Documente Academic
Documente Profesional
Documente Cultură
2001
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.
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Paper No.
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.
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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.
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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)
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.
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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)
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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
(sulfur inhibition not reported/known)
96 tubes OD = 152 mm, L = 10,000 mm
+ 24 u-bends
tubes and bends in Alloy 45 (45-Ni/35Cr)
No reported material failure.
2,000 MTPD
< 5 years (auto-reforming reactor)
(sulfur inhibition not reported/known)
68 tubes D = 152 mm, L = 10,000 mm
+ 68 tubes D = 100 mm, L = 10,000 mm
+ 68 u-bends
tubes and bends in Alloy 45 (45-Ni/35Cr)
No reported material failures since installation.
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# 2:
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.
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(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.
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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
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 /
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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
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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.
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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.
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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:
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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.
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CONCLUSIONS
2.
3.
4.
5.
6.
.
9.
10.
11.
12.
13.
14.
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REFERENCES
Alloy
No.
Trade
Mark
ACI
Design
Si
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
4852 micro
7.0
8.6
2.0
0.6
Alloy A
0.4
0.1
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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
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
20 - 30
CO / CO 2 rating
5.33
20 - 30
20 - 30
0.1Y
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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
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
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SULFUR
Or 203
'3
+ Cr3C 2
Cr depleted
M23c 6
dispersed
MTC3
~ersed
IC6
Initial Oxidation
FIGURE 3 -
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)
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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
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)
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0.30
G 4852
.
e'-"
e-"
mi,:ro7
~G4
2 ~ ~ ~~ ~/
950
FIGURE
1000
1050
1100
1150
1200 C
250
%
200
p=
1 bar
p = 10 bar
%
%
150
%
%
%
(J
co
.>
100
2
50
'l
600
700
800
900
1000
Temperature C
FIGURE
(acc. to Perez)
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.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 -
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;
Allocation of Thermodynamic Balance is Marked by a Star (*)
Stability Regions for Elemental Silicon, Silicon Oxide and Silicon Carbide
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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;
Allocation of Thermodynamic Balance is Marked by a Star (*)
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
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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
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
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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
Temperature 750 C, Surface Finish #50
FIGURE
15
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
Temperature 650 C, Surface Finish #50
FIGURE 16- Laboratory Controlled Metal Dusting Tests as a Function of Temperature and
Alloy Composition; Surface Finish: Grid # 50
Mass Loss for Alloy HP 40 (MW / MT) at 650 C
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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
---~~.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
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0.25
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FIGURE 19 - Failed Tube Section from a DRI Pre-Heater After six Months of Operation
Chain o
Oxides
Oxides
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Oxides
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
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Ch~
Oxiq
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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
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
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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
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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
o
0
0
0
0
0
0
0
0
0
with defined
growthconditions
MELTING
in induction furnace
START OF RUN in high temperature gas-reactor
under defined preoxidation conditions
I
ii
ill
Weight
Creep conditions under high temperature
and temperature gradients through the wall
Manual
(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
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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
FIGURE
29 -
20
40
60
FIGURE
30 -
"
"I
80
100
-12
-16
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04
E
L)
50-
Alloy 4
'
35/25
45/35
Cast alloys
60/23
60/25
72/16
Ni / Cr Ratio
Wrought alloys
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100-