coatings

Article
Corrosion Testing of Thermal Spray Coatings in
a Biomass Co-Firing Power Plant
Maria Oksa *, Jarkko Metsäjoki and Janne Kärki
VTT Technical Research Centre of Finland Ltd., P.O. Box 1000, FI-02044 VTT, Finland;
jarkko.metsajoki@vtt.fi (J.M.); janne.karki@vtt.fi (J.K.)
* Correspondence: maria.oksa@vtt.fi; Tel.: +358-50-5365844

Academic Editor: Pedro Neto

Received: 20 September 2016; Accepted: 19 November 2016; Published: 24 November 2016

Abstract: Large-scale use of biomass and recycled fuel is increasing in energy production due
to climate and energy targets. A 40% cut in greenhouse gas emission compared to 1990 levels
and at least a 27% share of renewable energy consumption are set in EU Energy Strategy 2030.
Burning fuels with high content of corrosive species such as chlorine and heavy metals causes
deterioration of boiler components, shortened lifetime, limited availability of a plant and hence
higher maintenance and investment costs and lower thermal and economic efficiency. Coatings
can be applied to protect the critical boiler components against high temperature corrosion. In this
study, five thermal spray coatings were tested in an actual biomass co-firing boiler for 1300 h with
a measurement probe. The coatings were analyzed after the exposure by metallographic means
and scanning electron microscope/energy-dispersive X-ray spectroscope (SEM/EDX). The deposits
formed on the specimens were analyzed by X-ray fluorescence. At 550 ◦ C, the coatings showed
excellent corrosion performance compared to reference material ferritic steel T92. At 750 ◦ C, tube
material A263 together with NiCr and NiCrTi had the highest corrosion resistance. To conclude,
thermal spray coatings can offer substantial corrosion protection in biomass and recycled fuel burning
power plants.

Keywords: thermal spray; coating; corrosion; high temperature; protection; boiler

1. Introduction
Response to the threat of climate change has taken a major step with the Paris Agreement [1],
which is an extensive and legally binding climate agreement with target of holding global warming
well below 2 ◦ C compared to pre-industrial levels. For the first time, almost all countries around
the world have agreed to take actions to combat climate change. Energy and climate targets to
prevent greenhouse gas emissions have been tightened from the 20-20-20 targets, including 20% cut in
greenhouse gas emissions from 1990 levels, 20% of EU energy from renewables and 20% improved in
energy efficiency, to 2030 targets of a 40% cut in the greenhouse gas emissions and at least 27% share
of renewable energy consumption [2]. While share of wind and solar energy are increasing rapidly,
other renewable energy forms producing base load are needed, during and beyond the transformation
period until the year 2050, when 26% to 29% of global electricity is predicted to be produced by wind
and solar power [3,4]. Bioenergy, especially production of thermal energy by biomass, is currently the
largest form of renewable energy and is expected to keep its dominant position. However, biomass
combustion together with enhanced recycled fuel (waste) combustion is detrimental to components of
the power plants due to very reactive species that cause slagging and high temperature corrosion.
Severe fireside corrosion, encountered especially in boilers using biomass and recycled fuel,
occurs when chemical reactions with the combustion gases and deposits at high temperatures cause
the loss of heat exchanger surfaces, e.g., superheaters. It is often caused by a gaseous or molten attack

Coatings 2016, 6, 65; doi:10.3390/coatings6040065 www.mdpi.com/journal/coatings

Coatings 2016, 6, 65 2 of 13

induced by compounds of chlorine, bromine, alkali metals (K, Na), sulfur, and heavy metals (Zn,
Pb, Cu, etc.) [5–8]. Corrosion may cause a leakage, which leads to a shut-down of the boiler and
hence severe costs by reduced availability and repair [9]. Other than using higher alloyed steels or
nickel-based alloy tubes, thermal spray coatings can be applied to low alloyed tubes for corrosion
protection with economical cost and high thermo-mechanical properties. In thermal spraying, the
coating is formed from molten or semi-melted droplets producing a lamellar structure. High velocity
spray methods generate coatings with good adhesion and low porosity [10], which are essential for
sufficient protection of the substrate material. Thermal spray coatings have proven their ability for
corrosion protection in laboratory tests, e.g., plasma sprayed NiCr coating against high temperature
corrosion under deposits simulating conditions of coal-biomass firing [11]. The performance was
strongly dependent on the amount of the chromium in the coating, as the corrosion protection took
place by a protective chromium oxide layer.
In this study, five thermal spray coatings were tested in a co-firing biomass boiler for 1300 h,
up to 750 ◦ C material temperatures, with a measurement probe in order to validate the corrosion
performance in actual conditions [12]. As reference, ferritic steel and nickel based alloys were exposed
to the same conditions.

2. Materials and Methods

High temperature corrosion performance of five thermal spray coatings were tested in a biomass
co-fired circulating fluidized bed boiler for about 1300 h with a controlled probe measurement.
Two tube metal alloys were used as reference materials. Test temperatures for the materials were
550 ◦ C and 750 ◦ C.

2.1. Thermal Spray Coatings

Five thermal spray coatings were manufactured for high temperature corrosion exposure in a
biomass co-firing boiler. Four of the coatings were sprayed by high velocity oxy-fuel (HVOF) method,
and one with a wire arc. The coating was performed on two substrate materials. The coating materials
were nickel based powders Ni-980-1/1260F from Praxair (NiCr), Diamalloy 1005 from Sulzer Metco
(IN625) and Diamalloy 4006 from Sulzer Metco (NiCrW), a wire TAFA Nickel Chrome 45 CT from
Praxair (NiCrTi), and an iron based powder SHS9172 from Nanosteel (FeCr). The substrate materials
were a ferritic steel T92 (ASTM A213 T92) and a nickel super alloy A263 (NIMONIC® Alloy 263, Special
Metals, Hereford, UK). Chemical composition of the coating and substrate materials are presented
in Table 1.

Table 1. Chemical composition of the coating and substrate materials (wt.%).

Material Ni Cr Fe Mo W Co Nb Si
NiCr Bal. >45 1.1 – – – – 2.1
IN625 Bal. 21.5 2.5 9.0 – – 3.7 0.2
NiCrW Bal. 20.5 <1.0 9.0 10.0 – – –
FeCr – <25.0 Bal. <6.0 <15.0 – <12.0 <2.0
NiCrTi Bal. 42–46 – – – – – –
T92 – 8–9.5 Bal. 0.3–0.6 1.5–2 – – ≤0.5
A263 Bal. 19–21 <0.7 5.6–6.1 – 19–21 – <0.4
Material Mn Cu Al Ti V C B
NiCr – – – – – – –
IN625 0.1 – – – – – –
NiCrW – 4.0 – – – 0.75 0.75
FeCr <3.0 – – – – <4.0 <5.0
NiCrTi – – – 0.3–1 – – –
T92 0.3–0.6 – ≤0.4 – 0.15–0.25 0.07–0.013 –
A263 <0.6 – <0.6 1.9–2.4 – 0.04–0.08 –
Coatings 2016, 6, 65 3 of 13
Coatings 2016, 6, 64  3 of 13 

was performed on the perimeter of tube rings with size of Φ 48 mm × 12.5 mm

The coating was performed on the perimeter of tube rings with size of Φ 48 mm × 12.5 mm for 
The coating
exposure at 550 C, and Φ 34 mm × 15 mm for 750 C. HVOF process with CJS (Carbide Jet Spray by 
for exposure at 550 ◦ C, and Φ 34 mm × 15 mm for 750 ◦ C. HVOF process with CJS (Carbide Jet
Thermico  GmbH  &  Co  KG,  Dortmund,  Germany)  spray gun  was  used for spraying  the  powders. 
Spray by Thermico GmbH & Co KG, Dortmund, Germany) spray gun was used for spraying the
Depending on process parameters, CJS produces high velocity and low thermal input on the sprayed 
powders. Depending
powders,  on process
generating  parameters,
thick  coatings  CJS
with  low  produces
oxidation  rate high velocity
and  good  and low
adhesion  thermal
to  the  input on
substrate 
the sprayed
material. However, small particle size would be optimal for CJS to enhance the melting of the powder  to the
powders, generating thick coatings with low oxidation rate and good adhesion
substrate material. However, small particle size would be optimal for CJS to enhance the melting of
particles and hence sufficient cohesion between the lamellas. In this study, the applied powders were 
designed 
the powder for  a  previous 
particles and hence generation 
sufficientspray  gun  (e.g., 
cohesion Diamond 
between Jet  Hybrid In
the lamellas. from 
thisSulzer 
study,Metco, 
the applied
Westbury,  NY,  USA),  and  therefore  slightly  too  coarse  for  the  used  method.  Arc  spraying  was 
powders were designed for a previous generation spray gun (e.g., Diamond Jet Hybrid from Sulzer
performed with Smart Arc (by Sulzer Metco). The process parameters of the spraying are presented 
Metco, Westbury, NY, USA), and therefore slightly too coarse for the used method. Arc spraying was
in Table 2. Powder feed rate was 50 g/min for HVOF and applied spraying distance was 250 mm. For 
performed with Smart Arc (by Sulzer Metco). The process parameters of the spraying are presented in
arc spraying, the spraying distance was 150 mm. Images of the cross‐section of the coated specimens 
Table 2.are presented in Figure 1. Both NiCr and IN625 showed reasonably large lamellas with very little 
Powder feed rate was 50 g/min for HVOF and applied spraying distance was 250 mm. For arc
spraying, the spraying distance was 150 mm. Images of the cross-section of the coated specimens
oxidation in the lamellar boundaries, whereas the arc sprayed NiCrTi was highly oxidized (darker 
areas in the micrograph) with fully molten structure. 
are presented in Figure 1. Both NiCr and IN625 showed reasonably large lamellas with very little
Porosity of the coatings was measured with image analysis from optical micrographs. Oxides at 
oxidation in the lamellar boundaries, whereas the arc sprayed NiCrTi was highly oxidized (darker
lamellar boundaries and pull‐outs due to specimen preparation may influence to the image analysis 
areas in the micrograph) with fully molten structure.
results.  According  to  the  analysis,  the  most  dense  coating  was  HVOF  sprayed  NiCrW  with  2.6% 
porosity. Porosity of other HVOF‐sprayed coatings varied from 3.3% for NiCr, 4.8% for IN625 to 5.8% 
Table 2. Process parameters for high velocity oxy-fuel (HVOF) spraying (L/min). Below: process
for FeCr coating. Arc sprayed NiCrTi had porosity of about 4.6%. 
parameters for arc spraying.
Table  2.  Process  parameters  for  high  velocity  oxy‐fuel  (HVOF)  spraying  (L/min).  Below:  process 
Coating parameters for arc spraying. 
Spray Method H2 Kerosene O2 N2 Sweeps Thickness (µm)
NiCr Coating 
CJS, 140 mm
Spray Method  100 H 2  16
Kerosene 1000
O2 N26 + 6Sweeps 14
Thickness (μm) 130
IN625 CJS, 140CJS, 140 mm 
NiCr  mm 100100  16 16  1000
1000  6 + 6 14 
6 + 6  10 130  140
NiCrW IN625 
CJS, 140CJS, 140 mm 
mm 100100  16 16  1000
1000  6 + 6 10 
6 + 6  20 140  270
FeCr CJS, 140CJS, 140 mm 
NiCrW  mm 100100  16 16  850
1000  6 + 6 20 
6 + 6  21 270  200
Coating FeCr  CJS, 140 mm 
Spray Method Voltage100  16 
Current 850 
Air 6 + 6  21  200 Thickness (µm)
Coating  Spray Method  Voltage Current Air     Thickness (μm)
NiCrTi NiCrTi 
Smart Arc
Smart Arc  30 V 30 V  220220 A 
A 3.5/2.5 bar
3.5/2.5 bar      180  180

 
Figure Figure 1. Optical micrographs of the thermal spray coatings before testing: (a) HVOF sprayed NiCr 
1. Optical micrographs of the thermal spray coatings before testing: (a) HVOF sprayed NiCr
and (b) IN625; (c) arc sprayed NiCrTi; (d) HVOF sprayed NiCrW and (e) FeCr. 
and (b) IN625; (c) arc sprayed NiCrTi; (d) HVOF sprayed NiCrW and (e) FeCr.

 
Porosity of the coatings was measured with image analysis from optical micrographs. Oxides at
lamellar boundaries and pull-outs due to specimen preparation may influence to the image analysis
results. According to the analysis, the most dense coating was HVOF sprayed NiCrW with 2.6%
porosity. Porosity of other HVOF-sprayed coatings varied from 3.3% for NiCr, 4.8% for IN625 to 5.8%
for FeCr coating. Arc sprayed NiCrTi had porosity of about 4.6%.
Coatings 2016, 6, 65 4 of 13

Coatings 2016, 6, 64  4 of 13 
2.2. Measurement Probe
2.2. Measurement Probe 
Measurement probes can be applied for corrosion monitoring and deposit analysis in high
Measurement  probes  can  be  applied  for  corrosion  monitoring  and  deposit  analysis  in  high 
temperature combustion plants. They can be used for analyzing both short- and long-term deposition
temperature combustion plants. They can be used for analyzing both short‐ and long‐term deposition 
build-up and corrosion risks. An advanced water-air-cooled probe was developed to test materials in
build‐up and corrosion risks. An advanced water‐air‐cooled probe was developed to test materials 
two different temperatures. The probe is approximately two meters in length and can accommodate
in  two  different  temperatures.  The  probe  is  approximately  two  meters  in  length  and  can 
twoaccommodate 
sections withtwo sections 
six test rings in each.test 
with six  One section
rings  is water-
in  each.  and air-cooled
One section  and is exposedand 
is  water‐ and air‐cooled  at metal
is 
temperatures ◦
exposed  at of approximately
metal  550
temperatures  C and the second
of  approximately  550  is
C air-cooled at metal
and  the  second  temperatures
is  air‐cooled  around
at  metal 
◦ C. The probe with two separate sample regions is presented in Figure 2.
750 temperatures around 750 C. The probe with two separate sample regions is presented in Figure 2. 

 
Figure 2. High temperature probe for corrosion testing at two temperature regions. 
Figure 2. High temperature probe for corrosion testing at two temperature regions.
There are several temperature measurements in different sides of the probe for both temperature 
There are several temperature measurements in different sides of the probe for both temperature
areas. The primary head consists of a stationary part, which has four thermo‐couples and area for 
areas. The primary
detachable  head
material  consists
rings.  The of a stationary
width  part, which
of  a  detachable  has four
material  ring thermo-couples
in  the  primary and area
head  is  for
12.5 mm/each. 
detachable In rings.
material the  secondary 
The widthhead,  the  detachable 
of a detachable material 
material ring rings 
in theare  connected 
primary head to  the  system 
is 12.5 mm/each.
through a separate extension ring. The width of a detachable material ring in the secondary head is 
In the secondary head, the detachable material rings are connected to the system through a separate
15 mm/each. There are two thermo‐couples in the extension ring and material temperatures of the 
extension ring. The width of a detachable material ring in the secondary head is 15 mm/each. There
are detachable material rings are measured at three rings. The flue gas temperature is measured in the 
two thermo-couples in the extension ring and material temperatures of the detachable material
tip of the probe with one covered thermo‐couple. The thermal expansion in primary and secondary 
rings are measured at three rings. The flue gas temperature is measured in the tip of the probe with
heads as well as in the casing is eliminated with a special spring system consisting of four separate 
one covered thermo-couple. The thermal expansion in primary and secondary heads as well as in the
springs. 
casing is eliminated with a special spring system consisting of four separate springs.
The probe is air‐ and water‐cooled with a separate controllable cooling unit. During the tests the 
The probe is air- and water-cooled with a separate controllable cooling unit. During the tests the
two meter casing remains cool by water cooling whereas the temperatures of the sample exposure 
twoheads are adjusted as desired by additional air cooling. The surface temperatures of the probes vary 
meter casing remains cool by water cooling whereas the temperatures of the sample exposure
heads are adjusted as desired by additional air cooling. The surface temperatures of the probes vary
depending on the direction of the flue gas flow. During the insertion of the probe into the boiler, the 
depending on the direction of the flue gas flow. During the insertion of the probe into the boiler, the
direction is chosen so that the windward (i.e., against the flue gas flux) temperature in the sample 
direction is chosen so that the windward (i.e., against the flue gas flux) temperature in the sample ring
ring area is maintained constant by adjusting the air cooling rate. The temperatures on the other sides 
areaof the probe vary depending on the deposit formation and cleaning stages. 
is maintained constant by adjusting the air cooling rate. The temperatures on the other sides of
the probe vary depending on the deposit formation and cleaning stages.
2.3. Test Facility—The Biomass Co‐Firing Plant 
2.3. Test Facility—The Biomass Co-Firing Plant
The  probe  exposure  trial  was  performed  at  the  Alholmens  Kraft  power  plant  located  in  the 
western coast region of Finland, in the town of Pietarsaari. The facility is one of the largest biomass 
The probe exposure trial was performed at the Alholmens Kraft power plant located in the
fueled power plants in the world producing electricity, district heating and process steam and heat 
western coast region of Finland, in the town of Pietarsaari. The facility is one of the largest biomass
for the UPM‐Kymmene plant. The exposure involved deployment of the corrosion probe in a 550 
fueled power plants in the world producing electricity, district heating and process steam and heat for
the MW th circulating fluidized bed boiler, which has live steam parameters of 194 kg/s, 165 bar, 545 °C. 
UPM-Kymmene plant. The exposure involved deployment of the corrosion probe in a 550 MWth
During the measurements the boiler was fired on average with 30% peat, 10% coal, 50% of biomass 
circulating fluidized bed boiler, which has live steam parameters of 194 kg/s, 165 bar, 545 ◦ C. During
(forest residues, industrial wood and bark etc.) and 10 % SRF (solid recovered fuel). Daily fluctuations 
the measurements the boiler was fired on average with 30% peat, 10% coal, 50% of biomass (forest
in the fuel shares in comparison to those averages can be wide as well as the fluctuations in the whole 
residues, industrial wood and bark etc.) and 10 % SRF (solid recovered fuel). Daily fluctuations in
process parameters. The probe was inserted into the superheater area after the cyclones. 
the fuel shares in comparison to those averages can be wide as well as the fluctuations in the whole
process parameters. The probe was inserted into the superheater area after the cyclones.
2.4. Specimen Characterization 
After the exposure the coated and reference ring specimens were removed from the probe and 
2.4. Specimen Characterization
embedded in cold setting resin on site. The embedded specimens were cross‐sectioned by grinding 
After the exposure the coated and reference ring specimens were removed from the probe and
with ethanol followed by polishing. The cross‐sections were studied by an optical microscope and a 
embedded in cold setting resin on site. The embedded specimens were cross-sectioned by grinding
Coatings 2016, 6, 65 5 of 13

Coatings 2016, 6, 64  5 of 13 
with ethanol followed by polishing. The cross-sections were studied by an optical microscope and
scanning  electron
a scanning electron  microscope
microscope  (SEM) 
(SEM) (FEI/Philips 
(FEI/PhilipsXL30 
XL30ESEM, 
ESEM,FEI, 
FEI,Eindhoven, 
Eindhoven,The  TheNetherlands) 
Netherlands)
equipped with energy‐dispersive X‐ray spectroscope (EDX) (UltraDry EDS Detector, Thermo Fisher 
equipped with energy-dispersive X-ray spectroscope (EDX) (UltraDry EDS Detector, Thermo Fisher
Scientific Inc., Waltham, MA, USA) for elemental analysis and mapping. Separate deposit samples 
Scientific Inc., Waltham, MA, USA) for elemental analysis and mapping. Separate deposit samples were
were detached from the probe near the test samples and they were analyzed by X‐ray fluorescence 
detached from the probe near the test samples and they were analyzed by X-ray fluorescence (XRF)
(XRF)  using 
using the Philips the  Philips X-ray
PW2404 PW2404  X‐ray  spectrometer 
spectrometer and  semiquantitative 
and semiquantitative SemiQ program SemiQ  program 
(PANalytical,
(PANalytical,  Almelo,  The  Netherlands).  The  samples  were  analyzed  for  fluorine  (F)  and 
Almelo, The Netherlands). The samples were analyzed for fluorine (F) and heavier elements excluding heavier 
elements  excluding  noble  gases.  The  detection  limit  of  the  method  is  typically  in  the  order  of 
noble gases. The detection limit of the method is typically in the order of 0.01 wt.%.
0.01 wt.%. 
3. Results
3. Results 
3.1. Process and Probe Measurement Data
3.1. Process and Probe Measurement Data 
Plant electricity output varied a lot in short intervals depending on the electricity markets, which
Plant electricity output varied a lot in short intervals depending on the electricity markets, which 
had a strong effect on the flue gas temperatures inside the boiler, and further on the temperatures at
had a strong effect on the flue gas temperatures inside the boiler, and further on the temperatures at 
the probe surfaces, Figure 3a. Some fluctuations were also present in the flue gas emissions, e.g., the
the probe surfaces, Figure 3a. Some fluctuations were also present in the flue gas emissions, e.g., the 
HCl and SO2 emissions presented in Figure 3b. Due to high variations in the plant load and process
HCl and SO2 emissions presented in Figure 3b. Due to high variations in the plant load and process 
temperatures, the probe temperature profiles were fluctuating as well, which influenced the stability
temperatures, the probe temperature profiles were fluctuating as well, which influenced the stability 
of the controlled temperature on the windward surface, as presented in Figure 4a. Hence, the actual
of the controlled temperature on the windward surface, as presented in Figure 4a. Hence, the actual 
material temperatures were lower than planned: 536 ◦ C for the primary and 697 ◦ C for the secondary
material temperatures were lower than planned: 536 C for the primary and 697 C for the secondary 
head in the windward side on average. For the leeward side, the average temperatures were 502 ◦ C
head in the windward side on average. For the leeward side, the average temperatures were 502 C 
for the primary and 609 ◦ C for the secondary head. Minimum values in the probe were in the leeward
for the primary and 609 C for the secondary head. Minimum values in the probe were in the leeward 
◦ C for the primary and 566 ◦ C for the secondary head. The maximum values in the windward
side; 331331 
side;  C  for  the  primary  and  566  C  for  the  secondary  head.  The  maximum  values  in  the 
side were 602 ◦ C (primary) and 764 ◦ C (secondary head). The temperatures are presented in the form
windward side were 602 C (primary) and 764 C (secondary head). The temperatures are presented 
of in the form of a stability curve, where the fluctuations, which followed the flue gas temperature, are 
a stability curve, where the fluctuations, which followed the flue gas temperature, are not shown.
The diagram shows overall temperature behavior to the exposure period, but not in a chronological
not shown. The diagram shows overall temperature behavior to the exposure period, but not in a 
order. Three short temperature and pressure changes occurred in the probe during the test period
chronological order. Three short temperature and pressure changes occurred in the probe during the 
due to shutting the cooling water circulation and cleaning the filter. Operational thermal cycling
test period due to shutting the cooling water circulation and cleaning the filter. Operational thermal 
◦ C flue gas) was caused by the electric output variation. After the exposure, the material
(627–874
cycling  (627–874  C  flue  gas)  was  caused  by  the  electric  output  variation.  After  the  exposure,  the 
testing probe was covered with a light brown deposit, which had partly detached. The probe is
material testing probe was covered with a light brown deposit, which had partly detached. The probe 
presented in Figure 4b.
is presented in Figure 4b. 

 
(a) 

Figure 3. Cont. 
Figure 3. Cont.  
Coatings 2016, 6, 65 6 of 13
Coatings 2016, 6, 64  6 of 13 
Coatings 2016, 6, 64  6 of 13 

 
(b) 
 
(b) 
Figure  3. Process
Process  data during
during  the test
test  exposure:  (a) 
(a) Plant 
Plant electricity 
electricityoutput 
output(MW) 
(MW)and 
andflue 
fluegas 
Figure 3.3. 
Figure  Process data
data  during the
the  test  exposure:
exposure:  (a)  Plant  electricity  output  (MW)  and  flue  gas
gas 
temperature (C) at the cyclone; (b) Flue gas data of sulfur dioxide SO
temperature ◦ 2 and hydrogen chloride HCl 
( C) at the cyclone; (b) Flue gas data of sulfur dioxide SO22 and hydrogen chloride HCl 
and hydrogen chloride HCl
temperature (C) at the cyclone; (b) Flue gas data of sulfur dioxide SO
during the test (mg/Nm
during the test (mg/Nm ). 
333).
during the test (mg/Nm ). 

 
(a)   
(a) 

 
 
(b) 
(b) 
Figure 4. (a) Probe measurement data presented in the form of stability curve for flue gas, windward 
Figure 4. (a) Probe measurement data presented in the form of stability curve for flue gas, windward 
and leeward temperatures (C) (S = secondary head, P = primary head); (b) Probe after the 1300 h 
Figure 4. (a) Probe measurement data presented in the form of stability curve for flue gas, windward
and leeward temperatures (C) (S = secondary head, P = primary head); (b) Probe after the 1300 h 
and leeward temperatures (◦ C) (S = secondary head, P = primary head); (b) Probe after the 1300 h
exposure, material samples at metal temperatures of approximately 550 C. 
exposure, material samples at metal temperatures of approximately 550 C. 
exposure, material samples at metal temperatures of approximately 550 ◦ C.
Coatings 2016, 6, 65 7 of 13

3.2. Formed Deposits

Coatings 2016, 6, 64  7 of 13 
The deposit after the exposure was light brown and easily detachable from the probe. At 750 ◦ C
probe section, the deposit layer was slightly thicker compared to the lower temperature section.
3.2. Formed Deposits 
Deposits were composed mainly of sulfur, calcium, potassium, silicon, sodium, iron and aluminum,
The deposit after the exposure was light brown and easily detachable from the probe. At 750 C 
as presented in Table 3. Other elements in the deposit were magnesium, phosphorus, titanium and
probe  section,  the  deposit  layer  was  slightly  thicker  compared  to  the  lower  temperature  section. 
manganese. The amount of zinc was considerable (0.4/0.7 wt.%) in the analyzed deposits. At the
Deposits were composed mainly of sulfur, calcium, potassium, silicon, sodium, iron and aluminum, 
lower temperature, amounts of sulfur, potassium and sodium were higher compared to the 750 ◦ C
as presented in Table 3. Other elements in the deposit were magnesium, phosphorus, titanium and 
temperature. At the higher temperature, no chlorine was detected in the deposit.
manganese. The amount of zinc was considerable (0.4/0.7 wt.%) in the analyzed deposits. At the lower 
temperature,  amounts  of  sulfur,  potassium  and  sodium  were  higher  ◦compared  ◦to  the  750  C 
Table 3. Composition of the formed deposits on the probe sections at 550 C and 750 C (wt.%).
temperature. At the higher temperature, no chlorine was detected in the deposit. 

Element S Ca K Si Na Fe Al Mg P Ti
Table 3. Composition of the formed deposits on the probe sections at 550 C and 750 C (wt.%). 
550 ◦ C 14 10 14 4.5 5.7 4.2 2.7 1.1 0.78 0.7
Element S  Ca  K Si Na Fe Al Mg P Ti 
750 ◦ C 11 10 9.8 9.7 1.6 5.2 4.7 0.91 0.91 0.84
550 C  14  10  14  4.5  5.7  4.2  2.7  1.1  0.78  0.7 
Element Zn
750 C  Mn
11  10 Ba 9.8  Cu9.7  Pb Sr 4.7  Cr0.91 
1.6  5.2  Rb Cl
0.91  0.84  Ni
550 ◦C Element
0.42 Zn  Mn 
0.38 0.3 Ba 0.12 Cu 0.08Pb Sr
0.06 Cr 0.15Rb Cl
0.06 Ni 
0.05 0.03
750 ◦ C 550 C 
0.71 0.42  0.38 
0.29 0.23 0.3  0.06
0.12  0.12
0.08  0.06 
0.05 0.15 0.09
0.06  0.05  0.03 
0.07 – 0.02
750 C  0.71  0.29  0.23  0.06  0.12  0.05  0.09  0.07  –  0.02 

3.3. Corrosion Resistance at 550 ◦ C

3.3. Corrosion Resistance at 550 C 
All the coated specimens showed high corrosion resistance against the biomass co-firing
All  the  coated  specimens  showed  high  corrosion  resistance  against  the  biomass  co‐firing 
◦ C without significant changes, whereas the uncoated
conditions and endured the exposure at 550
conditions and endured the exposure at 550 °C without significant changes, whereas the uncoated 
substrate material steel T92 had corroded strongly during the exposure. IN625 coating had minor
substrate material steel T92 had corroded strongly during the exposure. IN625 coating had minor 
corrosion within the top 20 µm of the coating at the flue gas side. Figure 5 presents SEM images of T92,
corrosion within the top 20 μm of the coating at the flue gas side. Figure 5 presents SEM images of 
NiCr and IN625 after the exposure. NiCrW, IN625, NiCr and NiCrTi had formed a 1–2 µm thin Cr rich
T92, NiCr and IN625 after the exposure. NiCrW, IN625, NiCr and NiCrTi had formed a 1–2 μm thin 
oxide layer, which protected against corrosion.
Cr rich oxide layer, which protected against corrosion. 

 
Figure 5. SEM (BSE–Back scattered electron) images of the cross‐section of the specimens after the 
Figure 5. SEM (BSE–Back scattered electron) images of the cross-section of the specimens after the
1300 h exposure at 550 C: (a–c) Windward side of T92, NiCr and IN625 coatings; (d–f) Same materials 
1300 h exposure at 550 ◦ C: (a–c) Windward side of T92, NiCr and IN625 coatings; (d–f) Same materials
at the leeward side. 
at the leeward side.
FeCr was found to be corroded at the side of 90 from the flue gas direction and it peaked at the 
FeCr was found to be corroded at the side of 90◦ from the flue gas direction and it peaked at the
leeward side (i.e., opposite to the flue gas flux), Figure 6, with a 30 μm thick corrosion product layer 
leeward side (i.e., opposite to the flue gas flux), Figure 6, with a 30 µm thick corrosion product layer
and internal coating degradation up to 20–40 μm depth. Chlorine was detected at the outer surface 
andof the FeCr coating in the leeward side. According to the EDX point analysis (wt.%), the separate 
internal coating degradation up to 20–40 µm depth. Chlorine was detected at the outer surface of
the chlorine containing areas on the coating (one marked with an arrow in Figure 6) contained 7.3% Cl, 
FeCr coating in the leeward side. According to the EDX point analysis (wt.%), the separate chlorine
50.2%  iron,  24.1%  oxygen,  9.1%  chromium.  There  was  also  tungsten  (5.2%),  niobium  (3.1%), 
aluminum and silicon (0.5 % each). In the internal degradation area, composition included Fe (44.1%), 
 Coatings 2016, 6, 64  8 of 13 

Coatings 2016, 6, 65 8 of 13
Cr (23.1%), W (11.9%), O (8.9%), Nb (8.3%), Si (1.8%), Cl (1.1%), Al (0.6%), and K (0.2%). Chlorine had 
formed a thin, about 5 μm in thickness, mixed iron‐chromium chlorine‐oxide layer on the surface of 
the coating. Right next to the coating, this layer contained Cr (22.3%), O (18.2%), Mo (19.3%), W (13.7), 
containing areas on the coating (one marked with an arrow in Figure 6) contained 7.3% Cl, 50.2% iron,
Fe (10.7%), Si (8.5%), Cl (5.1%), Al (1.9%), and K (0.4%). At about 3 μm from the coating surface, the 
24.1% oxygen, 9.1% chromium. There was also tungsten (5.2%), niobium (3.1%), aluminum and silicon
Coatings 2016, 6, 64  8 of 13 
layer consisted of Cr (47.9%), O (25.6%), Fe (15.7%), Zn (2.3%), S (2.2%), Mg (1.6%), K (1.4%), Al (1.0%), 
(0.5 % each). In the internal degradation area, composition included Fe (44.1%), Cr (23.1%), W (11.9%),
Cl (1.0%), P (0.4%), Ti (0.4%) and Si (0.3%). 
O (8.9%), Nb (8.3%), Si (1.8%), Cl (1.1%), Al (0.6%), and K (0.2%). Chlorine had formed a thin, about
Cr (23.1%), W (11.9%), O (8.9%), Nb (8.3%), Si (1.8%), Cl (1.1%), Al (0.6%), and K (0.2%). Chlorine had 
The uncoated T92 steel had up to 200 μm thick corrosion product layer both at the windward 
5formed a thin, about 5 μm in thickness, mixed iron‐chromium chlorine‐oxide layer on the surface of 
µm in thickness, mixed iron-chromium chlorine-oxide layer on the surface of the coating. Right next
and leeward side, as presented in Figure 7. The multilayered oxide iron‐chromium oxide was porous 
to the
and coating, this layerfrom 
contained Cr (22.3%),
the  metal  O (18.2%),
surface.  Next  to  the Mo (19.3%),
metal,  W (13.7),
internally  Fe mixed 
grown  (10.7%),
the coating. Right next to the coating, this layer contained Cr (22.3%), O (18.2%), Mo (19.3%), W (13.7), 
partly  detached  Si and 
iron  (8.5%),
Cl (5.1%), Al (1.9%), and K (0.4%). At about 3 µm from the coating surface, the layer consisted
Fe (10.7%), Si (8.5%), Cl (5.1%), Al (1.9%), and K (0.4%). At about 3 μm from the coating surface, the 
chromium oxide was comprised from several layers. A dense oxide containing a higher amount of  of Cr
(47.9%), O (25.6%), Fe (15.7%), Zn (2.3%), S (2.2%), Mg (1.6%), K (1.4%), Al (1.0%), Cl (1.0%), P (0.4%),
layer consisted of Cr (47.9%), O (25.6%), Fe (15.7%), Zn (2.3%), S (2.2%), Mg (1.6%), K (1.4%), Al (1.0%), 
chromium was detected above it, and the most outer iron oxide layer was mixed with the deposit, 
Ti (0.4%) and Si (0.3%).
Cl (1.0%), P (0.4%), Ti (0.4%) and Si (0.3%). 
containing mainly oxygen, iron, sulfur, calcium, potassium, aluminum and silicon. 
The uncoated T92 steel had up to 200 μm thick corrosion product layer both at the windward 
and leeward side, as presented in Figure 7. The multilayered oxide iron‐chromium oxide was porous 
and  partly  detached  from  the  metal  surface.  Next  to  the  metal,  internally  grown  mixed  iron  and 
chromium oxide was comprised from several layers. A dense oxide containing a higher amount of 
chromium was detected above it, and the most outer iron oxide layer was mixed with the deposit, 
containing mainly oxygen, iron, sulfur, calcium, potassium, aluminum and silicon. 

 
(a)  (b) 

Figure  6.  SEM  (BSE)  image  of  the  outer  surface  of  the  FeCr  coating  and  energy‐dispersive  X‐ray 
Figure 6. SEM (BSE) image of the outer surface of the FeCr coating and energy-dispersive X-ray
spectroscope (EDX) map analysis from the windward (a) and leeward side (b). 
spectroscope (EDX) map analysis from the windward (a) and leeward side (b).

The uncoated T92 steel had up to 200 µm thick corrosion product layer both at the windward and
leeward side, as presented in Figure 7. The multilayered oxide iron-chromium oxide was porous and
 
partly detached from the metal (a)  surface. Next to the metal, internally grown (b)  mixed iron and chromium
oxide was comprised from several layers. A dense oxide containing a higher amount of chromium
Figure  6.  above
was detected SEM  (BSE)  image 
it, and the of  the outer
most outer  surface  of  the 
iron oxide FeCr 
layer wascoating 
mixed and  energy‐dispersive 
with X‐ray 
the deposit, containing
spectroscope (EDX) map analysis from the windward (a) and leeward side (b). 
mainly oxygen, iron, sulfur, calcium, potassium, aluminum and silicon.

 
Figure 7. SEM (BSE) image of the T92 uncoated tube material with EDX mapping from the leeward 
side. 

3.4. Corrosion Resistance at 750 C 
The  coatings  exposed  at  750  °C  showed  distinct  differences  between  the  coatings  and  also 
between  locations  within  the  specimens.  Generally  the  flue  gas  direction  had  the  most  severe 
 
Figure 7. SEM (BSE) image of the T92 uncoated tube material with EDX mapping from the leeward side.
Figure 7. SEM (BSE) image of the T92 uncoated tube material with EDX mapping from the leeward 
side. 

3.4. Corrosion Resistance at 750 C 
The  coatings  exposed  at  750  °C  showed  distinct  differences  between  the  coatings  and  also 
between  locations  within  the  specimens.  Generally  the  flue  gas  direction  had  the  most  severe 
Coatings 2016, 6, 65 9 of 13

Coatings 2016, 6, 64  9 of 13 

3.4. Corrosion Resistance at 750 ◦C

corrosion and the leeward direction the least. The uncoated substrate material A263 had formed a   
The coatings exposed at 750 ◦ C showed distinct differences between the coatings and also between
1–10 μm thin Cr‐rich oxide scale, where 10 μm represents slight pitting. On average, the scale was 
around 3 μm thin. On the windward side, the protective oxide layer was dense and uniform. The 
locations within the specimens. Generally the flue gas direction had the most severe corrosion and
scale was observed to be thickest at the leeward orientation. S, Ti and Al were found in the Cr‐rich 
the leeward direction the least. The uncoated substrate material A263 had formed a 1–10 µm thin
oxide 
Cr-rich scale. 
oxide A  thin 
scale, porous 
where 10 µmoxide  layer  above 
represents the 
slight chromium 
pitting. oxide  layer, 
On average, the shown  with 
scale was an  arrow 
around in thin.
39 of 13 
µm
Coatings 2016, 6, 64 
Figure 8, contained mainly nickel, oxygen and iron, but also sodium (2.4 wt.%), sulfur (2.1 wt.%) and 
On the windward side, the protective oxide layer was dense and uniform. The scale was observed to
zinc  (1.8  wt.%).  Traces  of  chlorine  (0.2  wt.%)  were  detected  only  in  the  deposit  layer.  Deepest 
corrosion and the leeward direction the least. The uncoated substrate material A263 had formed a 
be thickest at the leeward orientation. S, Ti and Al were found in the Cr-rich oxide scale. A thin porous  
penetration into the material through grain boundaries was 10 μm. 
1–10 μm thin Cr‐rich oxide scale, where 10 μm represents slight pitting. On average, the scale was 
oxide layer above the chromium oxide layer, shown with an arrow in Figure 8, contained mainly nickel,
NiCr coating had formed a thin, 2 μm thick layer on the coating, Figure 9. EDX analysis revealed 
oxygenaround 3 μm thin. On the windward side, the protective oxide layer was dense and uniform. The 
and iron, but also sodium (2.4 wt.%), sulfur (2.1 wt.%) and zinc (1.8 wt.%). Traces of chlorine
that the thin layer contained high amounts of chromium and oxygen. EDX mapping confirmed that 
scale was observed to be thickest at the leeward orientation. S, Ti and Al were found in the Cr‐rich 
(0.2 wt.%) were detected only in the deposit layer. Deepest penetration into the material through grain
the thin layer had protected the coating against the environment: The coating forming elements Ni 
oxide  scale.  A  thin  porous  oxide  layer  above  the  chromium  oxide  layer,  shown  with  an  arrow  in 
boundaries was 10 µm.
and Cr were not found on the deposits, which contained mainly K, Ca and Na along with S and O. 
Figure 8, contained mainly nickel, oxygen and iron, but also sodium (2.4 wt.%), sulfur (2.1 wt.%) and 
zinc  (1.8  wt.%).  Traces  of  chlorine  (0.2  wt.%)  were  detected  only  in  the  deposit  layer.  Deepest 
penetration into the material through grain boundaries was 10 μm. 
NiCr coating had formed a thin, 2 μm thick layer on the coating, Figure 9. EDX analysis revealed 
that the thin layer contained high amounts of chromium and oxygen. EDX mapping confirmed that 
the thin layer had protected the coating against the environment: The coating forming elements Ni 
and Cr were not found on the deposits, which contained mainly K, Ca and Na along with S and O. 

 
Figure 8. SEM (BSE) image of the metal surface of A263 nickel alloy and EDX map analysis from the 
Figure 8. SEM (BSE) image of the metal surface of A263 nickel alloy and EDX map analysis from the
leeward side. The arrow pointing to the porous oxide scale containing zinc. 
leeward side. The arrow pointing to the porous oxide scale containing zinc.

NiCr coating had formed a thin, 2 µm thick layer on the coating, Figure 9. EDX analysis revealed
that the thin layer contained high amounts of chromium and oxygen. EDX mapping  confirmed that
the thin layer had protected the coating against the environment: The coating forming elements Ni
Figure 8. SEM (BSE) image of the metal surface of A263 nickel alloy and EDX map analysis from the 
and Cr were not found on the deposits, which contained mainly K, Ca and Na along with S and O.
leeward side. The arrow pointing to the porous oxide scale containing zinc. 

 
Figure 9. SEM (BSE) images of NiCr coating after the exposure at 750 C for 1300 h: (a) windward and 
(b) leeward side. 

IN625 coating exhibited pit corrosion not only at flue gas direction but also at side areas of the 
test ring. In many cases, the corrosion had already reached the substrate and continued deeper into 
it and also widened the pit. One such location was at the windward side, where the coating had been   
completely lost over a wide area and pits could be seen where there was still coating left. Figure 10 
Figure 9. SEM (BSE) images of NiCr coating after the exposure at 750 C for 1300 h: (a) windward and 
Figure 9. SEM (BSE) images of NiCr coating after the exposure at 750 ◦ C for 1300 h: (a) windward and
shows the remaining coating at windward orientation. 
(b) leeward side. 
(b) leeward side.
FeCr coating hade corroded rather uniformly. The highest corrosion rate was at the windward 
side with a 25–55 μm thick corrosion product that consisted of two irregular layers: topmost being 
IN625 coating exhibited pit corrosion not only at flue gas direction but also at side areas of the 
IN625 coating exhibited pit corrosion not only at flue gas direction but also at side areas of the
test ring. In many cases, the corrosion had already reached the substrate and continued deeper into 
porous iron oxide rich layer, which was partially mixed with the deposit. A porous Cr and Nb rich 
test ring. In many cases, the corrosion had already reached the substrate and continued deeper into it
it and also widened the pit. One such location was at the windward side, where the coating had been 
layer was under the topmost layer. The thickest parts of the corrosion product had the least dense 
completely lost over a wide area and pits could be seen where there was still coating left. Figure 10 
and also widened the pit. One such location was at the windward side, where the coating had been
shows the remaining coating at windward orientation. 
completely lost over a wide area and pits could be seen where there was still coating left. Figure 10
FeCr coating hade corroded rather uniformly. The highest corrosion rate was at the windward 
shows the remaining coating at windward orientation.
side with a 25–55 μm thick corrosion product that consisted of two irregular layers: topmost being 
porous iron oxide rich layer, which was partially mixed with the deposit. A porous Cr and Nb rich 
layer was under the topmost layer. The thickest parts of the corrosion product had the least dense 
 Coatings 2016, 6, 64  10 of 13 

CoatingsCr‐layer. At leeward and side orientations, the thickness of the corrosion product layer was around 
2016, 6, 65 10 of 13
20 μm. 

Coatings 2016, 6, 64  10 of 13 

Cr‐layer. At leeward and side orientations, the thickness of the corrosion product layer was around 
20 μm. 

 
10. SEM
FigureFigure  (BSE)
10.  SEM  image
(BSE)  of of 
image  the remains
the  remains of
of  the IN625coating 
the  IN625  coating and
and  EDX
EDX  map
map  analysis
analysis  from the
from  the 
windward side. 
windward side.

NiCrW coating was completely consumed on the flue gas orientation, but the corrosion products 
FeCr coating hade corroded rather uniformly. The highest corrosion rate was at the windward
and deposits were unfortunately lost during removal of the specimen from the probe. Prior to the 
side with a 25–55 µm thick corrosion product that consisted of two irregular layers: topmost being
removal, it was observed that the deposits around the specimen were massively bulging, unlike on 
porousthe other specimens. At the side area, some corrosion products were found. EDX analyses revealed 
iron oxide rich layer, which was partially mixed with the deposit. A porous Cr and Nb rich layer
that they were related to the corrosion of the substrate material, which indicates that the coating had 
was under the topmost layer. The thickest parts of the corrosion product had the least dense   Cr-layer.
been  completely 
At leeward and side lost,  even  before 
orientations, the  unfortunate  spallation  during  specimen  removal.  At  the 
Figure  10.  SEM  (BSE)  image the thickness
of  the  ofthe 
remains  of  the corrosion
IN625  coating product layeranalysis 
and  EDX  map  was around
from  the 20 µm.
leeward direction, a short piece of coating was found. The thickness of the remaining coating was 
NiCrW coating was completely consumed on the flue gas orientation, but the corrosion products
windward side. 
80 μm, of which 30 μm was badly degraded. EDX analyses showed that oxygen had penetrated the 
and deposits were unfortunately lost during removal of the specimen from the probe. Prior to the
coating and formed a layer with chromium next to the substrate. Nevertheless, sulfur had not been 
removal, itNiCrW coating was completely consumed on the flue gas orientation, but the corrosion products 
was observed that the deposits around the specimen were massively bulging, unlike on
able to penetrate the coating and was found only in the severely degraded topmost 30 μm. 
and deposits were unfortunately lost during removal of the specimen from the probe. Prior to the 
the other specimens. At the side area, some corrosion products were found. EDX analyses revealed
The only arc sprayed coating, NiCrTi, had uniform corrosion throughout the coating surface. 
removal, it was observed that the deposits around the specimen were massively bulging, unlike on 
that they were related to the corrosion of the substrate material, which indicates that the coating had
EDX analyses revealed that the coating forming elements were protected by a Cr‐rich layer on top of 
the other specimens. At the side area, some corrosion products were found. EDX analyses revealed 
the coating. The thickness of the Cr and O‐rich layer was at times up to 20 μm, but generally around 
been completely lost, even before the unfortunate spallation during specimen removal. At the leeward
that they were related to the corrosion of the substrate material, which indicates that the coating had 
2–4 
direction, μm. 
a It 
short is piece
been  completely  worth 
ofnoting 
lost,  that, 
coating was
even  before due  to 
found.
the  the The
arc thickness
unfortunate  spraying  method,  the 
of during 
spallation  coating 
the remaining
specimen  was  moderately 
coating
removal.  wasAt 80   of
µm,
the 
pre‐oxidized: Oxidation at the lamella boundaries is clearly visible in the elemental maps of Figure 
whichleeward direction, a short piece of coating was found. The thickness of the remaining coating was 
30 µm was badly degraded. EDX analyses showed that oxygen had penetrated the coating
11. Sulphur was unable to penetrate the coating. 
80 μm, of which 30 μm was badly degraded. EDX analyses showed that oxygen had penetrated the 
and formed a layer with chromium next to the substrate. Nevertheless, sulfur had not been able to
coating and formed a layer with chromium next to the substrate. Nevertheless, sulfur had not been 
penetrate the coating and was found only in the severely degraded topmost 30 µm.
able to penetrate the coating and was found only in the severely degraded topmost 30 μm. 
The only arc sprayed coating, NiCrTi, had uniform corrosion throughout the coating surface.
The only arc sprayed coating, NiCrTi, had uniform corrosion throughout the coating surface. 
EDX analyses revealed that the coating forming elements were protected by a Cr-rich layer on top
EDX analyses revealed that the coating forming elements were protected by a Cr‐rich layer on top of 
of thethe coating. The thickness of the Cr and O‐rich layer was at times up to 20 μm, but generally around 
coating. The thickness of the Cr and O-rich layer was at times up to 20 µm, but generally
around 2–4
2–4  µm.
μm.  It  It
is  is worth
worth  noting
noting  that,
that,  due  due to the
to  the  arc arc spraying
spraying  method,
method,  the coating
the  coating  was moderately
was  moderately   
pre-oxidized: Oxidation at the lamella boundaries is clearly visible in the elemental maps of Figure 11.
pre‐oxidized: Oxidation at the lamella boundaries is clearly visible in the elemental maps of Figure 
Sulphur11. Sulphur was unable to penetrate the coating. 
was unable to penetrate the coating.

 
Figure  11.  SEM  (BSE) image  of  the  outer  surface  of  the  arc  sprayed NiCrTi  coating  and  EDX  map 
analysis from the leeward side. 

 
11. SEM
FigureFigure  (BSE)
11.  SEM  image of of 
(BSE) image  the outer
the  outer surface of the 
surface  of  thearc 
arcsprayed NiCrTi 
sprayed NiCrTi coating
coating  and map 
and  EDX  EDX map
analysis from the leeward side. 
analysis from the leeward side.
Coatings 2016, 6, 65 11 of 13

4. Discussion
An exposure campaign with corrosion probe was conducted in a 550 MWth (produced thermal
power) circulating fluidized bed boiler at Alholmens Kraft power plant. During this 1300 h test
exposure, the samples with five thermal spray coatings NiCr, IN625, NiCrW, FeCr and NiCrTi were
exposed at two metal temperature ranges of 550 and 750 ◦ C together with reference tube materials
ferritic steel T92 and nickel super alloy A263. Due to high variations in the plant load and process
temperatures the probe temperature profiles were fluctuating and also fluctuations in the fuel shares
were wide. In this context the effects of fuels and boiler process parameters on corrosion phenomena
were not straightforward. However, the relatively high peak and average temperatures in the probe
surface and the high shares of biomass and SRF fuels used in the boiler sustained the risks for corrosion
phenomena, which were shown also in the analyzed samples.
The coating performance at 550 ◦ C was excellent compared to the ferritic tube material T92.
The corrosion layer thicknesses of the coatings were about 1/7 or negligible compared to the corrosion
layer thickness of the T92. The corrosion rates of the coatings varied between 1–5 µm/1000 h in the
windward side and 1–31 µm/1000 h in the leeward side at lower test temperature. The corresponding
corrosion rates of T92 steel were 186 µm/1000 h and 275 µm/1000 h. The corrosion mechanism differed
at 550 ◦ C in the FeCr coating between the different sides: only minor corrosion was detected in the
windward side, whereas in the leeward side the corrosion was pronounced. The non-protective layer
that formed in the leeward side may have been caused by lower material temperature, which allowed
zinc to deposit on the coating, which reacted with chlorine, chromium and iron, forming low melting
compounds and hence causing stronger corrosion. Zinc can condensate on heat transfer surfaces at
temperatures below 335 ◦ C (0.5% Zn in fuel) and 472 ◦ C (50% of Zn in fuel) [8]. This can explain the
occurrence of zinc in the FeCr coating at the leeward side, where the minimum temperature during
the exposure was 331 ◦ C and zinc may have reacted with the iron oxide layer, forming ZnCl2 , causing
accelerated corrosion.
At the higher temperature, clear differences between the coatings emerged: tube material
A263 together with NiCr and NiCrTi coatings were the top performers. The corrosion rate for A263
was 1 µm/1000 h in the windward side and 9 µm/1000 h for the leeward side. For coatings, the
corrosion rates varied between 5–22 µm/1000 h (windward) and 2–235 µm/1000 h (leeward). Zinc
together with sulfur was detected on A263 material in the leeward side, where the corrosion attack
was more pronounced compared to the protective oxide layer in the windward side. This is well in
accordance with a previous study with zinc compounds, in which zinc is predicted to form sulfates in
oxidizing conditions [7].
The amount of chromium in the composition of nickel based coatings was significant for the
corrosion resistance at 750 ◦ C. NiCr and NiCrTi coatings with 46 wt.% Cr showed very high corrosion
performance, whereas NiCrW and IN625 corroded severely in the conditions, Figure 12. Even though
FeCr coating contained less than 25 wt.% Cr, it showed better corrosion resistance in the boiler exposure.
FeCr coating had high amounts of refractory metals niobium and tantalum. On the other hand, the
amount of molybdenum, which can degrade by metal dusting at temperatures over 700 ◦ C, was lower
compared to NiCrW and IN625. The corrosion mechanism may also have changed from the lower
temperature (550 ◦ C) to the higher temperature (750 ◦ C). Chlorine-activated corrosion was detected in
the FeCr coating at 550 ◦ C, but at 750 ◦ C strong reactions of sulfur with nickel were observed. In a
corrosion mechanism, the type of attack can change from salt molten attack to gaseous attack, which
has strong influence on the corrosion rate [13]. In the case of NiCrW and IN625, the corrosion started
with pitting, and led to catastrophic corrosion, when the protective chromium oxide layer formation
failed after consuming the chromium. Similar accelerated corrosion and selective corrosion have been
reported for TP347H steel and IN625 weld overlay material in a biomass and a waste incineration
plant [5,6]. It has been concluded that corrosion rate accelerates above steam temperatures of 540 ◦ C
and selective corrosion occurs when Zn-K-Cl forms a molten phase.
Coatings 2016, 6, 65 12 of 13
Coatings 2016, 6, 64  12 of 13 

 
12.12. SEM ◦ C for 1300 h.
750C 
Figure
Figure  SEM (BSE)
(BSE) images
images of
of the
the HVOF Ni based 
HVOF  Ni  based coatings 
coatingsafter 
afterexposure 
exposureat at750  for  1300  h. 
Chromium content of the coatings varied from (a) NiCr with 46 wt.% Cr with deposit layer on top of
Chromium content of the coatings varied from (a) NiCr with 46 wt.% Cr with deposit layer on top of 
the coating to (b,c) NiCrW and IN625 with 21 wt.% Cr. 
the coating to (b,c) NiCrW and IN625 with 21 wt.% Cr.

Acknowledgments: This work was performed in the FP7 EU project NextGenPower—Efficiency increases in 
In the future, studies with actual coated boiler tubes should be performed in order to validate
existing  and  new  build  pulverised  coal  power  plants  with  a  view  to  CCS.  The  authors  would  like  to  thank 
the promising corrosion resistance of thermal spray coatings in biomass co-firing conditions at
Alholmens Kraft Ab for the opportunity to use the power plant for the experiments. 
high temperatures.
Author  Contributions:  Maria  Oksa  conceived  and  designed  the  experiments;  Janne  Kärki  performed  the 
experiments; Maria Oksa, Jarkko Metsäjoki and Janne Kärki analyzed the data; Maria Oksa wrote the paper with 
Acknowledgments: This work was performed in the FP7 EU project NextGenPower—Efficiency increases in
the assistance of other authors. 
existing and new build pulverised coal power plants with a view to CCS. The authors would like to thank
Alholmens Kraft Ab for the opportunity to use the power plant for the experiments.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design 
Author Contributions: Maria Oksa conceived and designed the experiments; Janne Kärki performed the
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the 
experiments; Maria Oksa, Jarkko Metsäjoki and Janne Kärki analyzed the data; Maria Oksa wrote the paper with
decision to publish the results. 
the assistance of other authors.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
References 
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the
1.
decision The Paris Agreement. United Nations, 12 December 2015. Available online: http://unfccc.int/paris_agreement/ 
to publish the results.
items/9485.php (accessed on 19 September 2016). 
2. 2030  Energy  Strategy.  Available  online:  https://ec.europa.eu/energy/en/topics/energy‐strategy/2030‐
References
energy‐strategy (accessed on 19 September 2016). 
1. The Paris Agreement. United Nations, 12 December 2015. Available online: http://unfccc.int/paris_
3. Technology Roadmap Wind Energy. Available online: https://www.iea.org/publications/freepublications/ 
agreement/items/9485.php (accessed on 19 September 2016).
publication/Wind_2013_Roadmap.pdf (accessed on 19 September 2016). 
2. 4. 2030 Energy Strategy. Available online: https://ec.europa.eu/energy/en/topics/energy-strategy/2030-
Solar Photovoltaic Roadmap. Available online: https://www.iea.org/publications/freepublications/publication/ 
energy-strategy (accessed on 19 September 2016).
pv_roadmap_foldout.pdf (accessed on 19 September 2016). 
3. 5. Technology
Montgomery, Roadmap Wind S.A.; 
M.;  Jensen,  Energy. Available
Borg,  online:
U.;  Biede,  O.;  https://www.iea.org/publications/freepublications/
Vilhelmsen,  T.  Experiences  with  high  temperature 
publication/Wind_2013_Roadmap.pdf (accessed on 19 September 2016).
corrosion at straw‐firing power plants in Denmark. Mater. Corros. 2011, 62, 593605. 
4. 6. Solar Photovoltaic Roadmap. Available online: https://www.iea.org/publications/freepublications/
Montgomery, M.; Hansson, A.N.; Jensen, S.A.; Vilhelmsen, T.; Nielsen, N.H. In situ corrosion testing of 
publication/pv_roadmap_foldout.pdf (accessed on 19 September 2016).
various nickel alloys at Måbjerg waste incineration plant. Mater. Corros. 2013, 64, 1425. 
5. 7. Montgomery, M.; Jensen, S.A.; Borg,
Bankiewicz,  D.;  Vainikka,  P.;  Lindberg,  U.; Biede, O.; Vilhelmsen,
D.;  Frantsi,  T. Experiences
A.;  Silvennoinen,  J.;  Yrjas, with high temperature
P.;  Hupa,  M.  High 
corrosion at straw-firing power plants in Denmark. Mater. Corros. 2011, 62, 593–605. [CrossRef]
temperature corrosion of boiler waterwalls induced by chlorides and bromides—Part 2: Lab‐scale corrosion 
6. Montgomery, M.; Hansson, A.N.; Jensen, S.A.; Vilhelmsen, T.; Nielsen, N.H. In situ corrosion testing of
tests and thermodynamic equilibrium modeling of ash and gaseous species. Fuel 2012, 94, 240–250. 
8. various nickel alloys at Måbjerg waste incineration plant. Mater. Corros. 2013, 64, 14–25. [CrossRef]
Enestam, S.; Backman, R.; Mäkelä, K.; Hupa, M. Evaluation of the condensation behavior of lead and zinc 
7. Bankiewicz, D.; Vainikka, P.; Lindberg, D.; Frantsi, A.; Silvennoinen, J.; Yrjas, P.; Hupa, M. High temperature
in BFB combustion of recovered waste wood. Fuel Process. Technol. 2013, 105, 161169. 
9. corrosion
Oksa,  M.;  Auerkari,  P.;  Salonen, 
of boiler waterwalls J.;  Varis, 
induced T.  Nickel‐based 
by chlorides HVOF  coatings 2:promoting 
and bromides—Part Lab-scale high  temperature 
corrosion tests and
corrosion resistance of biomass‐fired power plant boilers. Fuel Process Technol. 2014, 125, 236–245. 
thermodynamic equilibrium modeling of ash and gaseous species. Fuel 2012, 94, 240–250. [CrossRef]
8. 10. Enestam,
Oksa, M.; Metsäjoki, J. Optimizing NiCr and FeCr HVOF coating structure for high temperature corrosion 
S.; Backman, R.; Mäkelä, K.; Hupa, M. Evaluation of the condensation behavior of lead and zinc in
protection applications. J. Therm. Spray. Technol. 2015, 24, 436–453. 
BFB combustion of recovered waste wood. Fuel Process. Technol. 2013, 105, 161–169. [CrossRef]
9. 11. Oksa,
Hussain, T.; Dudziak, T.; Simms, N.J.; Nicholls, J.R. Fireside corrosion behavior of HVOF and plasma‐sprayed 
M.; Auerkari, P.; Salonen, J.; Varis, T. Nickel-based HVOF coatings promoting high temperature
coatings in advanced coal/biomass co‐fired power plants. J. Therm. Spray. Technol. 2013, 22, 797–807. 
corrosion resistance of biomass-fired power plant boilers. Fuel Process Technol. 2014, 125, 236–245. [CrossRef]
10.12. Oksa,
Oksa, M.; Kärki, J.; Metsäjoki, J. Coating Solutions against High Temperature Corrosion‐Performance Validation 
M.; Metsäjoki, J. Optimizing NiCr and FeCr HVOF coating structure for high temperature corrosion
and  Feasibility 
protection at  Biomass 
applications. Fired  Boilers; 
J. Therm. Spray. Pertti, 
Technol.A.,  Juha, 
2015, 24,V.,  Eds.;  VTT 
436–453. Technology:  Espoo,  Finland,  2013;   
[CrossRef]
pp. 656–670. 
11. Hussain, T.; Dudziak, T.; Simms, N.J.; Nicholls, J.R. Fireside corrosion behavior of HVOF and plasma-sprayed
coatings in advanced coal/biomass co-fired power plants. J. Therm. Spray. Technol. 2013, 22, 797–807.
[CrossRef]
Coatings 2016, 6, 65 13 of 13

12. Oksa, M.; Kärki, J.; Metsäjoki, J. Coating Solutions against High Temperature Corrosion-Performance Validation and
Feasibility at Biomass Fired Boilers; Pertti, A., Juha, V., Eds.; VTT Technology: Espoo, Finland, 2013; pp. 656–670.
13. Oksa, M.; Tuurna, S.; Varis, T. Increased lifetime for biomass and waste to energy power plant boilers
with HVOF coatings: High temperature corrosion testing under chlorine-containing molten salt. J. Therm.
Spray. Technol. 2013, 22, 783–796. [CrossRef]

© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).