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Richard Gundlach
Element Materials Technology, Wixom, MI, USA
Matthew Meyer
Kohler Co., Kohler, WI, USA
Leonard Winardi
Charlotte Pipe, Charlotte, NC, USA
Abstract
This work is the culmination of a literature review and at a carbon equivalent (CE) value of 3.9 to 4.0 and sufficient
foundry experiments designed to re-examine the roles of Mn alloying with Cu and Sn to assure a fully pearlitic structure.
and S on the strength of gray iron. Tensile strength, hardness, chill width, and thermal arrests
were determined.
A review of the literature showed that there are two princi-
pal regions in gray iron chemistries. A region where Mn and Tensile strength first increased with sulfur, reaching a
S levels are below the solubility limit of MnS at the solidifi- maximum strength level, and then decreased with further
cation temperature, and a region above the solubility limit. increases in sulfur. Maximum strength coincided with the
Twenty-four heats were produced in cast sections up to 3 solubility limit of MnS inclusions. Strengths reached 42 ksi
inches to investigate the influence of S on strength at three in the 1.2 inch B test bar, and 36 ksi in the 3 inch diameter
Mn levels, including low S concentrations, where S is fully test bar. For each Mn series, the differences in strength be-
soluble and no MnS precipitation occurs before the start of tween maximum and minimum values were 44% and 38%
eutectic solidification. At each Mn level, S was progressively for the B test bars and 3 inch bars, respectively. Variations
increased until MnS precipitated in the melt prior to reach- in chilling tendency were modest, except at the extreme low-
ing the eutectic temperature. est and highest S levels.
Master heats were produced at three Mn levels (0.3%, 0.5% Keywords: gray iron, cast iron, Mn:S ratio, MnS solubil-
and 0.8%). Sulfur was varied from 0.01% to 0.15%. The ity, free sulfur, tensile strength, chill, thermal analysis,
base chemistry was otherwise typical of Class 35 gray iron cell count
Tensile test specimens were machined from the A, B, C and The specimens were subsequently etched in 4% picral and
3 inch test bars. The specimens were machined with thread- once more examined for matrix structure and the presence
ed grips and the gauge sections measured 0.5 inch diameter of hard micro constituents such as chill carbides, intercel-
by 1.0 inch long for the A bars. For the B and C test bars lular carbides and phosphides, and for sulfide distribution.
and the 3 inch bars, the gauge sections measured 0.75 inch As anticipated, the metallic matrix in all specimens was fully
diameter by 1.0 inch long. The dimensions of the test bars pearlitic. The specimens were also inspected for degener-
conform to ASTM Standard E8. The test specimens were ate graphite forms resulting from elevated sulfur concentra-
tested using a crosshead speed of 0.10 inch per minute until tions. Samples from every Mn series displayed degenerate
failure. A total of 144 tensile flake forms at the higher sulfur
specimens were machined and concentrations (0.084% and
tested. The tensile test results above). Only samples from
are presented in Table 2. The the 0.28% Mn series displayed
test results are plotted in Fig- intercellular carbides, which
ures 1 through 3. were observed at the highest
sulfur concentrations. Repre-
Microstructure sentative photomicrographs
Evaluation displaying the “spiky” graphite
and the intercellular carbides
Metallographic samples were observed are shown in Figures
obtained from the gauge sec- 4 and 5.
tions of the broken tensile
specimens. One specimen The distribution of the man-
from each cast section for each ganese sulfide inclusions was
of the 24 ladle chemistries was Figure 1. Tensile strength as a function of % sulfur in evaluated in the as-polished
obtained for a total of 96 sam- the 0.28%Mn series. specimens. At lower S con-
Figure 2. Tensile strength as a function of % sulfur in the Figure 3. Tensile strength as a function of % sulfur in the
0.47%Mn series. 0.78%Mn series.
Figure 4. Spiky graphite in B-bar with 0.28%Mn and Figure 5. Intercellular carbides in C-bar with 0.28%Mn
0.087%S. and 0.10%S.
Figure 6. Interdendritic distribution of MnS inclusions in Figure 7. Uniform distribution of MnS inclusions in B-bar
B-bar with 0.28%Mn and 0.04%S. with 0.78%Mn and 0.11%S.
Figure 8. Graphite structure in B-bar displaying highest Figure 9. Graphite structure in B-bar displaying lowest
strength (with 0.28%Mn and 0.02%S). strength (with 0.28%Mn and 0.15%S).
ture difference between the Teu and the TELow was also For comparison, the theoretical solubility limit of sulfur, as
calculated. The results of these measurements are shown in well as the excess Mn content at the optimum sulfur con-
Table 3. centration in each Mn series, is listed in Table 4. The results
show that the optimum sulfur (%S at UTSmax) ranged from
Discussion 0.020% to 0.044%, it decreased with increasing Mn content,
and it was consistently below the “theoretical” (calculated)
At all three Mn levels, tensile strength was found to increase solubility limit of MnS. In contrast, the excess Mn content
and then decrease with increasing sulfur. The correlation of at the maximum strength decreased with increasing Mn con-
tensile strength with sulfur content for the three Mn levels centration. The excess %Mn increased from 0.21% to 0.74%
is shown in Figures 1 to 3. The maximum tensile strength as Mn increased from 0.28% to 0.78% when maximum
and minimum tensile strength in each bar size and for each strength was achieved. Furthermore, in the 0.78%Mn series,
Mn series are listed in Table 4 along with the sulfur content when an excess Mn of 0.3% (0.15%S) was reached, tensile
at the high and low strength levels. In addition, the ratio of strengths in all four sections reached their lowest values.
UTSmax to UTSmin is also listed in Table 4.
Statistical analysis was performed on some of the data for the
Within a given Mn series and bar size, the range in strength A and B test bars to verify that the observed trends in strength
between the lowest and highest values ranged from a low of are statistically significant. Tensile strength data for all three
16% to a high of 71%. The average range in strength was Mn series were plotted in the manner shown in Figure 15.
around 8 ksi, independent of section size. Note that these Each point in the graph represents the average tensile strength
lightly-alloyed Class 35 irons exceeded 40 ksi in the B pulled from a certain bar size and with specified sulfur content.
test bars of the 0.5% and 0.8%Mn series. Furthermore, at The error bar represents the “control limit” of the experiment
an optimum sulfur content, Class 35 iron properties were which indicates 95% probability of significant difference in
achieved in the 3 inch bars. The variation in strength with the data, if it is outside the error bar. The “control limit” takes
sulfur content observed in this study is consistent with pre- into account the experimental and measurement errors as well
dictions, and the findings in the literature review.5 Strength as the degree of freedom, or the sulfur levels in this case. A
correlated best with MnS solubility limit, rather than with trend of increasing, then decreasing tensile strength as a func-
stoichiometric balancing of Mn and S. tion of sulfur was observed throughout. The tensile strength
ture difference between the Teu and the TELow was also For comparison, the theoretical solubility limit of sulfur, as
calculated. The results of these measurements are shown in well as the excess Mn content at the optimum sulfur con-
Table 3. centration in each Mn series, is listed in Table 4. The results
show that the optimum sulfur (%S at UTSmax) ranged from
Discussion 0.020% to 0.044%, it decreased with increasing Mn content,
and it was consistently below the “theoretical” (calculated)
At all three Mn levels, tensile strength was found to increase solubility limit of MnS. In contrast, the excess Mn content
and then decrease with increasing sulfur. The correlation of at the maximum strength decreased with increasing Mn con-
tensile strength with sulfur content for the three Mn levels centration. The excess %Mn increased from 0.21% to 0.74%
is shown in Figures 1 to 3. The maximum tensile strength as Mn increased from 0.28% to 0.78% when maximum
and minimum tensile strength in each bar size and for each strength was achieved. Furthermore, in the 0.78%Mn series,
Mn series are listed in Table 4 along with the sulfur content when an excess Mn of 0.3% (0.15%S) was reached, tensile
at the high and low strength levels. In addition, the ratio of strengths in all four sections reached their lowest values.
UTSmax to UTSmin is also listed in Table 4.
Statistical analysis was performed on some of the data for the
Within a given Mn series and bar size, the range in strength A and B test bars to verify that the observed trends in strength
between the lowest and highest values ranged from a low of are statistically significant. Tensile strength data for all three
16% to a high of 71%. The average range in strength was Mn series were plotted in the manner shown in Figure 15.
around 8 ksi, independent of section size. Note that these Each point in the graph represents the average tensile strength
lightly-alloyed Class 35 irons exceeded 40 ksi in the B pulled from a certain bar size and with specified sulfur content.
test bars of the 0.5% and 0.8%Mn series. Furthermore, at The error bar represents the “control limit” of the experiment
an optimum sulfur content, Class 35 iron properties were which indicates 95% probability of significant difference in
achieved in the 3 inch bars. The variation in strength with the data, if it is outside the error bar. The “control limit” takes
sulfur content observed in this study is consistent with pre- into account the experimental and measurement errors as well
dictions, and the findings in the literature review.5 Strength as the degree of freedom, or the sulfur levels in this case. A
correlated best with MnS solubility limit, rather than with trend of increasing, then decreasing tensile strength as a func-
stoichiometric balancing of Mn and S. tion of sulfur was observed throughout. The tensile strength
Figure 15. Mean and range in tensile strengths in the A Figure 16. Hardness in B-bars as a function of sulfur
and B bars as a function of %Mn times %S at a 0.28%Mn content at three Mn levels.
level.
reaches a maximum at 0.03% sulfur and starts to decrease shown in Figure 16. In contrast, hardness increased continu-
around 0.1% sulfur. The effect of sulfur on tensile strength is ously with sulfur content for the B bars of the 0.28%Mn se-
also more pronounced in the smaller A test bar than the larger ries. Hardness increased from 185 to 218 HB, which is an
B test bar, but it is less significant with increasing Mn content. 18% increase in hardness with no change in pearlite content;
all samples were 100% pearlitic.
The maximum attainable strength increased with increas-
ing Mn concentration. The increase in strength with Mn was The increase in hardness with sulfur content in the low-
consistent in all four cast section sizes. The increase in Mn Mn alloy series is attributed to the influence of free sulfur
content was accompanied by a steady and modest decrease on pearlite transformation and combined carbon content.
in carbon equivalent due to some carbon loss over time. The At higher levels, sulfur is known to increase hardness,
carbon equivalent value ranged from a high of 4.03 in the based on past research.7,8 The influence of sulfur on hard-
0.28%Mn series to a low of 3.83 in the 0.78%Mn series, as ness was attributed to the concentration of sulfur at the
shown in Table 1. The increase in strength with increasing graphite-metal interface. At the very highest level, some
Mn content was largely attributed to the decrease in carbon intercellular carbides were present and they further in-
equivalent value and its influence on strength. creased hardness.
Hardness For the alloys with higher Mn levels, hardness was relatively
unchanged. It is surmised that at higher Mn levels, MnS pre-
Hardness was generally unchanged with increasing sulfur cipitation occurs and the soluble, or free sulfur content is
content in the two series containing higher Mn levels, as restricted to lower values.
The range in strength among the four bar sizes varied de-
pending on the sulfur content. The range was greatest at the
optimum sulfur level where UTSmax occurred, as shown in
Figures 1 to 3. The range in strength was lowest at the highest
concentration of sulfur. This finding suggests that the negative
effect of sulfur on graphite structure is greatest in the lighter
cast sections, where solidification rates are highest.
Figure 17. UTS/HB ratio in the B bars as a function of Figure 19. Maximum Àake size as a function of sulfur
sulfur content at three manganese levels. content and bar size.
The TElow temperature tended to increase and then de- When looking at the 1st derivative of the thermal analysis
crease with increasing sulfur concentration in all three cooling curve, the eutectic start (TES) temperature is de-
Mn series, as shown in Figure 22. In the 0.28%Mn series, tected by a change in the slope of the cooling curve in the
following an initial rise in temperature, TELow decreased region between the austenite liquidus and the temperature
continuously, producing a wide range in TELow values. of maximum undercooling (TElow temperature). The TES
The continuous decrease in TELow temperature with in- temperature was derived from the thermal analysis curve,
creasing sulfur is attributed to the negative influence of and the correlation of TES temperature with sulfur content
sulfur on the growth of graphite. is shown in Figure 23.
Figure 21. Chill width as a function of TElow temperature Figure 22. Temperature of maximum undercooling
in W2 chill wedges. (TELow) as a function of sulfur at three Mn levels.
The correlation of free sulfur and total sulfur for the three
Mn series is shown in Figure 26. At lower sulfur levels,
sulfur is fully soluble. When the MnS solubility limit is
exceeded, there is an inflection in the free sulfur vs. to-
tal sulfur curve. In the 0.28% Mn series, MnS solubility is
Figure 24. Cell count and chill depth as a function of sulfur
high and the free sulfur vs. total sulfur curve is linear up
in 0.75%Mn cast iron, after Muzumdar and Wallace11. to high sulfur concentrations. However, at higher Mn lev-