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