Correlation of Oxidation Carburization and Metal Dusting Controlling Corrosion by Corrosion (51300-01374-Sg)

01374
2001
CORROSION
CORRELATION OF OXIDATION, CARBURIZATION AND METAL DUSTING;

"CONTROLLING CORROSION BY CORROSION"
R. Kirchheiner
Manager of Central R&D Schmidt & Clemens GmbH + Co. KG.
Edelstahlwerk Kaiserau, D-51779 Lindlar, Germany
J. L. Jim~nez Soler
Manager of Local R&D Centracero S.A.
Carretera Estella-Vitoria, Km. 12, E-31280 Murieta / Navarra, Spain
ABSTRACT
Metal dusting has been observed in industrial high temperature process components such
as waste heat boilers in reformers and gas pre-heaters in direct reduction plants. This
corrosion phenomenon is a disintegration of metallic materials into carbon (graphite) and metal
dust. The degradation takes place in strongly carburizing atmospheres with carbon activities
greater 1 (ac>>l) and at intermediate temperatures between 400 C - 900 C. Slight
modifications in the process conditions may affect significantly the occurrence and extent of
metal dusting attack.
To correlate high temperature corrosion mechanisms, e. g. oxidation, carburization and
metal dusting for alloy design purposes, results of laboratory investigations are compared with
field observations and experience. Most of the work described herein is concerned with gas
mixtures of hydrogen and carbon monoxide used in the direct reduction of iron ores (DRI).
Considerations are given concerning the process variables as well as on the recent
development of new high performance alloys which should form an inherent stable oxide layer
formation.
A controlled formation of a dense, protective, self-healing alloy surface oxide gives
reasonable protection of plant components under most aggressive metal dusting parameters.
Keywords: syngas plants; reformers; hydrogen; carbon monoxide, direct reduction of iron ores;
gas pre-heaters; waste heat boilers; high temperature corrosion; carburization; oxidation; metal
dusting; high performance alloys; nickel-base alloys; HK 40; HP 40; 45 Micro; G 4879;
experimental alloys; coatings.
Copyright
2001 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are
solely those of the author(s) and not necessarily endorsed by the Association. Printed in U.S.A.
RANJEET SINGH - Invoice INV-785793-LJJQH0, downloaded on 4/11/2014 4:18AM - Single-user license only, copying/networking prohibited.
Paper No.
Metal Dusting Mechanisms of High Performance Alloys

Metal dusting is one of the most common high-temperature corrosion process observed in
petrochemical and reforming industries and direct reduction plants. Metal dusting was also
found in the heat treating industry and in coal gasification plants. This phenomenon occurs in
strongly carburizing atmospheres mainly in a most critical temperature range between 450 C 750 C. Corrosion products are carbonaceous deposits (coke) containing very fine metallic
particles.
Actually there is no Fe- or Ni-base alloy for which one can be sure that it is absolutely
resistant to metal dusting attack. Research work is focused on the reaction chain from the
formation of alloy substrate oxide layers and deteriorating conditions. Accordingly carbon and
coke deposition, carbide formation and decomposition are investigated.
Metal dusting as a catastrophic form of carburization has been investigated by Grabke et
al. 1'2'3'4 in flowing CO-H2-H20 mixtures at carbon activities ac>>l.
For the nickel-base alloys, Grabke et al. proposed the following mechanism:
.
.
3.
4.
.
.
carbon transfer from the gas phase and dissolution of carbon into the metal phase at
oxide defect sites
formation of a supersaturated solution of carbon in the Ni-Fe matrix
deposition of graphite on the alloy surface in different orientations
growth of graphite into the metal phase by carbon atoms from the solid
solution, attaching to graphite planes growing vertical to the metal surface
destruction of the metal phase by the inward growing graphite under transfer of metal
particles into the 'coke' layer
further graphite deposition from the gas phase on these catalytically active metal
particles (Fe, Ni)
The chemical reactions producing such high carbon activities, e. g. in reformer applications
are
Hydrogen reformer:
CH4 +
H20 = CO +
3H2
(1)
in a temperature regime between 550 C and 850 C. This gas composition may change due
the following reactions:
Reaction:
Boudouard reaction:
CO + H2 = H20 + C
2 CO = CO2 + C
(2)
(3)
In cases where carbon activities are calculated to be ac>> 1 for reactions (2) or (3) metal
dusting may occur as a catastrophic reaction of carbon monoxide and carbon with metallic
materials.
High performance alloys bear the potential to form a protective chromia scale (Cr203), even
at high carbon activities and concurrently low oxygen partial pressures. On these high-alloy
steels, attack develops locally, where oxide layers have failed. Then at first internal carbide
formation occurs of the stable carbides M7C3, this carburization also retards the over-saturation
and start of metal dusting somewhat. Metal dusting starts with the outgrowth of coke from
shallow pits that widen with time into hemispherical pit geometry or grooves.
INTRODUCTION
Corrosion mechanisms like oxidation and carburization govern metal dusting. Uniform
oxidation of the alloys definitely inhibits carburization and metal dusting temporarily through
formation of protective scales. Scale formation is supported by high chromium contents, medium
silicon contents, small grain sizes and induced surface deformation. All these factors make
chromium and other stable oxide formers (Mn, Si, AI ...) diffuse faster to the surface and
therefore increase the re-healing capacity of the dense protective chromia layer.
Controlling these most favored oxidation mechanisms therefore bears the potential to
control metal dusting. 5
According to G. Lai, Figure 1 shows the central role of oxidation in directing all other forms
of high temperature corrosion. Oxidation therefore plays a two-fold role in corrosion processes:
1. external and internal oxidation, corroding low chromium containing alloys
2. stable chromium oxide layer formation (Mn, Cr-spinel, chromia / Cr203) protecting high
chromium bearing alloys.
However, "real" metallic alloys contain a lot of microscopic defects which upon creep or
thermal cycling tend to destroy formerly grown oxide layers. Figure 2 acc. to Engel shows the
microscopic appearance of alloy structures with potential defect sites. These local defects,
e. g. grain boundaries, brittle carbon films, non-metallic inclusions and lattice dislocations are
able to disturb protective scale formation and cause its failure by cracking or spelling.
Figure 3 shows the potential reactions between gas and metal, whereas in phase I
carburization under oxidizing conditions is delayed by formation of a substantial chromium-rich
external scale. The initially formed dense oxide layers (phase I) are destroyed locally in phase
II and give way for the access of high carbon activity gases.
The existing carbides are primarily chromium carbides. The phase CrzC3 has a much lower
gas permeability than M7C3 which therefore protects the matrix a~ainst carbon ingress and
diffusion if this phase remains in a fine dispersed form, see Figure 4 ~'.
In principle no material, able to dissolve carbon, is immune to disintegration by metal
dusting, either by intermediate formation of a non-stable carbide M3C or by direct
decomposition of the supersaturated solution of carbon into metal and graphite. Long-term
corrosion resistance therefore is guaranteed by a stable oxide layer formation only.
Retardation is possible by low carbon solubility and diffusivity and a concurrently high content
of carbide forming elements.
Therefore the alloy composition is one of the major factors governing corrosion resistance
under metal dusting atmospheres.
This paper is addressed to the very beginning of the reaction chain, the formation and
interaction of protective oxide layers on high performance alloys. Within this research work it is
demonstrated that the concerted action of an optimum alloy substrate composition with
specifically controlled conditions for the formation of oxide layers is capable reducing metal
dusting attack.
Controlling Corrosion by Oxidation
Laboratory Investigations - Oxidation

Oxidation as a Function of Alloy Composition and Oxygen and Carbon Activities
An investigation was made to elucidate the effects of alloy composition on oxidation, carburization
/ decoking and post-coking oxidation treatmentsB. The kinetics of air-steam oxidation, coking
treatments at 1,000 C and air-steam re-oxidation treatments after decoking were investigated at
900 C. The materials investigated are listed in Table 1. The test gas atmosphere for oxidation
tests of virgin materials was generated by passing an air-stream through a near boiling water
reservoir producing a partial steam pressure of 0.046 MPa. The flow rate was adjusted at 400
ml/min air and 330 ml/min steam. Carburization and coking was executed at 1,000 C in an 89 %
hydrogen / 11% propylene atmosphere for two hours at a flow rate of 517 ml/min, followed by a
decoking procedure at 900 C again in an air-steam atmosphere. Post-coking air steam oxidation
was performedat 900 C for 24 hours to determine the different kinetics for the alloys. Specimens
used in this investigations were cut from industrial scale centricast tubes. In the case of HP 40 a
modified alloy was also made with an increased silicon content of 2.6 % Si, named alloy HP 40
hSi. Also an experimental Alloy "A" was included, based on a 30Ni-18Cr iron matrix bearing
1.7 % aluminum amongst other element additions.
Results are given in Table 2 and Figure 5. Table 2 shows the rate constants for air-steam
oxidation and post-coke air-steam oxidation. The rate constants indicate that the standard
reference Alloy HP 40 has the highest rate of reaction whereas the high silicon modified HP 40
shows a marked decrease in reaction speed. The lowest reaction rate, however, occurred with
experimental Alloy "A" where reaction was hardly measurable after the test. The morphology of
the scale formed on experimental Alloy "A" reveals a patchy sub-micron thick external scale with
a certain degree of internal oxidation in near surface areas. Results of x-ray diffraction analysis
(XRD) shows that oxidation in air-steam mixtures produced a duplex scale on virgin specimens at
900 C. An external layer of chromia (Cr203) and an inner layer of iron-chromium spinel Fe Cr204
was found on all materials. These findings might be explained with ongoing oxidation of the
initially formed spinels to chromium oxides under high partial pressures of oxygen. The coking
procedure produced M7C3 and carbon precipitates in a near-surface region. Experimental Alloy
"A" showed minor internal carburization at this temperature. After the post-coking air-steam
oxidation at 900 C traces of MTC3 were detected along with chromia and iron chromium spinels.
Experimental Alloy "A" also showed a stable and thin layer of alumina (AI203). A preliminary
conclusion is that alloys containing no aluminum are susceptible to internal carburization with
parabolic weight gain kinetics. Experimental Alloy "A" showed, that the aluminum content was
sufficient to suppress carburization almost completely in these short-time tests even at high
carbon activities. High silicon contents were found slightly to reduce the weight gain during
carburization / coking at 1,000 C. Silicon acts in altering the solubility and diffusivity of carbon
into the matrix metal.
EXPERIMENTAL PROCEDURE
Carburization as a Function of Oxygen Partial Pressures Cast austenitic steels were tested in
the form of samples made from investment casting and centricast materials 1. Prior to testing they
received a #600 grid finish grinding. Tests were performed in flowing gas mixtures at
temperatures of 900 C, 1,050 C and 1,150 C. The two gas mixtures were mixed to form
1) a highly reducing and strongly carburizing atmosphere / 89 vol.-% hydrogen
+ 11 vol.-% propylene (pre-dried)
2) a mildly oxidizing gas mixture / 89 vol.-% hydrogen + 11 vol.-% propylene
+ steam (H20).
Carbon activity of both gases was unity (carbon deposits on the samples) but, in comparison
to mixture 1, the oxygen potential in the second gas mixture was sufficient to oxidize both
chromium and silicon. However, iron and nickel could not be oxidized at these low partial
pressures (10 .24 atm / 900 C, 10.2o atm / 1,050 C). At 900 C the water content of gas mixture 2
amounted up to 3 x 10.3 atm., whereas at 1,050 C the steam partial pressure was 6 x 10.2 atm.
Carburization kinetics for a centricast Alloy HP 40 Micro (C6) as a function of time is given in
Figure 6 in reducing gas atmospheres as well as in oxidizing gases 1. For temperatures between
900 C and 1,150 C the kinetics is parabolic and can be described by the expression
X + X' = 2 . k p - t
X=
t =
X '=
k~ =
(4)
carburization depth in micrometer

time at temperature
constant
parabolic, constant.
In the "reducing gas" atmospheres, it was found that specific alloying additions decrease
carburization rates markedly. Comparing standard Alloy HP 40 Micro with 24 % Cr to an alloy
with 30 % Cr in the matrix at 900 C the carburization rate constant is decreased from
kp = 1.6 x 10-3 (prnz x h -1) down to
kp = 0.9 x 10"3 (prn= x h"1)
(5)
(6)
More or less the same reduction in carburization was found with alloys just differing in their
silicon content, e. g. Alloy HP 40 1.8 % Silicon to Alloy HP 40 hSi with 2.6 %. Silicon is effective in
altering the solubility and diffusivity of carbon in the fcc-matrix. Aluminum was found to be even
more effective in forming a dense and stable external oxide layer.
Carburization in Pack Cementation Tests To compare the properties of centricast alloys,
particularly concerning their carburization resistance, tests were performed in a carbon pack. Test
bars were cut from the tube wall and packed in a carburizing powder at temperatures increasing
stepwise (+ 25 C) from 950 C to 1,175 C. The total test duration was 260 hours. Test results
clearly differentiated between the standard HK 40 and the 45 % nickel - 35 % chromium
containing Alloy 45 Micro, see Figure 7. Due to a better balanced composition Alloy 45 Micro with
its optimum chromium content showed almost no visible carburization at 1,100 C. Also the
higher nickel content contributes to a lower rate of carburization.
Laboratory Investigations- Carburization
The Effect of Alloy Composition, Temperature, Pressure and Surface Rouqhness

The intention of an ongoing study is to obtain additional information concerning the role of
temperature and surface engineering on centricast high performance alloys. Four alloys were
tested in a flowing hydrogen - carbon-monoxide - carbon-dioxide - methane - nitrogen gas
mixture at 650 C and 750 C. Initial test periods were set to 180 hours. Mass gain or loss was
measured accompanied by microstructural and surface analysis. The alloy compositions are
given in Table 1, i. e. Alloys 45 MTZ (C12), 45 LC (C13) and HP 40 MW (C8), HP 40 MT (C9).
These four alloys are grouped in two families, e. g. HP 40 and Alloy 45. Predominating
differences are in the nickel and chromium contents (8 = 10 % Ni/Cr) as well as in minor alloying
constituents.
The composition of the test gas was chosen close to the gas atmospheres produced in
methane reforming plants and used in direct reduction of iron ore (DRI). The gas mixture is
composed out of 70 % H2, 16 % CO, 3 % CO2, 8 % CH4, 1.3 % N, 2 % H20. The gas flow was
maintained at I I/min.
Test pieces out of centricast tubes were cut in rectangular blocks (10 mm x 5 mm x 5 mm).
The machined surfaces were subsequently finished with # 50 or # 600 grade silicon carbide
paper under controlled conditions of grinding speed and force.
After heating the top-load autoclave (200 C/h) to 650 C and 750 C respectively, the system
pressure was adjusted to 0.1 Mpa (1 bar). Experiments were interrupted periodically for the
purpose of inspection and weighing. One sample of each alloy was removed for analysis using
XRD, SEM and optical methods.
To explain the intermediate results some preliminary remarks are essential. Thermodynamical
calculations show that the carbon activity values obtained in the studied gas mixture varied, as
expected with temperature and pressure. Up to 600 C, there is a marked difference in carbon
activities, yielding the highest ac values (ac ~ 230) for 1.0 MPa (10 bar) pressure, see Figure 8.
Beyond a temperature limit of about 700 C, carbon activities are obtained significantly less than
50. At around 800 C, irrespective of the pressure, the carbon activities are below 25.
Considering thermodynamics, the graphs of phase equilibrium of the main oxide-forming
elements of the materials have been marked (asterisk) for the corresponding gas mixture of these
experiments, see Figures 9, 10 and 11. For chromium, see Figure 9, the Cr203 stability field is
reduced with the temperature. The balance given by the gas mixture is placed close to the Cr3C2
carbide. This supports the hypothesis that Cr3C2-carbides (surface) and partially Cr7C3 (eutective
primary carbides) are transformed into chromium oxide Cr203 by a non-inhibited oxidation. CrTC3carbides also will be transformed into 0r2306 (secondary carbides) during the ageing process.
This is probably one of the deterioration mechanisms of the chromia scale, e. g. the oxidation
alongside internal carbides. According to Figure 10 silicon dioxide is the stable phase in these
experiments. In the vicinity of the metal dusting peak temperatures, e. g. between 600 C and
800 C the stability field of silicon dioxide is increased. This contributes to literature results,
referring to a better metal dusting resistance with increasing silicon contents.
In Figure 11 it is shown that the gas mixture point is placed close to the borders of Fe3C
(cementite) and Fe304 (hematite). Thermodynamically therefore it is possible that Fe3C carbides
may be oxidized into Fe~O4 causing micro cracks in a protective chromia scale.
A deterioration mechanism is schematically referenced in Figure 12 with formation of unstable
carbides at the surface followed by decomposition. These preliminary conclusions are in clear
opposition to the literature referenced above. Further tests under controlled conditions are
necessary to prove or disprove this hypothesis.
Laboratory Investigations - Metal Dusting
In the course of this investigation grid # 50 and # 600 silicon carbide paper was used to check
the impact of surface conditions on the metal dusting process. Preliminary results of weight
change analysis with Alloy 45 M are given below. Figure 13 shows both alloy modifications with a
weight gain of < 0.1 mg/cm 2. This indicates that the preformed scale is protective or if cracked,
the re-healing tendency is rather rapid. Weight gain under these conditions therefore is related to
the formation and growth of oxides. Contrarily at 650 C Figure 14 shows a mass loss of about
0.2 mg/cm 2 at equal surface finish # 50. XRD spectrum analysis showed that amongst others,
Cr23C~ carbides and traces of alpha phase (ferrite) were present. This true mass loss may be
related to "real" pitting attack under peak metal dusting corrosion conditions. This is true just for
the 750 C test and supports the idea that a much faster chromium diffusion in the partially recrystallized ferritic structure results in the formation of the more protective scale. These findings
were proven so far also in other samples of the same investigation.
Comparing results for HP 40 modified alloys similar mechanisms seem to be predominant.
Figure 15 shows a clear weight gain of about 0.4 mg/cm 2 at 750 C whereas Figure 16 shows
significant weight loss for the "low" temperature 650 C, finish # 50.
Microstructural investigation confirmed real re-crystallization at test temperatures of 750 C
and test duration of 180 hours.
XRD analysis of all investigated samples demonstrated the presence of Cr203, M2306,M3C as
well as (Cr, Mn)304 for HP 40 and Alloy 45. A more in depth analysis of Alloy 45 tested at 750 C
(SIC # 50) demonstrates a superior dense and protective oxide layer after conclusion of the test.
Therefore it may be concluded so far that all theoretical considerations are fulfilled in the
frame of this defined laboratory investigation.
Metal Dusting Investigations of Cast Nickel Alloys Carburization and metal dusting tests have
been performed in the central laboratories of a DRI plant. The test conditions were adjusted to
temperature 700 C
pressure0.15 MPa
gas flow 55 I/min
gas composition reformer gas with 6 % methane (CH4).
Rectangular samples were cut (15 mm x 8 mm x 4 mm) and ground with # 180 followed by a
chemical etching procedure. This special etching procedure was applied to reduce so-called
incubation times by activating bare metal surfaces. The materials tested were HP 40 (C5),
G 4879 (C14), G 4868 (C3) and Alloy 45 M (C11).
Weight gain or weight losses ranged in between -1 x 10-4 up to +7 x 10"4. With exception of
Alloy 45 all other alloys have shown some local pits or uniform attack over the entire surface.
Also randomly distributed carbon deposits were detected on almost any sample again with the
exception of Alloy 45 Micro.
Metal Dusting Behavior of Wrought Nickel Base Alloys In Reference 11 H. J. Grabke,
J. KlOwer et al. reported about the metal dusting behavior of several nickel based alloys at
650 C in carbon monoxide (CO) and hydrogen (H2) environments with a carbon activity
ac >> 1. Iron nickel chromium alloys showed susceptibility after rather short test times.
Wrought nickel base alloys with chromium contents of about 25 % seem to be resistant in
exposures even after 10,000 hours exposure. Table 3 shows a selection of alloys tested as
well as their surface condition.
Specific consideration was given to Alloy 601 which was tested in three different
conditions:
ground
electro-polished and
black (scale from hot rolling)
FIELD EXPERIENCE AND PLANT DATA

Most pronounced cases of metal dusting of high alloyed materials were found in gas preheaters of direct reduction plants, see Figure 18. Pre-heaters are designed to heat up the
reducing gas atmosphere, hydrogen (H2) plus carbon-monoxide (CO), to an optimum
temperature range for the iron ore reduction. The extremely high carbon activities along with
cyclic load operations result in significant metal dusting attack on lower alloyed stainless
steels. A few cases from practical experience will be described below.
Direct Reduction Plants
Three different single trains of DRI plants have been checked due to their material
performance in gas pre-heaters.
Direct Reduction Plant A / DRI A
# 1: capacity:
operation:
pre-heater:
alloy:
observations:
1,000 MTPD (metric tons per day)

> 20 years with standard alloys /
several years with Alloy 45
(sulfur inhibition not reported/known)
56 tubes OD = 152 mm, L = 10,000 mm
+ 14 u-bends
tubes and bends in Alloy 45 (45-Ni/35Cr)
No material failure / metal dusting since recent
re-vamping.
to study potential impacts of surface preparation. The activities of carbon were adjusted to ac =
14 for the first 5,000 hours and to ac = 19 for the second period of a further 5,000 hours. The
oxygen partial pressure was sufficient to enable formation of chromium-oxides but not the
oxidation of nickel and iron. Tests were performed at 650 C with frequent interruptions to
study corrosion effects over time. Results are given in Figure 17. Microscopic examinations
revealed, that metal dusting attack starts locally by the formation of pits, in areas where oxide
scales cracked or spalled. Under these severe test conditions several alloys had to be
removed from the test prior to the intended limit of time (10,000 h). These alloys are Alloy
800 H, HP 40, 600H and Alloy 601 black and electro-polished. Samples of centricast HK 40
ranged in the same catastrophic metal dusting attack as HP 40 and not far from Alloy 800H.
The high nickel Alloy 601 (60 % nickel) reacted quite sensitively to different surface
preparations. The as-ground condition was the most resistant against metal dusting, e. g. two
orders of magnitude lower than for the same alloy composition in the oxidized condition. Alloys
602CA and 690 both bearing chromium contents of and above 25 wt.-% showed only minor
mass loss rates after 10,000 hours exposure of between 10.5 mg/crrF x h and 10 -6 mg/crn= x ho
All high performance nickel alloys in the wrought condition, e. g. Alloy 602CA and Alloy 690
had developed dense oxide layers in the course of the exposure period. The pre-dominant
mechanism of protection seems to be supported by minimum chromium contents of 25 % with
Cr backed up by certain amounts of aluminum and rare elements addition.
capacity:
operation:
pre-heater:
alloy:
observations:
# 3:
capacity:
operation:
pre-heater:
alloy:
observations:
2,000 MTPD
> 15 years with standard alloys /
several years with Alloy 45
96 tubes OD = 152 mm, L = 10,000 mm
+ 24 u-bends
No reported material failure.
2,000 MTPD
< 5 years (auto-reforming reactor)
68 tubes D = 152 mm, L = 10,000 mm
+ 68 tubes D = 100 mm, L = 10,000 mm
+ 68 u-bends
No reported material failures since installation.
Direct Reduction Plant B / DRI B

capacity:
(not reported)
operating conditions: acc. to Table 4
operation:
< 12 months
material:
34 pipe loops per box (4 boxes)
HK 40 / HK 40 mod
alloy:
material protection: pre-oxidation treatments and dimethyl-disulphide
(DMDS) inhibition (max. 30 ppm)
After a nine months' period of operation, in four out of
observations:
14 areas severe metal dusting attack was observed.
Metal dusting attack occurred at weld protrusions of
the root bead up to 8 mm in width and to a depth
extension of 1.3 mm on the bare tube surface. In the
high silicon modified HK 40 M (< 2 % Si) the
frequency of attack was diminished but also present.
Concerning the performance of HK 40 rood (<_ 2 % Si)
several observations of weld cracking were made.
Along with weld cracking an increased void formation in the inner parts of the tube metal
wall was reported. After only nine months of operation in a defined temperature regime this
premature creep has shown up far to early.
# 2:
> 1,000 MTPD (metric tons per day)

< 10 months
H2 = 70 %, CO = 15 %, CH4 = 10 %, CO2 = 1.5 %,
N2 = 2 %, H20 = 1.3 %
process gas temperature: 700 C - 800 C
process pressure: 0.5 - 0.6 MPa, abs.
carbon activity:
>> 1
material:
tubes OD = 168, L = 9,500 mm
alloy:
HP 40 Nb
Catastrophic forms of metal dusting attack were observed after just six months of
operation. The inside surface was covered by multiple overlapping hemi-ellipsoidal pits with an
approximate peak height of more than 5 mm and a diameter of 10 - 15 mm. The pit surface
was partially covered by a dark grey appearing oxide in the center whereas the rim showed a
metallic appearance. The remaining wall thickness was less than 4 mm in this specific section,
see Figure 19. The rim of the pit contains a sponge-like surface with a glassy appearing
surface structure, see Figure 20. The surface is covered with a high density of micro-sized
pinholes with a maximum diameter of 6 pm.
In adjacent areas of the pits, a network of chop-stick-like carbides accumulated as shown in
Figure 21.
A first hint to the synergistic action of oxidation, carburization and metal dusting process is
given in Figure 22 and Figure 23. In these figures oxide infiltration is traced between the blocky
carbides in the near-surface layers. Figure 23 clearly shows the pattern of oxygen / oxide
distribution in that area. The explanation by Kleemann 12 was given as follows: "... in the top
M703 carbide zone are clearly visible the inter-carbidic oxidation spikes extending from the gas
metal interface downwards forming a hemi-ellipsoidal pit-like configuration. Visible in this
micrograph is a thin layer of surface oxides and an infiltration pass of inter-carbidic oxidation
spikes penetrating into this zone to a depth of < 100pm. The internal oxidation spikes engulfs
an area forming particles. ''12The total depth of carburization was found to be around 1,200 pm.
Figure 24 shows the significant loss of chromium in the profile of the surface area. This loss
of elemental chromium corresponds with the massive carburization and carbide formation.
Taking into account the inter-carbidic attack mechanism, it can be stated, that the different
carbide precipitation pattern of the tungsten alloyed G 4879 may be one of the reasonable
explanations for the better behavior under metal dusting conditions.
Direct Reduction Plant D / DRI D
2,000 MTPD (metric tons per day)
capacity:
< 2 years
operation:
gas pre-heater with 90 hairpin tube bundles
design:
86 mm x 6 mm x 10,000 mm (Figure 25)
materials:
Alloy 45 (Ni45Cr35)
Due to a number of non-scheduled incidents, the reformer
observations:
module along with the inter-connected gas pre-heater were
exposed to numerous load cycles. Up to now there is no
reported metal dusting problem in this plant. More in depth
information will be generated soon.
Direct Reduction Plant C / DRI C

capacity:
operation:
gas atmosphere:
Ethylene Cracker Plant E

capacity:
operation:
design:
temperature:
decoking:
materials:
(not reported)
> 36 months
ethylene cracker (naphtha-feed)
1,050 C - 1,070 C
frequent (60 days' interval)
HP 40, G 4879, Alloy 45
The materials have been tested under carburizing ethylene cracker conditions with frequent
burn-off of coke deposits for more than 36 months 13.
Carburization proceeded into the materials HP 40 and G 4879. The tungsten bearing Alloy
G 4879, compared to HP 40 showed just 40 % wall thickness penetration. HP 40, after 36
months of exposure was carburized up to 75 % wall thickness. It may be assumed that the
slightly higher chromium content (+ 3 %) associated with the much higher nickel content of
approximately 48 % was the reason for the good performance of G 4879.
In contrast, alloy Ni45Cr35 (Alloy 45) showed almost no signs of carburization. Comparing
in Figure 26 the alloys HP 40 and Alloy 45 it is clearly eminent, that after 36 months of frequent
alternating operations between strongly carburizing and oxidizing conditions HP 40 has no
longer a protective barrier against carbon ingress. Alloy 45, bearing 35 % chromium in an
austenitic matrix, showed an almost defect-free and therefore protective oxide layer. Also the
close-to-ideal double-layer structure of chromia (Cr203) followed by a sublayer of silica (SiO2)
is shown in the case of Alloy 45. The microscopic evaluation showed in a rather dense oxide
layer of 40 pm total thickness. In Figure 27 the negative contrast pictures show the presence
of only a few iron and nickel spots in the chromia layer (x-ray map). This "low density" pattern
of catalytically active iron and nickel spots may be the reason for a decreased catalytic coke
precipitation and minor carburization under frequent high carbon activities.
DISCUSSION
The discussion will follow the effects of oxidation and carburization as well as specific metal
dusting parameters, e. g. impacts of temperature on microstructure of alloys, variation of
diffusion speeds through cold deformation of fcc alloys and metal dusting peak intensity areas.
In general, the impact of alloy composition and structure will be discussed as a measure to
control metal dusting corrosion.
Ethylene Cracker Plants

The plant experience described herein was selected to show the excellent stability of
protective oxide layers formation under conditions of cyclic carburization attack. Carbon
activities are low (ac=l) compared to real metal dusting environments (at>>1).
Figure 28 demonstrates the controlled formation and alteration of protective oxide layers on
high performance centricast tubes. In the course of a "tube life" several stages of high
temperature - high oxygen partial pressure regimes are passed. In the very beginning this
starts with the melting of refined metals and ferric-alloys in induction furnaces. Secondly,
centricasting under air creates strongly oxidizing conditions. After the birth of the raw tube,
inside machining and cleaning, transforms thick oxide layers into rather thin and very
protective chromia and chrome spinel oxide films. Growth of these thin silvery shining layers
into colorful yellow to deep blue heat tints is encountered under shop and field welding
operations. Especially the brown and yellow colored heat tints must be removed prior to
service because of the non-protective character of these low temperature oxide films. Most
engineering companies issue operation manuals with a defined pre-oxidation condition
before the "start-of-run" phase in high temperature gas reactors. In these controlled
oxidation conditions a conversion of thin oxide films into thicker visible oxide layers is
achieved. In the course of normal operation cracking carbon precipitation takes place under
partial oxygen depletion in reducing gas atmospheres. Under these conditions a more uniform
alteration of the protective oxide layers is achieved, e. g. general thinning. Under normal
operation, e. g. creep conditions, local defect sites in oxide layers result in catalytically active
spots exposing iron and nickel.
It is decisive that the substrate alloy enables the delivery of sufficient amounts of oxide
layer forming elements by outward diffusion from the substrate alloy pool. Therefore the
availability of elements like chromium, silicon and aluminum plays a major role in long-term
protection of high performance centdcast tubes under metal dusting conditions.
Oxides, thermodynamically considered, are likely to form on a metal when the oxygen
pressure of the atmosphere is greater than the oxygen partial pressure in equilibrium with the
metal oxide under consideration, e. g. chromium oxide (chromia / Cr203). Lai s referenced the
~artial pressure of oxygen in equilibrium with chromium oxide (Cr203) at 1,000 C to about 10
atmospheres, see Figure 29. If no molecular oxygen is available in the gas atmosphere,
another potential source of oxygen is the water vapor dissociation:
H2 = =
H2 +
02
and the CO2 dissociation CO2 = CO + 02 or from CO = _C+ 02.
For that reason in any chemical or petrochemical high temperature reaction sufficient
amounts of oxygen are available from the atmosphere to form selected metal oxides.
Chromia and alumina forming alloys are considered as most resistant against high
temperature corrosion attack after controlled initial formation of their oxide layers. These
protective oxides are growing slowly. A ranking of the parabolic growth rates of chromia (Cr203),
silica (SiO2) and alumina (AI203) shows chromia with the relatively fastest rate of formation and
alumina and silica growing even by magnitudes slower. Despite the low rate of formation,
aluminum oxide is the most protective compound on high temperature corrosion resistant alloys.
The rather thin layers of alumina are atomistically highly ordered structures with little defects,
rendering them nearly impermeable for carburization attack. Chromium oxide (Cr203) is
converted and evaporates particularly in the temperature regime > 1,050 C, therefore loosing its
protective nature above this temperature. This is a limiting factor for high temperature resistant
alloys in case that they rely just on chromium as a stable oxide former. Optimum compositions of
high temperature resistant alloys for regimes over 1,100C contain chromium, silicon and
aluminum as well as minor doses of rare earth elements to improve oxide scale adherence
(pegging effect). The above mentioned own investigations on oxidation behavior of HP 40 /
Oxidation
Carburization
Thermodynamically considered, an alloy might be carburized when carbon activity of the
environment is greater than the carbon activity at the bare metal surface. Different compounds in
the corrosive high temperature atmosphere contribute to the carbon activity varying as a function
of temperature 5.
According to Kleemann 7 and Mitchell et al 1, high temperature corrosion under oxidizing and
carburizing conditions (< 1,050 C) will result in formation of a protective chromia scale and an
interrelated carbide denuded zone below this scale.
In absence of a protective oxide layer the ingress of carbon is diffusion-controlled. With
increasing carbon content in the alloy, chromium carbides of different compositions will be formed
starting with M2306 which later converted to M703 on the alloy surface sometimes 0r302 is
observed. In high performance alloys, reactive elements like niobium, titanium, tungsten and
others also form carbides. These so-called primary carbides are formed intentionally during the
casting and centricasting process of such high performance alloys to increase creep resistance.
Defect-free and dense protective oxide layers with tight adherence to the alloy matrix should
completely suppress carbon ingress, see Figures 6 and 7. Alloys with sufficient chromium
contents of more than 25 % Cr show a remarkably better carburization resistance under different
load conditions. The optimum carburization resistance is shown nowadays by Alloy 45 (45 % Ni +
35 % Cr). In the absence of thermal shock conditions as well as in secondary creep regimes with
minimum deformation rates, these layers should maintain their protective nature for years of
operation. With reference to Grabke 8 there is no way that carbon diffuses through dense oxide
layers. It was shown that carbon has no solubility in technically relevant oxides. Carburization
profiles and gradients depend on numerous factors in a complex manner. The detrimental effect
of carburization is secondary in nature, e. g. a loss in ductility due to carburization results in
premature cracking, and therefore accelerated high temperature corrosion can start within the
catalytically active crack tip areas. Interaction of creep and carburization was reported to be less
critical in a creep regime of smaller than 10-8 per second. Below these creep rates, the kinetics of
oxide layer re-healing are fast enough to close microscopic fissures.
A sequence of steps was reported by Grabke 8 in slow strain rate experiments with ~.=4.109/s
HP 40 hSi and experimental Alloy "A" confirmed these statements. Based on a comparable
chromium matrix alloy content of 24 % Cr in HP 40 and HP 40 hSi, the difference of
approximately 1 % silicon content shows a marked decrease in the speed of oxide layer
formation. This rate was further decreased when the experimental Alloy "A" with just 18 % Cr was
supplemented with 1.7 % aluminum. A "rule of thumb" is, that under these specific conditions, a
thin and therefore more "ductile" oxide layer is much more favorable than a thick, colored oxide
layer with numerous micro-fissures resulting from the growth process. Although the above
mentioned experiments were made to check different alloys' behavior versus load cycles in the
ethylene cracker industry some of these mechanisms may be applied to components in reformers
and gas pre-heaters which are, in general, operated at 100 C - 200 C lower temperature
regimes. As high silicon contents are able to diminish solubility and diffusivity of carbon in
austenitic matrix lattices, Alloy HP 40 hSi showed less weight gain in the intermediate
carburization / coking step compared to the standard reference Alloy HP 40. However, the
experimental Alloy "A", due to its balanced chromium, silicon and aluminum contents showed
almost no visible signs of carburization. Overall, in this laboratory investigation near-surface
carbide particles were oxidized, forming an external chromium-rich scale on top of a carbidedepleted zone in the subsurface.
grain boundaries sliding results in repeated cracking of oxide layers

carbon up-take while the crack is open (protective oxide layer not yet restored)
carbon diffusion into the grain boundaries
precipitation of carbides
depletion of the gradient area in chromium
grain boundary carbide conversion to oxides
Higher strain rates, e. g. L= 1.3.10-T/s resulted in a more uniform carburization.

The carburization resistance of nickel-chromium alloys depends on alloy composition and
controlled surface engineering. As shown in Figure 30 there is an optimum content between 45
and 80 % nickel in austenitic matrix alloys. This function relies on the decreased carbon diffusivity
in nickel alloyed materials. A decisive side effect in alloying with nickel is the increased ductility of
the lattice. This results in a lower crack evolution of protective oxide scales. Stepwise, these
increased nickel contents have been realized in cast alloys from 20 % Ni in alloy HK 40 to 35 %
Ni in HP 40 up to 45 % Ni in high performance alloys like Alloy 45 Micro. Norton et a114. have
shown that above the absolute content of nickel, a ratio of nickel to chromium plus iron is decisive
for carburization resistance. Figure 31 shows the ranking of cast and wrought alloys according to
their nickel chromium ratio after carburization at 1,100 C in pack cementation tests (32 days). It
is obvious, that high carbon, high chromium cast grades show satisfactory carburization results
up to nickel contents of 50 % compared to wrought alloys. Hot forming properties of wrought (low
carbon) nickel base alloys require a somewhat higher nickel content when chromium is fixed
above 25 % due to metallurgical reasons. A local concentration of > 4 wt.-% alumina is required
to suppress carburization effectively 8. Resistance against carburization actually is found in nickel
base alloys with aluminum contents above 2 % or well defined additions of silicon and rare earth
elements. A compromise regarding weldability is obtained with aluminum contents of 2.5 % in
bulk matrix of the nickel alloy.
In case of re-oxidation with sufficient partial pressures of oxygen, silicon creates a sub-layer of
silica (SiO2) under the preformed chromia structure. This substructure contributes to a higher
carburization resistance in blocking carbon ingress and concurrently increasing the re-healing
tendency of local defect sites.
Metal Dusting
Oxidation, carburization and metal dusting are linked high temperature corrosion phenomena
in a "natural reaction chain". Metal dusting is catastrophic form of carburization that deteriorates
alloys in high temperature regimes with high carbon activity gaseous environments reacting to
elemental carbon and metal dust. This description relates metal dusting to a specific form of
carburization. Generally, carburization of the metal matrix precedes the metal dusting process, in
the case of chromium-containing alloys the formation of carbides such as M23C6 and M7C3 takes
place in a zone of internal carburization 3. Precipitation of fine particles of M23C6 generates
stresses which lead to an accumulation of dislocations surrounding the particles. Chromium is
also consumed by oxidation, the resulting chromium depleted zone is easily attacked by metal
dusting, see Figure 16.
As there is no intermediate metallic carbide being formed in the metal dusting of high alloyed
nickel base materials there is another decisive mechanism in the reaction front. Graphite planes
are growing in an oriented manner into the metal matrix and therefore cause the distortion of
protective oxide layers. Further catalytical active iron and nickel spots will result in an increased
rate of metal dusting attack. Pippel, et al.gpresented the mechanism at the workshop "Coking and
Decoking" in Porto in May 1999."
1.
2.
3.
4.
5.
6.
a) better adherence of protective oxide layers, if peaks and valleys are not too steep and
b) the deformation which leads to many dislocations, sub-grains and a fine grain microstructure
therefore increased diffusion speed of chromium, silicon, and others outward from the metallic
matrix.
In contrast, under the specific circumstances of the heater of direct reduction plants, neither
measures of surface engineering (DMDS / pre-oxidation) nor minor alloy modifications, e. g. in
silicon could suppress metal dusting attack to 100 %. These findings support the hypothesis
that the best protection against metal dusting is probably a proper alloy selection with
increased capacity of a self-re-healing protective oxide layer, e. g. Alloy 45 with 35 %
chromium in the matrix.
Figure 24 shows the results of a microprobe analysis concerning the chromium profile of
the attacked sample. This figure clearly shows the dramatic depletion of chromium in an area
down to about 1,200 pm from the gas metal interface. This phenomenon of extreme
carburization and chromium depletion may be explained by additional local overheating of the
damaged tube section. The resulting "local alloy composition" points to a completely different
nickel iron lattice compared to the austenitic Ni-35 % Cr-25 %. The relative volume difference
between the virgin cast HP 40 and the resulting chromium depleted FeNi-alloy results in
microscopic scale stresses. The relieve of these stresses by fracture at the gas metal interface
will produce the forces required to eject the particles from the metallic matrix.
As is clearly visible from Figures 13 and 14 a shift of 100 C may completely alter the
performance of alloys in laboratory investigations. Depending either on thermodynamical
considerations at that temperature or on the kinetics of faster element diffusion at 100 C higher
temperatures in a partially re-crystallized structure, metal dusting oxidation leads to a weight
gain at Alloy 45 (750 C / # 50) due to oxidation and a true weight loss for the same Alloy 45 at
650 C due to pitting. Figure 15 and 16 more or less prove this trend with the lower alloyed HP
40. In the work of Grabke, KlOwer et al. 11 also the effect of "surface engineering", e. g. grinding
and pre-oxidation was mentioned as acting positive against metal dusting attack. Much more
pronounced was the effect of a balanced chemical composition of these wrought materials in
terms of a minimum required chromium content of 25 % + additional elements, e. g. aluminum (>
2 % AI) and rare earth metal additions, see Figure 17.
Comparing laboratory investigations as described above with real plant experience, the
general trend of a positive impact of a balanced alloy composition plus surface engineering is
confirmed. Catastrophic forms of metal dusting could be traced back to a lack of chromium in the
matrix of the alloys and / or a frequent deterioration of the non-stable chromia layers in
thermocycling operation or creep regimes. Decisive is the combined action of internal oxidation
and carburization as shown in Figures 21 - 23.
From results of laboratory investigations we know that metal dusting on high alloyed materials
results in hemispherical pits which are expanding into the metal matrix. These pits are filled with
fine coke and metallic powder which are removed after each test period. The origin of real metal
wastage is therefore difficult to determine. Most authors report about metal dusting attack in pit
depth and pit density according to ASTM specifications. Only at that point when all pits grow
together a general metal wastage rate in mm/year can be given.
Surface preparation of the material is another decisive parameter. Surface grinding induces
local stresses in face-centered cubic, austenitic alloys. This additional stress creates stacking
faults which might act as promoters for fast element diffusion in both directions. Also recrystallization is more probable at temperatures above 700 C in austenitic alloys. Grinding
therefore results in two major effects:
Further investigations are required to clarify the mechanism of the formation of the distinctly
located oxidation spikes in the metallic matrix between top carbide layers, see Figures 22 and
23. Preferential oxidation of chromium normally should not occur in this oxygen depleted
atmospheres.
The interaction of heavy carburization, forming coarse carbides followed by selective
internal oxidation alters the structure of the attacked matrix. Protective scales do not grow over
carburized regions and are partially substituted by non-protective iron oxide rich scales.
Therefore, there is no longer an effective barrier against carbon ingress. These factors may
result in rapid growth and deterioration of the tube wall.
A reasonable correlation between alloy composition, e. g. chromium contents and the
related formation and stability of oxide layers was shown after three years exposure in Plant E!
Plant E is synonymous for an ethylene cracker furnace operated under alternating conditions
with medium carbon activities (at=l), naphtha cracking followed by so-called decoking cycles
representing tough steam oxidation conditions. Here, a standard reference Alloy HP 40 with
25 % chromium experienced much stronger carburization compared to Alloy 45 with about
10 % more chromium in the matrix. Although, operating conditions in ethylene crackers are not
comparable to direct reduction plant gas pre-heaters, a principle of material protection by
stable oxide layer formation and re-healing may be derived. Unexpectedly to the believed
mechanism of dense stable oxide layers formation on Alloy 45, it was found, that the density of
catalytically active iron and nickel particles embedded in such an oxide layer is diminished
compared to standard reference alloys. This effect corresponds to observations made in CVDcoatings.
In general the effect of surface modifications, e. g. intentionally induced stresses and
modified surface roughness should be investigated further. Up to now there is no final
conclusion to be made about the best suited surface roughness or degree of cold deformation
in surface areas. The initial surface state is very important for the initial protective oxide
formation! From a practical standpoint, it should also be considered, that an initially engineered
surface from the supplier of centricast tubes will be altered rapidly under frequent load
conditions of reformers or DRI plants.
The most reliable solution seems to be the balanced alloy matrix composition capable of a
rapid delivery of strong oxide formers, e. g. chromium, silicon, aluminum accompanied by
sufficient amounts of oxide strengthening rare earth metals. These alloys will be presented in
short to the end-users and engineers of such plants.
Laboratory and plant experience are in faidy good correlation. Alloys with less than 25 %
chromium are endangered by metal dusting attack in lab and field tests. The positive effect of
silicon was found more pronounced in lab investigations. Under alternating load conditions of
real plant cycles, silicon < 2 % was less effective, possibly due to negative impacts on creep
life and weld ductility. The effect of AI in cast alloys as to date could not be evaluated under
plant conditions. The excellent lab results of such cast and wrought alloys under severe metal
dusting conditions are quite promising. Effects of surface engineering, e. g. stress induction by
cold deformation, e. g. shot peening or grinding could not be followed over long exposure
times. Also the durability of pre-oxidation treatment was not proven over long time. Lab results
indicate a positive effect in first plant cycles.
Metal dusting as a specific form of carburization deteriorates almost every known

commercially available material in the field. Laboratory investigations are in good correlation to
observations in real plants. It is the potential of the alloy system in forming and maintaining a
stable passive oxide layer, that is a life guarantee for the components operated in metal
dusting regimes. Concerning cast and centricast alloys, the following parameters are favorable
preconditions for proper alloy performance:
1) Nickel content should be well above 40 %.
2) Chromium contents of minimum 25 - 30 % are required along with the aforementioned
nickel content.
3) A compromise between carburization / metal dusting resistance and formability / weldability
is a silicon content between 1.5 % Si and 2.5 % Si.
4) Certain amounts of aluminum and rare earth metal additions may lead to a completely new
generation of cast and centricast alloys replacing CVD-coated products in those
applications.
At present the well designed Alloy 45, seems to have all required high temperature
properties to withstand metal dusting attack. New alloy developments are close to
commercialization with even better high temperature corrosion resistance.
Further investigations are required to clarify the mechanisms of surface engineering, e. g.
grinding, shot peening and / or pre-oxidation treatments especially under the aspects of cyclic
loads and long-term stability.
ACKNOWLEDGEMENTS
The extensive work of Professors D. Young (UNSW) and F. J. P6rez Trujillo (UCM) on
laboratory investigation under carburizing and metal dusting conditions are acknowledged.
The contribution of L. Engel in microstructural characterization of samples after high
temperature corrosion attack is worth to be named.
Finally we would like to express our thanks to Professor Grabke (MPI) for paper revision
and discussion as well as to Mrs. B. Oehm-Schnippering and P. WOlpert for setting up the
manuscript.
Part of this work was funded by the "Landeswirtschaftsministerium, NRW/Germany" under
contract No. TPMW-335-48-18.1 (1993).
CONCLUSIONS
2.
3.
4.
5.
6.
.
9.
10.
11.
12.
13.
14.
H. J. Grabke, R. Krajak, E. M. M(311er-Lorenz, "Metal Dusting of High Temperature Alloys",

Materials and Corrosion 44 (1993): p. 89 - 97
H. J. Grabke, "Metal Dusting of Low and High Alloyed Steels", Corrosion 51, 9 (1995):
p. 711 - 720
H. J. Grabke, R. Krajak, E. M. MQIler-Lorenz, S. Straul~, "Metal Dusting of Nickel Base
Alloys", Materials and Corrosion 47 (1996): p. 495 - 504
H. J. Grabke, C. B. Brancho-Troconis, E. M. MiJller-Lorenz, "Metal Dusting of Low Alloy
Steels", Materials and Corrosion 45 (1995): p 215 - 2 2 1
G. Lai, "High Temperature Corrosion of Engineering Alloys", ASM International (1990 1997)
D. J. Hall, M. K. Hossain, R. F. Atkinson, "Carburizsation Behavior of HK 40 Steel in
Furnaces used for Ethylene Production", High Temperatures- High Pressures 14 (1982):
p. 527
W. Kleemann, "A Kinetic and Morphological Study of High Temperature Coking,
Decoking and Oxidation Behavior of Heat Resistant Steels", non-published work
September (1998)
H. J. Grabke, "Carburization - A high Temperature Corrosion Phenomenon", MTI
Publication 52 (1998)
Q. Wei, E. Pippel, J. Woltersdorf, H. J. Grabke, "Microprocesses of Coke Formation in
Metal Dusting", Materials and Corrosion 50 (1999), p. 6 2 8 - 633
D. R. G. Mitchell, D. J. Young, W. Kleemann, "Carburization of Heat Resistant Steels",
Materials and Corrosion 49 (1998): p. 231 - 236
H. J. Grabke, E. M. M011er-Lorenz, J. KI6wer, D. C. Agarwal, "Metal Dusting of Nickel
based Alloys", Materials Performance 7 (1998), p. 58 - 62
W. Kleemann, L. Engel, Investigation Report "Microstructural Analysis of a Centricast HP
40 Nb Tube from a DRI - Pre-Heater Suffering from Metal Dusting Corrosion", 01 (1999)
P. W01pert, Investigation report "Carburization of four Centricast Alloys in the Ethylene
Service"
J. F. Norton and J. Barnes, in "Corrosion Fossil Fuel Systems, I. G. Wright, Ed., The
Electrochemical Society (1983): p. 277
REFERENCES
Alloy
No.
Trade
Mark
ACI
Design
Si
Nominal Chemical Composition (mass%)

Mn
Cr
Ni
Mo
Nb
W
Zr
Ti
C1
G 4848
HK40
0.40
1,5
1.5
25
20
C2
G 4848S
HK40
0.40
2.0
1.5
25
20
C3
G 4868
--
0.50
2.0
1.5
30
30
C4
G 4857
HP40
0.45
1.5
0.7
25
35
C5
G4852
HPmod.
0.40
1.5
1.5
25
35
C6
G4852micro
HPmicro
0.45
1.5
1.0
25
35
--
C7
G4852micro
high Si
HPmicro
0.45
2.6
1.0
25
35
C8
HP 40 M W
HPmod.
0.40
1.3
1.5
25
35
C9
HP 40 MT
HPmod.
0.4
1.8
1.5
25
35
C10
Experimental
Alloy A
0.42
0.7
0.41
18
31
Cll
Alloy 45 micro.
--
0.45
1.6
1.0
35
45
C12
Alloy 45 M T Z
--
.0.45
1.6
1.0
35
45
.
.
3.1
.
.
.
.
.
.
.
.
0.16.
0,8 . - -
0.04
0.12.-
. 1.5
1.5
0.4 - -
, 1.0 .
1.0
--
,0.15
1.6
1.0
35
45
. 1.0 .
C14
G 4879
--
.0.45
1.5
1.5
28
48
. . . . .
C15
Alloy D1
--
.0.42
1.91
0.95
28.2
. 0.04
others
0.08
Alloy 45 LC
--
0.8 - -
C13
19.5.
0.02
. 1.5
AI
--
RE
RE
0.46
0.3
<1.0
<1.0.
<1.0
<1.0
<1.0
<1.0
1.7
--
RE
--
RE
--
RE
5
0.05
TABLE 2
RATE CONSTANTS FOR AIR-STEAM OXIDATION AND POST-COKE AIR-STEAM
OXIDATION FOR CENTRICAST ALLOYS HP 40 / HP 40 HSI AND
EXPERIMENTAL ALLOY "A"
Alloy type
Air-steam
oxidation at
900 C
kp*10 s
mg2cm-4min -1
Post-coke airsteam oxidation at

9O0 C,
kp* 105
mg2cm4min -1
4852 micro
7.0
8.6
4852 micro, high Si
2.0
0.6
Alloy A
0.4
0.1
TABLE 1
NOMINAL CHEMICAL COMPOSITION OF CAST ALLOYS FOR
PETROCHEMICAL, REFORMER AND DIRECT REDUCTION OF IRON ORE PLANTS
Alloy
UNS No.
No.
W1
N080810
C4
Alloy
Design.
Surfaces
Nominal Chemical Composition (mass%)

Si
Fe
Cr
Ni
Ti
AI
others
Ground
800H
HP40
0.10
0.5
46
20
32
0.4
0.4
AI+Ti
0.40
1.5
38
25
35
<0,7
W2
N06600
600H
Ground
0.10
--
16
72
W3
N06601
601
Black
0.10
--
14
23
60
--
1.4
--
W4
N 06601
601
Polished
0.10.
--
14
23
60
1.4
--
W5
N06601
601
Ground
0.10
14
23
60
1.4
--
W6
N 06602
Black
0.20.
9.5
25
60
2.3
602CA
m
--
TABLE 4
DESIGN DATA FOR A PROCESS GAS HEATER IN A DRI PLANT
Gas Preheater operating conditions
Design rate
Normal opration
Mechanical rate
246.145
280
5.21
258.450
280
5.21
277.250 est.
280
5.21
Temperature, C
Pressure, bar(g)
Gas composition, Vol %
950
4.28
950
4.28 est.
970
4.28 est.
Hydrogen
Carbon Monoxide
70
16
70
16
70
16
Carbon Dioxide
Methane
Nitrogen
1.3
1.3
1.3
Water Vapour
Inlet conditions
Flow rate, Nm3/h
Temperature C
Pressure, bar(g)
Outlet conditions
Hydrogen Sulfide ppm
20 - 30
CO / CO 2 rating
5.33
20 - 30
20 - 30
0.1Y
TABLE 3
NOMINAL CHEMICAL COMPOSITION OF WROUGHT ALLOYS IN LABORATORY METAL
DUSTING EXPERIMENTS (ACC. TO GRABKE, KLOWER, ET AL.)
"-SJ.. , o~..
"
% "~'~Z':.
.,
a
z
."
o O
~.~.,~ "u+,s/,/.
LOW MELTING
7"
uJ
>
~
o
.J
ne
LLI
"r"
I.-0
CARBUR_IZA-EION~
COKING
~.
co. oUNO
---~
ME.
LOO$.,.G
y N
OZ
t
I
eta"
'~
,,
!
I
"~
..J
<
," 0 " ~
~,,~ , ~ '4.~
,~
O~,~.~X-"x" o
~ " zO,. oo
o~'
-,%
,
"~O0~X~
MOLTEN SALTS
FIGURE
The Central Role of Oxidation in High Temperature Corrosion Processes

(acc. to G. Lai ~)
Inter-Lattice located
Substituted
Foreign Atoms
Foreign Atoms
I
Step
\\ ~ |
t
. . . .
Umpjacement
..e~\~ll~
l
Coherend
High melting
Precipitations ForeignPhase
Incoherend Lattice
. . . . . . t-aces
/ oriented /
b11mng
Precipitaions /
_J / 1
Void
~E!ementary
cell
~ii~l~/'
~j~
~ . ~ i l ~ ~ b ~ / / ~
2.86 A -~0.28 nm
Screw-type
Dislocation
FIGURE
2 -
Scale shaped
Precipitations
on Grain
Boundaries
!~" Grain diam.~'

p.e. 50t~rn
= 50,000 nm
Microscopic Section of a Multi-Grain Structure of Face Centered Cubic Alloys

(fcc = Austenitic Structure); Crystallographic Defects in Real Alloy Lattices
SULFUR
Or 203
'3
+ Cr3C 2
Cr depleted
M23c 6
dispersed
MTC3
~ersed
IC6
Oxidation in a carburizing Environment
Initial Oxidation
FIGURE 3 -
Oxidation and Carburization on a Microscopic Scale;

Potential Reactions Between Gas and Metal Surface
(Left: Layer formation after 1st start-up / initial oxidation
right: Oxidation in a carburizing environment)
TUBE A
TUBE B
oxides (0.3)
oxidesM7C3
(03)~[
(2.0)
! (2.5)
M703 M2306
......~H (0.4)
M7C 3 M230 6
+ M2(C,N) . . . . . . ~ l (o.8)
M230 6 + M2(C,N )
IV (4.5)
I1 (2.8)
m (o.6)
IV (4.5)
oxides (0.2)
M 7 03
M7C3+ M2(C,N)
MTC3 + M23C6
+ M2(C,N)
~M2306+ M2(C,N)
oxides (0.4)
FIGURE 4 - Primary and Secondary Carbide Precipitation of two Alloy Modifications of HK 40

(acc. to Hall, et al. 6)
Spinel (Mn, Fe) Cr204

+ M7C3 and Cr3C2
0.25
G 4842 micro
E
o 0.20
o~
2 micro high Si
o~
0.15
ttO
""
t - 0.10
.mo ~
erimental Alloy A
0.05
10
20
30
40
Sqare root of time ~/min

FIGURE 5 -
Air-Steam Oxidation Kinetics at 900 C for Alloys HP 40 M, HP 40 hSi and

Experimental Alloy "A" (acc. to Kleemann)
700
.c
500 -
,,,0oc/ /
"10
cO
300
EL
100 -i
I
FIGURE 6 -
2
3
4
5
S q u a r e root of time (,g-if)
Carburization Kinetics as a Function of Time for Alloy HP 40 M (C6)

(acc. to Kleemann)
0.30
G 4852
.
e'-"
e-"
mi,:ro7
~G4
2 ~ ~ ~~ ~/
950
FIGURE
1000
1050
1100
1150
1200 C
7 - Comparison of Relative Carburization Resistance as a Function of Temperature;

Pack Cementation Tests for 2 6 0 Hours
250
%
200
p=
1 bar
p = 10 bar
%
%
150
%
%
%
(J
co
.>
100
2
50
'l
600
700
800
900
1000
Temperature C
FIGURE
8 - Carbon Activity Versus Temperature and Pressure in a Laboratory Investigation
(acc. to Perez)
.K40J
25
20
Cr(CO) 6
15
10
5
0
CrO 3
-5
-10
-15
r
-20
-50
-40
-30
-20
-10
10
[
20
J
~30
40
log PO2(g)
FIGURE 9 -
Phase Diagrams at 650 C in Contact with a Defined DRI Gas Mixture;

Allocation of Thermodynamic Balance is Marked by a Star (*)
Stability Regions for Chromium Oxide / Chromium Carbides
log pCO(g)
0
-2
-4
-6
-8
-10
SiO 2
-12
-14
-16
-45
-40
I .
-35
,,, I
-30
-25
-20
log PO2(g)
FIGURE 10 - Phase Diagrams at 650 C in Contact with a Defined DRI Gas Mixture;
Stability Regions for Elemental Silicon, Silicon Oxide and Silicon Carbide
log pCO(g)
\ 1 " '
2o Fe3C,/ ~
-2
-4 Fe~,
-6
Fe304 ~101.5(W )
Fe'9470 I ' ~
I
-35
-25
FeCO3
- 15
-5
r ,
r
5
I"-.
15
logPO2(g)
FIGURE 11 - Phase Diagrams at 650 C in Contact with a Defined DRI Gas Mixture;
Stability Regions for Metallic Iron, Iron Oxides and Iron Carbides (Cementite)
IV
Graphite
Cr203
~i ~.~
- ~
,~'~
Cr203
Alloy
II
Alloy
Cr2%
Alloy ' ~
Alloy
III
Metastable Carbide
Graphite
/
Alloy
Fe3C
Cr20 3
VI
Alloy ~
Fe,
= (Fe,X)3C
X=Ni, Cr
Cr,Ni+C
FIGURE 12 - Metal Dusting Process Proposed by the Investigators for High Performance
Centricast Alloys
logpCO(g)
0.3
E
0.2
o
o)
E 0.1
O3
'- 0
Alloy MTZ
Alloy LC
offl -0.1
:~ -0.2
-0.3
-0.4
Temperature 750 C, Surface Finish #50

FIGURE 13
Laboratory Controlled Metal Dusting Tests as a Function of Temperature and

Alloy Composition; Surface Finish: Grid # 50
Weight Gain for Alloy 45, Low (LC) and High (MTZ) Carbon Version at 750 C
0.4
0.3
0.2
E
o
o3 0.1
E
o3
0
EE
" -0.1
i
"
"
/}
Alloy MTZ
-0.2
.0.3 i
Alloy LC
-0.4
FIGURE 14 - Laboratory Controlled Metal Dusting Tests as a Function of Temperature and

Mass Loss for Alloy 45, Low (LC) and High (MTZ) Carbon Version at 650 C
0.4
0.3
M
E
tO
0.2
0.1-
a)
o)
ttO
t,/)
t,t}
Alloy MW
Alloy MT
-0.1
-0.2
-0.3
-0.4
FIGURE
15
Laboratory Controlled Metal Dusting Tests as a Function of Temperature and

Significant Mass Gain for Alloy HP 40 (MW / MT) at 750 C
0.4
0.3
E
O
E
E:
(.-
0,2
0.1
0
(o
-0.1
/)
/)
0~
-0.2
-0.3
i I
Alloy MW
, II
Alloy MT
-0.4
FIGURE 16- Laboratory Controlled Metal Dusting Tests as a Function of Temperature and
Mass Loss for Alloy HP 40 (MW / MT) at 650 C
0.4
5 -....
t,,I
E 0.2O
O
O)
E
(If
0.15
oC
O)
(II
--,
0.10
03
00
""; ]
0.05
6,697
1,988
1.0E-0.31 1.1E-0.5
0
Ground
800H
FIGURE
17
HP40
Ground
600H
Black
601
Polished Ground
601
601
Black
602CA
Metal Wastage Rates for Centricast and Wrought Nickel Base Alloys and
Stainless Steels Alloy compositions acc. to Table 3 (acc. to Grabke, Klbwer, et al.)
Iron Ore
Pellets
opt.~O2
H2+CO+CO2+H20
. . . . .
Gas Preheater
650 C- ~
Hydrogen
Reformer
<28 0C
]
/ ^
opt. H2
O~~-~
~crubbe r
H ~+ CO
,= {
~ L.r- "1
"1 M~v~ngl ~ J
y ,. j y ,0oc
~" ""=,
,
,
, ,
~
~ I
Z
~
'',
'
,
,=.
~,
AE /
~
I
I
""
Danger of
MetalDusting
' I ,, Outlet Coil

%-" ET 45 Micro
---~~.1"~Steam
a~orT H^O
Hz
Gener
Inlet/( ,oil
Danger of Embrittlement
ET 45 Micro (LC?)
FIGURE 18 - Flow Sheet of a Direct Reduction Plant for Iron Ores (DRI);
Gas Pre-Heater: T Inlet < 650 C, T Outlet = 950 C
I Reactorl
[
\~
,,J
/
I
~ Iron
VPellets
Top Gas Recycling Line
0.25
FIGURE 20 - Microscopic Evaluation of Structures Resulting on a Tube Surface of Centricast

Alloy HP 40; DRI Pre-Heater After six Months of Operation
Glassy Surface Scale Morphology Close to the Rim of the Pit
FIGURE 19 - Failed Tube Section from a DRI Pre-Heater After six Months of Operation
Chain o
Oxides
Oxides

Inter-Carbidic Oxide Infiltration and Carbide Morphology in Surface Layers

Localized Accumulation of Interwoven Carbide Fibers in Selected Areas
Oxides

X-Ray Map of Oxygen Distribution from FIGURE 15C
25
t.-
20
x"
I11
15
0f r"
('-"
10
(D
IZ
0
?
o
e~
<
FIGURE 24
i,
300
1000
1500
Distance from Surface, pm
2000
Chromium Content in a Centricast HP 40 Nb Matrix After Exposure to Metal

Dusting Corrosion in a DRI Pre-Heater (acc. to Kleemann, Engel)
Ch~
Oxiq
DRI Plant / Gas Pre-Heater Hairpin Tube Section made of Ni45Cr35 (Alloy 45);
in Frequent Operation for two Years
25 FIGURE
Some spots
of CrO + CrC
SiO dispersed in
Cr-depleted matrix
with pores and
coke Inclusions
No visible protective layer on the inner tube surface

HP40 (C4)
Precipitations of
M7C3 TiC and NbC
on grain boundaries
and fine dispersed
in the matrix
No carbon diffusion
beyond the depleted
zone.
Very small
Cr-depleted
zone with voids
where primary
carbides had
been located
Continuous layer of Cr203 followed by SiO2

Alloy 45 (C11)
FIGURE 26 - Sections of Inner Tube Wall (100 x)
Heavy secondary
carbides on the
grain boundaries
Black = Silicon O x i d e s
Dark Grey =
Chromium Oxides
(mixed with Si-oxides)
ID Surface
X-ray Mapping of
Iron in Cr-oxide
Layer
X-ray Mapping of
Nickel in Cr-oxide
Layer
FIGURE 27 - Oxide Layer Formation Under Frequent Alternating Cycles of Strongly

Carburizing and Oxidizing Cycles in an Ethylene Cracker Plant;
t = 1.050 - 1.100 C
Decarburized area
OXIDE F O R M A T I O N
APPLICATION
OXIDE F O R M A T I O N
Conversion of the
thin glass-like oxide film
o
0
0
0
0
0
0
0
0
0
Slag formation in liquid phases
into thicker oxide layers
Risk of nonmetallic inclusions (oxides)
with defined
growthconditions
MELTING
in induction furnace
START OF RUN in high temperature gas-reactor
under defined preoxidation conditions
I
Slag formation and strong oxidation

in the turbulent atmosphere
during pouring and
Carbon precipitation and partial oxide

decomposition in the reducing atmospheres
Removal of heavy, porous

oxide layers and controlled
formation of thin and
INSIDE MACHINING protective "Spinel-Oxide-Layers"
Automatic
ii
ill
resulting in catalytically active

spots of Ni / Fe under creep and
thermal shock conditions
Root protrusion is removed by grinding

ASSEMBLY OF TUBE SECTIONS
BY WELDING
Partial alteration of thin (light silvery)
oxide layers into coloured "heat tints"
must be removed after welding
Local defects in the oxide layers
Weight
Creep conditions under high temperature
and temperature gradients through the wall
Manual
protective oxide layer
at the inner surface of the tube
Uniform alteration of the
(thinning)
CENTRICASTI NG
in metallic molds
with refractory liner
~'~:'~!t~
;! J ( C )
Reheating of defect-sites
under oxygen depletion with
strong oxide forming elements
from the substrate alloy pool
Decoking or steam cleaning
during plant shut downs
from inside and outside surfaces.

F I G U R E 28 - The central Role of Oxidation in the Life Cycle of a Centricast High Alloyed Tu b e
PRODUCTION
PROCESS
,ogPcodPco
log PH20/PH2
0
~0
-r-16
I
-12
I
-16
-12
I
-8
I
-8
-4
-4
I
Cr3C2
12
8
I
O3
12
4 0
c (s)
"o
..(
Cr7C 3
/P
-4
"-4
0r230 6
-8
-8
Cr20 3
Cr
12
-12
-16
-50
-40
-30
-20
-10
16
+10
log P02 (ata)
FIGURE
29 -
Stability Diagrams of Cr-C-O Systems at 620 C

(acc. to Lai 5)
20
40
60
FIGURE
30 -
"
"I
80
100
Carburization as a Function of Nickel Content in FCC Alloys
-12
-16
04
E
L)
50-
, ~,.. _H~P M_i c___

ro
601,602
10-
Alloy 4
'
35/25
45/35
Cast alloys
60/23
60/25
72/16
Ni / Cr Ratio
Wrought alloys
FIGURE 31 - Alloy Ranking According to Typical Carbon Pick-up at 1.100 C in Solid

Carburization Cement / 32 Days
100-

Correlation of Oxidation Carburization and Metal Dusting Controlling Corrosion by Corrosion (51300-01374-Sg)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Correlation of Oxidation Carburization and Metal Dusting Controlling Corrosion by Corrosion (51300-01374-Sg)

Uploaded by

Copyright:

Available Formats

01374

CORRELATION OF OXIDATION, CARBURIZATION AND METAL DUSTING;

Metal Dusting Mechanisms of High Performance Alloys

Controlling Corrosion by Oxidation

Laboratory Investigations - Oxidation

carburization depth in micrometer

Laboratory Investigations- Carburization

The Effect of Alloy Composition, Temperature, Pressure and Surface Rouqhness

Laboratory Investigations - Metal Dusting

FIELD EXPERIENCE AND PLANT DATA

1,000 MTPD (metric tons per day)

Direct Reduction Plant B / DRI B

> 1,000 MTPD (metric tons per day)

Direct Reduction Plant C / DRI C

Ethylene Cracker Plant E

Ethylene Cracker Plants

and the CO2 dissociation CO2 = CO + 02 or from CO = _C+ 02.

grain boundaries sliding results in repeated cracking of oxide layers

Higher strain rates, e. g. L= 1.3.10-T/s resulted in a more uniform carburization.

Metal dusting as a specific form of carburization deteriorates almost every known

H. J. Grabke, R. Krajak, E. M. M(311er-Lorenz, "Metal Dusting of High Temperature Alloys",

Nominal Chemical Composition (mass%)

Post-coke airsteam oxidation at

4852 micro, high Si

Nominal Chemical Composition (mass%)

Hydrogen Sulfide ppm

The Central Role of Oxidation in High Temperature Corrosion Processes

!~" Grain diam.~'

Microscopic Section of a Multi-Grain Structure of Face Centered Cubic Alloys

Oxidation in a carburizing Environment

Oxidation and Carburization on a Microscopic Scale;

FIGURE 4 - Primary and Secondary Carbide Precipitation of two Alloy Modifications of HK 40

Spinel (Mn, Fe) Cr204

Sqare root of time ~/min

Air-Steam Oxidation Kinetics at 900 C for Alloys HP 40 M, HP 40 hSi and

Carburization Kinetics as a Function of Time for Alloy HP 40 M (C6)

7 - Comparison of Relative Carburization Resistance as a Function of Temperature;

8 - Carbon Activity Versus Temperature and Pressure in a Laboratory Investigation

Phase Diagrams at 650 C in Contact with a Defined DRI Gas Mixture;

Temperature 750 C, Surface Finish #50

Laboratory Controlled Metal Dusting Tests as a Function of Temperature and

Temperature 650 C, Surface Finish #50

FIGURE 14 - Laboratory Controlled Metal Dusting Tests as a Function of Temperature and

Laboratory Controlled Metal Dusting Tests as a Function of Temperature and

' I ,, Outlet Coil

FIGURE 20 - Microscopic Evaluation of Structures Resulting on a Tube Surface of Centricast

FIGURE 22 - Microscopic Evaluation of Structures Resulting on a Tube Surface of Centricast

FIGURE 21 - Microscopic Evaluation of Structures Resulting on a Tube Surface of Centricast

FIGURE 23 - Microscopic Evaluation of Structures Resulting on a Tube Surface of Centricast

Chromium Content in a Centricast HP 40 Nb Matrix After Exposure to Metal

No visible protective layer on the inner tube surface

Continuous layer of Cr203 followed by SiO2

FIGURE 27 - Oxide Layer Formation Under Frequent Alternating Cycles of Strongly

thin glass-like oxide film

Slag formation in liquid phases

into thicker oxide layers

Risk of nonmetallic inclusions (oxides)

Slag formation and strong oxidation

Carbon precipitation and partial oxide

Removal of heavy, porous

resulting in catalytically active

Root protrusion is removed by grinding

Local defects in the oxide layers