency. This was surprising because blowholes are mostly caused by entrapped air or by CO inclusions. The formation can be explained as follows: Manganese sulfide freezes at 1620 C, highest of any constituent in the melt. Manganese sulfide (has a specific gravity of 4,0), will segregate by flotation during solidification. The quantity of manganese sulfide in commercial irons has no influence on either casting or use properties, but cope surface blowholes (mainly sub-surface) may be encountered when a critical value of the product of the manganese times sulfur content is exceeded, particularly in combination with low pouring temperatures.

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009

MANGANESE: FRIEND OR ENNEMY GRAY IRON

These blowholes occur as a result of the reaction of a fluid oxide-rich surface slag and graphite precipitated during solidification of the iron to yield carbon monoxide gas. Manganese sulfide serves to aggravate this situation as it floats to the surface and dissolves in the iron silicate/ manganese silicate oxidation slag, and lowers its melting point, creating a very fluid slag even at the eutectic temperature. Only a very fluid slag can be brought into intimate contact with graphite at eutectic temperatures. Evolution of steam from improperly dried refractory can also produce a very fluid and oxide-rich surface slag. Ladle surface slag produced by oxidation and chemical action is very important gas hole producing agents. This type of gas defect can occur in all types of moulds and is aggravated by the presence of high sand moisture contents. However, researchers showed that the chief contributing factor is low pouring temperature associated with high sulfur and manganese contents of metal (Figure above). In the reaction Mn + FeS =MnS + Fe an increase in concentration of either manganese or sulphur will cause manganese sulfide to be precipitated. The reaction proceeds to the right with falling temperature.

It is also recognized that the following maximum is blowhole free: % Mn = 1,7 x %S + 0,6

BLOWHOLES IN GRAY IRON

0,35 0,3 0,25
S (%)

BLOWHOLES DUE TO MnS

0,2 0,15 0,1 0,05 0 0 0,2 0,4 0,6 0,8 1 1,2 1,4 Mn (%)

NO BLOWHOLES

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009

MANGANESE: FRIEND OR ENNEMY GRAY IRON

Conclusion
The addition of manganese must be done very carefully and after evaluation of the effects due to the chemical composition, melting furnace lining and casting section. If carefully calculated and controlled, there will be a benefit at low cost. If just added, it can cost a lot of disappointments and extra scrap. Sometimes it will be much more cost effective to add copper in stat of manganese due to the low segregation tendency, high pearlite promoting effect and no interaction with the ladle lining.

Ir G.D HENDERIECKX

GIETECH BV MARCH 2009