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Factors Affecting Scale Adhesion

on Steel Forgings
J. A. Zitterman, R. P. Bacco, and W. E. Boggs

SUMMARY

Occasionally, undesirable "sticky" adherent scale forms


on low-carbon steel during reheating for hot forging. The
mechanical abrading or chemical pickling required to remove
this scale adds appreciably to the fabrication cost. Charac-
terization of the steel-scale system by metallographic exam-
ination, x-ray diffraction, and electron-probe microanalysis
revealed that nickel, silicon, and/or sulfur might be involved
in the mechanism of sticky-scale formation.
Laboratory reheating tests were conducted on steels with
varied concentrations of nickel and silicon in atmospheres
simulating those resulting from burning natural gas or
sulfur-bearing fuels. Subsequent characterization of the scale
formed during the tests tends to confirm that the composi-
tion of the steel, especially increased nickel and silicon
contents, and the presence of the sulfur in the furnace
atmosphere cause the formation of this undesirable scale.

INTRODUCTION

When desirable "sticky" adherent scale occasionally forms


on low-carbon steel during reheating for hot-forging appli-
cations, mechanical abrading or chemical pickling is required
to remove the scale. This adds appreciably to the cost of
processing. Characterization of the scale and the metal-
oxide interface of pieces considered to have undesirable Figure 1. Photograph of forging showing undesirable adherent
scale adhesion (e.g., Figure 1) was attempted by metallo- scale.
graphic examination, x-ray diffraction analysis, and electron-
probe microanalysis. Nickel was enriched in the metal at oxide formed on pure iron heated to high temperatures.
the metal-oxide interface and formed a filigree in the scale These are: wiistite (FeO), comprising about 95% of the
in the immediate vicinity of the interface. Silicon and iron total oxide volume; magnetite (Fe304), about 4%; and hema-
were combined to form fayalite (Fe2Si02) in the scale adja- tite (Fe203), about 1%. However, they stated that in an
cent to the interface. atmosphere of low oxygen potential, such as would result
A literature search revealed a number of hypotheses from combustion with an excess of fuel (or a deficiency of
regarding which factors are most important in the forma- air), the higher oxide, Fe203, might not form. In most
tion of desirable, loose, non-adherent scale. Palin l suggested industrial furnaces, the fuel is burned with some excess of
that furnace temperature and heating time determine the air so that the combustion products usually contain enough
adhesion of the scale. He found that adhesion was greater excess oxygen to permit hematite to form on the outer
on killed steel than on rimmed steel; he felt that the surface of the scale.
oxygen content of the atmosphere of a gas-fired furnace Sachs and Tuck also dealt briefly with the effects of steel
had no influence on the adhesion of the scale. composition on the formation of scale. They suggest that a
Sachs and Tuck2 attempted to account for all the param- concentration of CO or C02 in cavities in the scale might
eters that influenced scale growth on commercial steels cause cracking and an increase in the scaling rate or pre-
reheated in industrial furnaces. They suggested that large vent collapse of the cavities, healing, and thus slow the
differences in scale formation were due to a variety of rate of oxidation. On the other hand, they felt that the
conditions created in industrial furnaces. They further stated gases might fill the gaps and void!'!, thus preventing heal-
that, in addition to these conditions, the adhesion of the ing of the defects and slowing the rate of oxidation.
scale was influenced by topographic configuration of the Sachs and Tuck found that in contrast to the scale modi-
scale-metal interface and the composition of the steel, They fiers carbon and phosphorus, other elements form separate
found that under normal heating conditions with a stoichi- phases. One of the most important of these is silicon, which
ometric balance between fuel and oxygen, three layers of is present at --{).25 wt.% in killed steels. They state that
22 JOURNAL OF METALS· April 1982
this amount is sufficient to form Fe-Mn-Si pools and string- Gesmundo9 reported that the formation of sulfides mixed
ers in the scale. They further state that with higher silicon with oxides is often observed in high-temperature reac-
concentrations, a film of silica may form at the metal-oxide tions of a pure metal in a complex atmosphere containing
interface. This film would slow the rate of scaling. Because both sulfur and oxygen. This effect, he stated, leads to
the oxygen potential of silica is much lower than that of accelerated attack of the pure metal or alloy. This effect
wustite, oxygen diffuses from the iron oxide into the iron appears to be related to the high diffusion rate of cations
to react with the dissolved silicon to form an internal in the sulfides as compared with that of corresponding
precipitate of Si02. These particles of Si02 are caught up oxides.
in the advancing metal-oxide interface to form a layer of
fayalite (Fe2Si04) under the scale.
Nickel and copper are less easily oxidized than iron. As PRELIMINARY STUDIES
the iron at the metal-oxide interface enters the wustite
lattice, the nickel and/or copper are rejected by the scaling An experimental program was undertaken to test these
reaction and are concentrated at the metal-oxide interface. hypotheses and to determine what factors are responsible
Boggs6 found that, because nickel does not diffuse rapidly for the descaling problems encountered in hot forging of
back into the steel, a discontinuous nickel-rich layer is low-carbon steels. In the preliminary study, specimens A
built up at the metal-oxide interface. According to Wagner,7 through D of steels with compositions listed in Table I
interfacial instability develops as iron is internally oxidized were reheated according to the schedule shown in Table II.
in preference to the nickel. Eventually a filigree of nickel- These specimens, approximately 89 mm square by 25 mm
rich alloy develops, extending for an appreciable distance thick, were reheated in a laboratory muffie furnace with
into the scale. This filigree forms a strong mechanical Globar electric heating but with the combustion products
bond leading to an adherent scale that is difficult to remove from burning natural gas at fixed fuel-air ratios fed into
in steel finishing. the furnace to produce a furnace atmosphere similar to
Melford8 studied the effects of residual elements on hot that of a reheating furnace fired with natural gas. Air-fuel
shortness of mild steel. He considered nickel, copper, and ratios were set to provide either a 5% excess of oxygen or a
tin especially, but he also considered antimony and arsenic. 5% deficit of oxygen with respect to combustion stoichiom-
Although his concern was primarily hot shortness and not etry. Total heating and soaking times of 200 and 400 min
scale adhesion, the enrichment of residual elements, espe- were used. The final temperature was 1230°C, approximating
cially nickel and copper, resulting from the oxidation of the reheating temperature of an industrial forging fur-
commercial steel at temperatures between 1100 and 1120°C nace. After completion of the reheating schedule, the sam-
is of special interest. By electron-probe micronanalysis, he ples were air cooled.
found that nickel in a steel having a bulk nickel Electron-probe microanalysis showed enrichment of nickel
concentration of 0.14% had segregated in the subscale to a in the metal at the metal-oxide interface to about 1% and
concentration as high as 5-6% after oxidation. Copper sul- enrichment of silicon to concentrations of 1-6% in isolated
fide (CU2S) was occluded in the scale. areas of the scale in the vicinity of the metal-oxide inter-

Table I: Composition of Steels Used In Reheat Experiments, wt.%

Heat C Mn P S Si Cu Ni Cr Mo AI
----r 0.32 0.61 0.009 0.013 0.19 0.03 0.10 0.22 0.05 N.D.·
B 0.35 0.90 0.Dl5 0.23 0.21 0.01 0.02 0.06 0.01 N.D.·
C 0.29 0.78 0.022 0.018 0.20 0.04 0.05 0.05 0.02 0.024
D 0.29 0.75 0.009 0.021 0.22 0.02 0.01 0.02 0.02 0.031
E 0.066 0.049 0.001 0.007 0.011 0.026 < 0.002 0.006 < 0.003 0.021
F 0.05 0.62 < 0.001 0.007 0.08 0.02 0.10 0.09 < 0.004 < 0.002
G 0.042 0.62 0.003 0.005 0.012 0.026 0.10 < 0.003 0.007 0.013
H 0.32 0.72 0.011 0.025 0.18 0.06 0.02 0.003 0.01 N.D.·
I 0.29 0.75 0.012 0.015 0.16 0.02 0.02 0.04 0.01 .D.·
J 0.34 0.70 0.010 0.010 0.18 0.03 0.13 0.16 0.02 N.D.·
K 0.34 0.71 0.009 0.015 0.25 0.03 0.02 0.09 0.02 N.D.·
• Not dotermined

Table II: Schedule of Research Laboratory Reheating Tests at Furnace Temperature of 123O"C

% Deficiency or
Time in Excess of 02 in Furnace Scale Constituents
Test Number Heat Furnace, min Atmosphere· Major Minor Trace
1 A 200 +5 FeO FesO. Fe20 a
2 B 200 +5 FeO Fea04 F820a
3 C 200 +5 FeO FeaO. Fe20 a
4 D 200 +5 FeO FeaO. Fe20 a
5 C 400 +5 FeO FeaO. Fe20 a
6 D 400 +5 FeO FeaO. F820a
7 C 400 -5 FeO FeaO. Fe20S
8 D 400 -5 FeO FeaO. Fe20 S
·With respect to stoichiometric combUltion Hi'i, 95~ of the amount of 0, required and +5 i. 105"< ofthe 0, required for theorolically complete combustion).

JOURNAL OF METALS· April 1982 23


face. Results of x-ray diffraction analysis are shown in 1.1 % sulfur, a second series of reheat tests was run in the
Table II. Each of the scales contained a major concentration manner of the first series, except that 668 ppm S02 was
of wllstite, a minor concentration of magnetite, and a introduced into the furnace atmosphere during heating to
trace concentration of hematite. No fayalite was detected. simulate the furnace atmosphere resulting from burning
The silicon detection by electron-probe microanalysis may No. 4 fuel oil. Many of the samples the water quenched
have been present as fayalite or crystalline silica at less after heating, to stop air oxidation of the specimen during
than the 5% detectability limit for x-ray diffraction analysis cooling.
or may have been present as amorphous silica. Of the 20 samples reheated in the second series shown in
Table III fayalite was detected by x-ray diffraction analysis
as a trace constituent in the adherent scale of 13 samples.
STUDIES IN SULFUR-CONTAINING ATMOSPHERES As shown in Table IV, the heats on which detectable
Since steel used to forge the piece shown in Figure 1 was quantities of fayalite did not form were sample G, reheated
heated in an industrial furnace using No.4 fuel oil containing in oxidizing and reducing atmospheres, and samples H, I,
and K with the indicated silicon and nickel concentrations
in the bulk steel, heated in reducing atmospheres.
In addition to qualitative and quantitative electron-probe
microanalysis, characteristic x-ray imaging was performed
on preselected areas to show the distribution of specific
elements. Optical photomicrographs of the approximate
areas used for x~ray imaging are shown with photographs
of the images. Figure 2 shows a optical photomicrograph of
the approximate area used for characteristic x-ray imaging
for one of the steels studied. Photographs of the distribu-
tion of iron, silicon, nickel, and sulfur at a grain boundary
in the metal at the metal-oxide interface are shown in
Figure 3. Figure 4 shows the elemental distribution in an
area of the scale near the metal-oxide interface of the same
sample. The characteristic x-ray images for virtually all
the samples studied in Table III shows:
1. Enrichment of nickel in the steel at the metal side of
the metal-oxide interface, in grain boundaries of the metal
matrix, and in the filigree structure in the scale.
2. The association of iron and silicon as fayalite as a
distinct phase (determined by x-ray diffraction analysis) in
grain boundaries of the metal matrix, at the metal-oxide
interface, and in the grain boundaries of the scale.
3. The association of iron and sulfur as FeS (determined
by x-ray diffraction analysis) in the grain boundaries of
Figure 2. Optical photomicrograph showing area used for char- the metal matrix, at the metal-oxide interface, and in the
acteristic x-ray imaging, test no. 19, Heat F, 100x. grain boundaries of the scale.

Table III: Schedule and Results of Samples Heated 400 Min at 2250°F in Atmosphere Containing 668 ppm S02

% Deficiency
or Excess of O2
in Furnace Cooling Loose Scale Adherent Scale
Test Number Heat Atmosphere Method* Major Minor Trace Major Trace
13 D +5 W.Q. FeO Fea04 FeO FezSi04
14 C +5 W.Q. FeO Fe304 FeO FezSi04
15 D -5 W.Q. FeO Fe304 FeO FezSi04 + FezOa
16 C -5 W.Q. FeO Fe304 FeO FezSi04 + Fe Z03
17 F +5 W.Q. FeO Fe 304-U** FeO FezSi04
18 G +5 W.Q. FeO Fe304 U FeO
19 F -5 W.Q. FeO Fe304 U FeO Fe2Si04 + Fe203 + Fe304
20 G -5 W.Q. FeO Fe304 U FeO Fe304 + U
21 I +5 W.Q. FeO Fe304 U FeO FezSi04 + Fe20a
22 H +5 W.Q. FeO Fe30 4 U FeO Fe2Si04 + Fe304
23 -5 W.Q. FeO Fe304 FeO
24 H -5 W.Q. FeO Fe304 Fe 3 04-U FeO Fe203+ Fe304
25 J +5 W.Q. FeO U FeO Fe203 + FezSi04
26 K +5 W.Q. FeO FeO Fe2Si04
27 J -5 W.Q. FeO Fe304 FeO FezSi04
28 K -5 W.Q. FeO Fe30 4 Fe304 FeO
29 D -5 A.C. FeO U FeO FezSi04 + Fe304
30 C -5 A.C. FeO Fe30 4 U FeO FezSi04+ Fez03 + Fe304
31 I -5 A.C. FeO Fe304 U FeO Fea04
32 H -5 A.C. FeO Fe304 Fe304 + U FeO Fe304
*W.Q. = Water quenched, A.C. = Air cooled
**U =: Unidentified x·ray diffraction pattern

24 JOURNAL OF METALS· April 1982


4. The association of iron, silicon, and sulfur in what fayalite are evident in characteristic x-ray images of cross
appears as a complex compound of the elements, but is section of these specimens.
probably a mixture of iron sulfide (FeS) and iron silicate
(Fe2Si04). CONCLUSIONS
Even though fayalite was not detected by x-ray diffrac-
tion analysis of the steels shown in Table IV, there is It can be concluded that the presence of nickel contri-
reason to suspect that these iron sulfide and fayalite com- butes to the formation of an undesirable adherent scale.
pounds were present in quantities below the 5% detectability The presence of sulfur in the furnace atmosphere enhances
limit of this technique, Small amounts of iron sulfide of the oxidation of iron and silicon. Grain-boundary attack by

Table IV: Reheating Tests in Sulfur-Bearing Atmosphere


Scale Showed No Detectable Fayalite

% Deficiency or
Excess of 02 Sulfur Dioxide
in Furnace in Furnace
Test Number Heat %Si %Ni Atmosphere Atmosphere, ppm
18 ------cr 0.012 0.10 +5 668
20 G 0.012 0.10 -5 668
23 0.16 0.02 -5 668
24 H 0.18 0.02 -5 668
28 K 0.25 0.02 -5 668
31 0.16 0.02 -5 668
32 H 0.18 0.02 -5 668

Figure 3. Characteristic x-ray Images showing elemental distribution at grain boundary in test no. 19, Heat F, 500 x.

JOURNAL OF METALS· April 1982 25


sulfur exposes more silicon to oxidation and to reaction References
with iron oxide to form fayalite. It therefore appears that 1. G. M. Palin, STAL 8,119651, pp. 677-670.
the concentrations of nickel and silicon in the steel and the 2. K. Sachs and C. Tuck, Iron and Steel Institute Publication III, 119681, pp. 1-17.
3. K. Sachs and G. T. F. Jay. Journal of Iron and Steel Institute, 196, 119591. pp.
concentration of S02 in the reheat furnace atmosphere 34-44.
must be controlled to permit reheating of low-carbon steels 4. H. P. Haast;,r, W. Meischsner, W. Luckerath, and J. Williams, Thyssenforschung,
4,11969), pp. 127-135.
for hot-forging applications without formation of sticky 5. N. G. Vannerberg and I. Svedung, Corrosion Science, 11, 119711, pp. 915-927.
adherent scales. 6. W. E. Boggs, "The Role of Structural and Compositional Factors in the Oxydati on of
Iron and Iron-Based Alloys," in High Temperature Gas-Metal Reactions in Mixed Envi-
ronment, edited by S. A. Janson and Z. A. Foroulis, Metallurgical Society of AIME,
(1973), pp. 84-128.
7. C. Wagoer, J. Electrochem, Soc" 103, 119561, pp. 571-580.
8. D. A. Melford, J. Iron and Steel Institute, (19621, pp. 290-299.
9. F. Gesmundo, Oxidation of Metals, 13, (19791. pp. 237-244.

ABOUT THE AUTHORS

J. A. Zitterman, Research Engineer, Analytical


Chemistry Division, U.S. Steel Research Labo-
ratory, 125 Jamison Lane, Monroeville, Penn-
sylvania 15146.
Mr. Zitterman received his BS in chemical
engineering from the Pennsylvania State Uni-
versity in 1947. He has been involved in studies
of the effects of oxidation, corrosion, and diffu-
sion in steel and titanium alloys.

R. P. Bacco, Research Engineer, Analytical


Chemistry Division, U.S. Steel Research Labo-
ratory, 125 Jamison Lane, Monroeville, Penn7
sylvania 15146.
Mr. Bacco received his BS in materials sci-
ence from the University of Pittsburgh in 1973.
He has been involved in the materials analysis
techniq!Jes of transmission and scannihg elec-
tron microscopy, electron microprobe, x-ray
spectrometry, and x-ray diffraction analysis.

W. E. Boggs, Research Consultant, Basic


Research, U.S. Steel Research Laboratory, 125
JamiSon Lane, Monroeville, Pennsylvania 15146.
Mr. Boggs received his BS in chemistry in
1949 and his MS in 1962 from Carnegie-Mellon
University. He is the author or co-author of
experimental and/or theoretical papers and
research reports in various aspects of gas-metal
reactions, particularly the oxidation and scaling
of iron and iron-based alloys.

Coming in May
Journal of Metals
• Aluminum plant implementation of electromagnetic
casting
• Analytical methods for calcination control and
alumina properties
• Titanium technology
• Steelmaking technology
Plus:
Class of 1982-Seniors in Metallurgy/Materials
Science
Figure 4. Characteristic x-ray Images showing elemental dis-
tribution In the scale, test no. 19, Heat F, 500x.

26 JOURNAL OF METALS· April 1982