VDM REPORT No.

25
High-temperature alloys from
Krupp VDM for industrial engineering

ThyssenKrupp

A company of
Krupp Thyssen
Stainless
Krupp VDM
Table of contents 1

Introduction 2

Strength at
high temperatures 5
Strengthening mechanisms 7
Solid solution hardening 7
Precipitation hardening 8
Dispersion hardening 12
Influence of grain size
and grain boundaries 13
Degree of cleanness 15
Factors influencing
mechanical properties 15
High-temperature corrosion
and abrasion 15
Microstructural influence 16
Cold deformation 17

High temperature corrosion 18

Appearance of
high temperature corrosion
and influencing factors 19
Behaviour of materials
in corrosive media 19
Oxidation 19
Carburization 23
Carburization in gas Workability/fabricability Standards, codes Applications of
atmospheres with ac < 1 23 Joining techniques 39 and specifications high temperature,
Carburization in gas Welding 39 TÜVIS Principles for high strength materials in
atmospheres with ac >> 1 25 Application engineering Testing of Steam Boilers, industrial engineering 52
Sulphidation 26 qualities of the welded joints 41 Vol. 1, Position after the
Chloridation 28 Working and heat treatment 43 56th revision, Dec. 1994 51 References 56
Nitridation 29 Hot forming 43 TÜVIS Principles for
Molten salt corrosion 30 Cold working 44 Testing of Pressure Vessels, Sales organization 59
Heat treatment 44 Vol. 2, edition of July 1980
Corrosion in complex Descaling 44 in the version Imprint 64
gas atmospheres Machinability 44 of February 1989 51
Municipal waste incineration 33 TÜVIS Principles for
Coal gasification 36 Mechanical design of Testing of Compressed-Gas
Pulp and paper industry 36 components for high- Installations, Vol. 1,
Behaviour with regard temperature service 47 Position after the 46th
to abrasion and corrosion 37 revision, August 1994 51
DIN standards (general) 51
DIN standards (specific) 51
Specifications of national
approval organizations 51
Classification societies 51
Client specifications 51
Iron and steel catalogue /
test specifications /
material data sheets 51
Key to steels 51
 2 High-temperature alloys
from Krupp VDM
for industrial engineering.

U. Brill, M. Rockel The present definition of high- “corrosive medium”. As a rule,

Krupp VDM GmbH temperature alloys applies,
Postfach 18 20 however, only to the corrosion
D-58778 Werdohl medium “air” for reasons of
Germany simplified testing and ease of
understanding. Hence “high
Introduction temperature” can be defined
firstly in terms of a material’s
High-temperature alloys from oxidation behaviour – incipient
Krupp VDM are alloys which fulfil FeO formation is an appropriate
industrial engineering needs at indicator – and secondly in
high temperatures. However, the terms of the change in its
judgment as to whether a tem- mechanical properties; here, the
perature should be regarded as theoretical recrystallization
“high” is relative and naturally temperature is undoubtedly an
depends to a great extent on the important parameter1) – 2).
corrosive media.
There has, of course, been no
lack of mathematical approach-
es to predicting corrosion
behaviour at high temperatures.
The threshold temperature,
i.e. the temperature at which
the onset of degradation under
high-temperature conditions
can be expected, has to be
determined individually for
each material in relation to its
composition for a particular
the threshold temperature of
approx. 550 ˚C (1000 ˚F) stated
in DIN 17 459 for austenitic
steels containing at least
13 % chromium is accepted by
industry3) – 5). To ensure a
reasonable relationship between
properties and cost, high-alloyed
austenitic steels and nickel-base
alloys are used above 550 ˚C
(1000 ˚F) and up to approx.
1200 ˚C (2200 ˚F). Higher
temperatures require the use of
alloys of niobium, molybdenum,
tantalum or tungsten.
These refractory alloys must be
protected by suitable coatings
if used in air due to their poor
oxidation resistance.
These materials offer adequate
high temperature strength up
to about 1500 ˚C (2730 ˚F),
but require a surface coating to
protect against air unless used
in an inert atmosphere.

Material Alloy des. UNS Mat. no. Ni Cr Mo C Al Ti Fe Others

(DIN)

Cronifer 2520 310 SS S31008 1.4841 20 25 – 0.06 – – 53 0.05 SE, 1.4 Si

Nicrofer 3718 330 N08330 1.4864 36 16 – 0.08 – – 46 1.5 Si
Nicrofer 3220 H 800 H N08810 1.4958 31 21 – 0.07 0.25 0.35 47 –
Nicrofer 45 TM 45 TM N06045 2.4889 47 27 – 0.08 – – 23 0.1 SE, 2.7 Si
Nicrofer 6023 H 601 H N06601 2.4851 60 23 – 0.06 1.4 0.5 14 –
Nicrofer 7216 H 600 H N06600 2.4816 74 16 – 0.07 0.2 0.2 19 –
Nicrofer 4722 Co X N06002 2.4665 48 22 9 0.07 – – 18 1 Co
Nicrofer 5120 CoTi C-263 N07263 2.4650 51 20 6 0.06 0.5 2.1 10.5 20 Co
Nicrofer 5219 Nb 718 N07718 2.4668 53 19 3 0.05 0.6 0.9 18 5.2 Nb
Nicrofer 5520 Co 617 N06617 2.4663 54 22 9 0.06 1 0.5 11 12 Co
Nicrofer 6025 HT 602 CA N06025 2.4633 62 25 – 0.18 2.3 0.2 19.5 0.1 Y, 0.1 Zr
Nicrofer 6325 Ta 2100 GT – 2.4677 63 25 – 0.3 3 – 11 8 Ta, 0.1 Y
Nicrofer 7016 TiNb X-750 N07750 2.4669 72 16 – 0.05 0.6 2.7 17 1 Nb
Nicrofer 7520 Ti 80 A N07080 2.4952 75 20 – 0.06 1.4 2.3 – –
Cronix 70 NS 70 NS – – 67 30 – 0.08 0.15 – 11 0.2 Y, 0.4 N
Table 1 – Chemical composition of typical high temperature materials in mass %
 3

At temperatures below 550 ˚C

(1000 ˚F), high-alloyed austenitic
steels and nickel-base alloys
need only be used if the process
media are highly corrosive.
400
Table 1 gives an overview of
the heat-resistant and high-
103-h creep rupture strength, N/mm2

temperature, high-strength
alloys in common use. If the 300
corrosion conditions are moderate Light Heat- Superalloys Refractory
and the requirements as to the alloys resistant metals and
and high- alloys
material's heat resistance are 200 temperature
not too demanding, austenitic Titanium
steels
Composite
CrNi stainless steels and ferritic alloys materials
Cr stainless steels are perfectly
100
adequate, especially if the
equipment design allows the use High-
polymeric
of suitably heavy-walled compo- materials
nents. 0
0 400 800 1200 1600
Although unalloyed and low- Temperature, °C
alloyed steels only permit service
temperatures well below those
applying to, for instance, CrNi
steels, cladding, coating and
surface diffusion processes e.g.
Fig.1 – 1000-h creep rupture strength of various materials in relation to temperature 7)
with aluminium, allows the ser-
vice temperature to be increased
to approx. 550 ˚C (1000 ˚F).

Figure 1 gives a clear graphical

illustration of the service
temperatures of various groups
of materials 6) – 7). HT corrosion
Workability
attack
With regard to the type of stress
or attack on the materials in
Mechanical s
Conditions of service aracteristic
subsequent service, two main stress Working ch
categories have to be considered:

• Purely mechanical stress; in

furnace construction, this is
Material behaviour
mainly creep stress. Working characteristics
HCF (High Cycle Fatigue) and
LCF (Low Cycle Fatigue) play High ce to
Workability Resistan
a minor role, except in rotating temperature strength
HT corro
sion
components.
• Pure high-temperature corro-
sive attack, with the variants HT corrosion
of oxidation, sulphidation, car- Mechanical attack
burization, nitridation and halo- stress
genation, or a combination
thereof. These modes of deg- High Resistance to
temperature strength HT corrosion
radation are especially com-
mon in industrial engineering. Fig. 2 – Design for elevated temperature
 4

The above two categories are of

course not singly encountered in
their pure forms; in practice,
the mechanical stresses and the
corrosive attack are generally
superimposed on each other
1000 (Fig. 2). Regardless of the type
of stress or corrosive attack,
Rp 1,0 adequate workability of the
material must always be en-
sured, i.e. the starting material
Stress, N/mm2

Rp1,0/10000 in mill product form must be able

100 Rp 1,0 624 °C to be fabricated into the desired
1.5
final shape by means of forming
Rp1,0/100000
processes and be capable of
being assembled into larger
units if necessary. Hence the
final component must be able
1
to meet both the mechanical
0 100 200 300 400 500 600 700 800
requirements and the high tem-
Temperature, °C perature corrosion resistance
requirements of the specific
industrial engineering application.

If the material of construction’s

properties regarding mechanical
Fig.3 – Comparison of short-time and long-time strengths with reference to the alloy Nicrofer 6025 HT – alloy 602 CA (2.4633)
stresses and corrosion
resistance can be imparted to
the component, as depicted
schematically in Fig. 2, it is then
possible to speak of “design for
elevated temperature”.

500
13CrMo44
X22CrMoV121
300

200 NiCr23Co12Mo (617)

100
Stress, N/mm2

50

30
C-steel
20
X8CrNiMoNb1616
10
X10NiCrAlTi3220H
(800 H)
5
300 400 500 600 700 800 900 1000

Temperature, °C

Fig.4 – 100,000-h creep rupture strengths of some steels and a nickel alloy in relation to temperature
 Strength at 5

high temperatures

In contrast to materials for wet-

corrosion service, strength is a
far more critical parameter in
the case of high-temperature
materials is. This is because of 40
the influence of time-dependent Nicrofer 3220 H (800 H)
30
properties of stress rupture
Creep rupture strength Rm/104, N/mm 2

and creep (plastic region of 20 Nicrofer 7216 H (600 H)

deformation) as a function of
temperature, which must be
taken into account when 10 Nicrofer 6025 HT (602 CA)
designing the component.
Nicrofer 3718
By comparison, materials for 7
(330)
wet-corrosion service are 5
generally exposed only to elastic 4
Nicrofer 6023 H
strain and do not enter the 3 (601 H) Cronifer 2520 (310 SS)
plastic region of deformation.
2
Fig. 3 shows, with reference to
the alloy Nicrofer 6025 HT – 800 900 1000 1100 1200
alloy 602 CA, the influence of Temperature, °C
the exposure time on the
material's long-time strength
and the resulting threshold
temperature for the design
Fig.5 – 10,000-h creep rupture strengths of some austenitic, heat-resistant steels and nickel alloys in the temperature range
of components on the basis
800 – 1200 °C (1470 – 2190 °F)
of creep rupture strength.

Fig. 4 shows the creep rupture

strengths of various materials,
starting with unalloyed carbon
steel and proceeding via ferritic
and ferritic-martensitic Cr
stainless steels and austenitic 70
stainless steels to a high- 50
temperature, high-strength 40 Nicrofer 4722 Co (X)
Creep rupture strength Rm/104, N/mm2

nickel-base alloy. 30

20 Nicrofer 7216 H (600 H)

Fig. 5 amplifies the temperature
range 800 – 1200 ˚C Nicrofer 6025 HT (602 CA)
(1470 – 2200 ˚F) in more detail. 10
It is clear that the nickel-base 7
alloy Nicrofer 6025 HT – 5
alloy 602 CA contrasts 4 Nicrofer 45 TM
significantly with the alloys 3
Nicrofer 6023 H – alloy 601 H Nicrofer 6023 H
and Nicrofer 7216 H – alloy 2 (601 H) Nicrofer 5520 Co (617)
600 H, which lie in the scatter 800 900 1000 1100 1200
band of the iron-based alloys
Cronifer 2520 – alloy 310 SS, Temperature, °C
Nicrofer 3718 – alloy 330 and
Nicrofer 3220 H – alloy 800 H.

Fig.6 – 10,000-h creep rupture strengths of various nickel-base alloys in relation to temperature
 6

Of the nickel-base alloys, at

approx. 850 ˚C (1560 ˚F) the
alloy Nicrofer 5520 Co – alloy
617 has the highest strength.
1000 At higher temperatures up to
700 Nicrofer 5120 CoTi (C-263) 1200 ˚C (2200 ˚F), the alloy
Nicrofer 6025 HT – alloy
500
Creep rupture strength Rm/104, N/mm 2

602 CA is significantly superior

400
(see Fig. 6).
300 Nicrofer 7520 Ti (80 A)
Nicrofer 7016 TiNb (X-750)
200 The creep rupture strengths
of the age-hardening alloys in
Nicrofer 5219 Nb (718)
precipitation-hardened condition
100
are shown in Fig. 7 in com-
70 parison with Nicrofer 6025 HT –
50 alloy 602 CA. The exceptionally
40
high strengths of the age-
30 hardening alloys are sustained
Nicrofer 6025 HT (602 CA)
20 only up to approximately 800 –
850 ˚C (1470 – 1560 ˚F), after
which they fall off precipitously.
500 600 700 800 900

Temperature, °C In industrial engineering,

components exposed to fatigue
loading are typically found in
rotating components such as
Fig.7 – 10,000-h creep rupture strengths of various age-hardening nickel-base alloys in relation to temperature
rotary kilns, furnace rollers or
conveyor rollers, in agitators
subjected to vibration, vibrating
chutes, and components in
which reversals of stresses are
set up by pulsating gas flows.
However, these applications
are much less common than
60 Cyclic stress components subjected to creep
ultimate number of cycles n = 1.106 cycles stresses.
T = 1100 °C
σ0, N/mm2 at ultimate number of cycles

In contrast to studies at room

40 temperature or moderately high
temperatures, at elevated tem-
peratures the fatigue strength
of heat-resistant alloys is greater
than their creep rupture strength.
20
Fig. 8 shows, for the alloy
X
Rm/100 Nicrofer 6025 HT – alloy 602 CA
X at 1100 ˚C (2010 ˚F),
Rm/1000
a comparison of the fatigue
0 strength with the corresponding
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 creep rupture strength for the
Frequency, Hz ultimate number of 1 million
cycles. The fatigue strength falls
with decreasing frequency
(Fig. 9) and rising temperature
(Fig. 10).
Fig.8 – Fatigue strength of Nicrofer 6025 HT – alloy 602 CA in relation to frequency (grain size = 40 µm)
 7

Strengthening mechanisms

To guarantee satisfactory high-

temperature strength, all
measures are appropriate which,
firstly, raise the temperature of
incipient melting and, secondly,
obstruct diffusion and grain 100
boundary sliding, i.e. hinder the T=1100 °C

movement of dislocations, delay

80
polygonization and dissociation
Loading ± σm, N/mm 2

of dislocations, and enable new

dislocations to form. The route 60
most commonly followed is 3 Hz
alloying with elements which
40
improve both heat resistance 1 Hz
0.1 Hz 0.3 Hz
and corrosion resistance.
By selection of the basic 20
constituents and appropriate
alloying additions, it is nowadays
0
possible to raise the service
1E+02 1E+03 1E+04 1E+05 1E+06 1E+07
temperature of alloys to 0.9 Tm
(Tm = melting point in ˚C). Number of cycles

The strengthening mechanisms

by alloying that are used in the
case of high-temperature alloys Fig.9 – Fatigue strength of Nicrofer 6025 HT – alloy 602 CA (σm = 0)

to attain high creep rupture

strengths are varied. With
reference to the alloys mentioned
so far, the following mechanisms
apply:

Solid solution hardening

100
1000 °C
The term “solid solution harde- 1100 °C
ning” signifies the attainment of 1150 °C
80
an increase in matrix strength by 0.1 Hz
Loading ± σm, N/mm 2

the addition of an element which

is soluble in the matrix. This is 60
achieved mainly by distortion
and straining of the atomic lattice,
40
thus inhibiting dislocation
movement. However, movement
of dislocations is necessary for 20
deformation processes, which
include creep. One way of
0
straining the atomic lattice is to
1E+02 1E+03 1E+04 1E+05 1E+06 1E+07
introduce elements which have
a larger atomic radius than the Number of cycles
matrix lattice.

Fig. 10 – Fatigue strength of Nicrofer 6025 HT – alloy 602 CA (σm = 0)

8

Solid solution hardening also This shows that for alloys

has the effect of decreasing the which are predominantly solid
stacking fault energy in the solution hardened, there is a
crystal lattice, leading primarily clear correlation between the
to inhibition of dislocation sum of these elements and the
cross-slip, which is the main creep rupture strength. The
mode of deformation in higher contents of the elements
imperfect crystals. At high Cr, Co, Mo and W produce an
temperatures (> 0.6 Tm , in this increase in the creep rupture
case above 820 ˚C [1510 ˚F]), strength, whereas silicon has a
the main mechanism by which markedly detrimental effect on
high-temperature mechanical creep rupture strength.
properties, especially time-
dependent creep, are influenced Precipitation hardening
is diffusion. In this case the
slow-diffusing elements Mo, A considerable increase in the
W, Hf and Ta are particularly creep strength of alloys for high-
suitable for solid solution temperature applications can
hardening. However, the element be obtained by precipitation
molybdenum is often preferred hardening. In the case of nickel-
due to its considerably lower or iron-based alloys, this can
relative atomic mass and lower be achieved by means of the
cost. elements Ti, Al and Nb.
These elements are only
On the basis of the effectiveness soluble to a limited extent in the
and the percentage of solid systems, with the result
solution hardening elements, that, by means of suitable heat
the alloys can be classified treatment, finely distributed
according to their creep rupture precipitates can be generated in
strengths (Table 2). The criterion the matrix from a supersaturated
for their classification as shown solid solution. The precipitates
in Table 2 was their 10,000-h resulting from such temperature-
creep rupture strength at 800 ˚C dependent decrease in solubility,
(1470 ˚F). generally Ni3 (Ti, Al)-γ’-phase
and Ni3Nb- γ”-phase, inhibit the
movement of dislocations, thus
increasing the high temperature
strength.

Material Alloy UNS Weighted content Rm/10,000

des. of solid solution hardening N/mm2
elements
1 x (Cr + Co) + 2 x (Mo + W) - 5 x (Si)

Nicrofer 45 TM 45 TM N06045 14.5 19

Nicrofer 7216 H 600 H N06600 16 29
Nicrofer 6023 H 601 H N06601 23 31
Nicrofer 4626 MoW 333 N06333 32 42
Nicrofer 4722 Co X N06002 41 59
Nicrofer 5520 Co 617 N06617 51 65
Table 2 – Influence of solid solution hardening elements on the creep rupture strength Rm/10,000 at 800 °C (1470 °F) of nickel-base alloys
 9

Movement of dislocations in the

matrix can take place either by
cutting through or by bypassing
the precipitated particles. Fig. 11
400 Ageing temperature, °C
shows the best lattice state,
for the greatest hindrance to 650
movement of dislocations is 700
750
in a matrix with finely distributed 800
precipitates, having a diameter
of the order of 20 – 50 nm.
Where the particles are too
Hardness, HV

small, cutting through the 350

particles is energetically more
favourable for dislocations.
In the case of coarser particles
at a lower degree of dispersion,
i.e. greater particle spacing,
bypassing the particles involves
the least energy expenditure.
Both cases cause a drop in the 300
mechanical properties of the 0 10 100
material 8).
Average particle diameter, nm

The use of view of γ’ and γ”

precipitation hardening high-
temperature alloys is limited Fig.11 – Hardness of a nickel alloy containing 22 % chromium, 2.8 % titanium and 3.1% aluminium in dependence on the diameter
from the point of view of service of precipitated particles, after Mitchell 15)
temperatures, since high-tempe-
rature mechanical properties are
impaired by over-ageing and/or
particle dissolution. This can be
counteracted to a certain extent
by using cobalt as an alloying 1150

element. As shown in Fig. 12,

this raises the solubility limits
1100
for Ti and Al at the solution
annealing temperature, and thus 59 % Ni - 22 % Cr - 19 % Co
the upper limit for the service 1050
Temperature, °C

temperature. A further restriction

on applications for precipitation
hardened high-temperature 1000 γ
materials is their low ductility 78 % Ni - 22 % Cr
and limited weldability 9). 950

900 γ+γ’

850
0 1 2 3 4 5 6
Titanium, %

Fig.12 – Saturation solubility of titanium in a nickel-base alloy containing 22 % chromium and influence on solubility of addition
of 19 % cobalt. The Ti/Al ratio was kept constant at 1:1, after 3)
 10

Another form of precipitation

strengthening is hardening by
means of secondary carbide
precipitates. Increasing creep
strength by carbide hardening
is of great significance,
28 Rm/10000 h bei 900 °C particularly for heat-resistant
austenitic stainless steels.
This is because solid solution
26 hardening of these alloys, using
elements such as Mo, W, etc.,
Stress, N/mm2

is only possible to a limited

24 extent, due to their limited
solubility. With these alloys, pre-
cipitation of chromium carbides
22 and of titanium, niobium and
vanadium carbonitrides is impor-
tant.
20
0.03 0.04 0.05 0.06 0.07 0.08 In addition to the above, strength-
increasing stacking faults are
Carbon, % also produced, though these
occur at the expense of ductility.
An increase in the nickel content
of austenitic alloys decreases
Fig.13 – 10,000-h creep rupture strength of Nicrofer 3220 H – alloy 800 H at 900 °C (1650 °F) as a function the carbon solubility, which, for
of the carbon content of the alloy11) a given carbon content, leads to
increased carbide precipitation.
This occurs mainly at the grain
boundaries for thermodynamic
reasons.

Correctly applied, this strengt-

hening phenomenon can be
particularly useful for increasing
the creep strength of these
alloys, for under service loads,
creep processes at high tempe-
ratures mainly take place at the
grain boundaries. As shown for
example in Fig. 13, the creep
strength of nickel-chromium-iron
based high-temperature alloys
show a functional relationship to
their carbon content and thus to
the amount of carbides, which
precipitate preferentially at the
grain boundaries and thus
inhibit grain boundary sliding.
Creep processes are therefore
transferred, due to carbide
precipitates, from the grain
20 µm 20 µm
boundary to the interior of the
Fig.14 – Microstructure of a Nicrofer 5520 Co – alloy 617 creep Fig.15 – Microstructure of a Nicrofer 5520 Co – alloy 617 creep
specimen after 7,209 h at 850 °C (1560 °F) and a stress of specimen after 10,000 h at 1000 °C (1830 °F) and a stress of
grain. Small, globular, non-
54 N/mm2 6 N/mm2 cohesive carbides are best

suited for stabilizing the grain
boundaries. These are mainly
primary precipitates of MC and
M6 C carbides based on Mo, W,
Ti and Nb. Since most high-tem-
perature alloys have high chro-
mium contents (c. 16 – 30 %)
for corrosion-related reasons,
the formation of M23C6 carbides
is unavoidable. With prolonged
exposure to high temperatures,
the MC and M6C carbides also
tend to transform into M23C6 10).
As can be seen in Fig. 14, this
type of carbide tends towards
the formation of cohesive grain
boundary precipitates.
Since carbides are inherently
brittle due to their structure,
these cohesive grain boundary
precipitates represent a
preferred path for crack growth,
and this can result in a decrease
in creep resistance.
In contrast, with non-cohesive
globular precipitated carbides
stresses can be reduced by
slight grain boundary sliding,
and thus the formation of
microcracks can be prevented or
hindered. As shown clearly by
Fig. 15, at high temperatures
M23C6 carbides also tend, on the
other hand, to agglomeration,
i.e. to the formation of fewer
and larger carbides on grain
boundaries. These represent
points for crack initiation, and
slippage of grain boundaries
is also promoted. Both produce
a decrease in creep strength.
In solid solution hardened high-
temperature alloys, the carbide
forming elements molybdenum
and tungsten also tend
to precipitate as carbides at
the grain boundaries after long-
term exposure to high tempe-
ratures. This causes the grain
boundary zones to become
depleted in these elements.
This has the disadvantage
that solid solution hardening
decreases in this area, but also
the advantage that stresses
occurring are dissipated via
these “softer” zones and not via
the brittle carbide-decorated
grain boundaries. The result is a
beneficial influence on creep
rupture strength and ductility.
1100
1000
Temperature, °C
900
800
700
600
500
0.1
Fig.16 – Schematic time-temperature preciptation diagram of the precipitation of the π-phase in Cronix 70 NS
and the γ’ and δ-phases in Nicrofer 5219 Nb – alloy 718 (2.4668)
In 1992 primary carbide
hardening for wrought alloys
was achieved commercially
for the first time. The alloy
Nicrofer 6025 HT – alloy 602 CA,
which is strengthened by pre-
cipitation of primary carbides,
offers excellent creep rupture
strengths at service tempe-
ratures up to 1200 ˚C (2190 ˚F),
and at temperatures above
approx. 1000 ˚C (1830 ˚F) is
markedly superior to the pure
solid solution hardened nickel-
base alloys in terms of creep
rupture strength.
Besides carbide hardening,
attempts have been made
in recent years to use secondary
nitride precipitates to strengthen
a Ni matrix. The high nitrogen
content necessary in order
to provide a sufficiently high
volume of precipitated nitrides
is achieved by means of the
DESU technology (pressurized
π-Phase
δ-Phase
γ ‘-Phase
0.5 1 5
Time, h
11
electroslag remelting). A typical
analysis of the nitride-strengt-
hened alloy Cronix 70 NS is
given in Table 1. This alloy is
precipitation-hardenable in the
temperature range 750 –
1150 ˚C (1380 – 2100 ˚F) due
to the precipitation of π-phase,
which is a Cr13Ni7N4 nitride.
Because of the stability of
the precipitates up to approx.
1150 ˚C (2100 ˚F), the pre-
cipitation of π-phase is more
useful in terms of the hardenabi-
lity of nickel alloys than γ’-, γ”-
or δ-phase precipitates, as used
at present, for example, in
Nicrofer 5219 Nb – alloy 718
or Nicrofer 5120 CoTi – alloy
C-263 (Fig. 16).
10
 12

Dispersion hardening

Another means of increasing

the heat resistance and creep
rupture strength of an alloy is
by dispersion hardening.
The difference between age-
precipitation- hardening and dispersion harden-
hardened ing is that the age-hardenable
precipitates are soluble in the
matrix at higher temperatures,
Yield strength

where as particles of a phase

which is largely insoluble in the
dispersion- matrix are used for dispersion
hardened
hardening.

The dispersoids used nowadays

are almost exclusively oxides
generally yttrium oxide for the
high-temperature, high-strength
nickel-base alloys. These so-
Temperature
called ODS (oxide dispersion
strengthened) alloys are manu-
factured by powder metallurgy
and are at present marketed
in the mill product forms sheet,
Fig.17 – Comparison of the dependence of the yield strength on the temperature for precipitation hardening and dispersion hardening
plate, rod, bar and wire.

The advantage of dispersion-

hardened alloys lies in the
insolubility, or at least the very
low solubility, of the dispersoid
in the matrix, with the result that
1000 Ageing time: 1000 h
no dissolution or coagulation
Nicrofer 7216 H (600 H) occurs, even at very high
Nicrofer 3220 H (800 H) temperatures. Therefore these
800 Nicrofer 6023 H (601 H)
Cronifer 2520 (310 SS) materials attain significant
Nicrofer 6025 HT (602 CA) strength values at service tem-
peratures at which age-hardened
Grain size, µm

600
precipitates are already dissolved
(Fig. 17) 2).

400
These alloys have the drawback,
however, that the dispersion is
dissolved by welding and the
200
strength of the weld metal is of
the same order as the non-
dispersion-strengthened matrix.
0 To avoid this, the materials
1000 1100 1200
should be joined by means of
Temperature, °C bolted and plug-and-socket
connections. Also, these alloys
have lower ductility and special
precautions are needed during
Fig.18 – Grain growth of various alloys fabrication.
 13

Influence of grain size and with a very coarse grain size As well as the grain size, is simplified by the build-up of
grain boundaries there is the danger of cohesive the grain boundaries or, in more these elements in the distorted
decoration of the grain bound- general terms, the trace grain boundary lattice regions.
The typical final heat treatment aries with brittle carbides and elements play an important part At least a clearly adverse
for high-temperature alloys the corresponding disadvantage in influencing creep resistance influence of these elements on
is generally solution heat treat- of rapid crack propagation. at elevated temperatures. the creep rupture strength,
ment, which is carried out at c. It also leads to loss of ductility The trace elements under which is determined by creep
1100 – 1200 ˚C (2010 – 2190 ˚F) and low-temperature embritt- consideration occur either as processes, has been empirically
followed by water quenching or lement. Long practical experi- unintentional impurities or as established. The precise
fast air cooling. In this operation, ence indicates that selection of deliberate alloying elements and maximum acceptable contents
carbides present are mostly an average grain size of between have in general only a limited of these impurities are however
dissolved. In the case of coarse approximately 100 and 200 µm solubility in the matrix. They not known and can also vary
carbides, which because of the (ASTM grain size 3.5 – 1.5) is therefore tend to segregate from alloy to alloy. For instance,
time-limited solution heat treat- most beneficial for the creep preferentially at grain boundaries in the case of the widely used
ment cannot be completely strength and ductility of high- and affect their stability under alloy Nicrofer 3220 H – alloy
dissolved, equalization, at least, temperature materials. creep loading. This can have 800 H upper limits for the
of the element depletion or both positive and negative elements Pb and Bi of 7 and
concentration takes place at consequences for the creep 1 g/t (ppm) respectively have
the phase boundary between strength. proved favourable for creep
the carbide and the matrix 12). rupture strength.
Little is known about the mecha-
The solution heat treatment also nisms of action of the trace
causes an increase in the grain elements Pb, Bi, Sb, Sn, As, Te,
size, as shown, for example, for Ga, S, P, Ag and their negative
various high-temperature alloys influence on creep strength.
in Fig. 18. It can be assumed, however,
that the decohesion process
Coarse grains present consider-
ably less potential for slip
processes than fine grains. This
is illustrated by Fig. 19, which
shows the dependence of the
creep rupture strength of the
alloy Nicrofer 5520 Co – alloy
617 on grain size. A substantial
increase in creep rupture strength, 60 850 °C 180 µm (ASTM 2)
particularly at very high tempe- 90 µm (ASTM 4)
50
ratures, can be attained by con- 45 µm (ASTM 6)
trolled increases in grain size. 40
Duplex structures, i.e. the simul- 950 °C
Stress, N/mm2

taneous presence of coarse and 30

fine grains, should be avoided if
possible, since zones of different 20
180 µm (ASTM 2)
creep behaviour would then be
present, leading to an overall
decrease in creep resistance. 90 µm (ASTM 4)

Regarding the grain size, carbide

45 µm (ASTM 6)
precipitation and distribution 10
should always be considered as 100 1000 10000 100 000
a variable affecting creep Time, h
strength. With a fine-grained
alloy, the density of carbide
precipitation is low, greatly facili-
tating slippage processes at the
grain boundaries. In contrast, Fig.19 – Creep-rupture strength of Nicrofer 5520 Co – alloy 617 at 850 °C (1560 °F) and 950 °C (1740 °F) with different grain sizes 13)
 14

However, it is a question of In addition to the impurities

economics whether it is worth
accepting the considerably
higher material costs associated
with a further reduction of these
unwanted impurities for only a
slight increase in the creep
rupture strength. In particular,
it should also not be forgotten
that, in statistical terms, these
slight improvements may in
practice be lost in a scatter band
of properties in different heats
(Fig. 20)14).
80
Nicrofer 7216 H (600 H)
70
60
50
Scatter (±), %
recognized as detrimental, there
are a number of helpful trace
elements. These are the ele-
ments Zr, B and Mg15). Like the
impurities discussed above,
these elements segregate at
grain boundaries.
There they either fix detrimental
impurities, such as sulphur, or
are integrated into the distorted
lattice. The latter phenomenon
produces a strengthening of the
grain boundaries, since the
diffusion processes responsible
for grain boundary sliding are
inhibited or retarded. Boron and
zirconium also inhibit the
agglomeration of M23C6 carbides
at the grain boundaries and thus
reduce the danger of microcrack
formation. Boron additionally
reduces the solubility of carbon
at the grain boundaries.
This means that the amount of
carbide at the grain boundaries
increases, but the formation
both of coarse carbides and of
continuous carbide layers
is impeded. Both would be
detrimental to creep rupture
strength. Furthermore, zirconium
inhibits grain growth at elevated
temperatures. However, these
elements should be used with
great caution, since any excess
can be extremely harmful. For
instance, boron contents of up
to 50 g/t (ppm) have proved

Nicrofer 6020 hMo (625) extremely beneficial, whereas

40
even a slight amount in excess
30
of this limit can produce the
Nicrofer 3220 H (800 H) reverse effect. There is then, for
Nicrofer 4722 Co (X)
20 example, a danger of formation
of low melting point borides,
10 Nicrofer 5520 Co (617)
thus leading to embrittlement of
the grain boundaries.
0
600 700 800 900 1000

Temperature, °C

Fig. 20 – Scatter of 100,000-h creep-rupture strength data for various alloys in relation to temperature14)
 15

Degree of cleanness Reconstructed original cross-section

A0 = 78.54 mm2

Trace elements which react with Cross-section without corrosive deposits

A1 = 38.48 mm2
the matrix or with other
dissolved elements, forming Cross-section without selective corrosion
A2 = 24.63 mm2
sulphides, phosphides or oxides,
impair the non-metallic “degree
of cleanness” of an alloy and
generally lead to a decrease
in creep rupture strength and
Testing stress at start of test
fatigue strength. This can be σ0 = 200 MPa
remedied first of all by lowering Stress adjusted for corrosion
the contents of these elements σ2 = 638 MPa
through selection of the raw
materials prior to melting. Adherent Selective corrosion
corrosive deposits
For more demanding require-
ments, melting and casting can Fig. 21 – Reduction of the load-bearing cross-section by corrosion
be carried out under vacuum,
followed by secondary refining
such as ESR (electroslag
remelting) or VAR (vacuum arc
remelting).

Factors influencing
mechanical properties

The mechanical properties of

high-temperature materials are
subject to various influences
during their service life.
The most important influencing
factors are high-temperature
corrosion and abrasion, changes
in microstructure after prolonged
exposure, and cold working.
40 Nicrofer 3220 H (800 H)
High-temperature T=800 °C
55 N/mm2
corrosion and abrasion
30
Whereas high-temperature
abrasion simply causes a
Strain, %

reduction in the cross-section 20

Air
of the component and thus
decreases the load-bearing
cross-section, the influence of S-O Gas
10
high-temperature corrosion is
S-O-C Gas
more varied and complex.
It ranges from uniform damage
0
via local corrosion damage with
0 200 400 600 800 1000 1200 1400
an accompanying decrease in
strength due to this reduction Time, h
of the cross-section (Fig. 21),
to a temporary increase in strength
due to the influence on the
material's microstructure (Fig. 22)16). Fig. 22 – Creep curves for Nicrofer 3220 H – alloy 800 H in air, a sulphidizing atmosphere and a sulphidizing/carburizing atmosphere16)
 16

In general terms, strength is

adversely affected by the
elements oxygen and sulphur
and by halides. Temporary
increases in strength can be
produced by the elements
350
carbon and nitrogen, which
cause precipitation of thermally
300
very stable carbides and
103 -h creep rupture strength, N/mm2

nitrides. Only when a critical

250 amount and size of precipitates
are exceeded does the strength
200 550 °C decrease again – in fact,
even below the strength in
150 original condition.

100 Microstructural influence

600 °C

50 650 °C Changes in microstructure can

700 °C
be caused by, for example, the
750 °C residual strain hardening in the
0
0 10 20 30 40 component after welding,
straightening or force-fitting
Cold deformation, % of components. Strain hardening
leads, depending on the service
temperature and service life,
Fig.23 – Influence of cold deformation on the creep behavior of an austenitic steel at various temperatures18)
to recrystallization of the micro-
structure and generally, as a
result, to a decrease in the creep
rupture strength (Fig. 23) 17) +18).

Exposure to high temperatures

over a long period causes
substantial grain coarsening,
thus leading to an increase
in creep rupture strength
800 (Fig. 24) and a loss of ductility.

Since high-temperature
materials are generally used in
the solution heat treated
200 and water-quenched condition,
Life, h

depending on the service con-

ditions they are frequently in a
100 thermal disequilibrium.
In practice, this means that they
60 undergo a microstructural trans-
40 formation, e.g. by precipitation
of intermetallic phases and
0
0.1 0.5 1 5 10 carbides, which leads to a
Grain size, mm
reduction of impact toughness
(Figs. 25 and 26).

Fig.24 – Creep rupture strength (life at 980 °C [1800 °F] and 105 N/mm2) in relation to grain size for a nickel alloy18)
 17

Cold deformation

A knowledge of the influence

of cold deformation on the creep
behaviour of materials is Notch impact
energy, J
especially important for two
reasons: ISO V-notch specimen On delivery: Av = 281 J
Subsequent heat treatment Av > 300 J
• Firstly, compared with alloying, 250
cold deformation is an inexpen-
sive way of increasing creep
200
strength;
• Secondly, cold deformation of
components is often unavoid- 150
able, which gives rise to uncer-
tainty, since the original
mechanical design is usually 100
10% c.d. + 8000 h
based on fully recrystallized
8000 h
materials.
50 10% c.d. +4000 h
4000 h
In general, the increase in 10% c.d.+1000 h
dislocation density produced by 0 1000 h
cold working (plastic deforma- 500 640 750 860
tion) improves a material’s
Temperature, °C
creep behaviour. However, the
influence of the resulting grain
elongation and the associated
Fig.25 – Influence of ageing on the toughness of Nicrofer 3220 H – alloy 800 H
changes in the grain boundary
slip planes is difficult to quantify.
This improved creep behaviour
can only be exploited if the
metalís service temperature
is significantly below the
recrystallization temperature. Notch impact
energy, J
ISO V-notch specimen On delivery: Av = 238 J
Fig. 23 clearly illustrates the fact Subsequent heat treatment Av = 260–290 J
that the larger the difference 250
between the service temperature
and the temperature at which
200
removal of strain hardening
begins, the greater is the
beneficial effect of cold deforma- 150
tion17) +18). If the service temper-
ature is higher than the
recrystallization temperature and 100
10% c.d.+ 8000 h
the material has been highly
8000 h
strain-hardened, a marked loss
50 10% c.d. +4000 h
of creep rupture strength may
4000 h
occur18). This is probably due to 10% c.d. +1000 h
recrystallization (forming new 0 1000 h
strain-free small grains. This 500 640 750 860
new microstructure no longer
ensures an optimum influence Temperature, °C
on the creep rupture strength in
the same way as the original
microstructure. Fig.26 – Influence of ageing on the toughness of Nicrofer 5520 Co – alloy 617
 18 High temperature corrosion

How does high temperature

corrosion affect the material and
what consequences does it have
for a plant's operational safety
and reliability?

The following events are possi-

Surface film formation Surface film and porosity formation
Multi-layered surface film Surface film formation and decarburized zone
Surface film with internal corrosion Extensive surface removal
without film formation
ble:
• Failure of the component due
to reduction of the load-bearing
cross-section, thus failure of
the plant due to mechanical
overloading.
• Localized failure of the com-
ponent, causing leakage of
substances harmful to health
or the environment, while the
mechanical integrity of the
plant is fully preserved.
• Destruction of and/or damage
to the products by contamina-
tion with corrosion products
causing product damage, while
the mechanical integrity of the
component is fully preserved.
• Contamination of an inter-
mediate product leading to
contamination of the end
product, and/or corrosion of
other associated equipment.

It is therefore essential to study

Surface film with intergranular corrosion Erosion corrosion in detail the interaction between
the alloy and the process me-
dium at high temperatures
especially since high tempera-
ture corrosion has a more radical
effect on a material’s behaviour
than wet corrosion. This is
because the importance of the
Pitting corrosion ”Solder embrittlement” with alloy formation interaction between corrosion
and mechanical loading is much
greater at high temperatures,
since the materials are generally
exposed to plastic strain.

Stress-corrosion cracking Contact corrosion

Fig.27 – Schematic illustration of the manifestations of high-temperature corrosion

 19

Appearance of The product of the reaction Behaviour of materials in

high temperature corrosion
and influencing factors
The forms in which high tempera-
ture corrosion manifests itself
are in many ways similar to
those of wet corrosion. Here too,
therefore, the uniform corrosion,
localized corrosion (pitting and
crevice corrosion), stress-
corrosion cracking and erosion
corrosion can occur. Besides
these, however, there are
other forms attributable to the
diffusion processes which
occur to a large extent at high
temperatures, such as contact
corrosion and alloy formation.
Another aspect is the fact that at
high temperatures the corrosion
medium and/or the corrosion
product may be molten and/or
gaseous, resulting in phenomena
such as “solder embrittlement”,
decarburized surface zones and
porosity (Fig. 27).
between the medium and the
material, i.e. the corrosion pro-
duct, also decisively influences
the progress of corrosion, since
it plays a crucial role in the
transportation of the medium
and the resulting corrosion
product. Important criteria here
are the mechanical and physical
properties of the corrosion
product, e.g. melting point,
vapour pressure, coefficient
of thermal expansion and
thermal conductivity.
Also important are the rate of
diffusion and the formation
enthalpy (Fig. 28).
corrosive media
However, the impact of the
processes described depends
primarily on the corrosion
medium to which the material
is exposed. Therefore the be-
haviour of materials in contact
with the corrosion media most
commonly encountered in prac-
tice is described in detail below.
Oxidation
The protective effect of the alloys
listed in Table 3 when exposed
to an oxidizing environment at
high temperatures mainly stems
from the formation of a dense,
homogeneous layer of chromium
oxide (chromia). Other protective
oxides such as aluminium oxide
(alumina) or silicon oxide (silica)
may also protect against
oxidation attack, depending on
the alloy composition.

All the factors which influence

high temperature corrosion
can be divided into influences
attributable to the corrosion
medium, the material and the 1. Medium
resulting corrosion product. ● Temperature
Those attributable to the ● Concentration and composition
medium particularly include the ● Velocity (gases, melts, solutions)
temperature of the medium, its ● Particle size, shape, velocity and consistency and
composition, its velocity in the angle of impact
case of gases, molten salts and
solutions and, if particles are 2. Material
present, their size, shape,
● Surface condition
velocity, consistency and angle
● Heat treatment/strain hardening
of impact. Those stemming
● Microstructural condition
from the material include, in
● Temperature
particular, the surface condition,
the heat treatment, residual or 3. Corrosion product
selected work hardening, the
● Diffusion rate
microstructural condition and
● Melting point
the material temperature.
● Vapour pressure

● Mechanical/physical properties

● Formation enthalpy

Fig.28 – Factors influencing high-temperature corrosion

 20

For stainless and heat-resistant Hence, where feasible in terms

steels, therefore, first of all the
rule of thumb is that oxidation
resistance increases with the
chromium content. Oxidation
resistance also increases as the
nickel content rises, up to a
chromium content of about
30 wt. %19). Other measures are
the alloying addition of silicon,
aluminium and elements with a
greater affinity for oxygen 20),
which improve the adhesion of
the oxide layer.
Above 950 – 1000 ˚C (1740 –
1830 ˚F), the service life of
the components protected by
chromia can be expected to
decrease sharply with further
rises in temperature, since at
these temperatures the protec-
tive chromia layer suffers
significant volatilization 21).
of economics and alloying
technique, alternative materials
which form protective layers of
alumina should then be chosen
if possible. Table 3 includes such
materials, which are designed
accordingly for high heat resist-
ance, meaning high resistance
to oxidation.
The high-temperature, high-
strength materials listed in Table
4 generally have to be heat-
resistant materials as well, which
in the majority of cases means
that they are required to have
not only high heat resistance but
also high oxidation resistance.
In order to achieve high heat
resistance, they are frequently
alloyed with elements such as
Mo, Nb, W and Co; however, the
influence of these elements on

Material Alloy des. UNS Mat. no. Ni Cr Si C Al Ti Fe Others

(DIN)

Nicrofer 2020 840 – 1.4847 20 20 – 0.06 10.3 0.4 58 –

Nicrofer 3220 800 N08800 1.4876 31 20 – 0.06 10.25 0.4 47 –
Nicrofer 3718 DS*) – 1.4862 36 18 2.2 0.08 10.15 0.15 42 –
Nicrofer 6023 601 N06601 2.4851 60 23 – 0.06 11.4 0.4 14 –
Nicrofer 6030 690 N06690 2.4642 61 29 – < 0.02 – – 49 –
Nicrofer 7216 600 N06600 2.4816 74 16 – 0.07 10.2 0.2 49 –
Nicrofer 7520 75 N06075 2.4951 75 20 – 0.10 10.2 0.4 43 –
Nicrofer 45 TM 45 TM N06045 2.4889 47 27 2.7 0.08 – – 23 0.1 RE
Nicrofer 6009 Al 10 10 Al – – 57 8 – – 10 – 26 0.1 Hf
Cronix 70 NiCr 70/30 N06008 2.4658 68 30 1.3 0.05 – – – 0.03 RE
Cronix 80 NiCr 80/20 N06003 2.4869 78 20 1.3 0.06 – – – 0.03 RE
*) Alloy 330 (mat. no. 1.4864) has a slightly lower chromium and silicon content than alloy DS
Table 3 – Chemical composition of heat-resistant nickel alloys and special stainless steels in mass %
 21

oxidation resistance is negative The cyclic oxidation behaviour

at very high temperatures.
Oxidation resistance tests under
realistic conditions are therefore
a must. They are carried out in
the temperature range 700 –
1200 ˚C (1290 – 2190 ˚F) 22) + 23)
in 24-hour cycles, each cycle
comprising 16 hours at the test
temperature with intervening
cooling and heating periods
of 6 and 2 hours respectively.
At 700 ˚C (1290 ˚F) the rate of
oxidation, measured as the
change in mass, was so low for
all the materials tested that
none failed the required property
demands.
of various nickel- and iron-based
alloys in air is illustrated in
Fig. 29. The best performances
are exhibited by the three nickel
alloys Nicrofer 6023 H – alloy
601 H, Nicrofer 45 TM – alloy
45 TM and Nicrofer 6025 HT –
alloy 602 CA. The relatively
high mass losses of Nicrofer
7216 H – alloy 600 H at 1100 ˚C
(2010 ˚F) are attributable to the
inadequate chromium content
for such temperatures, while the
sharply increasing mass losses
of Nicrofer 3228 NbCe – alloy
AC 66 from 1000 ˚C (1830 ˚F)
upwards are due not to an
insufficient chromium content,
but to the detrimental effect of
niobium, and not having any
Al or Si to form either alumina
or silicon sub-layer protective
oxide.

Material Alloy des. UNS Mat. no. Ni Cr Mo C Al Ti Fe Others

(DIN)

Nicrofer 3220 H 800 H N08810 1.4958 31 21 – 0.07 0.25 0.35 47 –

Nicrofer 3220 HT 800 HP N08811 1.4959 30 21 – 0.09 0.5 0.5 47 –
Nicrofer 3228 NbCe AC 66 N33228 1.4877 32 28 – 0.05 – – 39 0.8 Nb, 0.07 Ce
Nicrofer 6023 H 601 H N06601 2.4851 60 23 – 0.06 1.4 0.5 14 –
Nicrofer 7216 H 600 H N06600 2.4816 74 16 – 0.07 0.2 0.2 19 –

Nicrofer 4626 MoW 333 N06633 2.4608 46 25 3 0.05 0.1 – 17 3 W, 3 Co, 1 Si

Nicrofer 4722 Co X N06002 2.4665 48 22 9 0.07 – – 18 1 Co
Nicrofer 5120 CoTi C-263 N07263 2.4650 51 20 6 0.06 0.5 2.1 10.5 20 Co
Nicrofer 5219 Nb 718 N07718 2.4668 53 19 3 0.05 0.6 0.9 18 5.2 Nb
Nicrofer 5520 Co 617 N06617 2.4663 54 22 9 0.06 1 0.5 11 12 Co
Nicrofer 6025 HT 602 CA N06025 2.4633 62 25 – 0.18 2.3 0.2 19.5 0.1 Y, 0.1 Zr
Nicrofer 6125 GT 603 GT N06603 2.4647 62 25 – 0.22 2.8 0.2 19 0.1 Y, 0.1 Zr
Nicrofer 6325 Ta 2100 GT – 2.4677 63 25 – 0.3 3 – 11 8 Ta, 0.1 Y
Nicrofer 7016 TiNb X-750 N07750 2.4669 72 16 – 0.05 0.6 2.7 17 1 Nb
Nicrofer 7520 Ti 80 A N07080 2.4952 75 20 – 0.06 1.4 2.3 – –
2.3 Si, 0.4 N,
Cronix 70 NS 70 NS – – 67 30 – 0.08 0.15 – –
0.2 Y
Table 4 – Chemical composition of high-temperature, high-strength nickel alloys and special stainless steels in mass %
 22

If the limit for a tolerable change

in mass is fixed (somewhat
arbitrarily) at ≤ 0.10 g/m2h,
the iron-based alloys Nicrofer
3718 – alloy 330 and Nicrofer
3228 NbCe – alloy AC 66 tested
0
Cronifer 2520 (310 SS) here can only be used up to
1000 ˚C (1830 ˚F). At 1100 ˚C
-200
Nicrofer 3220 H (800 H) (2010 ˚F), on the other hand,
the alloy Cronifer 2520 –
-400
Nicrofer 3718 (330) alloy 310 SS still exhibits a
satisfactory oxidation behaviour,
-600
owing to its high chromium
Specific mass change, mg/m2h

content and the addition of rare

-800
earths.
Nicrofer 3228 NbCe (AC 66)
-1000
However, it should be borne
700 800 900 1000 1100 1200
in mind, especially considering
Nicrofer 45 TM the influence of oxidation on
0 the mechanical properties,
that as the service temperature
-200 increases or when approaching
Nicrofer 6025 HT (602 CA) the maximum service tempera-
-400 Nicrofer 7216 H (600 H) ture of a material, uniform
general wastage is superseded
-600 by marked selective oxidation, as
shown, for example, in Fig. 30
-800 Nicrofer 6023 H (601 H) for Nicrofer 3228 NbCe – alloy
AC 66.
-1000
700 800 900 1000 1100 1200

Temperature, °C

Fig.29 – Cyclic oxidation behaviour of some iron- and nickel-base alloys in air as a function of temperature

20 µm, T = 750 °C, t =1000 h 20 µm, T = 850 °C, t =1000 h 20 µm, T = 1000 °C, t =1032 h
Fig.30 – Oxidation attack of Nicrofer 3228 NbCe – alloy AC 66 in the temperature range 750 – 1000 °C (1380 – 1830 °F) through the light-optical microscope

Carburization
Besides oxygen attack, at high
service temperatures high-
temperature materials are fre-
quently subject to attack by
carbon. This is usually formed
by decomposition of hydro-
carbons and diffuses into the
material via the grain
boundaries, where rapid
diffusion of the carbon atoms
takes place. The pick-up of
carbon by the material may,
inter alia, result in lowering
of the melting point (to 350 ˚C
[660 ˚F] in the case of NiCr
alloys) 24), carbide formation with
chromium depletion 24), or loss
of ductility due to carbide for-
mation 25).
A more recent form of carburiza-
tion (metal dusting) occurs in
gases with a very high carbon
activity. In practice, therefore,
it is necessary to make a clear
distinction between atmospheres
with carbon activities ac < 1 and
those with ac >> 1.
Carburization in gas
atmospheres with ac < 1
As Fig. 31 shows, carburization
is a clear function of the alloys’
iron content 22), i.e. it decreases
as the nickel and cobalt contents
increase. Because of the very
low solubility of carbon in nickel,
materials with a high nickel
content are often used in strongly
carburizing environments 26).
Deviations from the relationship
shown in Fig. 31 in the direction
of lower specific changes in
mass are exhibited by alloys
with a high aluminium content
(Nicrofer 6025 HT – alloy 602 CA)
and a high silicon content
(Nicrofer 45 TM – alloy 45 TM).
23
In contrast, materials with High chromium contents also
high contents of stable carbide promote resistance to carburiza-
formers (e.g. niobium) show tion, especially if diffusion-
deviations in the direction of inhibiting layers of chromia can
higher specific changes in be produced on the metal’s
mass (Nicrofer 6020 hMo – surface. As Fig. 32 illustrates,
alloy 625, Nicrofer 3228 NbCe – the carburization resistance of
alloy AC 66). the new high-temperature alloy
Nicrofer 6025 HT – alloy 602 CA
If alternating heat treatments in is significantly better than that
carburizing and in oxidizing of the alloy Nicrofer 6023 H –
gases are carried out, however, alloy 601 H and is close to that
these alloys can only be used of Nicrofer 5520 Co – alloy 617.
with certain limitations, as
the carbides precipitated in large This is partly attributable to the
amounts due to the low higher chromium content, but
C-solubility are converted to the other alloying constituents
oxides and the resulting carbon (cf. Table 4) are also effective.
monoxide gas widens the grain For instance, the relatively high
boundaries, thus loosening the carbon content of Nicrofer 6025
oxide layer 24), 27). HT – alloy 602 CA brings the
carbon activities of the material
and the gas atmosphere closer
together, thereby reducing
the driving force for diffusion
of carbon into the material.
Nicrofer 3228 NbCe (AC 66)
400
Mass change per unit area, g/m2
300
Nicrofer 3320 H (800 H)
Nicrofer Nicrofer 45 TM
6020 hMo (625)
200
Nicrofer 6023 H
(601 H)
Nicrofer Nicrofer 4722 Co (X)
5520 Co
Nicrofer 4626 MoW (333)
(617)
100
Nicrofer 6025 HT (602 CA)
0 10 20 30 40 50
Fe content, %
Fig. 31 – Carburization as mass gain after 864 h in CH4/H2 (ac = 0.8) at 1000 °C (1830 °F) with
periodic intermediate cooling as a function of the alloys’ iron content 22)
 24

A very effective alloying element

in resisting carburization attack
is silicon 24). Its effectiveness is
further enhanced by the addition
400 of small amounts of rare earths.
Nicrofer 3228 NbCe (AC 66) The probable reasons for this
are the lowering of the carbon
solubility and the inhibition of
300
carbon diffusion via the grain
Cronifer 2520 (310 SS)
boundaries.

200 The carbon picked up by the

Nicrofer 3718 (330) metal leads to precipitation of
Specific mass change, mg/m2h

carbides in large amounts, as

shown, for example, in Fig. 33
100 for Nicrofer 6025 HT – alloy 602
Nicrofer 3220 H (800 H)
CA and Nicrofer 3220 H – alloy
800 H. These changes in the
0
microstructure due to high-
700 800 900 1000 1100 1200
temperature exposure in corrosive
media also cause changes
200 in terms of the mechanical
Nicrofer 45 TM Nicrofer 7216 H (600 H)
properties. In creep rupture
tests, for instance, the tendency
Nicrofer 6023 H (601 H) is towards higher creep rupture
100
strengths accompanied by a slight
Nicrofer 5520 Co (617) reduction in creep ductility when
Nicrofer 6025 HT (602 CA) compared with tests in air 16).
0
700 800 900 1000 1100 1200

Temperature, °C

Fig. 32 – Cyclic carburization behaviour of some iron- and nickel-base alloys in CH4/H2, ac = 0.8

Nicrofer 6025 HT – alloy 602 CA Nicrofer 3220 H – alloy 800 H

Gas = CH4/H2, T = 1000 °C, t = 1056 h 20 µm Gas = CH4/H2, T = 1000 °C, t = 1056 h 20 µm

Fig.33 – Appearance of carburization through the light-optical microscope, using the nickel-base alloy Nicrofer 6025 HT – alloy 602 CA
and the iron-based alloy Nicrofer 3220 H – alloy 800 H as examples
 25

Carburization in gas atmos- Tests have shown that nickel

pheres with ac >> 1 alloys with high chromium,
aluminium and/or silicon con-
In gas mixtures, e.g. H2-H2O-CO tents have good resistance
media with very high carbon to metal dusting. In Figs. 35
activity (ac >> 1), a particular and 36, Nicrofer 6025 HT – alloy
form of corrosion which is a 602 CA in particular exhibits
manifestation of carburization, exceptionally good resistance.
the so-called “metal dusting”, As a result, this new alloy has
occurs in the temperature range been accepted and specified in
c. 500 – 800 ˚C (930 – 1470 ˚F). practice as a solution to metal
The micrographs in Fig. 34 dusting problems of various
show the typical appearance of industries.
a damaged material.

This type of material attack

clearly takes the form of severe
pitting. The term “metal dusting”
signifies that the generally rapid
corrosive attack proceeds by
disintegration of the metal with
deposition of pure carbon, which
is clearly visible in relatively large
amounts at the corresponding
points on the surface of the
metal. Metal dusting can lead
to rapid material failure 28),
due to extensive metal wastage.

20 µm 500 µm
Fig. 34 – Typical appearances of metal dusting
 26

Sulphidation

In contact with sulphur and

sulphur compounds such as
sulphur dioxide and hydrogen
sulphide, metal sulphides are
1.00E+00 formed which generally lead to
severe damage to the material.
1.00E - 01
The reasons for this are 24), 27):
Corrosion rate, mg . cm-2 . h-1

Nicrofer 7216 (600)

development of porous scale
1.00E - 02
layers offering little protection,
Nicrofer 6023 (601) since the volume of the metal
1.00E - 03 sulphides is 2.5 to 2.9 times
greater than that of the corre-
1.00E - 04 sponding metal oxides and the
resulting stresses lead to severe
Nicrofer 6025 HT (602 CA) spalling, cracking and possibly
1.00E - 05
to catastrophic corrosive attack
1.00E - 06 owing to the low melting point
0 2000 4000 6000 8000 10000 (635 – 1070 ˚C [1175 – 1960 ˚F])
of the metal sulphides formed 29).
Ageing time, h

Especially harmful, in relation to

the chromia, are reducing gases,
as here the protective effect of a
chromia layer is significantly
Fig. 35 – Resistantce to metal dusting of nickel-base alloys at 650 °C (1200 °F) in a strongly carburizing CO-H2-H2O-atmosphere
reduced. The corrosion-inhibiting
effect of dense oxide layers can,
however, be exploited in practice
by ensuring adequate pre-oxi-
dation wherever there is a risk of
sulphidation 30) + 31).

The scope for reducing sulphida-

80 1) oxidized
2) bright 73 tion attack by means of alloying
3) ground metallurgy is limited, although
improved corrosion resistance
60 can be achieved by raising the
Nicrofer 6025 HT 1) (602 CA)
Corrosion, µm/year

chromium content, adding

Nicrofer 5520 Co 2) (617)

Nicrofer 6616 hMo (C-4)

Nicrofer 6030 2) (690)

Nicrofer 6023 1) (601)

Nicrofer 6023 3) (601)

aluminium and silicon, or adding

larger amounts of cobalt. These
Nicrofer 45 TM 1)

40
elements reduce the rate of sul-
phur diffusion in the material 32),
HR 160
HR 214

as shown by the cobalt-sulphur

20 phase diagram 29), and shift the
12.0 melting point of the eutectics in
5.8 6.3 the direction of higher tempera-
<1 <1 <1 <1 1.2 <1
0 tures. Another method is to add
other elements which fix sulphur
Alloy
in a stable form and thus inhibit
reactions, especially with nickel
and chromium; examples are
manganese, magnesium,
Fig. 36 – Corrosion of various high-temperature alloys under metal dusting conditions
calcium, cerium and yttrium.
(T = 650 °C [1200 °F], ac >>1, H2-H2O-CO atmosphere, t = 10,000 h, after Grabke et al. 1996)
 27

The sulphidation behaviour of

various alloys was tested in
N2 + 10 % SO2 in the temperatu-
re range 650 – 850 ˚C (1200 –
1560 ˚F) (Fig. 37). These tests 5000
again confirmed what is known
from the relevant literature, i.e.
high chromium contents signifi- 4000
cantly improve the sulphidation Cronifer 2520 (310 SS)
resistance of heat-resistant and 3000 Nicrofer 3220 H (800 H)
high-temperature materials 33).
At the same time, the tests on
2000
the recently developed material
Nicrofer 45 TM – alloy 45 TM
Corrosion rate, mg . cm-2 . h-1

demonstrate the beneficial 1000

Nicrofer 3228 NbCe (AC 66)
effects of silicon on sulphidation
resistance 32). Nicrofer 3718 (330)
0

600 700 800 900

The results of the mass change
4000
tests indicate that nickel alloys
are more resistant than iron-
based alloys; however, a closer 3000
examination of the micrographs
in Fig. 38 clearly shows that only 2000
Nicrofer 45 TM – alloy 45 TM
possesses sufficiently good Nicrofer 7216 H (600 H)
1000
corrosion resistance to ensure a Nicrofer 6020 hMo (625)
long service life. Nicrofer 45 TM
Nicrofer 6023 H (601 H)
0

600 700 800 900

Temperature, °C

Fig. 37 – Cyclic sulphidation behaviour of some iron- and nickel-base alloys in 10 % SO2/N2

Nicrofer 3220 H – alloy 800 H Nicrofer 6020 hMo – alloy 625 Nicrofer 45 TM – alloy 45 TM
T = 750 °C, t = 1008 h 20 µm T = 750 °C, t = 1008 h 20 µm T = 750 °C, t = 1008 h 20 µm

Fig. 38 – Sulphidation seen through the light-optical microscope, using the alloys Nicrofer 3220 H – alloy 800 H,
Nicrofer 6020 hMo – alloy 625 and Nicrofer 45 TM – alloy 45 TM as examples
 28

Chloridation

10 % HCl/H2 Halogens and halogen com-

Nimofer 6928 (B-2) + Ni 205
pounds (generally chlorine or
0
fluorine compounds) come in
Nicrofer 45 TM
contact with the material via the
-100 Nicrofer 5923 hMo (59) gaseous phase or molten salts.
Elemental halogens, as well as,
Nicrofer 3220 H (800 H) for instance, gaseous halogen
-200
Nicrofer 7216 H (600 H)
compounds given off in chemical
processes, fiercely attack heat-
-300
resistant alloys even at moderate
Specific mass change mg/m2h

500 600 700 800 900 1000 temperatures. Whereas salts

generally cause slagging and
0 disintegration of the oxide layer
0,25 % Cl2, and thus only affect the metallic
20 % O2, Ar region indirectly, the halogens
-100
Nicrofer 7216 H (600 H) themselves may penetrate
deep into the material without
-200
destroying the oxide layer.
They react with the material to
-300 Nicrofer 5923 hMo (59) form heavy metal halides, which
are thermodynamically far less
-400
stable than the corresponding
Nicrofer 3220 H (800 H) oxides 34).
-500
-1200 Due to the low vapour pressure
Ni 205
-1600 of nickel halides compared with
Nimofer 6928 (B-2)
other metal halides 34) (Table 5),
-3650 alloys with high nickel contents
500 600 700 800 900 1000 are used wherever there is a
danger of corrosion by halogens,
Temperature, °C
e.g. Nickel 99.2 – nickel 200/201,
Nicorros – alloy 400 and
Fig. 39 – Cyclic chloridation behaviour of a iron-based alloy and various nickel-base alloys in 10 % HCI/H2 and 0.25 % Cl2/20 % O2/Ar Nicrofer 7216 – alloy 600.
As extensive tests 35) show,
corrosion resistance in oxygen-
free hydrogen/hydrogen chloride
atmospheres between 650 ˚C
(1200 ˚F) and 850 ˚C (1560 ˚F)
generally increases with a rising
nickel content, but even more so
as the molybdenum content of
the alloys increases. Silicon, on
the other hand, has a detrimen-
tal effect.

Fig. 39 illustrates the chlorida-

tion behaviour of these alloys in
an oxygen-free H2 + 10 % HCl
atmosphere and in an oxidizing/
chloridizing 0.25 % Cl2 +
20 % O2 + Ar atmosphere in the
temperature range 550 – 850 ˚C
(1020 – 1560 ˚F). According

to the test results, the high-
nickel alloys, and especially
those which also have a high
molybdenum content, perform
very well in the oxygen-free
atmosphere. In the oxidizing/
chloridizing test medium, on the
other hand, nickel alloys with
high molybdenum contents did
not perform well.
There are indications that at
even higher temperatures, layers
of alumina may possibly have a
better protective action than
chromia layers. For instance, in
a mixed gas atmosphere con-
sisting of Ar/5.5 % O2/0.96 %
HCl/0.86 % SO2 under thermo-
cyclic conditions at 900 ˚C
(1650 ˚F), an Al2O3-forming NiCr
alloy was found to have a slightly free from
improved mass loss rate in
comparison with other nickel-
and cobalt-base alloys .34)
It is known from practical
experience that fluorine-
containing corrosive media are develop, which causes spalling
less aggressive than chlorine-
containing media and therefore
permit higher material service
36)
temperatures . This is
explained by the higher melting nitride layers due to their lack of
points and lower vapour
pressures of heavy metal
fluorides compared with
the corresponding chlorides.
Chlorides
FeCl3
FeCl2
CoCl2
NiCl2
CrCl3
CrCl2
Table 5 – Temperature at which the vapour pressure of the chloride is 10 -4 bar 34)
29
Nitridation compounds (Ni3N, for example,
decomposes at only 190 ˚C
The inertness of molecular [375 ˚F] when heated in a
nitrogen means that at low vacuum and at around 450 ˚C
temperatures, there is no danger [840 ˚F] in nitrogenous atmos-
of nitrogen pick-up due to pheres), nickel-base alloys
molecular nitrogen. At higher perform better than steels in
temperatures, material behav- nitriding media. At high tempe-
iour depends to a great extent ratures (> 1000 ˚C [1830 ˚F]),
on the composition of the alloy; the reactivity of the nitrogen
for example, low-alloy steels increases markedly due to the
undergo a considerable increase increased dissociation of the
in nitrogen content in ammonia molecular nitrogen.
at 300 – 500 ˚C (570 – 930 ˚F)
due to internal nitridation. The alloying elements
At around 500 ˚C (930 ˚F) and chromium, titanium, aluminium,
above, high-chromium stainless vanadium, niobium and
steels are particularly at risk due zirconium, which act as strong
to chromium’s high affinity for nitride formers, decrease the
nitrogen. Although the nitride material's resistance. Boron,
layers which form are initially carbon and silicon, on the other
cracks and may also hand, reduce the rate of nitrogen
act as a diffusion barrier against diffusion in the material and
further penetration of nitrogen, hence improve its resistance in
the large increase in volume nitriding media.
which accompanies the
formation of the nitride layer
causes severe stresses to
of nitride layers.
Thermo-cyclic stress, too,
leads to rapid spalling of the
ductility and their inability to
accommodate any strain, and
hence to “genuine” high-tempe-
rature corrosion damage.
Due to the low nitrogen solubility
and thermal instability of Ni-N
Tv in °C
167
536
587
607
611
741
 30

To test the fundamental

corrosion resistance of the
new Krupp VDM alloys
Nicrofer 45 TM – alloy 45 TM
and Nicrofer 6025 HT – alloy
602 CA in a nitriding atmos-
200 1100 °C phere, extensive tests were
10 % H2/N2 Nicrofer 3220 H (800 H) carried out at 1000 ˚C (1830 ˚F),
Nicrofer 6025 HT (602 CA)
1100 ˚C (2010 ˚F) and 1200 ˚C
150
(2190 ˚F) 37), some well-known
Nicrofer 6023 H (601 H)
iron-based alloys being included
Mass change, g/m2

Cronifer 2520 (310 SS)

for reference. The results can be
Nicrofer 45 TM summarized as follows: all the
100
Nicrofer 3718 So (DS)
high-temperature alloys pick up
nitrogen at 1000 – 1200 ˚C
(1830 – 2190 ˚F) (Fig. 40).
50

Nicrofer 7216 H (600 H) The internal nitridation which

results from nitrogen pick-up
0
leads to a decrease in toughness
0 200 400 600 800 1000 1200
at room temperature. However,
Ageing time, h this decrease is markedly
smaller for nickel-base alloys
than for iron-based alloys,
as the calculation of the relative
losses in Fig. 41 confirms.
Fig. 40 – Mass change as a function of time after ageing in a nitriding 10 % H2/N2 gas mixture at 1100 °C (2010 °F)

Metallographic examinations
show that it is not only the depth
of internal nitridation (Table 6)
and the size of the nitrides that
determine the loss of notch im-
pact toughness, but rather that
Nicrofer 6025 HT (602 CA) the ductility is also influenced by
Nicrofer 7216 H (600 H) the shape and location of the
50 Nicrofer 6023 H (601 H)
nitride precipitates. Cohesive
Relative loss of impact toughness, %

Nicrofer 3718 So (DS)

Nicrofer 45 TM grain boundary precipitates are
Cronifer 2520 (310 SS) particularly detrimental (Fig. 42).
Nicrofer 3220 H (800 H)

0 As the individual test results

show, the nickel-base alloy
Nicrofer 7216 H – alloy 600 H
exhibits the highest resistance
-50 to nitrogen pick-up.

Molten salt corrosion

-100 In a large number of industrial

1000 1100 1200 processes, corrosive deposits
Temperature, °C consisting mainly of alkali
sulphates, chlorides and/or
carbonates form, especially on
the surface of heat exchanger
Fig. 41 – Relative loss of impact toughness after ageing for 1008 hours in a 10 % H2/N2 gas mixture as a function of temperature,
tubes. Due to their low melting
in relation to the impact toughness after ageing for 1008 hours in air at the same temperature point, these alkali salts can
 31

Cronifer 2520 – alloy 310 SS 20 µm

Nicrofer 3220 H – alloy 800 H 20 µm Nicrofer 3718 So – alloy DS 20 µm Nicrofer 45 TM – alloy 45 TM 20 µm

Nicrofer 7216 H – alloy 600 H 20 µm Nicrofer 6023 H – alloy 601 H 20 µm Nicrofer 6025 HT – alloy 602 CA 20 µm
Fig. 42 – Specimen cross-sections after ageing for 1008 hours in 10 % H2/N2 at 1100 °C (2010 °F)

Material Alloy des. UNS Mat. no. Depth of internal nitridation in µm cause acidic or basic fluxing of
(DIN) 1000 °C 1100 °C 1200 °C the oxide layers and thus lead to
dissolution of the metal beneath,
Cronifer 2520 310 SS S31008 1.4841 60 >2000 >2000 causing rapid material wastage
and failure. Problems arising
Nicrofer 3220 H 800 H N08810 1.4958 1100 >2000 >2000 from molten salt corrosion occur
especially in pulp and paper
Nicrofer 3718 So DS – 1.4862 650 >2000 >2000
industry plants and equipment,
Nicrofer 45 TM 45 TM N06045 2.4889 1000 110 >2000 waste incineration plants and
coal gasification plants. Know-
Nicrofer 7216 H 600 H N06600 2.4816 >2000 >2000 >2000 ledge about molten salt corro-
sion has been gained mainly
Nicrofer 6023 H 601 H N06601 2.4851 – >2000 >2000 through research into so-called
“hot corrosion”, i.e. high-tempe-
Nicrofer 6025 HT 602 CA N06025 2.4633 – 800 >2000
rature corrosion caused by alkali
Table 6 – Depth of internal nitridation after ageing for 1008 hours in 10 % H2/N2 sulphates in gas turbines 38).
 32

In addition, sulphate deposits

may form on boiler tubes, which
then lead to so-called sulphate-

Nicrofer 6616 hMo (C-4)

induced corrosion. Molybdenum-

Nicrofer 5923 hMo (59)

containing alloys in particular
exhibit relatively high corrosion
rates. Fig. 43 depicts the results

Nicrofer 3127 hMo (31)

1m Na2SO4
1m Na2SO4+0,01 KCl after 1008 hours of tests with
specimens coated with sodium
8 sulphate and with a sodium
sulphate/ potassium chloride
Corrosive attack, mm/year

Nicrofer 6020 hMo (625)

mixture.
6
The corrosion rates clearly show
Nicrofer 3228 NbCe (AC 66)
Nicrofer 3220 H (600 H)

that the molybdenum-containing

Cronifer 2520 (310 SS)

4 alloys, and especially the alloys

Nicrofer 3127 hMo – alloy 31,
Nicrofer 45 TM

Nicrofer 6616 Mo – alloy C-4

2 and Nicrofer 5923 hMo – alloy
59, which were actually designed
for wet-corrosion service, have
0 the highest wastage rates; in
fact, a direct correlation with the
molybdenum content was
established. The molybdenum-
Fig. 43 – Corrosive attack suffered by specimens coated with Na2SO4 and with free alloys perform significantly
Na2SO4/KCI and then aged under cyclic conditions for 1008 hours at 750 °C (1380 °F) better in this case; these include
the new Krupp VDM alloy
Nicrofer 45 TM – alloy 45 TM.

To test the corrosion behaviour

under sulphate-containing depos-
its, immersion tests were addi-
tionally carried out at 700 ˚C
(1290 ˚F) for 1000 hours in a
T = 750 °C
400 t = 1000 h molten sulphate bath consisting
53 mol-% Na2SO4 of 53 mol-% Na2SO4, 40 mol-%
40 mol-% MgSO4
7 mol-% CaSO4 MgSO4 and 7 mol-% CaSO4. The
metallographically determined
300
Corrosive attack, µm

depth of damage is plotted

in Fig. 44. Compared with the
alloys Nicrofer 7216 H – alloy
200 600 H, Nicrofer 6023 H – alloy
601 and Nicrofer 3220 – alloy
800 which were tested as well,
100 Nicrofer 6025 HT – alloy 602 CA
is clearly the best-performing
material, with a damage depth
of only 10 µm 38).
0
Nicrofer 6025 HT Nicrofer 7216 H Nicrofer 6023 H Nicrofer 3220 H
(602 CA) (600 H) (601 H) (800 H)

Fig. 44 – Comparsion of the corrosion resistance of variours materials in a eutectic molten sulphate bath
 Corrosion in complex 33

gas atmospheres

Municipal waste incineration

The flue gases from incineration

of municipal waste (MW) can
250 N2+9 % O2
vary widely in their composition +2.5 g/m3 HCl
and generally contain acidic +1.3 g/m3 SO2
gases such as HCl, H2S or sul- 0
t=1000 h
phur oxides and other corrosive Nicrofer 45 TM
species. High-nickel materials -250
Mass change, g/m2

are in fact unsuitable for this Nicrofer 6020 hMo (625)

application. The general level of -500
knowledge indicates that an Nicrofer 3228 NbCe (AC 66)
attempt should be made to use
-750
a material with the highest
possible chromium content. Nicrofer3220 H (800 H)
-1000
If silicon is added as well, it is
possible to design a material
which is also sufficiently resis- -1250
tant to carburization for it to be
suitable for an MW pyrolysis -1500
plant. This train of thought result- 550 650 750 850
ed in the new material Nicrofer Temperature, °C
45 TM – alloy 45 TM, which has
already been presented in Table 1.

The media selected for tests Fig. 45 – Mass change of the new alloy Nicrofer 45 TM – alloy 45 TM (2.4889) in an MW incineration atmosphere
included flue gas consisting of compared with other high-temperature alloys
nitrogen with 9 % O2, 2.5 g/m3
HCl and 1.3 g/m3 SO2. The test
results on alloy 45 TM are
promising. Fig. 45 illustrates
this material's outstanding corro-
sion resistance in flue gas from
MW incineration up to 850 ˚C 1000 N2+9 % O2
Nicrofer 6020 hMo (625)
Nicrofer 3220 H (800 H)

+2.5 g/m3 HCl

(156 ˚F), where as the other- +1.3 g/m3 SO2
wise versatile high-temperature
Nicrofer 3220 H (800 H)

t=1000 h
800
alloy Nicrofer 3220 H – alloy
Depth of damage, µm

800 H is no longer usable at

temperatures of over 650 ˚C 600
Nicrofer 6020 hMo (625)

(1200 ˚F) 38).

Nicrofer 45 TM
Nicrofer 6020 hMo (625)
Nicrofer 3220 H (800 H)

The nickel-base alloy Nicrofer 400

6020 hMo – alloy 625 performs
Nicrofer 45 TM

Nicrofer 45 TM

comparatively well. In fact, this

type of alloy is currently used 200
extensively in the USA for re-
pairing the waterwalls of MW
0
incineration plants; it is applied
650 750 850
to the corroded steam generator
tubes by overlay welding 39). Temperature, °C

Fig. 46 – Maximum depth of damage of the new alloy Nicrofer 45 TM – alloy 45 TM (2.4889) in an MW incineration atmosphere
compared with the high-temperature alloys Nicrofer 6020 hMo – alloy 625 (2.4856) and Nicrofer 3220 H – alloy 800 H (1.4958)
 34

0.6

Nicrofer 3127 hMo (31) Nicrofer 3220 H – alloy 800 H

20 µm
Corrosive attack, mm

0.4

0.2 Cronifer 2520 (310 SS)

Nicrofer 3220 H (800 H)
Nicrofer 45 TM
Nicrofer 6020 hMo (625)
Nicrofer 6219 Si (626 Si)

0 Nicrofer 6020 hMo – alloy 625

400 450 500 550 600 650 700 750 20 µm

Temperature, °C

Fig. 48 – Max. corrosive attack (internal corrosion and metal wastage) after ageing for 1008 hours in a waste incineration gas.
Gas: 2.5 g/m3 HCI, 1.3 g/m3 SO2, 9 % O2, N2, deposit: 1 mol Na2SO4, 0.01 mol KCI

These test results show that well as the change in mass, Because the operating condi-
Nicrofer 45 TM – alloy 45 TM is is shown in Fig. 46. Here too, tions of a MW incineration plant
markedly superior to Nicrofer the new alloy Nicrofer 45 TM – (MWIP) also lead to the forma- Nicrofer 45 TM – alloy 45 TM
6020 hMo – alloy 625 in terms alloy 45 TM proves its superiority tion of thick ash deposits in the 20 µm
of corrosion resistance. under such operating conditions, boiler zone, severe corrosion has Fig. 47 – Appearance of the alloys through
the light-optical microscope after cyclic
The depth of damage, which as confirmed by metallographic been reported. These conditions testing at 750 °C (1380 °F) for 1000 hours
should be considered as examinations (Fig. 47). have been simulated in labora- in a synthetic MW incineration gas

Material Alloy UNS Mat. no. Mass change Internal corrosion Metal wastage
des. (DIN) ∆m in g/m2 Ci in mm (A-B)/2
Average Specimen 1 Specimen 2 Specimen 1 Specimen 2
(4 specimens)

St 52-3 – – 1.0570 – – – – –
Cronifer 2520 310 SS S31008 1.4841 -1999 ± 537 0.31 0.29 0.38 0.35
Nicrofer 3220 H 800 H N08810 1.4958 -2556 ± 272 0.36 0.55 0.645 0.49
Nicrofer 3127 hMo 31 N08031 1.4562 -35,4 ± 3,6 0.055 0.05 0.005 0.005
Nicrofer 45 TM 45 TM N06045 2.4889 -312 ± 108 0.48 0.46 0.23 0.21
Nicrofer 6020 hMo 625 N06625 2.4856 -1,1 ± 1 0.03 0.09 0 0
Nicrofer 6219 Si 626 Si N06219 2.4855 – 0.025 0.030 – –
Gas: 2.5 g/m3 HCI/1.3 g/m3 SO2/9 % O2/N2 Salt: boiler ash, Iserlohn MWIP
Test duration: 1008 h Cycle: 24 h Temperature: 600 °C
Table 7– Results of high-temperature corrosion tests under MWIP ash
 35

tory tests. In these, the normal

MWIP atmosphere was estab-
lished, but the specimens were
additionally coated with ash from
the Iserlohn MWIP. The tests Cronifer 2520
were carried out at temperatures Nicrofer
(310 SS) Nicrofer
1 Nicrofer 3127 hMo
of 450 ˚C (840 ˚F), 600 ˚C 3220 H 45 TM (31)
(1110 ˚F) and 750 ˚C (1380 ˚F) St 52 (800 H)
Nicrofer
over a period of 40 days (1008 0.8 6020 hMo
(625)
hours). The metal wastage rate
Corrosive attack, mm

was calculated from the mass

losses and the internal corrosion 0.6
was determined by subsequent
metallographic examinations of
0.4
all the tested specimens.

Where as at 450 ˚C (840 ˚F) 0.2

the metal wastage for all the
materials is well below 0.05 mm Nicrofer 6219 Si (626 Si)
0
(except in the case of the
400 450 500 550 600 650 700 750
C-steel, which also exhibited
severe internal corrosion), Temperature, °C
the alloys Cronifer 2520 – alloy
310 SS, Nicrofer 3220 – alloy
800 and Nicrofer 45 TM – alloy
45 TM show substantially Fig. 49 – Max. corrosive attack (internal corrosion and metal wastage) after ageing for 1008 hours in a waste incineration gas.
increased losses at 600 ˚C Gas: 2.5 g/m3 HCI, 1.3 g/m3 SO2, 9 % O2, N2, deposit: boiler ash from the Iserlohn MWIP
(1110 ˚F) (Table 7). In contrast,
the chromium-rich alloy Nicrofer
3127 hMo – alloy 31 still per-
forms relatively well. The best
performance at this temperature,
however, is attained by the nickel
alloys Nicrofer 6020 hMo – alloy
625 and the newly developed H2S-containing gas
0.12 Ageing time: 2100 h Nicrofer 3220 H (800 H)
silicon-containing alloy Nicrofer Cronifer 2520 (310 SS)
6219 Si – alloy 626 Si. At 750 ˚C
(1380 ˚F), however, the condi-
Depth of corrosion, mm

tions become extremely corro- 0.09

AISI 446
sive, as is evidenced by the corre- Nicrofer 3220 LC (800 L)
sponding data for metal wastage
0.06 Nicrofer 5520 Co (617)
and internal corrosion. The alloys
Nicrofer 6020 hMo – alloy 625 Nicrofer 6030 (690)
and Nicrofer 6616 hMo – alloy Nicrofer 3228 NbCe (AC 66)

C-4 still perform well; here, the 0.03

latter was also tested as a mate- Nicrofer 45 TM

rial for wet-corrosion service on

account of its high Mo content. 0
200 400 600
In contrast to their action in the Temperature, °C
case of sulphate deposits,
chlorides clearly have a very
corrosive effect in conjunction
with fly ash. These results as a Fig.50 – Corrosive attack suffered by stainless steels and nickel alloys after ageing in the Krupp Koppers pilot
function of temperature are coal gasification plant in Fürstenhausen as a function of temperature
 36

clearly show in Figs. 48 and 49.

Besides the general (averaged)
metal wastage, the internal
corrosion is also considerable in
the case of some materials.
These results should always be
0 Nicrofer 3127 hMo (31) borne in mind when selecting
Cronifer 2520 (310 SS)
Nicrofer 3220 H (800 H) materials for actual service 38).
Nicrofer 45 TM
Specific mass change, g/m2

-200 Nicrofer 6020 hMo (625)

Coal gasification
Nicrofer 3228 NbCe (AC 66)
-400 Reducing, sulphur-containing
gases such as are encountered
-600 in coal gasification processes
are particularly damaging to
metallic materials. Extensive
-800 Nicrofer 5923 hMo (59) laboratory and field tests have
shown, however, that NiCrFe
-1000 alloys containing at least 25
0 200 400 600 800 1000 mass -% chromium withstand
coal gasification environments
Ageing time, h
well 18), 40). Additions of silicon
were found to additionally improve
resistance to sulphidation.
The field tests carried out in the
Fig.51 – Specific mass change after ageing in air under molten salt deposits (45 % Na2S, 21 % Na2CO3, 21 % Na2SO4, 13 % NaCl) PRENFLO pilot plant of Krupp
at 600 °C (1110 °F) Koppers in Fürstenhausen,
Germany, showed that
Nicrofer 45 TM – alloy 45 TM,
with 27 mass-% chromium and
2.7 mass -% silicon, had the
highest resistance of all the
alloys investigated 40). Fig. 50
shows the depths of corrosion
0 attack measured after 2000
Cronifer 2520 (310 SS)
Nicrofer 6020 hMo (625) hours of plant exposure in diffe-
Nicrofer 3127 hMo (31) rent locations and at various
Specific mass change, g/m2

-1000 Nicrofer 45 TM
temperatures.

-2000 Pulp and paper industry

High-temperature corrosion of
-3000 Nicrofer 3220 H (800 H) superheater tubes in the heat
recovery system is one of the
Nicrofer 5923 hMo (59)
-4000 main problems in the pulp and
paper industry. High tube wall
Nicrofer 3228 NbCe (AC 66) temperatures, deposits arising
-5000
from entrainment of black liquor,
550 600 650 700
and condensing-out of salts
Temperature, °C from the combustion gases lead
to formation of molten alkali
salts, which can cause severe
metal wastage and consequently
Fig.52 – Specific mass change after ageing for 1008 hours in air under molten salt deposits
rapid failure of heat-resistant
(45 % Na2S, 21 % Na2CO3, 21 % Na2SO4, 13 % NaCl) as a function of temperature stainless steels at temperatures
 37

of 550 ˚C (1020 ˚F) and above.

These deposits are very complex
and consist mainly of sodium
sulphate and sodium carbonate
with small amounts of sodium
and potassium chloride, potas- 1200 v = 0.23 m/s
Gas: 2.5 g/m3 HCI
sium carbonate and vanadium 1.3 g/m3 SO2
pentoxide. 1000 9 % O2/N2

Tests with seven commercial Nicrofer 3220 H (800 H)

800
iron- and nickel-base alloys 38) in
Metal loss, g/m2

a molten alkali simulating such

conditions at 550 – 650 ˚C 600
Nicrofer 3228 NbCe (AC 66)
(1020 – 1200 ˚F) showed that
all the materials suffer general 400
Cronifer 2520 (310 SS)
corrosion (Fig. 51), but several
others additionally exhibit Nicrofer
200 45 TM
marked internal sulphidation.
Nicrofer
6020 hMo (625)
The results (Fig. 52) can be 0
600 650 700 750 800 850 900
interpreted as indicating that
Nicrofer 3220 H – alloy 800 H, Temperature, °C
Nicrofer 3228 Ce – alloy AC 66
and Nicrofer 6616 Mo – alloy
C-4 are very vulnerable to
molten alkali salts. The silicon- Fig.53 – Metal losses of materials rotated for 1008 hours in an erosive mass of particles in the presence of a synthetic MWIP gas,
containing alloys Cronifer 2520 – as a function of temperature
alloy 310 SS and Nicrofer 45 TM –
alloy 45 TM, but also Nicrofer
3127 hMo – alloy 31 and Nicrofer
6020 hMo – alloy 625, performed
significantly better. However,
the subsequent metallographic
examinations revealed marked 1400
internal sulphidation in the case
Nicrofer 3220 H (800 H)
of Cronifer 2520 – alloy 310 SS, 1200
Nicrofer 3127 hMo – alloy 31 and
Nicrofer 6020 hMo – alloy 625. 1000
The recently developed Krupp VDM
Metal loss, g/m2

alloy Nicrofer 45 TM – alloy 45 TM 800

Nicrofer 3228 NbCe (AC 66)
performed best of all, with mini-
mal to no internal sulphidation. 600

Nicrofer 6020 hMo (625)

Behaviour with regard 400
to abrasion and corrosion Cronifer 2520 (310 SS)
200
Nicrofer 45 TM
Rotary kilns and pyrolysis plants
in particular are subjected to 0
combined attack by corrosion 0 0.1 0.2 0.3 0.4 0.5
and erosion. Here, abrasive Velocity, m/s
particles can have a marked in-
fluence on corrosion behaviour.
Fig. 53 shows the metal losses
suffered by various materials in
a synthetic MW incineration envi- Fig.54 – As Fig. 53, but as a function of the relative velocity between particles and specimen
 38

ronment as a function of tempe-

rature. The iron-based materials
have high wastage rates with a
maximum at 75 ˚C (138 ˚F),
while the nickel-base alloys
2400 Specimen velocity
Nicrofer 45 TM – alloy 45 TM and
0 m/h
Nicrofer 6020 hMo – alloy 625
880 m/h
2000 performed best 38).
Mass loss after ageing for 1,000 h, g/m2

1660 m/h

1600 Fig. 54 illustrates the relation-

ship between metal wastage and
1200 the relative velocity of the parti-
cles on alloy specimens at 750 ˚C
800
(1380 ˚F). The results demon-
strate that the resistance to
erosion corrosion arises predom-
400
inantly from the material’s
corrosion resistance in the
0 medium in question, which
Nicrofer Nicrofer Nicrofer Cronifer Nicrofer
45 TM 3220 H 6020 hMo 2520 3228 NbCe
explains the good performance
-400 (800 H) (625) (310 SS) (AC 66) of the chlorine-gas-resistant
alloys Nicrofer 45 TM – alloy 45
TM and Nicrofer 6020 hMo –
alloy 625 in the synthetic MWIP
gas. Although Nicrofer 3220 H –
Fig.55 – Mass loss of some high-temperature materials after ageing for 1000 hours in an MW incineration plant alloy 800 H generally exhibits
(2.5 g/m3 HCI, 1.3 g/m3 SO2, 9 % O2, N2) at various specimen and particle velocities good resistance to erosion
according to the relevant litera-
ture, this material suffers high
mass losses. This shows that
materials for thermal treatment
plants should be selected
chiefly according to the criteria
40 500 h
of corrosion resistance, even in
700 h cases where erosion corrosion
35 1000 h is expected to occur. Corrosion
tests under simultaneous abra-
Specific mass change, g/m2

30 sive conditions have been car-

ried out in a simulated MWIP
25
atmosphere. Fine sand 0.5 mm
20 in size, in which the specimens
were immersed while rotating,
15 was used as abrasive. The results
in Fig. 55 reveal that the chro-
10
miumrich, silicon-containing alloy
5 Nicrofer 45 TM – alloy 45 TM,
and also Nicrofer 6020 hMo –
0 alloy 625, perform-ed very well 38).
Nicrofer Nicrofer Nicrofer Nicrofer Nicrofer
6025 HT 3220 H 7216 H 6030 45 TM
(602 CA) (800 H) (600 H) (690) In tests of scaling in air under
simultaneous abrasive condi-
tions, the new high-temperature
alloy Nicrofer 6025 HT – alloy
Fig.56 – Corrosion behaviour of some high-temperature materials under combined high-temperature corrosion
602 CA exhibits the lowest spe-
and abrasion at 1000 °C (1830 °F) and a specimen or particle velocity of 830 m/h cific mass losses (Fig. 56).
 Workability
Joining techniques
The most commonly used tech-
nique for joining high-tempera-
ture materials in industrial
engineering is welding. Solder-
ing as well as bolted, plug-and-
socket or clamping joints, are
only used as joining means in
special cases.
Welding
The material development work the following requirements:
of the preceding decades was
strictly dominated by the appli-
cation-related material proper-
ties like heat resistance, creep
strength, oxidation resistance
and hot-gas corrosion resist-
ance. The development of join-
ing techniques, and especially
of welding, the most important
method of joining, often occurred
separately and with a time lag.
This often resulted in dramatic-
ally increased material costs
later on, since unpredictable and
uncontrollable metallurgical
reactions led to severe cracking
during welding. Despite many
difficulties, welding is and will
remain the most important join-
ing method in industrial engineer-
ing. Welding enables large struc- less favourable properties than
tural components to be fabri-
cated at low cost without
additional weight or significant
reductions in the service charac- When welding nickel alloys,
teristics. As soldering and bra-
zing are of little importance in
industrial engineering, the reader • The low thermal conductivity
is referred to the relevant
literature 41) + 42).
39
In welding of nickel alloys for Straight butt weld Sheet thickness up to 2.5 mm
industrial engineering, preserva-
tion of the heat resistance, creep
rupture strength and corrosion 60 – 70° Sheet/plate thick-
resistance is of course the most Single-V weld ness 2.0 – 15 mm
important requirement. For this
reason, the well-known principle 1.5 – 3.0 mm 0.5 – 3.0 mm
that welding should be perform-
ed with at least a similar filler
metal applies here as well. Plate thickness
Single-U weld 15° 12 – 25 mm
The filler metal used to join two
R=6
dissimilar materials should meet
1.0 – 3.0 mm 1.5 mm
• High solubility for elements
such as iron, nickel and chro-
mium, while avoiding the forma- 60 – 70° Plate thickness
Double-V weld 16 – 25 mm
tion of alloys susceptible to
brittle fracture or cracking (for-
mation of intermetallic phases, 2 mm
extensive carbon diffusion).
• The coefficient of thermal 1 – 3 mm
expansion should lie between
those of the alloys to be joined.
• The corrosion resistance, Double-U weld 15°
strength and ductility should
at least be equal to those of R=6 2 mm
the weakest alloy in the joint.
It would of course be desirable 1 – 3 mm
to use filler metals whose prop- Fig.57 – Edge preparation for welding of nickel and
erties are at least equivalent to nickel alloys 43)
the higher alloy in the joint, as
the cast state in which the filler
metal is available often exhibits
the wrought alloy of the same
composition.
special attention should be paid
to the following points:
and higher thermal expansion
of these materials compared
with carbon steel.
• The danger of porosity forma-
tion in the weld metal due to
pick-up of oxygen and nitrogen.
• The effect of welding heat on
precipitation characteristics.
• Risk of hot cracking due to sul-
phur pick-up.
 40

All these points are taken into
account in the following instruc-
tions for welding work:
• Nickel alloys are welded in the
soft-annealed or the solution-
heat-treated condition depend-
ing on the service tempera-
ture.
• Mill scale should be removed
by sand-blasting, pickling
or grinding before welding.
• The sidewalls of the joint and
the top side and underside of
the sheet or plate should be
clean, i.e. free from grease,
colour markings and traces of
paint, up to at least 25 mm
from the edge of the weld.
Cleaning should be carried out
with sulphur- and chloride-free
agents.
• The edges should be prepared
as shown in Fig. 57.
• Porosity-inducing gases must volume of the weld pool and the
be kept away at all costs (gas- resulting low rate of cooling, as
shielded welding, active gas well as the metallurgical influence
welding, deoxidizing electrode of the powder composition. Alt-
coatings, prevention of moisture hough gas welding is feasible in
pick-up by electrodes). principle, it is rarely employed
• Reaction of the weld pool with nowadays. Plasma arc and active
oxidizing gas constituents gas welding are increasingly
should also be avoided, as the being used for special applica-
resulting selective burn-off of tions. Shielded metal arc (SMAW),
the elements with an especially gas metal-arc (GMAW) and gas
high affinity for oxygen can tungsten-arc (GTAW) are the
lead to permanent impairment most widely used processes.
of the oxidation and corrosion Brief information on these is
resistance of the weld. given in Table 8 44) + 45).
• Appropriate welding processes
and recommended filler metals
are shown in Table 8.
• Any tarnish discoloration
should be removed after
welding.
In general, resistance, shielded
metal arc and inert-gas welding
give very good results, while
submerged arc welding can only
be used in certain circumstances
owing to the relatively large

Base metal Alloy des. UNS Mat. no. (DIN) Welding process Filler metal

Nicrofer 3718 330 N08330 1.4864 SMAW, GTAW, GMAW Nicrofer S 7020 (2.4806)
Nicrofer 6030 690 N06690 2.4642 GTAW Nicrofer S 6030 (2.4642)
Nicrofer 3220 H 800 H N08810 1.4958 SMAW, GTAW, GMAW Nicrofer S 7020 (2.4806)
Nicrofer 3220 HT 800 HP N08811 1.4959 SMAW, GTAW, GMAW, SA Nicrofer S 5520 (2.4627)
Nicrofer 3228 NbCe AC 66 N33228 1.4877 SMAW, GTAW, GMAW Nicrofer S 6020 (2.4831)
Nicrofer 45 TM 45 TM N06045 2.4889 SMAW, GTAW, Plasma Nicrofer S 3028 (1.4563)
Nicrofer 6023 H 601 H N06601 2.4851 SMAW, GTAW, GMAW Nicrofer S 6025 (2.4649)
Nicrofer 7216 H 600 H N06600 2.4816 SMAW, GTAW, GMAW Nicrofer S 7020 (2.4806)
Nicrofer S 4722 (2.4613)
Nicrofer 4722 Co X N06002 2.4665 SMAW, GTAW, GMAW
Nicrofer S 5520 (2.4627)
Nicrofer 5520 Co 617 N06617 2.4663 SMAW, GTAW, GMAW Nicrofer S 5520 (2.4627)
Nicrofer 6025 HT 602 CA N06025 2.4633 SMAW, GTAW, Plasma, SA, MAG Nicrofer S 6025 (2.4649)
Nicrofer 6219 Si 626 Si N06219 2.4855 SMAW, GTAW, GMAW, SA Nicrofer S 6219 (2.4832)
SMAW: shielded metal arc welding GTAW: gas tungsten-arc welding GMAW: gas metal-arc welding
Plasma: tungsten plasma arc SA: submerged arc MAG: metal active gas welding
Table 8 – Welding processes and recommended filler metals for some typical industrial engineering materials
 41

Application engineering of almost 20 % in the strength of

qualities of the welded joint the welded joints compared with
the base metal over the tempe-
To ensure the safe, reliable oper- rature range investigated should
ation of the plant, the welded be expected (Fig. 60).
joint should have application
engineering qualities comparable Similar results were established
to those of the parent metal. on additional specimens made
This is true for all the critical by the welding processes GMAW,
regions of a weld: the weld MAG, MMA and submerged arc
metal, the interfacial area and welding. Bending tests across the
the heat-affected zone. Whereas capping and root passes attain-
in the case of materials for ed at least 160˚ in all cases.
wet-corrosion service all that is The tensile tests, too, did not
required is an adequate corro- show any reduced quality of the
sion behaviour compared with welded joint compared with the
the base metal, in the case of base metal; the strengths and
high-temperature materials the elongation are comparable with
heat resistance and elongation those of the base metal.
at fracture should also be com-
parable with those of the base Results of tests of the corrosion
metal 46). resistance of the welded joint
did not show any reduction com-
In the following paragraphs, pared with the base metal,
some data for the alloy Nicrofer as demonstrated, for example,
6025 HT – alloy 602 CA deter- for the oxidation resistance
mined from welded specimens (Fig. 61). The three micrographs
are given and compared with show specimens tested in air
the unwelded base metal. at 1000 ˚C (1830 ˚F), 1100 ˚C
(2010 ˚F) and 1200 ˚C (2190 ˚F)
The GTA weld is free from poro- for a period of 1008 hours.
sity and hot cracks, and has an The weld metal can be seen in
adequate reinforcement of the the left half of the photos.
capping pass and a drop-through
in the root area (Fig. 58). It should be noted, however, that
The bending tests across both welds made by submerged arc
root and capping passes were welding have a somewhat poorer
crack-free up to 180˚. cyclic oxidation resistance than
the base metal, due to marked
The results of tensile testing of aluminium depletion in the weld
the GTA-welded specimen at metal. This is illustrated, for
room temperature correspond example, in Fig. 62 for oxidation
to those for the base metal tests at 1100 ˚C (2010 ˚F) and
(Table 9), with the fracture loca- 1200 ˚C (2190 ˚F) 46).
tions solely in the base metal.
Note: For GTAW welding of
The mechanical properties of the alloy 602 CA the recommended
welded joint, which were deter- shielding gas is Ar + 2 % N2 to
mined up to 1200 ˚C (2190 ˚F), prevent any hot cracks.
actually tend to be somewhat
better than those of the parent
metal (Fig. 59).

With regard to the creep rupture

strength, however, a reduction
 42

300

R Nicrofer 6025 HT (602 CA)

m (GTA-welded with matching filler)

200 Rp 0.2
Rm, Rp 0,2, N/mm2

Nicrofer 6025 HT (602 CA)

(Base metal)

100

0
800 900 1000 1100 1200

Testing temperature, °C

1000 µm
Fig. 58 – Section through a multi-pass GTA- Fig.59 – High-temperature rupture and yield strength of Nicrofer 6025 HT – alloy 602 CA, GTA-CW-welded with matching filler
welded joint of the alloy Nicrofer 6025 HT –
alloy 602 CA

Type of weld Rp 0.2 Rm A5 Fracture

N/mm2 N/mm2 % location

490 761 31 BM
GTAW-CW 486 752 33 BM
486 750 27 BM
492 630 16 WM
GTAW-HW
488 721 21 WM
458 762 32 BM
SMAW 449 750 31 BM
469 761 32 BM
372 787 34 BM
GMAW 354 786 34 BM
361 786 34 BM
– 735 – BM
MAG
– 741 – BM
430 775 28.5 WM
SA 378 758 30.5 BM
418 – 25.0 WM
BM: base metal WM: weld metal
Table 9 – Results of tensile tests at room temperature

Working and heat treatment
Like stainless steel, nickel-base
alloys can be cold-worked by
rolling, spinning, deep-drawing
and bending.
The outstanding ductility of
nickel-base alloys enables high
degrees of deformation to be
attained without interstage
annealing. Excessive cold de-
formation can lead, however,
to irreversible microstructural
and surface damage. If there
is a risk of this happening, more
frequent interstage annealing or
hot forming should be carried
out. Surface damage should be
removed by grinding or polish-
ing, provided that it has not
yet affected a significant propor-
tion of the component's cross-
section.
It is important to ensure that the
materials are clean and free from
contaminants of any kind (oil,
grease, sulphur compounds,
dirt etc.) before and during heat
treatment. Phosphorus, lead,
copper and other low-melting
metals can lead to damage
during heat treatment of the
materials. Sources of such con-
taminants also include marking
and temperature-indicating
paints and crayons, lubricating
grease, oils, fuels and the like.
Fuels should have the lowest
T = 1000 °C
Fig.61 – Cyclic oxidation behaviour of base metal, HAZ and weld metal of the joint made by GTA-CW-welding with matching filler
43
30
25
Creep rupture strength Rm/104, N/mm2
20
Nicrofer 6025 HT (602 CA)
15 (Base metal)
-18 %
10
Nicrofer 6025 HT (602 CA)
(GTA-welded with matching filler)
-16 %
5
-18 %
-16 %
800 900 1000 1100 1200
Temperature, °C
Fig.60 – Comparison of the creep rupture strengths of the base metal and the GTA-CW-welded joint
possible sulphur content. Natural pieces, they should be placed in
gas should contain less than Hot forming the furnace at temperature,
0.1 mass -% sulphur. Fuel oil con- except when heating a large
taining no more than 0.5 mass-% Hot forming of most high-tem- cast ingot. In this case a special
sulphur is also suitable. The fur- perature materials is carried out heat-up cycle is recommended
nace atmosphere should be neu- in the temperature range 1200 – to prevent thermal stress cracks.
tral to slightly oxidizing and must 900 ˚C (2190 – 1650 ˚F), follow-
not fluctuate between oxidizing ed by rapid cooling in water
and reducing. The workpiece or air. Heat treatment is recom-
must not come in direct contact mended after hot forming in
with the flames. order to establish optimum
properties. To heat up the work-
100 µm T = 1100 °C 100 µm T = 1200 °C 100 µm
 44

herent than those of stainless

steels. Polishing with very fine
abrasive belts or wheels is
recommended.

0.2 Base GTAW-CW/GTAW- SMAW-arc Submerged-arc

If pickling is required, pickling
metal HW-arc welding welding welding with times should be kept short; this
UTP 6225 Al FX 50-11 applies to all high-temperature
±0 alloys. Before pickling in mixed
nitric/hydrofluoric acid, it is
necessary to pretreat the oxide
-0.2
Corrosion rate, mm/a

films by abrasive blasting,

polishing, or in a molten salt
-0.4 bath. As hot-forming and heat-
treatment temperatures are
different for every material, the
-0.6 appropriate Krupp VDM material
data sheet should always be
-0.2 consulted.

1100 °C Machinability
-1.0 1200 °C
Machining of parts made of
nickel-base alloys is an impor-
tant process in the manufacture
of components and sub-assem-
Fig. 62 – Comparison of the cyclic oxidation resistance of various types of welds compared with the base
blies.
metal Nicrofer 6025 HT – alloy 602 CA

Cold working Heat treatment For example, 90 % of the overall

cost of turbine blades is accoun-
Most high-temperature, high- Solution heat treatment is gener- ted for by the cost of machining.
strength materials have a higher ally carried out at 1100 – 1200 ˚C For furnace components, the
strain-hardening rate than (2010 – 2190 ˚F). For optimum corresponding percentage is far
austenitic stainless steels; this creep rupture strengths, acceler- lower, and can fall to as low as
should be taken into account ated cooling with water should 10 % for geometrically simple
when selecting the working para- be carried out. Below approx. components due to the use of
meters. The work should be in 3 mm thickness, rapid air cooling large sheets or plates.
the solution-heat-treated condi- is also practicable. Pre-oxidation
tion. Interstage annealing is in air or the use of materials which The fact that nickel-base alloys
necessary if extensive cold-work- are already pre-oxidized on are harder to machine than steel
ing operations are carried out. delivery can produce markedly is an inherent material charac-
If the degree of deformation in increased corrosion resistance. teristic possessed particularly
cold working exceeds 10 %, a In every heat treatment opera- by alloys with high strength at
repeat solution heat treatment tion, the cleanliness requirements elevated temperatures.
should be performed. stated above should be met. With nickel-base alloys, cutting
speeds and tool lives, for exam-
Descaling ple, are five to ten times lower
than those achieved with steel
High-temperature alloys form (Fig. 63).
protective oxide films in service.
The necessity of descaling
should therefore be checked.
Oxides of most high-tempera-
ture, high-strength and heat-
resistant alloys are more ad-
 45

S
321 S
45

40

35

H
7P
17-
ys
allo 30
a se
a lt - b Iro
C ob n -b
a se
a ll

oy
s
5
alloy

15
N
25

6
28
A
allo
y1

TD
N
88

i
MA
R

X-
M

TD N 40
30

iCr (H
S
2

31
) A
-1 0
AF 2
WASPALLOY
RENÉ 77
RENÉ 63
RENÉ
) REN 80
alloy 722 (W R É1
RE ENÉ 00
NÉ 41
85
RE IM

706
U D D IM E

alloy
NÉ ET 7

01
95 00

y6
U
SEL 1

allo
SEL

0
60
T
M 252

oy
18

(A
25

500

all
901
X

ST
y7
6
y
lo

RO
oy
al

a llo

alloy
all

LO
Y)

Nickel-base alloys

Fig.63 – Machining rates of superalloys and reference materials. The index 100 refers to a life of 30 min (≅ 0.381 mm metal removal)
of the carbide cutting tool for a distance of 244 m/min for B 1112 47)
46

The normal machining opera-

Process Metal removal rate, cm3/min tions are:
• Turning
Turning 250 • Straightening
Milling 250 and bending
• Spot-drilling increasing
Grinding 200
• Shaping difficulty of
Electrochemical machining and milling machining
(ECM) 216
• Drilling
Electrical discharge machining • Thread cutting
(EDM) 221.6
• Broaching
Laser beam machining
(LBM) 220.005 The normal rates of metal remo-
Table 10 – Typical removal rates for conventional and special machining processes
val with conventional processes
range from 50 to 200 cm3/min.
Table 10 lists typical metal remo-
val rates for conventional and
special machining processes.

For successful machining of

nickel-base alloys, the following
points should be observed:
• Maximum rigidity of tool and
workpiece and constantly
sharp tools (smooth surface
and sharp edges) are required
to ensure a clean cut.
• To support the cutting edge,
the lip angle should not be
larger than necessary.
• Leave as much material as
possible on the lip of roughing
tools.
• Supply plenty of cutting fluid
(sulphur-free).
• Use a much lower cutting
speed than with steels; the
depth of cut should be larger
rather than too small in order
to prevent strain hardening.
• Provide as much space as
possible for swarf removal for
cutting and machining tools.

Details of tools, machining para-

meters, etc. are given in the
brochure “Working Instructions
for High-Alloyed Austenitic
Steels and Nickel-Base Alloys” 48),
which is available from Krupp
VDM's Technical Marketing or
Application Engineering depart-
ment on request.
 Mechanical design
of components for
high-temperature service
When designing components for
high-temperature service, many
design engineers feel uneasy.
At room temperature or mode-
rate temperatures, generally
fixed material behaviour over
time can be expected; at high
temperatures, however, time-
dependent creep deformation
and/or fatigue loading has to
be taken into account as well.
Fig. 64 – Schematic depiction of the procedure for designing components exposed to high temperatures
Fig. 64 shows, in schematic form,
the individual stages in the pro-
cess of designing a component
for high-temperature service 49).
When the design drawing has
been produced and the acting
forces and the operating tem-
perature and time have been
specified, the applicable load
case has to be defined, i.e. it
has to be clarified whether the
component should be designed
on the basis of:
• Short-time strength
• Long-time strength
• Buckling strength
• Fatigue strength.
47
Design drawing,
service conditions (T, t),
Standards, codes,
specifications etc.
Load case
Max. load,
load-bearing capacity
Operational safety
•safety with regard to loading
•safety with regard to temperature
•safety with regard to time
The decision as to whether the There are similar diagrams for
design calculation should be rupture strength in the case of no
based on short-time or long-time creep-design-specific limits or if,
values can be made on the basis for corrosion-related reasons,
of diagrams, as shown, for the plastic strain of the pro-
example, in Fig. 3 for Nicrofer tective film does not need to be
6025 HT – alloy 602 CA. It can considered.
be clearly seen that the range of
acceptable stress extends in the
direction of lower stresses as the
exposure time increases from
Rp 1,0 to Rp 1,0/100,000. The point
where the long-time strength
and short-time strength curves
intersect indicates the threshold
temperature above which it is
necessary to use the materials'
long-time strength data for the
design calculation. In the present
case, the threshold temperature
is approx. 600 ˚C (1110 ˚F).
48

In equation 4, is the resulting stress, MB is the bending moment and

W is the section modulus.

This calculation therefore also incorporates the load distribution

and the clamping. For example, for a beam supported at both ends
with symmetrical loading, the maximum bending moment can be
calculated according to equation 5:
1
M = MBmax. = · F· I eq. 5
2
In equation 5, F is the force and I the length of the beam.

The geometry of the component is taken into account by means of

For designing components which require monitoring, the following the section modulus. For a thin-walled tube, for example, the sec-
safety factors also have to be applied 49): tion modulus is calculated according to eq. 6:
Short-time strength: Rp Rpl
s s I
W= s~π·s·r eq. 6
2
with safety factor s = 1.5
r+
Rm 2
s
with safety factor s = 3.5 for In equation 6, s is the wall thickness and r the radius of the tube.
untreated and welded parts
Long-time strength: Rpl/t The optimization of components to withstand high section moduli
s or moments of inertia may lead, in individual cases, to additional
with safety factor s = 1.0 buckling conditions. Buckling should always be taken into account
Rm/t in the design if, for slender components with thin walls, equations
s 7 – 8 apply:
with safety factor s = 1.5 σK > σB eq. 7
σK > σmax. eq. 8
The component may then only be designed according to the lowest
load determined in accordance with the above criteria in each
where σB = limiting stress and σmax. = maximum actual stress. For
case, i.e. the most conservative value.
elastic buckling, the buckling stress is calculated according to the
For calculating the linear-stressed state, for example, equations Euler buckling formula (equation 9) 50):
1 and 2 are generally used 50):
σγ = F · cos γ/s` = σ · cos2 γ eq. 1 F = σ2 · E · l/s2 eq. 9

1 From this, the buckling stress is derived as the Euler hyperbola

τγ = F · sin γ/s` =· σ · sin2 γ eq. 2
2 according to equation 10 50):
σγ and τγ are the normal and shear stresses acting at an angle γ to
the vertical. F σ2 · E · l/s σ2 · E eq.10
σK = = =
For calculating the safety factor (V) in eq. 3 A A2 λ2

limiting stress σB In equations 9 and 10, F denotes the force, E the modulus of elas-
V= = >1.0 eq. 3
maximum actual stress σmax. ticity, I the moment of inertia, s the straight buckling length and A
the area.
the respective valid and accurate creep rupture strength Rm/t is
used for the limiting stress, in order to take sufficient account of The boundary value shown in Fig. 65, which divides the anelastic
the time-dependent strength behaviour of the high-temperature from the elastic region, is, for steel and for nickel alloys:
alloys.
For designing components to withstand bending, as at room tem- λ0 (steel) = π · 215,000/230 ~ 96
perature or moderately high temperatures equation 4 can be used λ0 (nickel alloy) = π · 207,000/350 ~ 76
as the basis for calculation:
The significantly lower λ0 value for nickel-base alloys means that
M they can withstand markedly higher buckling stresses before the
σ= B eq. 4
W boundary between elastic and plastic strain is reached.
 49

500

400
σk, N/mm2

300
σαP
Buckling stress

200

100

λ0
0
0 25 50 75 100 125 150 175 200

anelastic elastic region

Slenderness ratio λ

Fig.65 – Euler hyperbola

Besides stationary components,
rotating components, e.g. fur-
nace rollers or rotary kilns,
often have to be mechanically
designed. These components
too are designed almost exclu-
sively on the basis of creep
rupture strength, since either no
material- and loading-specific
fatigue strength data are avail-
able or a conservative design is
considered necessary in case of
an unintended roller standstill at
the service temperature. If the
process ensures that roller stand-
still cannot occur or is at least
limited to a few minutes, it is
possible to base the calculation
on a substantially higher fatigue
strength σW. Fig. 8 shows a
comparison of the creep rupture
strength and the fatigue strength
of the alloy Nicrofer 6025 HT –
alloy 602 CA at 1100 ˚C (2010 ˚F)
for the limiting ultimate number
of cycles n = 1 · 106 cycles in the
frequency range 0.3 – 3.0 Hz.
Often, operating conditions, and
particularly the temperature, are
not homogeneous enough for
the calculation to be based on
a uniform temperature or load
distribution. Designing a compo-
nent for the maximum likely tem-
peratures or loads would lead to
uneconomic over-dimensioning
of the component and make it
very bulky.
Here, the damage accumulation
hypothesis of Robinson 51) and
Taira 52), for example provides a
remedy. This proceeds from the
simple assumption that the
damage between the onset of
the stress and acceptable compo-
nent deformation or component
failure proceeds linearly and
failure will occur when the dam-
age totals D = 1. Figs. 66 and 67
show the calculation of the life of
a component according to the
life-fraction rule of Robinson and
Taira 49) for a material bearing a
stress of 30 N/mm2 in the tem-
perature range 800 – 950 ˚C
(1470 – 1740 ˚F).
 50

1000

Operating temperature, °C
Temperature universe
5 900
°C
550
2
800
600
102
650
700
5
σ oper. 700 101 102 2•101 5•102
Stress, N/mm2

750 Operating time toper. in h Σ = 630 h

2
800
i T(°C) toper.i tmi Di=toper.i/tmi
101
850 1 950 101 5·101 0.2
5 2 900 2·101 5·102 0.1
900
3 850 5·102 1.5·103 0.3
4 800 102 104 0.01
2 950
D 1
tmi tmax. = = = 1.64 ∑ Di = 0.61
∑ Di 0.61
1 The temperature profile can be withstood 1.64 times
100 101 102 103 104 105 106 n
∑ t oper.i
Time, h i = 1 t mi = D (Total damage) D = 1 according to Robinson, Taira

Fig.66 – Demonstration of service life based on an assumed temperature universe and the creep rupture curves of Nicrofer 6023 H – alloy 601 H
for the temperature range 550 – 950 °C (1020 – 1740 °F)49)

Operating time: 10,000 h Operating time: 100,000 h

180 180

160 Rp1/10000 Rm/10000 160

1.5 Rm
Rm
3.5 Rp1/100000 Rm/100000
140 3.5 140
1.5
Rp 0.2
120 Rp 0.2 120
1.5
1.5
Stress, N/mm2

Stress, N/mm2

100 100

80 80

60 Range of 60 Range of
permissible permissible
stress stress
40 40

20 20
550 °C 510 °C

0 0
0 200 400 600 800 1000 0 200 400 600 800 1000

Temperature, °C Temperature, °C

Fig.67 – Permissible stress for equipment requiring supervision, constructed of Nicrofer 7216 H – alloy 600 H 49)
 Standards, codes
and specifications
The following standards, codes
and specifications are of course
only a selection from the large
range of literature available.
Each individual case should be
examined separately to determi-
ne which standards, codes, spe-
cifications and test certificates
are applicable.
TÜVIS Principles for Testing
of Steam Boilers, Vol. 1, Posi-
tion after the 56th revision,
Dec. 1994
– Part-collection A: Regulations
– Part-collection B: Structure
and Application (TRD 001)
– Part-collection B2: Overview of
the AD rules
– Part-collection E: Strength
calculations (TRD 300 – 320),
e.g. for TRD 300 with AD
information sheets B0 – B13,
N1 – N4 and S1 – S3/4
TÜVIS Principles for Testing
of Pressure Vessels, Vol. 2,
edition of July 1980 in the
version of February 1989
– TRD 100: Materials with AD
information sheets W0 – W13
and N1 – N4
TÜVIS Principles for Testing of
Compressed-Gas Installations,
Vol. 1, Position after the 46th
revision, August 1994
– TG - Technical Principles
– Decisions of the German
Compressed Gas Committee
– Decisions of the German
Pressure Vessel Committee
– VdTÜV information sheets
DIN standards (general)
– e.g. Nicrofer 3220 H – alloy
800 H:
17 460 (sheet, plate, rod, bar)
17 459 (tube and pipe)
– or Nicrofer 6023 H – alloy 601 H:
17 742/17 750 (sheet and plate)
17 742/17 751 (tube and pipe)
17 742/17 752 (rod and bar)
51
The DIN standards comprise the
material analysis, mechanical
properties, heat treatment,
welding filler metals and condi-
tions for testing.
DIN standards (specific)
e.g. DIN 65236 for wire and steel,
nickel and cobalt alloys for the
aerospace industry (technical
delivery conditions).
Specifications of national
approval organizations
– e.g. Stoomwezen
(Netherlands), ANC (Italy)
Classification societies
– e.g. Germanischer Lloyd,
Lloyds Reg. of Shipping,
Norske Veritas
Client specifications
Common in e.g. the aerospace
industry (Rolls Royce, MTU)
Iron and steel catalogue / test
specifications / material data
sheets
– Analyses related to the
German (DIN) material number
Key to steels
Non-binding analyses according
to the DIN material number.
At the present time, high-tempe-
rature materials are not governed
by separate standards or specific
codes and specifications. The
design engineer should therefore
endeavour to obtain appropriate
standard data applicable to the
specific application or material.
 52 Applications of high temperature,
high strength materials
in industrial engineering

Fig. 68 – Radiant tubes for enamelling furnaces made of Nicrofer 6023 H – alloy 601 H Fig. 69 – Flame hoods made of Nicrofer 3220 H – alloy 800 H for flaring of natural gas

Owing to the diversity of available Oxidation Sulphidation Corrosion by molten glass

applications, only a brief out-
line of existing fields of applica-
tion can be given. Equipment
and components are classified
according to the corrosion me-
dium, where this could be pre-
sented in this way to simplify
matters: 44), 53) – 56).
– Heat exchangers for heating
steel (T = 1200 ˚C [2190 ˚F])
– Ceramic firing kilns and
kiln internals (T < 1200 ˚C
[2190 ˚F])
– Radiant tubes (T < 1100 ˚C
[2010 ˚F])
– Kiln and furnace internals
such as furnace rollers,
hangers, mountings, flanges,
transport rails (T < 1100 ˚C
[2010 ˚F])
Carburization
– Furnace components for
gas carburizing (T < 1100 ˚C
[2010 ˚F])
– Carbon regeneration
(T < 1000 ˚C [1830 ˚F])
– Pyrolysis tubes in ethylene
crackers (T < 1150 ˚C [2100 ˚F])
– Heat exchangers in coal
gasification and combustion
plants (T < 900 ˚C [1650 ˚F])
– Methanol plants (T < 900 ˚C
[1650 ˚F])
– Steam reformers (T < 1000 ˚C
[1830 ˚F])
– Heat exchangers in petroleum – Melting vessels and spinners
coal calcining plants (T < 900˚C in fibreglass production
[1650 ˚F]) (T < 1000 ˚C [1830 ˚F])
– Internals in gas-fired furnaces – Melting vessels and tools for
– Heat exchangers in combus- vitrification of radioactive
tion gases waste (T < 1200 ˚C [2190 ˚F])
– Glass melting furnace
Corrosion due to combustion accessories (T < 1000 ˚C
gases (salts, sulphur, halides) [1830 ˚F])
– Heat exchangers in aluminium
melting furnaces (T < 1000 ˚C
[1830 ˚F])
– Heat exchangers in fibreglass
production (T < 1200 ˚C
[2190 ˚F])
– Heat exchanger and super-
heater tubes in MW incinera-
tion plants (T < 900 ˚C
[1650 ˚F])
– Furnace internals in MW pyro-
lysis plants (T < 800˚C [1470˚F])
– Internals and superheater
tubes in the pulp and paper
industry (T < 900 ˚C [1650 ˚F])
– Heat exchanger and super-
heater tubes for coal gasifica-
tion and combustion plants
(T < 900 ˚C [1650 ˚F])
 53

Fig. 70 – Bell-type furnace for bright annealing of wire Fig. 71 – Controlled-atmosphere annealing furnace for fine-gauge wire

Nitridation Halogenation We are regrettably unable to Flame hoods

– Ammonia cracking plants
(T < 500 ˚C [930 ˚F])
– Heat treatment baths
(sodium and potassium nitrate)
for tempering of steel or
heat treatment of aluminium
(T < 600 ˚C [1110 ˚F])
– Nitrocarburizing baths for
carbonitriding of steel surfaces
( T < 850 ˚C [1560 ˚F])
– Controlled-atmosphere and
bright annealing furnaces for
steel (T < 1150 ˚C [2100 ˚F])
– Furnaces for ethylene dichlo-
ride production (T < 500 ˚C
[930 ˚F])
– Materials for uranium process-
ing (T = 600 ˚C [1110 ˚F])
– Plants for vinyl chloride
monomer production (T = 600 –
700 ˚C [1110 – 1290 ˚F])
– Materials for fuel cells
(T = 600 – 700 ˚C [1110 –
1290 ˚F])
– Heat exchanger tubes in MW
incineration plants handling a
high proportion of household
refuse (T < 900 ˚C [1650 ˚F])
– Heat exchanger tubes for
fluidized-bed combustion
(T < 900 ˚C [1650 ˚F])
– Equipment items for TiO2 pro-
duction (T < 900 ˚C [1650 ˚F])
– Salt bath furnaces for heat tre-
atment of steels ( T = 750 –
1000 ˚C [1380 – 1830 ˚F])
recommend particular materials
for these applications. This is
because the selection of a mate-
rial is not determined by its high-
temperature corrosion behaviour
alone, and even this varies from
one type of plant to another owing
to different temperatures and
gas compositions; the require-
ments with regard to mechanical
properties and, not least, the
cost of materials – that is to say,
the cost over the whole service
life – also play a crucial role.
Typical examples of the use of
high temperature alloys are:
Radiant tubes
Radiant tubes are used for in-
direct heating of kiln and furnace
interiors. They are internally
heated by burning gas or oil and
release part of the resulting
energy to the furnace interior in
the form of radiant heat. Fig. 68
shows radiant tubes for an
enamelling furnace made of
Nicrofer 6023 H – alloy 601 H.
Flame hoods made of Nicrofer
3220 H – alloy 800 H, illustrated
in Fig. 69, are used in flaring of
natural gas.
Bell-type furnaces
Fig. 70 shows a gas-fired high-
convection bell-type furnace
installation of EBNER-Industrie-
ofenbau (Linz, Austria) for bright
annealing of coils of nickel-base
alloy wire. Since temperatures in
excess of 1100 ˚C (2010 ˚F) are
attained and may be maintained
during annealing times of several
hours’ duration, the racks of
Nicrofer 6025 HT – alloy 602 CA
have to be highly heat-resistant.
High resistance to thermal shock
is also required, as the coils of
wire are cooled in a water bath.
 54
Fig. 72 – Muffle of a bright annealing furnace made of Nicrofer 6025 HT – alloy 602 CA
Controlled-atmosphere
annealing
Fig. 71 shows a 12-strand con-
tinuous controlled-atmosphere
annealing furnace for fine-gauge
wire. Admission of shielding gas
to the tubes often takes place in
the centre of the furnace.
The shielding gases are usually
hydrogen or hydrogen/nitrogen
mixtures. For this reason,
the alloy Nicrofer 7216 H – alloy
600 H is often still used.
Continuous furnace
Fig. 72 shows the muffle of a
bright annealing furnace made
of Nicrofer 6025 HT – alloy
602 CA for continuous annealing
of steel strip. This suspended
Fig. 73 – All-metal furnace roller made of Nicrofer 6025 HT – alloy 602 CA
muffle is operated at up to Oil and gas burners
as a material of construction for
1180 ˚C (2150 ˚F). The outside Advanced heating boilers
kiln and furnace fans (Fig. 74).
of the muffle is in the burner employing low-temperature or
zone. Rotary furnaces/tubes condensing technology offer
Fig. 75 shows the tube of a energy savings of up to 40 %
Rollers for rotary furnace made of Nicrofer and emit correspondingly
continuous furnaces 3220 H – alloy 800 H. High heat smaller amounts of pollutants.
Fig. 73 shows an all-metal resistance is required here owing Newly developed, technologi-
furnace roller made of Nicrofer to the large unsupported length. cally mature oil and gas burners,
6025 HT – alloy 602 CA. The external firing demands such as the RotriX oil burner and
After five years, this roller is still good resistance to oxidation and the MatriX gas burner from
in use in a continuous annealing carburization on the outside of Viessmann, additionally reduce
furnace operating in air at up to the tube, while the inside may nitrogen oxide emissions and
1220 ˚C (2230 ˚F). be exposed to a variety of condi- help to improve air quality.
Note: For other applications of tions depending on the particular Nicrofer 45 TM – alloy 45 TM
alloy 602 CA, please ask for field of application. and Nicrofer 6025 HT – alloy
Corrosion 2000 Paper No. 52157). 602 CA are currently used for
these applications.
Fans
The alloy Nicrofer 3220 H – alloy
800 H is used mainly in indus-
trial furnace engineering, e.g.
 55

Fig. 76 – RotriX oil burner made of Nicrofer 45 TM – alloy 45 TM

Fig. 74 – Nicrofer 3220 H – alloy 800 H as a material of construction for furnace fans

Fig. 75 – Tube of a rotary furnace Fig. 77 – MatriX gas burner made of Nicrofer 6025 HT – alloy 602 CA
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Nickellegierungen und hoch-
legierte Sonderedelstähle,
expert verlag, Sindelfingen,
1983, pp. 78 – 105
44. Brochure published by
Vereinigte Deutsche
Metallwerke AG, 1985
45. G. Rudolph and
T. Hoffmann:
Verbesserung der Schweiß-
technik und Schweißeignung
von Nickellegierungen,
Teil 1 und 2, Metall 41, 1987,
Issue 10, p. 988 ff. and
Metall 41, 1987,
Issue 12, p. 1210 ff.
58
46. U. Brill:
Schweißverhalten und Eigen-
schaften der artgleichen
Schweißverbindung des
hochwarmfesten Ofenbau-
Werkstoffes Nicrofer 6025 HT
(W.-Nr. 2.4633),
Internationale Konferenz
Schweißtechnik, Werkstoffe
und Werkstoffprüfung,
Bruchmechanik und
Qualitätsmanagement,
TU Wien, 1997,
eds. S. Felber, T. Varga,
I. L. Zeman, Chytra Druck &
Verlag Gesellschaft m.b.H.,
Wien, Vol. 1, pp. 237 – 256
47. C. T. Sims and W. C. Hagel:
The Superalloys I,
John Wiley & Sons,
New York, 1972,
pp. 533 – 564
48. Working Instructions for
High-Alloy Austenitic Steels
and Nickel-Base Alloys,
brochure published by
Krupp VDM GmbH,
Application Engineering
49. K. Drefahl:
Auslegung zeitstandbe-
anspruchter Bauteile für den
Hochtemperaturbereich,
demonstriert anhand
praktisch ausgeführter
Anlagen, VDM Report No. 14,
October 1990
50. Dubbel:
Taschenbuch für den
Maschinenbau, Bd. 1,
13. Auflage, Springer Verlag,
Berlin, 1974, p. 351, p. 413
51. C. L. Robinson:
Trans. ASME 74 (1952),
p. 777
52. S. Taira:
Stanford University (Calif.),
Int. Union of Theoretical
and Applied Mechanics, 1960
53. W. Z. Friend:
Corrosion of Nickel and
Nickel-Base Alloys,
John Wiley & Sons,
New York, 1980,
pp. 178 – 180
54. P. Elliott, C. J. Tyreman and
R. Prescott:
High Temperature Alloy
Corrosion by Halogens,
Journal of Metals,
July 1985, pp. 20 – 23
55. K. Hauffe:
Gegen Fluoride beständige
Nichteisenmetalle
sowie anorganische und
organische Werkstoffe,
Metall, 40th year, Issue 3,
March 1986, pp. 257 – 259
56. G. Y. Lai:
High-Temperature Corrosion
Problems in the Process
Industries, Journal of Metals,
July 1985, pp. 14 – 19
57. D. C. Agarval and U. Brill:
Performance of alloy 602 CA
in high temperature
environments up to 1200° C
(2200° F), Corrosion 2000,
Paper No. 521, NACE,
Houston, Texas, 2000
 Krupp VDM sales offices, 59

subsidiaries and representations

Germany Germany Europe Europe

Head office Berlin Austria/Eastern Europe Greece

Krupp VDM GmbH Krupp VDM GmbH Krupp VDM Austria GmbH INTERAG Ltd.
Plettenberger Strasse 2 Wittestrasse 49 Tenscherstrasse 3 P.O. Box 65060
D-58791 Werdohl D-13509 Berlin A-1230 Wien 8, Pambouki Str.
P.O. Box 1820 Phone: (30) 4 32 40 36 Phone: (1) 6 15 06 00 GR-15410 Psychico (Athens)
D-58778 Werdohl Fax: (30) 4 35 29 68 Fax: (1) 6 15 36 00 Phone: (1) 6 72 67 11
Phone: (23 92) 55-0 (1) 6 72 67 15
Fax: (23 92) 55-22 17 Dresden Belgium/Luxembourg Fax: (1) 6 71 12 74
E-Mail: Krupp VDM GmbH S.A. Krupp VDM Belgium N.V.
kruppvdm@vdm.thyssenkrupp.com Oskar-Röder-Strasse 3 Avenue du Champ de Mai, Italy
http://www.kruppvdm.de D-01237 Dresden 14 Bte 34 Krupp VDM Italia S.R.L.
Phone: (3 51) 2 52 28 06 Résidence Saturne Via Milanese 20
Fax: (3 51) 2 52 28 07 B-1410 Waterloo I-20099 Sesto San Giovanni (Mi)
Phone: (2) 3 54 29 00 Phone: (02) 26 25 12 50
Nuremberg Fax: (2) 3 54 36 26 Fax: (02) 26 25 14 56
Krupp VDM GmbH
Dieselstrasse 55 Bulgaria Netherlands
D-90441 Nürnberg Krupp VDM Austria GmbH Krupp VDM Nederland B.V.
Phone: (9 11) 6 63 26 00 Slavianska 38 A Stationsweg 4
Fax: (9 11) 6 63 26 01 BG-1000 Sofia NL-3311 JW Dordrecht
Phone: (2) 9 88 37 58 P.O. Box 750
Stuttgart Fax: (2) 9 88 37 58 NL-3300 AT Dordrecht
Krupp VDM GmbH Phone: (78) 6 31 69 66
Am Ostkai 15 Croatia and Slovenia Fax: (78) 6 31 58 57
D-70327 Stuttgart Krupp VDM Austria GmbH
Phone: (7 11) 9 32 88-0 Zajceva 44a, Predstavnistvo Norway
(7 11) 9 32 88-36 HR-1000 Zagreb A/S Stavanger Røhandel
Fax: (7 11) 32 89 30 Phone: (51) 243 1334 Gamle Forusvei 53
Fax: (51) 243 1333 P.O. Box 184
Werdohl N-4033 Forus
Krupp VDM GmbH Denmark Phone: (51) 81 85 00
Plettenberger Strasse 2 Carl A. Plesner A/S Fax: (51) 81 86 00
D-58791 Werdohl P.O. Box 119
P.O. Box 1820 Klintehøj Vænge 6 Poland
D-58778 Werdohl DK-3460 Birkerød Krupp VDM Austria GmbH
Phone: (23 92) 55-25 88 Phone: (42) 81 96 00 Rzeznicza 13/15
Fax: (23 92) 55-25 26 Fax: (42) 81 96 22 PL-30530 Krakow
Phone: (12) 429 32 62
Finland Fax: (12) 429 33 43
Oy Cronimo Ab
Karhutie 6
SF-01900 Nurmijärvi
Phone: (9) 2 76 42 10
Fax: (9) 27 64 21 50

France
Krupp VDM S.a.r.l.
30, Bd. Bellerive
F-92566 Rueil Malmaison
Cedex
Phone: (1) 41 39 04 20
Fax: (1) 47 16 78 20
(1) 47 16 78 14
 60
2

Europe North America South America Africa

Romania Canada Argentina Egypt

Krupp VDM Austria GmbH Krupp VDM Canada Ltd. Walvoss S.R.L. OSAB Trade
Frank G. Schmidt 11 Allstate Parkway Humberto 1° 1333 Dr. O. Abbas
Str. Popa Savu nr. 74 Suite 203 1103 Buenos Aires 6, EL NIL EL ABIAD ST.
RO-71262 Bucuresti 1 Markham, Ontario L3R 9T8 Phone: (11) 43 04 87 70 Lebanon Square
Phone: (1) 2 22 75 55 Phone: (905) 4 77-20 64 Fax: (11) 43 05 06 91 Giza
Fax: (1) 2 22 28 63 Fax: (905) 4 77-28 17 Kairo
Brazil Phone: (2) 3 03 46 33
Spain/Portugal USA Thyssen Acos Especiais Ltd. Fax: (2) 3 46 08 00
Krupp VDM IBERICA Krupp VDM Technologies Corp. Rua da Mooca, no. 1615/1637
Oficina Representación 306 Columbia Turnpike CEP 03103-003, Sao Paulo-SP Samir L.W. El Ayoubi
Krupp VDM GmbH en España Florham Park, New Jersey 07932 Phone: (11) 60 96-75 37 P.O. Box Maadi 191
Calvet, 30 – 32, 2.°, 1.a Phone: (973) 2 36-16 64 Fax: (11) 60 96-73 91 House 30, Street 11
E-08021 Barcelona Fax: (973) 2 36-19 60 Maadi-Cairo
Phone: (93) 2 00 90 11 Chile Phone: (2) 3 50-21 12
Fax: (93) 2 00 22 54 México Thyssen Aceros y Servicios, S.A. Fax: (2) 3 78 31 15
Krupp VDM de México, San Eugenio 820
Sweden S.A. de C.V. P.O. Box Casilla 3097 South Africa
ESMA AB Bulevard Manuel Avila Correo Central Krupp VDM Technology (SA) (Pty.)
Domnarvsgaton 8 Camacho No. 80 PH-A Santiago Ltd.
P.O. Box 8027 Col. Lomas de Sotelo-El Phone: (2) 239 2234 P.O. Box 84
S-16308 Spanga Parque Fax: (2) 239 2346 Wendywood 2144
Phone: (8) 47 44 200 Naucalpan de Juarez, Phone: (11) 4 44-36 20
Fax: (8) 47 44 260 Edo. de México Colombia Fax: (11) 4 44-39 50
Phone: (5) 557 1471 HERGUT Ltda.
Switzerland Fax: (5) 557 1476 Cra. 43 A No. 1,
Krupp VDM (Schweiz) AG Sur-31, Of. 208
Lange Gasse 90 Medellin
P.O. Box Phone: (4) 266-17 37
CH-4002 Basel (4) 266-17 57
Phone: (61) 2 05 84 88 Fax: (4) 268-61 92
Fax: (61) 2 05 84 15
Ecuador
Tschech Republic/Slovakia Importadora Schiller Cia. Ltda.
Krupp VDM Austria GmbH Toledo 1328 y Coruña
Nejedleho 9 Quito
CZ-62800 Brno Phone: (2) 542 662
Phone: (5) 45 22 23 40 Fax: (2) 562 891
Fax: (5) 45 22 23 40
Peru
Turkey AMSET E.I.R.L.
Akkurt A.S. Eckhard Thode R.
Ahmediye Köyü José Maria Eguren
TR-34904 Cekmece-Istanbul (Chumbiongo) 107, Dpto. 302
P.K. 140 Miraflores (Lima 18)
TR-34711 Bakirköy-Istanbul Phone: (1) 440 4953
Phone: (212) 8 87 14 15 – 17 Fax: (1) 442 1233
Fax: (212) 8 87 10 79
Uruguay
United Kingdom Fierro Vignoli S.A.
Krupp VDM (U.K.) Ltd. Av. Uruguay 1274/76
VDM House Montevideo
111, Hare Lane Phone: (2) 91 45 60
Claygate-Esher, Surrey. Fax: (2) 92 12 30
KT10 OQY
Phone: (1372) 46 71 37 Venezuela
Fax: (1372) 46 63 88 Gunz Industrial, C.A.
2da. Av. c/c 1ra. Transversal.,
Edf. La Pradera, Torre B.,
Piso 9, P.H. 90-B,
Urb. Los Palos Grandes,
Caracas 1060
Phone: (2) 284-24 96
Fax: (2) 978-12 85
 61

Middle East Asia Asia Australia

Islamic Republic of Iran Japan Hong Kong Krupp VDM Australia Pty. Ltd.
Krupp Iran Ltd. Krupp VDM Japan K.K. Krupp VDM Hongkong Ltd. 724 Springvale Road
Dr. Ing. Ali Ghazanfari 2nd Floor Unit 1301, 13th Floor Mulgrave, Vic., 3170
P.O. Box 141 55-1979 Ochanomizu Itoh Bldg. Fook Lee Commercial Centre Phone: (3) 95 61-13 11
Ostad Motahari 368 3-3, Kanda-Surugadai Town Place, Fax: (3) 95 61 44 65
Phone: (21) 890 3706 Chiyoda-Ku No. 33 Lockhart Road,
Fax: (21) 890 3706 Tokyo 101-0062 Wanchai, Hong Kong
Phone: (3) 32 95-45 91 Phone: 25 27 20 08
Israel Fax: (3) 32 95-45 94 Fax: 25 27 20 45
Middle East Metals Ltd.
1, Korazin St. Philippines People’s Republic of China
Givatayim 53 583 MESCO Inc. Thyssen Krupp AG
Phone: (3) 5 71 53 74 MESCO Building Beijing Representative Office
Fax: (3) 5 71 53 71 Reliance Corner Brixton Streets East Ocean Centre, 8/F.
1603 Pasig City 24A Jianguomenwai Ave.
Jordan Metro Manila Beijing 100004
International Technical Phone: (2) 6 31 17 75 P. R. China
Construction Company Fax: (2) 6 31 40 28 Phone: (10) 65 15 55 98
P.O. Box 95 02 79 Fax: (10) 65 15 62 06
Amman Singapore/Malaysia
Phone: (6) 5 51 49 63 Leong Jin Corporation Pte. Ltd. Thyssen Krupp AG
Fax: (6) 5 53 70 69 No. 11, Benoi Crescent Shanghai Representative Office
Jurong Industrial Estate 14/F, Office No. 4 – 6
Saudi Arabia Singapore 629974 Novel Plaza 128
Al-Bassam Petroleum Phone: 2 66 11 32 Nanjing Road West
Equipment Co. Fax: 2 66 15 22 Shanghai 200003
King Street, P.O. Box 2611 P. R. China
Damman South Korea Phone: (21) 63 50 91 58-9
Phone: (3) 8 34 07 19 Krupp VDM Korea Co., Ltd. Fax: (21) 63 50 91 60
Fax: (3) 8 33 26 71 12F-13ho
Hyundai office B/D Fordley Development Ltd.
U. A. E. 9 – 4 Sunai-dong, Room 706 – 707
Eastern Union Corporation Bundang gu Yu Sung Boon Bldg.
P.O. Box 3489 Sungnam-Si, 107 – 111 Des Voeux Rd.
Tourist Club Area Kyunggido Central
Abu Dhabi Phone: (342) 711-1583 Hong Kong
Phone: (2) 78 24 62 Fax: (342) 717-1583 Phone: 25 41 00 00
Fax: (2) 77 19 58 Fax: 28 54 19 16

Taiwan
Blue Bridge Industrial
(Taiwan) Corp.
Indien/India 1st Fl. No. 37, Lane 96
Chung Shan N. Rd., Sec. 2
Variety (Agents) Private Ltd. Taipei
301, Kakad Chambers Phone: (2) 2565-1306
132, Dr. Annie Besant Road Fax: (2) 2531-1082
Worli, Bombay-400 018
Phone: (22) 4 93-60 99/-2691 Transcrystal Alloy
Fax: (22) 4 95-05 78 Industrial Corp.
10F-1, No. 76, Sec. 3
Roosevelt Road
Taipei
Phone: (2) 23 67-88 11
Fax: (2) 23 68-54 75

Thailand
Sahakol Trading Co. Ltd.
89/2 – 4 Paholyothin Road
Lampang 52100
Phone: (54) 22 18 04
Fax: (54) 22 19 45
 62 Krupp VDM stockholders
and distributors

Europe North America Africa Australia

France USA South Africa Krupp VDM Australia Pty. Ltd.

Jacquet S. A. Sheet and plate Krupp VDM Technology S. A. 724 Springvale Road
B. P. 61 (Pty.) Ltd. Mulgrave, Vic., 3170
Corrosion Materials
Rue du Bordelais 40, Desmond Street Phone: (3) 95 61-13 11
P.O. Box 666
F-69802 Saint-Priest Cedex Kramerville 2148 Fax: (3) 95 61 44 65
2262 Groom Road
Phone: 4 72 23 23 23 Baker, LA 70714 Phone: (11) 444-36 20
Fax: 4 72 23 23 00 Phone: (225) 775-3675 Fax: (11) 444-39 50
Fax: (225) 778-6452
Germany
F. W. Hempel & Co. RASCO
Geschäftsbereich Halbzeug (Reynolds Aluminium Supply Co.) Middle East
Weissensteinstrasse 70 P.O. Box 26885
D-46149 Oberhausen-Sterkrade Richmond, VA 23261
Phone: (2 08) 6 20 41-0 Israel
Phone: (804) 281-2000
Fax: (2 08) 6 20 41-74 Fax: (804) 281-4059 SCOPE
Metal Trading &
Great Britain Rolled Alloys Technical Services Ltd.
Philip Cornes & Co. Ltd. P.O. Box 310 Industrial Zone
Lanner Building, Clews Road 125, West Sterns Road P.O. Box 3
Redditch, Worcestershire B98 7ST Temperance, MI 48182 Mazkeret Batia 76804
Phone: (15 27) 55 50 00 Phone: (734) 847-6917 Phone: (8) 34 99 43
Fax: (15 27) 54 70 00 Fax: (734) 847-0270 Fax: (8) 34 94 02

Italy Strip
Chun & Vollerin S.R.L. Ed Fagan, Inc.
Via Veneto 7 769 Susquehanna Ave.
I-20094 Buccinasco (Milano) Franklin Lakes, NJ 07417
Phone: (02) 48 84 21 60 Phone: (201) 891-40 03
Fax: (02) 488 26 97 Fax: (201) 891-32 07

Norway Rod and bar

A/S Stavanger Rørhandel Corrosion Materials
Gamle Forusvei 53 P.O. Box 666
P.O. Box 184 2262 Groom Road
N-4033 Forus Baker, LA 70714
Phone: (51) 81 85 00 Phone: (225) 775-3675
Fax: (51) 81 86 00 Fax: (225) 778-6452
Sverdrup Hanssen The Trident Company
Kvitsøygt. 95 405 North Plano Road
N-4014 Stavanger Richardson, TX 75080-3900
Phone: (4) 89 18 00 Phone: (972) 231-5176
Fax: (4) 89 18 18 Fax: (972) 437-6569
 Krupp VDM division 63
3

Precision Rolled Products

USA

Precision Rolled
Products, Inc.
Corporate Office
14255 Mt. Bismark Street
P.O. Box 60010
Reno, Nevada 89506
Phone: (775) 972 02 72
Fax: (775) 972 43 68
http://www.prpusa.com

Precision Rolled
Products, Inc.
306 Columbia Road
Florham Park, N.J. 07932
Phone: (201) 822 91 00
Fax: (201) 822 09 32

Manufacturing program:
Ingots, billets and bar products
made of high-temperature alloys
(nickel and cobalt-base alloys)
titanium and specialty steels in form
of flats, rounds and shapes

Plants:
Reno, Nevada – bar production

Florham Park, New Jersey – melting

plant and billet production
 64 Imprint

VDM Report No. 25

High-temperature alloys
from Krupp VDM for industrial
engineering

Published by
Krupp VDM GmbH
Plettenberger Strasse 2
D-58791 Werdohl
Postfach 1820
D-58778 Werdohl
Germany
Phone: +49 (23 92) 55-0
Fax: +49 (23 92) 55-22 17
E-Mail: kruppvdm@vdm.
thyssenkrupp.com
Internet http://www.kruppvdm.de

The information in this brochure

is based on results of our
research and development at
the time this document went to
press. We reserve the right to
make changes.

The information in this brochure

is provided according to the best
of our knowledge but without
any liability on our part, and does
not imply a guarantee of par-
ticular characteristics. We shall
be liable only in connection with
an actual order in accordance
with the terms of the trans-
action, and in particular with our
General Conditions of Sale.

August 2000
Krupp VDM GmbH
Plettenberger Strasse 2
58791 Werdohl
Postfach 18 20
58778 Werdohl
Germany
Phone: +49 (23 92) 55-0
Fax: +49 (23 92) 55-22 17
E-Mail: kruppvdm@vdm.thyssenkrupp.com
Internet http://www.kruppvdm.de