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University Bayreuth, Metals and Alloys, Ludwig-Thoma-Str. 36b, D-95447 Bayreuth, Germany
University Bayreuth, Ceramic Materials Engineering, L.-Thoma-Str. 36b, D-95447 Bayreuth, Germany
c
EnBW Kraftwerke AG, Schelmenwasenstrae 13-15, D-70567 Stuttgart, Germany
b
h i g h l i g h t s
Corrosion wall thickness losses of 400 mm/2 weeks occurred in a waste incinerator.
Abrasion is a major problem on superheater tubes in waste incinerators.
Laboratory salt melt tests can simulate metal corrosion in waste incinerators.
Corrosion protection coatings for steel (temperature: max. 530 C) were developed.
Higher steam temperatures are possible in WIs with the developed coatings.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 August 2013
Received in revised form
2 March 2015
Accepted 11 March 2015
Available online 31 March 2015
Thermal recycling of refuse in waste-to-energy plants reduces the problems connected to waste disposal,
and is an alternative source of electric energy. However, the combustion process in waste incinerators
results in a fast degradation of the steam-carrying superheater steel tubes by corrosive attack and
abrasive wear. Higher ring temperatures are used to increase their efciency but lead to higher
corrosion rates. It is more economical to apply protective coatings on the superheater steel tubes than to
replace the base material.
In-situ tests were conducted in a waste-to-energy plant rst in order to identify and quantify all
involved corrosive elements. Laboratory scale experiments with salt melts were developed accordingly.
The unprotected low-alloyed steel displayed substantial local corrosion. Corrosion was predominant
along the grain boundaries of a-ferrite. The corrosion rate was further increased by FeCl3 and a mixture
of HCL and FeCl3. Coatings based on pre-ceramic polymers with specic ller particles were engineered
to protect superheater tubes. Tests proved their suitability to protect low-alloYed steel tubes from corrosive attack under conditions typical for superheaterS in waste incinerators, rendering higher ring
temperatures in waste-to-energy plants possible.
2015 Elsevier B.V. All rights reserved.
Keywords:
Corrosion (tests)
Interfaces
Polymers
Ceramics
Coatings
1. Introduction
Steel corrosion still leads to enormous economic losses and the
protection of steel constructions and industrial plants is therefore a
topic of current research. A multitude of laboratory corrosion tests
appear in the technical literature for both uncoated and coated steel
[[1e4]; to name but a few]. Varied test parameters include the
temperature, the chemical, physical and mechanical environment
as well as the testing time [5]. Material corrosion due to chemicals
or electrochemical inuences (chlorides, nitrates, sulphates,
* Corresponding author.
E-mail address: uwe.glatzel@uni-bayreuth.de (U. Glatzel).
http://dx.doi.org/10.1016/j.matchemphys.2015.03.023
0254-0584/ 2015 Elsevier B.V. All rights reserved.
different plant systems and combustion methods [26]. The European Waste Framework Directive has set targets for municipal WI
plants of 60% recycling and 40% energy recovery by 2020 [27]. One
way to increase their efciency is to raise the temperature of the
steam entering the turbines. Along these lines, a temperature raise
from 400 C to 500 C will result in a 20% increase of the generated
power [27] but also entails a higher corrosion rate of reside materials, namely heat exchanger tubes, leading to shorter revision
intervals with shutdown periods of the whole incineration plant
[28]. Valid corrosion tests should therefore focus on one specic
section of the waste incinerator with a specic temperature range,
corrosive elements and mechanical load.
Great efforts are made to reduce corrosion in WIs. Ferritic steel
oxidises more easily than austenitic steel in chloride containing
high temperature atmospheres [29]. While steel shows a higher
corrosion rate than the more expensive nickel alloys, it tends to be
covered with a thick, non-protective Fe2O3 layer, austenitic highnickel alloys show localised pitting corrosion and the NiO scale is
not protective [30]. High-alloyed steel with high chromium and/or
nickel content shows a greater resistance to high-temperature
corrosion. However, sulphur can penetrate through the protective
chromium oxide scale making it less protective [31]. Therefore, the
use of the more expensive high-alloy steel in WIs is limited.
Approaches to protect the steel heat exchanger tubes from
corrosive attack include pack cementation coatings [32,33], thermally sprayed coatings [34,35], high velocity oxy-fuel nickelechromium containing coatings [29], or cladded coatings [36,24].
Furthermore, plasma sprayed coatings [37]; plasma immersion ion
implantation [38] and plasma nitriding [39] have been studied to
act as protective coatings. Despite great progress with these
advanced coatings there is still a need for further research in order
to enhance the durability of coatings under the extreme conditions
of WIs.
The objective of the presented research was to develop a cheap
coating system that could protect superheater tubes in WI plants
from corrosion for a period of one to two years. Corrosion mechanisms on uncoated steel tubes need to be understood to set up
laboratory-scale tests to investigate the protective properties of the
coatings. The present paper describes this development process
from determining the factors inuencing corrosion on superheater
tubes in a WI, over developing lab tests to testing actual coatings.
The coatings were meant to equally protect steel tubes in biomass
incinerators, where corrosion caused by high alkali contents plays
also a major role [40,41]. Especially potassium chloride is detrimental for the steel in biomass incinerators [42]. Therefore, it was
used in the presented laboratory tests, too.
2. Experimental
2.1. Steel samples
All investigations were performed with the low alloy boiler steel
1.7335 (13CrMo4-5, mild steel, corresponding to ASTM A-213 T11;
AISI A182 e F11 or F12). Different sample geometries were used
(plates and tubes). The samples were ground to RA 0.6 mm (RZ 4 mm)
before their use.
A simple before-and-after-weighing of the samples and test
rings was not suitable to determine the corrosive loss, since mass
changes during the test can have different origins (deposition of
combustion residues, formation and/or loss of corrosion products,
and so on). Hence, inert markers of the original surface were
required to measure the material loss from the tubes diameter
during the probe tests. Therefore, nickel alloy rings were applied
directly on the probe ring surface by laser cladding using a ne
powder of Ni 748-3 (Praxair) and a Nd-YAG laser DY 044/DILAS DL
11
040H (Ron Sinar) - without actually melting the probe ring surface
(Fig. 1).
The deposits on the probe ring samples were analysed after the
two-week test in the WI for the presence of chlorides and analysed
with inductively couple plasma optical emission spectroscopy (ICPOES).
Metallographic cross sections were prepared from all tested
rings. They were cut and embedded in the resins DUROFAST or
Technovit. The cross sections were ground and polished with silicon carbide to mirror nish in ethanol. The metallographic crosssections were sputtered with graphite for all SEM investigations.
In some cases, the metallographic cross sections were etched using
an ethanol solution with 3 vol.% HNO3 to investigate the grain
structure and corrosion mechanisms.
2.2. Coatings
Coated steel plates and tubes were initially sand blasted and
cleaned with acetone before the coatings were applied. Three
different types of coating were developed and tested on the probe
rings to investigate the effect of the WI conditions on the actual
coating. Coatings consisted of two layers that were consecutively
applied onto 1.7335 substrates. The bond coat was always prepared
from a commercial pre-ceramic polymer as a precursor (polysilazane PHPS, supplied as a 20 wt.% solution in di-n-butylether by
Clariant Advanced Materials GmbH) that forms a pre-ceramic layer
after a heat treatment at 110 C for 1 h in air [43].
Coating type one: BN (Henze BNP GmbH, Germany) particles or
alumina particles (Alfa Aesar, 042572, D50 5.14 mm) were added
to a polymer suspension described in the previous section.
Coating type two: A subsequently applied topcoat consisted of
an equal volume fraction mixture of borosilicate particles (8470
glass particles, Schott AG) and commercial barium silicate particles
(G018-311 glass particles, Schott AG) which have similar thermal
expansion coefcients (9e10 106/K [44]) as the steel substrate
(14.5 106/K [45]). Homogeneous coating slurries were achieved
by dispersing the different powders in ether using a commercial
dispersing agent (disperk ether). The coatings were applied by a dip
or spray coating process.
Coating type three: In some cases, zirconia particles (bought
from Alfa Aesar, USA), alumina particles (Alfa Aesar, 042572,
D50 5.14 mm) as well as the polycarbosilazane PSZ (Clariant
Advanced Materials) were used in addition to the mixture of glass
particles (same particles as in coating type 2).
After coating with the suspensions, all steel samples were heat
treated in air at 700 C for 1 h. This allowed the interface to form
and the glass particles to completely soften. The preparation of the
coatings is described in more detail in reference [46]. The coatings
and their interface with the steel substrates have been thoroughly
Fig. 1. Steel probe ring with surface markers for corrosion test in the WI plant.
12
Fig. 2. Schematic view of the probe head with electrical wiring; from [23].
Table 1
Composition of the salt melt corrosion tests.
Initial salt mixture
NaCl
Na2SO4
KCl
K2SO4
ZnCl2
ZnSO4
wt.%
Gas atmosphere
vol.%
19.0
N2
71.2
22.8
O2
18.2
24.7
H2O
10.0
28.5
SO2
0.02
2.5
HCl
0.08
2.5
13
Table 2
Element concentration (weight ppm) in the deposits on probe rings 1 and 4 from a WI plant (ICP-OES).
C
400
Ag
40
Al
32,000
Co
40
B
5500
Li
160
Mg
11,000
Ba
3300
Mn
850
Bi
41
Na
72,000
Ca
135,000
Ni
450
Cd
120
Cr
900
Cu
1000
P
6300
Pb
700
S
104,000
Fe
17,000
Si
57,000
Ga
110
In
50
K
77,000
Sr
300
Ti
9500
Zn
17,000
14
Fig. 6. Metallographic cross section of the probe ring (Fig. 1) after two weeks of corrosive/abrasive wear in the WI plant. The horizontal line marks the original steel surface.
can actually decrease the corrosion rate (and lower abrasion) since
they reduce the metal surface temperature [21]. In those deposits,
HCl is the predominant species over Cl2 (i.e. at low oxygen partial
pressure [51]). A further factor in corrosive decay is the removal of a
possible passivation layer due to abrasive forces of the particle
freight. Deposits on the superheater tube would prevent the mechanical removal.
The measured element concentrations and corrosion rates are
subject to temperature uctuation and varying waste composition.
A corrosion rate of 350e450 mm/2 weeks was determined in the
present study. For comparison with current literature values: The
corrosion rates of the ferritic steel Fe2Cr1Mo in circulating uidised
beds burning refuse derived fuel at 460 C are 5 mm/year; at 516 C
corrosion rates of 13 mm/year were measured [57]). This highlights
the inuence of an increased temperature on the corrosion rate.
Hence, the temperature for laboratory corrosion tests should be
chosen at the maximum temperature that is aspired to be attained
in the specic part of the power plant.
Although the waste is being homogenised before being red in
WI power plants, the two weeks probe test will only reect a
fraction of reactions which occur on the superheater tubes of
different WI plants over a two-year period of time (optimum
revision interval).
One important nding of the probe tests was the discovery of
the abrasive loading of the silicate particle freight contained in the
ue gas/ashes. Developed protective coatings need to have a high
abrasion resistance at elevated temperatures, for example at
530 C; otherwise a good corrosion resistance is not of much worth
during operation. Particles are deposited onto the superheater
tubes and act as abrasion protection. This could be seen from the
probe tests.
The examined scales contained oxides of the alloys components.
Other researchers reported Fe3O4 deposits close to the metal, and
bauer spectroscopy allowed the
Fe2O3 further out [57]. Mo
detection of even more phases in literature: a-Fe2O3, Fe3O4, gFe2O3, d-FeOOH, a-FeOOH, Fe(OH)2, Fe(OH)3 (180 h steam oxidation
15
Fig. 7. Crystalline phases detected on samples after 168 h corrosion test of uncoated 1.7335 steel in salt melt (composition: see Table 1) A: Fe3O4; B: NaCl; C: KCl; D: ZnFe2O4; E:
K2SO4; F: Fe2(SO4)3; G: Cr2(SO)4; H: Na2SO4; I: CrCl3.
Fig. 8. Comparison of corrosion rates for uncoated 1.7335 steel in single laboratory salt
melt tests.
Using precursor derived ceramic coatings as corrosion protection for WI tubes is a completely new approach. It was assumed
that the coatings should have a critical thickness of at least 100 mm
to withstand the test of time. Different coatings have been developed using the corrosion tests results in an iterative process. Results are summarised in Table 3. Initially unlled and BN- or Al2O3powder lled precursor based coatings (type one) were tested as
protective coatings. They were permeable to the ions of the corrosive salts due to shrinkage porosity of the precursor. Hence, those
coatings offered no protection of 1.7335 steel in the salt melt tests
(Fig. 10).
Only samples without open porosity offered sufcient protection from corrosive attack in the laboratory corrosion tests
(Table 1). Corrosion occurs at sites with permeable coating defects
(as shown in [61]: Al2O3e13%TiO2 tested with electrochemical
impedance spectroscopy). A compensation of the shrinkage
porosity during the ceramisation regime of the precursor was
achieved when a mixture of glass particles was employed (coating
type two) [46]. Still, coating defects such as delamination or very
large gas inclusions were a major issue to be addressed during the
development process. Only intact, gas tight coatings showed no
16
Table 3
Developed and tested coating systems.
Substrate
Bond coat
Functional coat
Abrasion resistance
1.7335
PHPS
Precursor
Precursor
Precursor
Precursor
Precursor
Precursor
Precursor
No (shrinkage porosity)
No (shrinkage porosity)
No
yes
Yes
Yes
Yes
Not tested
Not tested
Not tested
Low
Medium
High
High
(type 1)
BN (type 1)
Al2O3 (type 1)
molten glass particles
molten glass particles
molten glass particles
molten glass particles
(type 2)
ZrO2 (type 3)
ZrO2 Al2O3 (type 3)
ZrO2 PSZ (type 3)
Fig. 10. Element distribution of a porous precursor derived coating on 1.7335 steel after a corrosion test in the initially used salt mixture. Corrosive elements penetrate the coating
easily and can be detected in the underlying steel substrate, too.
Fig. 11. An optimised composite coating with a high abrasion resistance (at 530 C) on
a 1.7335 steel substrate after one week salt melt test at 530 C.
4. Conclusions
Initial corrosion rates are extremely high in the waste incineration plants in the superheater section. A wall thickness loss of
approximately 400 mm/2 weeks occurred in a waste incinerator.
Although the corrosion rate slows down, protection is required for
superheater tubes.
17
Fig. 13. Metallographic cross section of a coating containing glass and ZrO2 particles on
1.7335 steel after a two week test in a WI.
Abrasion is a major problem on superheater tubes in waste incinerators. Corrosion protection coatings must show a high abrasion resistance.
Laboratory salt melt tests can simulate metal corrosion in waste
incinerators. They should contain large amounts of chlorines and
sulphates and have a low melting point.
Corrosion protection coatings for steel (temperature: max.
530 C) were developed. Higher steam temperatures are possible in
WIs with the developed coatings.
Acknowledgements
The authors acknowledge the nancial support of the Bavarian
State Ministries of Science, Research and Art, and that of Economy,
Infrastructure, Transport and Technologies, Germany and the
companies Clariant AG and EnBW Kraftwerke AG as a part of the
research initiative KW21 (Project Nr. BY 7 DE). Christoph Wieland
t Munich contributed the FactSage calcuof Technische Universita
lations. The authors acknowledge this contribution. The authors
also thank Tobias Katzmann and Eva Eisinger for their support of
some of the experiments (Tobias Katzmann (corrosion rate of
probes); Eva Eisinger (tests with FeCl3 addition).
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