12th North American Waste to Energy Conference

May 17-19, 2004, Savannah, Georgia USA

NAWTEC12-2216

Experience with Weld Overlay and Solid Alloy Tubing Materials in

Waste to Energy Plants

Larry Paul

Michael Eckhardt

ThyssenKrupp VDM USA Inc.

Andreas Ossenberg-Engels

116 W. Madison st.

ThyssenKrupp VDM GmbH

Tipton, IN 46072

Barenstein 5

(765) 675-9964

D-58791 Werdohl, Germany

Gregg Clark

Bern Hoberg

ThyssenKrupp VDM USA, Inc.

ThyssenKrupp VDM GmbH

20 Towne Drive #198

Kleffstrasse 23

Bluffton, SC 29910 USA

D-58762 Altena, Germany

(843) 757-8368
which

1.0 Introduction

corrosion

decreases.

Likewise

for

sulfate rich deposits or salts: the onset of

Corrosive
boilers

conditions in

produce

rapid

waste

to energy

wastage

traditional boiler tube materials.

melting sharply increases

corrosion rates

of

and vaporization of the sulfates at even

It is not

higher temperatures results in a decrease of

rates

unusual to see corrosion rates in the range

corrosion.

of 1 to 3 mm/y (40-120 mpy) on carbon steel

mechanisms give rise to somewhat different

boiler

tubes

occurs

at

and

even

occasionally
higher

corrosion

rates.

In

alloy

corrosion

failures

of

requirements,

various

corrosion

depending

on

the

temperature of the metal in the refuse-fired

the

boiler

mid1980's there were several boilers that

experienced

These

carbon

steel waterwall tubes in less than 6 months

The

of service (1,2). Because of this experience,

occurs on water wall tubes, which typically

main

corrosion

mechanism

which

it has become accepted that some type of

operate

corrosion protection is required for boiler

range, is corrosion by molten chloride salts.

tubes in refuse-to-energy boilers.

The

years,

many

different

alloys

Over the

have

been

in

most

the

200-315C

successful

(400-600F)

alloys

used

for

waterwall tubes are generally high in nickel

evaluated to improve tube life in waste-to

and molybdenum with moderate amounts of

energy

chromium, such as Alloy 625 and Alloy 50 (a

boilers.

The

most

successful

materials used for corrosion protection are

recently introduced alloy from ThyssenKrupp

nickel alloys.

VDM). These alloys are applied to waterwall

tubes as a weld overlay.

Waterwall tubes are generally attacked by

Because of the mixed corrosion modes in

molten chloride salts (3) and superheat

tubes
appear
to
be
attacked
by
a

the

combination of molten chloride/sulfate salts

alloys is more complicated.

superheater

region, the

selection

of

Figure 2 shows

as well as gaseous chloride constituents

a photomicrograph of a Fe-Ni-Co-Cr alloy

(primarily HCI) (4-7).

that

Figure 1 shows the

was

exposed

in a

refuse

boiler at

corrosion rates of carbon steel as a function

approximately 900C (1650F) (8).

of

shows that multiple corrosion mechanisms

temperature

for

various

corrosion

Figure 2

mechanisms. The corrosion due to gaseous

are

chloride

sulfidation (evidenced by the chromium rich

atmospheres

with temperature.
chloride rich

increases

steadily

salts

at

this

temperature;

increases

the internal voids caused by volatile metal

rapidly once the melting point of the salts is

chlorides) are observed.

reached;

material not

corrosion

rates

continue

both

sulfides) and chloride attack (evidenced by

Corrosion produced by

deposits or

active

to

increase with temperature until the chloride

salt becomes hot enough to vaporize, after

content

to

only
resist

In this case, a

requires
chloride

high nickel
attack

(both

gaseous and molten salts), but also requires

111

Copyright 2004 by ASME

a high chromium content to resist sulfidation.

spray coatings all have some degree of

Solid Alloy 825 and weld overlay Alloy 625

porosity.

This allows corrosive gases to

are perhaps the most common materials

permeate

beneath

now used in superheater tubes in waste-to

and corrode the carbon steel substrate. The

the

protective

coating

chromium

extremely corrosive nature of the waste-to

material was recently introduced in Europe

energy boiler is severe enough to cause

for this application with good success: Alloy

disbonding

45TM.

carbon steel base metal. Diffusion coatings

energy

boilers.

Another

high

of

spray

coatings

from

the

and other coating systems have also been

While Alloy 825 solid tubes and Alloy 625

tried in refuse-to-energy boilers with mixed

weld overlay have a proven track record in

success.

many boilers, there are also many boilers

systems have some degree of porosity or

Generally all of these

coating

where corrosion continues to be a problem.

have inherent defects in the coating system,

Alloy 825 also has been unsatisfactory in

which

many superheater applications.

corrosion.

Alloy 625

leads

to

unacceptable

localized

Therefore, weld overlays and

weld overlay also does not always give the

solid tubing are the most reliable options for

desired superheater tube life. It is fair to say

deploying corrosion resistant alloys.

that most of the chronic corrosion problems

For

are in superheater applications.

waterwall

tubing,

weld

overlays

are

Since these tubes are

exclusively used.
The corrosion problems in waste-to-energy

water wetted on the inside surface, the use

boilers vary with unit design, geographical

of solid austenitic materials is generally not

region, time of year, and other factors.

allowed

One

by

the

ASME

boiler

Therefore, application of nickel

clear trend that has been observed is that

code.

alloys to

the increased use of plastics has led to an

waterwall tubes will be as a clad or coating;

increase

weld overlays have proven to be the most

in

the

chloride

household waste.
content

of

increase

the

in

the

content

of

the

reliable process for economically applying

This increase in chloride

fuel

corresponds

corrosivity

of

to

the

this corrosion barrier.

an

boiler

environment.

For superheater applications, both solid and

Because of the variability among waste-to

decision on whether to use a solid or weld

energy boilers, site specific testing is always

overlay tube for a superheater application

weld overlay tubing are both used.

ThyssenKrupp

recommended.
continues

to

work

with

will

VDM

operators

depend

schedules.

and

on

economics

and

The

delivery

The relative costs of various

applicators to test new overlay materials in

superheater tube options are given in Table

the field.

2.

Solid Alloy

825 tubes are the least

expensive option and are used in the first

few rows in the superheater tube banks,
where gas temperatures are highest.

2.0 Material Options

625

weld

overlay

tubes

are

the

Alloy

closest

There are many materials that have been

option, relative to cost, to solid Alloy 825

evaluated in refuse-to-energy boilers.

tubes.

The

Alloy 625 overlay tubes have given

most successful of these materials include

good tube life in numerous applications and

Alloys 625, 50, 59, 825, and 45TM.

also have the advantage in that they usually

The

can be provided more quickly than solid

chemistry of these alloys is given in Table 1.

tubing.
Alloys 625, 50, and 59 are applied as a weld
A solid tube material that has been used in

overlay onto carbon steel boiler tubes and

Alloy 825 and 45TM are used as solid tubing

Europe is Alloy 45TM (.

only for superheater applications.

of solid Alloy 45TM tubing is also shown in

Table

Alternate

methods

of

applying

45TM

waste-to-energy

applications.

(9,

10).

the

relative

cost

is

options, the

increased corrosion performance of Alloy

Spray

coatings have not historically worked well in

boilers

While

somewhat higher than other

corrosion

resistant alloys have been tried.

2.

The relative costs

Flame

112

has

justified

its

use

in

several

Copyright 2004 by ASME

occurs more rapidly on the dendrite cores of

When comparing the prices of solid tubes to

the weld, which are depleted in Mo and Nb

weld overlay tubes, it is noted that the price

due to segregation.

differential increases with tube size.

material and so does not exhibit segregation

This

Alloy 50 is a Nb free

trend is a result of the increasing differential

of Nb; however, some segregation of Mo is

between the amounts of nickel alloy used in

unavoidable. Alloy 50 does have a fairly fine

weld overlay versus solid tubing as the tube

uniform microstructure with less segregation

diameter increases.

than observed for Alloy 625 in the welded

Another factor when

considering solid versus weld overlay tubes

condition.

is the life of the tube. The corrosion rates of

preferential attack

weld overlay tubes will increase rapidly after

overlay, which in turn reduces the overall

the

corrosion rate.

cladding

has

been

corroded

away.

These

features
of

the

help

Alloy

avoid

50

weld

Cladding thickness of weld overlay tubes are

generally in the range of 1.5-2mm (0.0600.080").
not

3.1 Superheater tubes

Corrosion rates on solid tubes will

change

thinning.

as

the

result

of

tube

Corrosion of superheater tube materials was

wall

Therefore, solid tubes may last

measured in the laboratory using a high

longer than weld overlay tubes at the same

refuse-boiler
simulated
3
combustion gas consisting of 2.5 g/m HCI +
3
1.3 g/m S02 + 9% O2 + balance N2.

corrosion rate.

temperature

Solid tubes have a greater

thickness of corrosion resistant

material.

The relative life of solid tubes versus weld

Results of

overlay tubes increases as the minimum

shown in Figure 5.

wall requirement of the superheater tube

the Alloy 45TM corrodes at lower rates than

decreases

Alloy

(i.e.

economical

solid

as

tubes

more

wall

are

loss

more

can

be

625

tests in this environment are

and

In this laboratory test,

the

other

temperatures tested.

alloys

at

all

Alloy 625 was the

second best material and was much better

tolerated)

than Alloys 800H and AC66.

Alloy 45TM

3.0 Corrosion Testing

can be used only as solid tubing and Alloy

3.1 Waterwall tubes

to current ASME code regulations).

625 can only be used as a weld overlay (due

Alloy 50 is a Nb-free welding product that is

4.0 Field Testin g

being considered as a replacement for Alloy

625 in numerous applications.

Figure 3
4.1 Waterwall tubes

shows the mass loss of single pass GMAW

weld overlay specimens when exposed to a
refuse

simulated
atmosphere.

boiler

The

mass

Several

combustion
loss

of

field

tests

of

ongoing in Europe.

the

Alloy

specimens corresponds to the amount of

in progress for nearly 2 years.

corrosion.

information

While this laboratory test does

so

50

are

still

These tests have been

far

is

Most of the

based

on

visual

inspection; so far the Alloy 50 is performing

not exactly duplicate the temperatures and

environment that the waterwall tubes might

very well.

see, it does give a direct comparison of

overlay samples and showed that Alloy 50

Alloys

indeed

50

chloride
data

and

show

corrosion

625

in

environment.
that

Alloy

resistance

corrosive

These
as

50
a

high

laboratory

has
weld

One customer removed the weld

performed

better than Alloy 625.

Based on these tests, approximately 50,000

excellent

pounds of Alloy 50 will be installed onto

overlay

waterwall tubes in the spring of 2004 in this

providing

European waste-to-energy boiler. Testing of

corrosion resistance better than Alloy 625

Alloy 50 weld overlays is also on-going in

weld overlays in environments applicable to

North America, after 1Yz years in a refuse

material

and

is

capable

of

refuse-to-energy plants.

fired boiler, a

weld

overlay of Alloy

50

visually shows little sign of attack.

Figure 4 shows an example of corrosion
attack of an Alloy 625 weld overlay removed

Figure 6 compares several alloys in the so

from a coal fired boiler after an extended

called Varistrant test.

exposure time (11).

the tendency of a material to exhibit hot

The corrosion attack

113

This test measures

Copyright 2004 by ASME

cracking

and

welding.

Figure 6 shows that Alloy 50 will

form

micro-fissures

during

Discussion

be less likely to form fissures and cracks

The use of Alloy 625 in the refuse-to-energy

during welding than Alloy 625.

market has a long and mostly successful

history.

4.2 Superheater tubes

Waterwall tubes that have been

covered with Alloy 625 weld overlay have

Testing in the late 1970's at the refuse-to

generally shown few problems; most of the

energy plant in Saugus, MA lead to use of

observed

Alloy 825 solid tubes (5), this material was

application issues (such as pin-holes in the

subsequently

weld).

adopted

by

several

boiler

today

in

some

boilers.

Recently,

were

attributed

ThyssenKrupp

to

VDM

introduced Alloy 50 as an alternative to Alloy

designers ( as a standard material and is still

used

problems

625 for weld overlay applications in refuse

Another

Alloy 50 exhibits better

common superheater material being used is

to-energy plants.

Alloy 625 weld overlay onto standard carbon

corrosion resistance in the laboratory and

steel boiler tube materials.

has also show excellent results in field tests.

However, as
the

Alloy 50 is also less likely to form micro

corrosiveness of the environment increases

cracks and fissures than Alloy 625, making it

(such as by the increasing amount of plastic

a more forgiving alloy for weld applications.

steam

temperatures

increase

and

in the municipal waste being burned), these

Lastly, the Alloy 50 has a more uniform

standard

microstructure and exhibits less segregation

tube

materials

are

not

always

than Alloy 625; this helps improve corrosion

adequate.

resistance
One

alloy

recently

introduced

ThyssenKrupp VDM is Alloy 45TM.

by

reducing

the

degree

of

selective corrosion attack.

by
This

alloy was specifically designed to have a

Alloy 45TM has been successfully used in

high

several superheater applications in refuse

corrosion

contaminated

resistance
high

in

highly

to-energy

temperature

boilers.

Alloy

45TM

is

only

available as solid tubing. V'vtlile Alloy 45TM

environments, such as are found in refuse

Figure 7 shows test data that

can be readily joint welded with selected

compares the corrosion behavior of Alloy

filler metals (typically FM28 or Alloy 625), it

45TM

cannot be directly used as a weld overlay,

fired boilers.
with

traditional

superheater tubes (13).

carbon

steel

due to the higher Si content in this material.

This figure shows

tube wall thickness measurements of the

Alloy 45TM

superheater tubes from an operating refuse

resistance and has improved the tube life in

fired boiler in Bielefeld, Germany; the tube

several

wall thickness was measured periodically

tube wastage issues.

using

ultrasonic

thickness

(UT)

can give excellent corrosion

boilers

with

chronic

superheater

sensors.

Conclusions

The corrosion rates of each material are

calculated from the average wall loss versus
Figure 7 shows that the Alloy 45TM

Based on the information from laboratory

was able to improve the service life by a

and field tests, the following conclusions on

factor of over 6 times, when compared to

materials

standard boiler tube materials.

made:

time.

Since the mid

several

1990's, there

installations

of

Alloy

1)

have been
45TM

for

refuse-fired boilers can

be

Alloy 625, applied as a weld overlay,

has demonstrated that it is quite

into

refuse-fired boilers. The performance of the

resistant

Alloy 45TM as a superheater material has

boiler operating conditions.

2)

been quite good. As with any new material,

to

corrosion under most

Alloy 50, a new Ni-Cr-Mo-Fe Alloy,

field trials are suggested to demonstrate the

exhibits

performance

laboratory tests and also has given

under

actual

operating

lower

conditions. This is especially true for refuse

excellent

fired boilers, where the conditions are know

field tests.
3)

to vary widely between units.

corrosion

corrosion

rates

resistance

in
in

Alloy 50 exhibits less tendency to

form micro-cracks and fissures than

114

Copyright 2004 by ASME

6.

Alloy 625 during weld trials in the

4)

Alloy

50

has

microstructure

5)

more

and

825

uniform

shows

and

625

in

in Waste Incineration Systems, NACE,

Houston TX, 1992.
7.

Solid alloy superheater tubing can

a

viable

alternative

to

M.

Fukusumi,

Temperature

weld

overlay tubing; smaller tube sizes

Waste

and a thinner allowable minimum

Combustion

tube

wall

thickness

make

8.

Incineration

High

Solid

10.

MSW-fired

Temperature

Performance

in

and

Superheater

Waste

Incinerator",
in

Waste

Materials

Incineration
with

communication

Private

boiler

operating

in

Columbus, OH.
11.

K. Luer, J. Dupont, A. Marder, C.

Skelonis, Corrosion Fatigue of Alloy 625

the

Environments,

communication

Lawrence,

MA

Weld

waste-to-Energy

Claddings

in

Combustion

Materials

at

High

Temperatures, 17 (4).

P.L. Daniel, L.D.

"Fireside

Corrosion

Boilers",

Materials

Incineration

Paul, J.
in

12.

Barna,

Performance
Systems,

J.S.

Gittinger,

W.J.

Arvan,

"Considerations for the Design of RDF

Refuse-Fired

Fired

in

Refuse

Bolers",

Power-Gen

Europe, Milan, Italy, 1998.

NACE,
13.

Houston TX, 1992.

D.C.

Agarwal,

Grossmann,

G.Y. Lai, "A New Alloy for Solving

J.

Alloy

Kloewer,

45TM

in

G.K.

Waste

Fireside Corrosion Problems in Waste

Incineration

Incinerators", Materials Performance in

CORROSION/97, NACE, Houston, TX,

Waste Incineration
Houston TX, 1992.
5.

of
161

with
personnel involved with tube failures at

Waste
4.

Lai, p.

Performance in a Municipal

refuse-fired

Systems, NACE,

facility.
3.

Corrosion

personnel involved with testing at the

Houston TX, 1992.

Private

Incineration

Systems, NACE, Houston TX, 1992.

A. L. Plumley, W.R. Rocznia, E.C.

Lewis, "Materials Performance of Heat
Materials

Waste

in

Performance

Incineration

Materials

"Combustor

Materials

References

Incinerator",

of

Ashes",

G.A. Whitlow, P.J. Gallagher, S.Y.

Lee,

Waste

Municipal

Influence

ASM, Metals Park OH, 1990.

9.

in

in

Engineering Alloys, G.Y.

to-energy superheater applications.

Surfaces

Okanda, "High

Systems, NACE, Houston TX, 1992.

Solid Alloy 45TM shows excellent

Transfer

Y.

Corrosion

Performance

solid

corrosion resistance in most refuse

2.

Incineration
Performance

segregation in the welded condition

tubing more attractive.

1.

Waste

Environments", Materials

less

than Alloy 625.

be

6)

G.D. Smith, W.G. Lipscomb, "Field

and Laboratory Performance of Alloys

Varistrant test.

J.A. Harris,

Systems,

1997.

NACE,
14.

w.G.

Lipscomb,

Alloys

in

D.C.

Agarwal,

G.K.

Alloys in Municipal
Fueled

Waste

& Hazardous Waste

Activities",

Incinerators", Materials Performance in

CORROSION/2001,

Waste

TX,2003.

Incineration

Systems,

Grossmann,

"Case Histories on the Use of Nickel

D.o.

Smith, "Field Experience of Hig Nickel

Containing

Applications", Paper 155,

NACE,

Paper
NACE,

01177,
Houston,

Houston TX, 1992.

115

Copyright 2004 by ASME

Ta ble 1. Chenustnes 0f common a11 oys used III

waste-to-energy b011ers
ThyssenKrupp VDM

Alloy

UNSNo.

Designation

Nicrofer S6020
Nicrofer S5923
Nicrofer S5020
Nicrofer 422 1
Nicrofer 45TM

Ni
0/0

Cr
0/0

Mo

Fe%

Other
0/0

FM625

N06625

63

22

FM59

N06059

59

23

16

FM50

N06650

53

19.5

11

14

825

N08825

42

2 1.5

45TM

N06045

46

27

<1

3.4Nb
0. 25Al 0.25Nb 1.5W
2.2Cu 0.9Ti

23

2.75Si O. IRE

Table 2. Relative pricing of Alloy 625 weld overlay compared to solid tubing.
625 Weld
Tube Size

45TM Solid

Overlay

Tube

Tube

Relative

Relative

Relative

Price'"

Price'"

Price'"

1.5" x 0. 150" MW

0.75

1. 18

2.0" x 0. 150" MW

0.78

1.44

3.0" x 0. 150" MW

0.80

1.64

Relative Price Compared to Alloy 625 Overlay (i. e. Alloy 625 Overlay

250

200

..
CD

150

>a..

825 Solid

1)

Chloride and sulfate

salts decompose and
vaporize at higher
temperatures
Molten
Chloride
Attack

c
0

"en

0
U

100
50

Gaseous
Chloride Attack

0
0

200

400

600

800

1000

1200

1400

Temperature (OF)
Figure l. Schematic of the influence of temperature upon various corrosion mechanisms.

116

Copyright 2004 by ASME

.' ..... i1
." .

'.. .;.;.C'..
..
.
.

. "

Figure 2. Photomicrograph of a Fe-Ni-Co-Cr alloy from a refuse-fired boiler. Operating

temperature was about 900C ( l650F). Note the presence of chromium sulfides and
internal voids that indicate that both sulfidation and chloride attack are occurring
simultaneously.
-

Ne 1400
-

C)

rn

1200

...

::l
0
s:.
0
I()
0

1000

600

c::
rn
rn
0
...J
rn
rn
J

:!:

-D-Alloy 625
-trAlloy 50

.-.

/
/

800

400
200
0

.-.

,/\

/"

..I'('"

r:i

750C
Temperature (OC)
Figure 3. Comparison of the corrosion resistance of Alloy 50 compared to Alloy 625 in a
simulated refuse boiler combustion environment at various temperatures after 1050 hours
3
3
of exposure. Atmosphere is 2.5 g/m HCI + 1.3 g/m S02 + 9% O2 + balance N2.

117

Copyright 2004 by ASME

12.0

...

=
0

..
rIl

0
Q.,

delldlile
Inlenlt'ndli1lc
n-glon

Interdendritic Region

10.0

nondrit,

8.0

CO"!

6.0
4.0
2.0
0.0
0

10

15

20

Distance,

lOuin

25

30

urn

Figure 4. Examples of corrosion attack associated with segregation of Nb and Mo in

Alloy 50

200
0
N

E
E
-

en

-200
-400

CP
en
c::
cu
.s::.

0
'"
'"
cu

:E

-600

"

""
'\
'"
" '\
"'. '\
'" '\
"
.

-800
-1000

-1200

t--

-1400

t--

-45TM
625
-AC66
-800H

-1600
550

600

650

700

750

800

850

900

Temperature (OC)

Figure 5. Mass change after 1050 hours for selected alloys in a high temperature
3
3
simulated refuse-boiler combustion gas consisting of 2.5 glm Hel + 1.3 glm S02 + 9%
02 + balance N2.

118

Copyright 2004 by ASME

8
-Alloy 625
-Alloy 22

/'

Alloy 59

-Alloy 50

.,/"
/

/
/

o
1

__
___
__
c

.......-...
....

Strain (%)
Figure 6. Varistrant testing of various weld overlay materials. Alloy 50 is much less
prone to fissuring and hot cracking than Alloy 625. Alloy 59 is the most resistant
material to cracking in this Varistrant test.

--

45TM Corrosion Rate

0.8776 mm/y (22. 3 mpy)

'""

45TM

15Mo3

15Mo3 Corrosion Rate

6.1362 mm/y (155.8 mpy)

1 r-- -15Mo3 (linear)

- 45TM (linear)
o
o

1000

2000

3000

4000

5000

6000

Time (hours)

Figure 7. Corrosion rates of Ally 45TM in a superheater application in a European waste

to energy facility. The 45TM showed much lower overall corrosion rates than the
traditional boiler tube material 15M03.

119

Copyright 2004 by ASME