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CHEMISTRY
BACK
CHEMISTRY
Ir G HENDERIECKX
GIETECH BV
CONTENT
1. INTRODUCTION
2. IRON
3. CARBON
4. SILICON
5. MANGANESE / SULFUR
6. PHOSPHORUS
7. NITROGEN
8. LEAD
9. ALLOYING
1. INTRODUCTION
Grey iron is produced already over several thousand years. And yet there is a
continuous improvement and understanding of the material.
The foundry has control over the chemistry and temperatures, but everything
else is up to Mother Nature and sometimes she makes it very difficult because
the foundrymen do not always understand her.
Grey iron does exist, besides of the iron atom, thanks to 5 basic elements:
* carbon C
* silicon Si
* manganese Mn
* sulfur S
* phosphorus P.
It is not true that P and S are undesired elements and they only have a harming
effect to the iron.
At the end, the alloying elements, especially the ones to get higher strength will be
discussed.
2. IRON
Iron does consist of “cubic” crystals with a different lattice depending on the
temperature:
The simple cubic lattice is not found in grey iron (see figure).
When other elements are mixed with iron (Fe), there are 2 possibilities for entering
the atom:
substitutional
interstitial.
Substitutional:
One atom replaces another existing one. This is only possible if the size is
nearly equal. The elements that can do this are Mn, Cr and Si.
Interstitial:
A smaller atom will locate itself in between the other existing ones. This is only
possible if the size is much smaller. The elements that can do this are: C.
All elements, that have a much larger size, will mostly not be solved and will create
compounds that are pushed out of the metal as is slag. The most common ones are:
Mg, Ca and Ba.
Sulfur is a special element because it is too small and too large. See table.
Element Ba Ca Mg Cr Fe Mn Si S C
Diameter 4,34 3,94 3,19 2,49 2,48 2,48 2,34 2,12 1,54
During the solidification (starting at the T L-temperature and running till the TS-
temperature is reached), the liquid goes over to solid.
The common grey irons (Ceq from 3,7 to 4,2) mostly solidify as follows:
Iron with a low carbon equivalent (Ceq < 4,3 or hypo-eutectic) will always (partly)
solidify with dendrites and the free graphite will show up as type D and E.
A decreasing Ceq will tend to have more undercooling and dendritic solidification.
Iron with a high carbon equivalent (Ceq > 4,3 or hyper-eutectic) will solidify
eutectic without dendrites.
3. CARBON
3.1 Introduction
Carbon is the most essential element for iron. A lot of the properties are highly
influenced by carbon, which will appear as “free graphite”.
1. cementite or Fe3C
It contains 7 % of carbon and has a hardness of 550 – 600 HB.
In a lamellar structure, together with the ferrite structure, it forms
pearlite (ferrite + cementite).
2. free graphite
In the ferrite structure, only 0,025 % of carbon can be solved, the extra
appearing as free carbon. In pearlite there is maximum 0,87 % of
carbon (no alloying elements) to 0,60 % (due to alloying elements like
Si, Cr…).
In a commercial grey iron, example ASTM A48, class 30, containing
about 3,45 % of carbon, 80 % of it (or 2,76 %) will appear as free
graphite.
The free graphite, flakes for grey iron, is one of the major factors for the iron
properties. The graphite can appear in 5 different forms: A, B, C, D and E. This is not
taking in account the length of the flakes!
Graphite appearance:
1. Appearance A
This is associated with a chemistry
close to the eutectic (Ceq = 4,3), with
slow cooling and a potent nucleation.
2. Appearance B
This is a mixed appearance in this
way that the center of the cell will
contain type D and around the cell
periphery it will be A.
3. Appearance C
This is the appearance for a hyper-
eutectic composition where the first
solid phase is graphite rather than
austenite. The flakes are large and
coarse and called “pro-eutectic
graphite”.
4. Appearance D
This is the appearance when there is
a strong undercooling (high cooling
rate) or a low nucleation metal
situation.
5. Appearance E
This is the appearance when the chemistry has a low Ceq. It is a
complete dendritic cooling and solidification.
For the equal chemistry, metal with a graphite appearance D or E will have a
lower tensile strength than metal with an appearance of A.
The flake size is a crucial factor for the properties of grey iron:
The best way to control the number of flakes, the graphite appearance and the flake
length, especially for hypo-eutectic irons (Ceq > 4,3) is:
The addition of carbon is very important and has a different result depending on the
type of melting.
1. Electrical melting:
Requires time because the absorbing is a process
Carbon pick-up will increase by 10 % for each 50 °C of temperature.
Carbon must be added to a slag free metal bath to avoid that carbon is
hold by the slag or that it reacts with other elements in the slag.
The best addition is together with the steel charge because it will be
absorbed very quickly. The silicon is to be added after the carbon is solved.
Low ash containing recarburizers will increase the carbon pick-up
efficiency.
For a medium and high frequency furnace, the addition of carbon should be
done with a small size material. A main or low frequency furnace (50 Hz)
can have some larger sizes.
2. Cupola melting:
2.1 system
consistent coke bed preparation
symmetrical charging (compared to the furnace diameter and section)
maintenance of full stack to maintain a constant preheating of the
charged metal
control of the air addition and temperature
addition of coke with constant physical properties and size
addition of constant quality metallic charge
proper weighing of all charges (metallic and cokes)
addition of corrective amount of coke trough the tuyeres.
4. SILICON
4.1 Purpose
Without the addition of silicon, the graphite flakes will never be the correct and
desired ones.
The silicon will have a combined effect with carbon and therefore the carbon
equivalent (Ceq) is set: Ceq = C + Si / 3 + P / 3.
The phosphorous content is mostly less than 0,12 % and has a small influence.
Silicon is a graphitizer and will promote the eutectic solidification.
If silicon is added in an amount over the required one for graphitizing, it will promote
ferrite structure. The ferrite structure has a low strength and hardness.
If silicon is in excess of 3,5 %, it will harden the ferrite structure and make it more
brittle.
The difference between the eutectic graphite curve and the iron carbide curve (see
figure) is about 8 °C if the silicon content in the iron is zero. If silicon is increased, the
gap between the two lines is widening (see figure):
Percentage of silicon 0% 1% 2%
Difference between the two lines 8 °C 15 °C 35 °C
If the real cooling curve goes below the iron carbide eutectic line, due to a high
cooling rate and or the presence of carbide stabilizing elements, more carbides will
be formed.
For an equal Ceq, melting method, pouring temperature, inoculation and cooling rate,
an increase in carbon (and appropriate decrease in silicon) will:
The tensile strength can be calculated according to one of the following methods:
Method 1
This formula is valid for a grey iron if the composition is according following
conditions:
%C 2,90 – 4,00 % %P 0,05 – 1,00 %
% Si 1,00 – 3,30 % %S 0,03 – 0,18 %
% Mn 0,25 – 1,00 %
Method 2
This formula is valid for a grey iron if the composition is according following
conditions:
%C 2,90 – 4,00 % %P 0,05 – 1,00 %
% Si 1,00 – 3,30 % %S 0,03 – 0,18 %
% Mn 0,25 – 1,00 %
The real tensile value will be different from the calculated one. But if the basic
formula is good, the difference, in ratio, will be equal. Therefore the following factor is
set:
RG = Treal / Tcalculated.
5. MANGANESE / SULFUR
5.1 Sulfur
Sulfur will decrease the hardness and toughness and bring hot shortness.
If no manganese is present, it will form FeS with a melting temperature of 1193 °C. It
concentrates in the eutectic solidifying iron and forms thin films at the grain
boundaries.
5.2 Manganese
Totally solvable in iron because the atom dimension is equal to this of iron (Fe).
Manganese has a higher affinity to S, C and O than iron (Fe) and will first react with
them. It will be mostly present as (FeMn)3C and MnS.
Manganese will:
5.3.1 general
Forms MnS (see figure) with a freezing temperature of 1620 °C and a density of 4,0
g/cm3 containing 1,7 times more Mn than S (atomic weigh Mn is 55 and of S is 32):
Mn = 1,7 * S.
But to combine all the sulfur, there must be an excess of manganese to prevent the
formation of FeS, because also:
5.3.2 amount
So the amount of manganese will be: Mn = 1,7 * S + a %. How much must “a” be?
* a = 0,30 %: gives the lowest tensile strength in the absence of Cr, Mo and Cu
* a = 0,10 %: the tensile will increase due to the refining of the graphite and
the increased pearlite content, but the tendency to chilling will also
increase
* a > 0,30 %: the tensile will increase due to the pearlite formation and refining
of the grains
* a > x % (depending from foundry to foundry): tensile strength will decrease
due to the manganese segregation, which is accompanied by grain
coarsening and undesired grain boundary conditions.
This effect is depending on the presence of residual and alloying
elements. Some tests are given below as well as a figure.
* a > 0,50 %: will form sub-surface blowholes especially with low pouring
temperatures.
5.3.3 blowholes
The MnS dissolves in the FeSi & MnSi oxidized slag, which is very oxygen rich, on
the surface metal. It dissolves also carbon that forms carbon oxide (CO), which
escapes or stays in the metal, below the solidified top layer, as blowholes.
This reaction can go on for a long time and at low temperatures, because the new
formed slag has a low melting temperature.
The appearance can be seen in next figure. In the area of the blowhole, there will be
an excess of MnS and other complex slag.
5.3.4 nucleation
Because MnS is a high temperature component, it can act as nuclei together with Sr,
Ce and Ca, which also forms sulfides.
The influence of S on a non-inoculated iron is shown in next figure.
So especially the Ca, Ce and La and Sr are matching very well and should be
present in the inoculants for grey iron.
5.4 Conclusion
6. PHOSPHOROUS
P < 0,20 %
P > 0,20 % with a low strength.
Phosphorous does increase the tendency to form porosity in the hot spots. This
potential porosity is difficult to feed by risers and will look “spongy” or like “micro-
shrinkage”. See figure. The problem will start from P > 0,06 %.
If the casting has to be pressurized, the phosphorous content should be anyhow <
0,06 % and preferably < 0,02 %. The tendency to form porosity increases with the
presence of Cr, Mo and V, due to the increase in ternary eutectic. See figures.
Low phosphorous irons do have a higher tendency to metal penetration and fining!
Too much inoculation can also cause this, which can only be compensated by
increasing the phosphorous content from 0,02 to 0,06 % to 0,08 to 0,12 %. But the
risk for an increased porosity is still there.
7. NITROGEN
This element is mostly forgotten by the foundries. This can be due to the fact that, in
the time that iron was melted by cupola, the nitrogen content was fairly stable
because it was mainly introduced by the cokes.
Later when electrical melting entered the scene, the graphite introduction was done
by other material than coke.
The second fact was that the foundries started producing ductile iron, which has a
problem with too high sulfur content. To decrease the sulfur addition, the pure
graphite additions were introduced: electrode graphite, synthetic graphite…
But with the sulfur also the nitrogen was decreased or nearly disappeared!
Of course these figures are valid for castings with a wall thickness from 10 to 50 mm.
For larger sections, the maximum content (for problem of gas) must be lowered.
8. LEAD
Lead is one of the elements that really harm the grey iron metal quality.
Spiky graphite requires and the presence of lead and hydrogen, both above the
critical (high) level. Because the destroying of the flake graphite does take time
(similar to chunky graphite in ductile iron), this deformed graphite (spiky graphite) is
mostly present in thick section castings. The following rules are valid:
Lead does decrease the amount of ferrite and does increase hardness.
8.3 Remarks
Lead should be avoided totally. It mostly comes in the metal by improper copper or tin
or painted charged material. Cupola melting has fewer problems than electric melting
because most of the lead can evaporate during the melting.
9. ALLOYING
Alloying to increase the strength can be done by adding several elements, which all
have a different effect. The effect for some of the elements is:
It is known that each (alloying) element has an influence on the eutectic temperature.
This temperature, as shown in next figure, does influence the solidification
temperature range.
1. Properties of copper
It has a density of 8,93 kg/dm3, a face centered cubic lattice (FCC) and
a melting temperature of 1083 °C (1981 °F).
2. Solubility in iron
It is soluble from 3,0 to 3,5 % in iron. This solubility does increase if
nickel is added: 0,4 % by an addition of 1 % Ni.
3. Effect
* The main effect is:
low graphitizing effect if iron has common silicon level (Si from
1,7 to 2,4 %)
good pearlite promoter
poor pearlite refiner.
* It increases the tensile strength, the transverse strength and the
hardness. See figure on next page.
* It decreases the deflection (transverse test) a little.
* It does not influence the impact value.
4. Combination of elements
The combination with a pearlite refiner will have the best effect.
Example:
1 % Cu tensile strength +5%
0,5 % Mo + 20 %
1 % Cu + 0,5 % Mo + 40 %.
5. Risks
If copper is added in excess of the best percentage, the risk for the
metal properties are very low (see figure previous page).
If tin (Sn) is add in excess, the metal will embrittle very quickly.
If antimonies (Sb) is added in excess, the metal impact strength will
decrease and the graphite shape will become irregular.
Pay attention with the addition of copper because a lot of material does
have a residual amount of harmful elements like Sn, Pb, As and Te.
Formula 1
Sc = (% C) / {4,26 – 0,31 (%Si) – 0,33 (%P) – 0,047 (%Ni) – 0,40 (%S) + 0,015 (%Mo)
+ 0,063 (%Cr) + 0,135 (%V) + 0,027 (%Mn)} for aloyed iron
R2-correlation of the formula is 62.
Standard deviation of the formula is 27 MPa.
Formula 2
For alloyed cast irons an estimation of the tensile strength can be made with the
following formula (D is the diameter of the test coupon in mm):
To use this formula the following limitations are valid (in plus to the above limitations
for C, Si, Mn, P and S):
% Cr 0,2 – 0,6 % Cu 0,50 – 1,50
% Mo 0,2 – 1,0 %V 0,10 – 0,20
% Ni 0,6 – 1,0 % Sn 0,04 – 0,08
Formula 3
The influence of the particular elements is shown in the next table. If more alloying
elements are used, it is not allowed to add the influences per element.
It is very important to recognize that nitrogen (N) has an important influence on the
tensile strength. If the nitrogen content exceeds 90 ppm, there will be gas inclusions.
Formula 4
CE = (% C) + (% Si) / 3 + (% P) / 4
b: see figure
fi: see figure
Factor "b"
16
14
12
Factor "b"
10
8
6
4
2
0
1 10 100 1000
Equivalent diameter (mm)
Example:
Example 1
Diameter: 30 mm
Chemical analysis: C = 3,35 %, Si = 2,10 %, P = 0,08 %
Example 2
Diameter: 30 mm
Chemical analysis: C = 3,35 %, Si = 2,10 %, P = 0,08 %, 1 % Cu, 0,3 % Mo
Remark
The main difference between the formulas is mainly due to the effect of manganese,
which is different depending a lot on the manganese-sulfur ratio.
Equally to the formula of non alloyed grey iron, it is possible to use one formula and
set up the efficiency ratio:
RG = Treal / Tcalculated
This will be less usable as for the non-alloyed irons but can be of good help.
9.5 Conclusion
But this is not always possible to achieve the required strength. Therefore the
addition of alloying elements is necessary.
The best combination is one element to promote pearlite and one element to refine
the pearlite, both having a very low (or no) tendency to form carbides.