Dr.-lng.

Herbert Richter

7 Nickel alloys and special stainless steels in power engineering

7.1 Introduction

There can be no doubt that electricity generation will, even on a long-term basis,
continue to increase in importance, especially in the developing countries of the
world, where the consumption of electrical energy provides an approximate
measure of the standard of living. Particular attention must be paid to the
reliability and safety of new plants, and to their effects on the environment.
Figure 7.1 shows a diagram of the influences which affect the service life of a
power station. The significance of materials, their properties, working (including
welding) and resistance to corrosion can clearly be seen..

transferability of
temperature material "eldin9 experimental data
l | scatter band i

forming

heat treatment strength

hypothesis
welding

I I I I I
internal temperature external forces, geometry
pressure difference moments

Figure 7.1 : Factors affecting the service life of a power station component1 *

185
In use, electrical energy is environmentally acceptable, but it is becoming
necessary to pay increasing attention to environmental problems where the
generation of electricity is concerned. We shall therefore deal in some detail
with such questions.

7.2 Principles of a power station

In considering the application of materials in power stations, we shall only be

dealing with thermal power stations. In these, primary energy from fossil fuels or
nuclear energy is initially used to produce heat, which in turn heats water or
another medium to drive a turbine which generates electrical power.

The transfer medium is subsequently returned to begin the cycle again. Even this
very basic description indicates the requirements made on materials. These are
(Figure 7.1):

adequate mechanical strength under the relevant temperatures and pressures;

adequate ductility to resist fracture;
resistance to corrosion from the liquid, solid and gaseous media at the
application temperatures;
workability, i. e. suitability for the production of the required semi-finished
forms, apparatus, piping systems and components, and the ability to produce
welds which are operationally reliable.

We shall not be discussing hydro-electric and wind power stations here, since
material problems do not play a significant role in such plants.

Figure 7.2 shows a diagram of a power station. In a pressurised-water-reactor

nuclear power plant, the hot pressurised water produced in the reactor core is
passed at 300 — 350°C to the nuclear steam generator and there transfers its
heat (Figure 7.3) to the secondary turbine circuit. In a power station heated by
fossil-fuel (Figure 7.2), the steam generator, which supplies the turbine circuit,
is directly exposed to the combustion gases produced by the burning of oil or coal.

A portion of the heat energy from the steam is with-drawn from the turbine
circuit as mechanical energy. The mechanical energy is then converted to usable
electrical energy in a power generator. However, more than 50 % of the heat
produced is inevitably lost to the cooling water, which is taken from rivers,
lakes or the sea. It is customary to circulate the cooling water through cooling
towers if the volume of water available is not sufficient to provide 100 %
direct cooling.

186
 steam generator
and reheater

EL extraction pipe
FDL fresh steam pipe
HZÜL hot reheater pipe
KZÜL cold reheater pipe
KDL condensate discharge pipes
KSL condensate suction pipe
SDL feed-water pressure pipe
SSL feed-water suction pipe

Figure 7.2: Diagram of a conventional power station

steam generator n reactor pressure vessel

EL extraction pipe
FDL fresh steam pipe
KDL condensate discharge pipe
KSL condensate suction pipe
KRL main coolant pipe cold (return)
KVL main cooland pipe hot (supply)
SDL feed-water discharge pipe
SSL feed-water suction pipe
ZOL reheater pipe

Figure 7.3: Diagram of a nuclear power station with pressurised-water

reactor1*
According to Carnot, the efficiency r; of a heat engine can be described by the
formula

where Ts = steam temperature, and Tc = condensate temperature. For the

maximum efficiency the aim must therefore be to keep steam temperature as
high and condensate temperature as low as possible (cf. Figure 7.4).

In nuclear power stations, steam temperature is limited to approximately

300 — 350 °C by the decreasing corrosion resistance of the Zircaloy-2 or
Zircaloy-4 fuel cladding, while in fossil-fuel fired plants attempts are being made
to raise the temperature from its present maximum of 530°C (Figure 7.4).

steam turbine for

conventional power
station with reheater

steam turbine for

nuclear power station
with reheater and
simple external drain

ki/kgl

Figure 7.4: Expansion curves in the steam turbine1'

7.3 Materials for steam generators

Materials for steam generators are shown in Table 7.1. As long as temperatures
remained at around 530°C, low-alloy steels and stainless ferritic chromium
steels were the standard materials for steam-generator tubes, since they also
had relatively good resistance to the heating gases. With the trend towards
higher temperatures, such alloys are adequate neither with regard to strength
nor with respect to their tendency to embrittlement, with the result that
only nickel-alloyed austenitic steels can be considered. These materials are
also shown in Table 7.1. Data on the long-term behaviour of these steels with
regard to strength and corrosion have been obtained in extensive testing.

The austenitic stainless steels shown in Table 7.1 have the advantage of
considerably better weldability when compared to the stainless ferritic
chromium steels. Due to their relatively low chromium and high nickel content,
such steels have no tendency to become embrittled. Their service temperature
ranges up to approximately 800°C. The fact that these materials have not yet
been used to a great extent can be explained by the complexity of controlling
a steam generator operated at high temperatures. However, price trends in the
energy market are making it imperative to consider again higher operating
temperatures.

Completely different demands are made of steam generators in nuclear power

stations. Components are not exposed to corrosive attack from heating gases,
but must possess resistance to hot pressurised water — itself is an aggressive
medium — at 300 — 350 °C. Another extremely important consideration is the
fact that the steam generator is a component in the primary circuit (Figure 7.3)
of a nuclear plant, giving only limited access for repair purposes, should damage
occur. For this reason, only materials with extremely high resistance to
corrosion can be considered for steam generator tubes; such materials are shown
in Table 7.2. These are the two fully austenitic materials Nicrofer 3220 LC-alloy
800 L (Material No. 1.4558) and Nicrofer 7216 LC-alloy 600 L (Material No.
2.4817), and the nickel-copper alloy Nicorros-alloy 400 (Material No. 2.4360).
The first of these materials counts as a steel in German linguistic usage, but is
shown as a nickel-based alloy in British and American standards; the other two
materials are indisputably nickel-based alloys. Selection from these three
materials is dependent on reactor design. For instance, Nicrofer 3220 LC-alloy
800 L is used in the KWU series of pressurised-water reactors, and in the largest
units of the Canadian CANDU series.

Material 2.4816, equivalent to Nicrofer 7216-alloy 600, is used in the Westing-

house series of nuclear power stations. The nickel-copper alloy Nicorros-alloy
400 is used in CANDU power-station units up to 600 MW, for instance in the
190
Table 7.1: Steel grades for steam generators and piping1*

Material DIN VDM Composition (%) Tube

No. designation designation type
C Mn Cr Mo Ni V

1.5415 15Mo3 — <0.20 0.65 — 0.30 — — - ST WT-

1.7335 13CrMo44 - <0.18 0.55 0.85 0.45 - - - ST WT -
1.7380 10CrMo910 - <0.15 0.50 2.25 1.0 - - - ST WT -
1.4922 X20CrMoV12 1 - <0.23 0.55 12.0 1.0 0.55 0.50 - ST -
1.4961 X8CrNiNb1613 Cronifer 1613 Nb <0.10 1.20 16.0 - 13.0 - Nb ST-
1.4981 X8CrNiMoNb1616 Cronifer 1616 Nb <0.10 1.20 16.0 1.8 16.0 - Nb ST-
1.4988 X8CrNiMoVNb1613 Cronifer 1616 V <0.10 1.20 16.0 1.3 13.0 0.7 Nb ST

1.4301 X5CrNi1810 Cronifer 1809 <0.07 2.0 18.5 _ 10.0 _ — ST WT

1.4541 X6CrNiTi1810 Cronifer 1809 Ti <0.10 2.0 18.0 - 10.0 - TE ST WT
1.4550 X6CrNiNb1810 Cronifer 1809 Nb <0.10 2.0 18.0 - 10.0 - Nb ST WT
1.4571 X6CrNiMoTi17122 Cronifer 1810 <0.10 2.0 17.5 2.25 11.0 - Ti ST WT
1.4580 X6CrNiMoNb17122 Cronifer 1810 Nb <0.10 2.0 17.5 2.2 12.0 — Nb ST WT

ST = supplied as seamless tubes

WT = supplied as welded tubes

() (> 1>
 c <r

Table 7.2: Materials for nuclear steam generators

Designation Material Composition (%)

No.
C Mn Cr Ni Al Ti Cu

Nicrofer 3220 LC 1.4558 < 0.03 0.7 21 32 0.25 0.5

X2NiCrAITi3220
alloy 800 L
Nicrofer 7216 LC 2.4817 < 0.025 0.2 16 73 0.15 0.2
NiCr15Fe
alloy 600 L
N ¡corros 2.4360 < 0.15 1.0 64 — 32
NiCu30Fe
alloy 400

Mechanical properties
Rp0.2 Rm A
(N/mm2 ) (N/mm2 ) (%)

Nicrofer 3220 LC annealed > 280 450 - 700 > 45

cold-worked > 340 > 570 > 30

Nicrofer 7216 LC annealed > 180 > 550 > 30

Nicorros annealed > 193 > 483 > 35

cold-worked > 379 > 586 > 15
eight 540 MW units at the Pickering A and B power stations (Figure 7.6), and in
the identical power stations in India and Pakistan. The CANDU series features a
heavy-water moderator system, i. e. the primary circuit consists of heavy water.
As far as corrosion chemistry is concerned, there is no difference between heavy
and light water.

The tube-sheet of the steam generator (Figure 7.5), which is equipped with
U-shaped tubes, is usually made of boiler-plate clad either by rolling or welding
with the tube material. The good weldability of the nickel-based alloys
mentioned earlier permits the application of fully automatic tube-to-tube-sheet
welding processes.

The required degree of reliability in the steam generator must also be ensured by
the use of extensive non-destructive testing programmes in the manufacture and
welding of tubes and tube-sheets. With these thin-walled tubes, a combination of
several non-destructive techniques, such as eddy-current, ultra-sonic and
hydraulic testing, carried out on every component, is now standard practice.
During the service life of steam generators, eddy-current tests employing internal
probes are particularly useful in detecting and monitoring defects arising from
corrosion.

Figure 7.5:
primary medium Steam generator for a nuclear
power station

192
 Figure 7.6:
Pickering A G. S.
nuclear power station

7.4 Condenser materials

Inevitable heat losses in power stations are transferred to the cooling medium in
a condenser which due to the magnitude of such losses, is usually a tubular heat
exchanger of large proportions, (see Figure 7.7).

Figure 7.7:
Power station condenser

The condenser tubes are not exposed to high temperatures or pressures, but
must be resistant to corrosion from the cooling water. It should be noted that,
despite the increasing level of environmental consciousness, the quality of
cooling water available from lakes, rivers and from the sea around the coasts has
declined drastically. In addition, because downtime for repair purposes is
extremely expensive in major plants, the requirement for corrosion-reistant
condenser-tube materials is continuously gaining in significance.

Whereas copper alloys, as shown in Table 7.3, have sufficied for many years, and
are even today still the first choice where cooling is carried out using sea-water,
it is now necessary to use materials which are less susceptible to corrosion by

193
Table 7.3: Copper-based alloys for condensers and coolers

Designation Material Composition (%)

No. Ni Cu Mn Fe Sn Zn Al

Hecorros 71 2.0470 - 73 - - 1 28 -
CuZn39Sn

Hecorros 76 2.0460 - 78 - - - 20 2
CuZn20AI

Cunifer 10 2.0872 10 88 0.7 1.5 - - -

CuNilOFe

Cunifer 30 2.0882 30 68 0.7 0.6 - - -

CuNi30Fe

Cunifer 302 2.0883 30 66 1.8 1.8 - — —

CuNi30Fe2Mn2

Table 7.4: Stainless steels for condenser tubes

Material Composition (%) Pitting index

Designation No. C Cr Ni Mo Cu %Cr+3.3 x
%Mo

Cronifer 1809 1.4301 <0.07 17.5 11.5 - - 17.5

X5CrNi1810
Cronifer 1810 1.4401 <0.07 17.5 11.5 2.2 - 25
X5CrNiMo17122
Cronifer 1713LCN 1.4439 <0.04 18 13 4.5 - 31.5
X2CrNiMoN17135
Cronifer 1925 LC 1.4539 <0.02 21 25 4.8 1.5 37
X2NiCrMoCu25205
alloy 904 L
Cronifer 1925 hMo 1.4529 <0.03 21 25 6.2 0.8 41
X2NiCrMoCu25206
alloy 904 hMo

194
abrasive constituents and to pitting corrosion than the materials shown in
Table 7.3. The use of titanium tubes has resulted in considerable technical
success, but titanium is so expensive that it is only used in cases of extremely
high corrosive attack, e. g. due to contaminated sea-water, or in the case of rivers
with very high salt content. Tubes in austenitic stainless steels such as Cronifer
1809 (Material No. 1.4301) and Cronifer 1810 (Material No. 1.4401) have been
used successfully as condenser-tube materials in clean fresh water (Table 7.4),
but are not completely immune to stress-corrosion cracking or to crevice or
pitting corrosion should chloride ions be present in the cooling water.

The breakthrough finally came for this group of materials with the development
of highly corrosion-resistant stainless steels with high molybdenum contents, and
thus with correspondingly good resistance to pitting corrosion. These improved
steels are also shown in Table 7.4. Cronifer 1713 LCN (Material No. 1.4439), a
stainless steel with high molybdenum content and added nitrogen for austenite
stabilisation, is at present being employed in numerous power stations in
Germany. Its operating conditions include chloride contents of up to 1000 ppm,
representing a substantial salt burden.

Due to its high nickel content, Cronifer 1925 LC-alloy 904 L (Material No.
1.4539) has even better resistance to stress-corrosion cracking. A variant of this
material with increased molybdenum content, Cronifer 1925 hMo-alloy 904 hMo
(Material No. 1.4529) is, thanks to its high pitting resistance index (see below),
also suitable for high chloride contents. This material is at present under test in
locations which include a power station at Wilhelmshaven featuring brackish-water
cooling. The so-called pitting resistance index, i.e. the sum of the Cr content and
3.3 times to molybdenum content, provides an indication of resistance to pitting
corrosion. It demonstrates most convincingly the improvement attained in the
later steel grades shown in Table 7.4 as compared to materials 1.4301 and
1.4401.

7.5 Materials for hijgh-pressure feed-water pre-heaters

In feed-water preheaters, condensate is heated for re-evaporation. On the high-

pressure side, to main corrosion danger comes, as in the case of nuclear steam
generators, from hot water. Since any leak in a high-pressure preheater caused
by erosion corrosion (impingement attack) can lead to extensive secondary
leakage and even complete destruction of the unit, it is advisable to select tube
alloys from those proven standard to be reliable in nuclear plants. The carbon
steels and standard austenitics, such as Material No. 1.4301, are therefore
increasingly being replaced by the highly corrosion-resistant materials shown

195
in Table 7.5. A detailed analysis of failures in high-pressure preheaters in the
USA has shown that damage occurs most frequently to preheater tubes in
carbon steel, with slightly better results being obtained for type TP 304 steel,
equivalent to Material No. 1.4301. The best behaviour in this respect was
manifested by the material Alloy 400 (NiCu30Fe).

Alloy 400 (NiCu30Fe Material No. 2.4360) is therefore the standard material in
the USA for this purpose, and is furthermore clearly superior to the more highly
copper-alloyed material copper-nickel 70/30 (CuNi30Fe). Alloy 400 (NiCu30Fe)
and copper-nickel 70/30 (CuNi30Fe) are used for cold-formed, stress-relieved,
high-pressure pre-heaters, so that relatively small wall thicknesses can be
employed (Table 7.5), a requirement which could not be met using carbon steel
or Material No. 1.4301, due to their susceptibility to SCC. A new material for
this application is the fully austenitic Nicrofer 3220 LC-alloy 800 L which has
also proven successful in nuclear engineering applications. In the USA, many
plants are being equipped with tubes in this material.

In nuclear plants, the high-pressure preheaters are in some cases integrated with
the steam generators for instance the preheaters in the Canadian CANDU series.
Thus very significant references exist for Nicorros-alloy 400 (NiCu30Fe) and
Nicrofer 3220-alloy 800 L (X2NiCrAITi3220) as constructional materials for
high-pressure preheaters. In the case of Nicorros-alloy 400, semi-finished

Table 7.5: Corrosion-resistant materials for high-pressure heaters,

mechanical properties

Designation Material Material Mechanical properties

No. condition at 20 C
RP 0,2 a5
o
(N/mm2) (N/mm2) (%)

Cunifer 30 2.0882 heat-treated. > 120 > 370 > 30

CuNi30Fe cold-worked > 345 > 495 > 12
Nicorros 2.4360 heat-treated. > 193 > 483 > 35
alloy 400 cold-worked > 379 > 586 > 15
stress-relieved
Cronifer 1809 1.4301 heat-treated > 185 500-700 >35
X5CrNi189
Nicrofer 3220 LC 1.4558 heat-treated >200 450-700 >35
X2NiCrAITi3220 cold-worked >340 >570 >30
alloy 800 L

196
Table 7.6: Mechanical properties of straight tubes in Nicorros-alloy 400
(NiCu30Fe10))

Material Proof Tensile Elonga- Hardness Internal stress

condition stress strength tion HRB
Rp0.2 Rm A
IN/mm1) (N/mm2) (%) (N/mm1) (psi)

heat-treated 260 570 47 62 45 6 400

(recrystallised). 4 200
straightened 29 4 200

heat-treated, 480 640 21 91 130 18 600

hollow-drawn 134 19 200
and stress- 149 21 300
relieved 89 12 800

heat-treated. 670 720 10 98 153 21 800

mandrel- 139 19 800
drawn 148 21 200
101 14 500
102 14 600

heat-treated. 470 640 22 89 29 4 200

hollow-drawn 44 6 300
and stress- 16 2 200
relieved 12 1 700
35 5 100

heat-treated. 490 640 23 91 156 22 600

mandrel- 62 8 900
drawn, stress- 65 9 300
relieved and 85 12 200
straightened 118 15 500
heat-treated. — — — __
29 4 200
mandrel-drawn. 31 4 400
stress-relieved. 31 4 400
straightened, 29 4 200
stress-relieved
again
heat-treated, 495 635 21 89 29 4 200
mandrel-drawn, 29 4 200
straightened. 19 2 800
stress-relieved 10 1 400

197
products must be stress-free from the manufacturing stage, to avoid high-
temperature stress-corrosion cracking, especially if the tubes are to be supplied
in the cold-formed stress-relieved condition. The degree of internal stress is thus
a quality criterion. A level of 70 N/mm2 is normally accepted as maximum
internal stress, and must be verified by means of a slit test. Table 7.6 shows some
values achieved with various tube-manufacturing processes. It can be seen that
simple hollow drawing (sinking), with a deformation of approximately 15—20 %,
produces impermissible internal stresses, while carefully matched mandrel
drawing, in which diameter and wall thickness are reduced, facilitates the
attainment of low stress levels. As Table 7.6 shows, the straightening process
may produce unacceptable stresses, signifying that careful monitoring of the
manufacturing process is advisable for this critical application.

Figure 7.8 shows that stress distribution is maintained within specified limits
when manufacturing adheres to the set parameters.

Figure 7.8:
Stresses in NiCu30Fe
tubes101

7.6 Piping materials

A power station features innumerable piping systems both for connecting

individual plant components and for control and adjustment purposes. Such
pipes are made in the materials shwon in Tables 7.1, 7.2 and 7.5. Selection
criteria include temperature, pressure and the criticality of the plant at specific
points. High-alloy austenitic materials therefore find additional use for piping
systems in nuclear power stations (see lower half of Table 7.1).

198