5.

Welding of High-Alloy Steels, Corrosion

5. Welding of High-Alloy Steels, Corrosion

58

Basically stainless steels are characterised by a chromium content of at least 12%. Figure 5.1 shows a classification of corrosion resistant
stainless steels corrosion-resistant steels

steels. They can be singled out as heat- and scale-resistant and stainless steels, depending on service temperature. Stainless steels are used at room temperature conditions and for water-

scale- and heat-resistant steels

perlitic martensitic

semi-ferritic

ferritic

ferritic-austenitic

austenitic

X40Cr13

X10Cr13

X8Cr13

X20CrNiSi25-4

non-stabilized (austenite with delta-ferrite) X12CrNi18-8

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stabilized (austenite without delta-ferrite) X8CrNiNb16-13

ISF 2002

based media, whilst heatand scale-resistant steels are applied in elevated temperatures and gaseous media. Depending on their microstructure, the alloys can be divided into perlitic-martensitic, ferritic, and austenitic steels. Perlitic-martensitic steels have a high strength and a high wear resistance, they are used e.g. as knife steels. Ferritic and corrosion resistant steels are mainly used as plates for household appliances and other decorative purposes. The most important group are austenitic steels, which can be used for very many applications and which are corrosion resistant against most media. They have a very high low temperature impact resistance. Based on the simple Fe-C
T d A4 g A3 a a A4 g A3 a(d) A3 g T T A4 d

Classification of Corrosion-Resistant Steels

Figure 5.1

phase diagram (left figure), Figure 5.2 shows the effects of two different groups of alloying elements on the equilibrium diagram.
Alloy elements in % Nickel Manganese Cobalt

Alloy elements in %

Alloy elements in % Chromium Vanadium Molybdenum Aluminium Silicon

Ferrite

developers

with

chromium as the most important element cause a

ISF 2002

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Modifications to the Fe-C Diagram by Alloy Elements

strong reduction of the aus-

Figure 5.2

5. Welding of High-Alloy Steels, Corrosion

59

tenite area, partly with downward equilibrium line according to Figure 5.2 (central figure). With a certain content of the related element, there is a transformation-free, purely ferritic steel. An opposite effect provide austenite developers. In addition to carbon, the most typical member of this group is nickel.
Element Carbon l l l Chromium l Nickel l l Oxygen l Niobium l Manganese l l Steel type, no. All types l l l All types l All types Special types l 1.4511,1.4550, 1.4580 u.a. All types l l Effect Increases the strength, supports development of precipitants which reduce corrosion resistance, increasing C content reduces critical cooling rate Works as ferrite developer, increases oxidation- and corrosion-resistance Works as austenite developer, increases toughness at low temperature, grain-refining Works as strong austenite developer (20 to 30 times stronger than Nickel) Binds carbon and decreases tendency to intergranular corrosion

Austenite developers cause an extension of the austenite area to Figure 5.2 (right figure) and form a purely austenitic and transformation-free steel. The table in Figure 5.3 summarises the effects of some selected elements on high alloy steels.

Increases austenite stabilization, reduces hot crack tendency by formation of manganese sulphide Improves creep- and corrosion-resistance Molybdenum 1.4401,1.4404, l 1.4435 and others. against reducing media, acts as ferrite l developer l 1.4005, 1.4104, Phosphorus, 1.4305 Improve machinability, lower weldability, selenium, or l reduce slightly corrosion resistance l sulphur l l All types l l Improves scale resistance, acts as ferrite developer, all types are alloyed with small contents for desoxidation

Silicon l Titanium l l Aluminium l Copper l l l

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1.4510, 1.4541, Binds carbon, decreases tendency to 1.4571 and others intergranular corrosion, acts as a grain refiner l and as ferrite developer Type 17-7 PH Works as strong ferrite developer, mainly l used as heat ageing additive Type 17-7 PH, 1.4505, 1.4506 l l Improves corrosion resistance against certain media, decreases tendency to stress corrosion cracking, improves ageing
ISF 2002

Effects of Some Elements in Cr-Ni Steel

Figure 5.3

The binary system Fe-Cr in Figure 5.4 shows the influence of chromium on the iron lattice. Starting with about 12% Cr, there is no more transformation into the cubic face-centred lattice, the steel solidifies purely as ferritic. In the temperature range between 800 and 500 C this system contains the intermetallic -phase, which decomposes in the lower temperature range into a low-chromium solid solution and a chromium-rich -solid solution. Both, the development of the -phase and of the unary --decomposition cause a
Figure 5.4

5. Welding of High-Alloy Steels, Corrosion

60

strong embrittlement. With higher alloy steels, the diffusion speed is greatly reduced, therefore both processes require a relatively long dwell time. In case of technical cooling, such embrittlement processes are suppressed by an increased cooling speed. Nickel is a strong austenite developer, see Figure 5.5 Nickel and iron develop in this system under elevated temperature a complete series of face-centred cubic solid solutions. Also in the binary system Fe-Ni
1600 C 1400 d 1200 g S+d

Fe Ni3

S+g

decomposition range take place.

processes

d+g

in the lower temperature Along two cuts through the ternary system Fe-Cr-Ni, Figure 5.6 shows the most
Fe Ni3

Temperature

1000 800 600 a 400 200 0 Fe a+g

important
90 % Ni
ISF 2002

phases

which

develop in high alloy steels.

10 20 30 40 50 Nickel 60 70 80

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Binary System Fe - Ni

A solidifying alloy with 20% Cr and 10% Ni (left figure) forms at first -ferrite. ferrite is, analogous to the

Figure 5.5
70 % Fe 1600 C 1500 1400 1300
S+d S S+d+g S+g

60 % Fe 1600 C 1500 1400 1300 1200

S+d S S+d+g S+g

Fe-C diagram, the primary from the melt solidifying body-centred cubic solid solution. However -ferrite

Temperature

1200
d d+g g

d+g

1100 1000 900 800

d+ g+ s
g+s

1100 1000 900 800

d+s g+s d+s

is developed by transformation of the austenite, but

d+g+s

is of the same structure from the crystallographic

15 25 20 20 25 15 % Ni % Cr

700

700 5 25 10 20 15 15 20 % Ni 10 % Cr 0 40 5 35 10 30

0 30
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point of view, see Figure 5.4.

ISF 2002

Sections of the Ternary System Fe-Cr-Ni

Figure 5.6

5. Welding of High-Alloy Steels, Corrosion

61

During an ongoing cooling, the binary area ferrite + austenite passes through and a transformation into austenite takes place. If the cooling is close to the equilibrium, a partial transls ls st ee ls ee iti cfe st ee st rri tic

formation of austenite into the brittle -phase takes place in the temperature range below 800 C. Primary ferritic solidifying alloys show a reduced tendency to hot cracking, because -ferrite can absorb hot-crack promoting elements like S and P. However primary austenitic solidifying alloys show, starting at a certain alloy content, no transformations during cooling (14% Ni, 16% Cr, left figure). Primary austenitic solidifying alloys are much more susceptible to hot cracking than primary ferritic solidifying alloys, a transformation into the -phase normally does not take place with these alloys. Figure 5.7 shows some typical compositions of certain groups of high alloy steels.

si tic

M ar te n

en

iti c

rri tic

Au

3.

C Si Mn Cr Mo Ni Cu Nb Ti Al V N S
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0.1 max. 1.0 max. 1.0 15 18 up to 2.0 1.0

1.

2.

0.1 1.2 max. 1.0 max. 1.5 12 18 up to 1.2 2.5

0.1 max. 1.0 max. 2.0 17 26 up to 5.0 7 26 up to 2.2

0.1 max. 1.0 max. 2.0 24 28 up to 2.0 4 7.5

+ + + +

+ +

4.

Au

Fe

+ + +

st en

st

ls

+ indicates that the alloy elements can be added in a defined content to achieve various characteristics

st ee

ISF 2002

Typical Alloy Content of High-Alloy Steels

Figure 5.7

The diagram of Strau and Maurer in Figure 5.8 shows the influence on the microstructure formation of steels with a C-content of 0,2%. The classification of high-alloy steels in Figure
28 % 24 20 16 12 8 4 ferrite / perlite 0 0 2
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5.1 is based on this diagram. If a steel only contains C, Cr and Ni, the
austenite

lowest austenite corner will be at 18% Cr and 6% Ni. And also other elements
austen ite / ma rt ensite
austenite / ferrite

Nickel

than Ni and Cr work as an austenite or ferrite developer. these The influence is of denickel elements and

martensite / troostite / sorbite 4 6 8 10 12 14 Chromium 16

austenite

/ martens
20

ite / ferrite
24 % 26

martensite / ferrite 18 22
ISF 2002

Maurer - Diagram

scribed by the so-called chromium

Figure 5.8

5. Welding of High-Alloy Steels, Corrosion

62

equivalents. The Schaeffler diagram reflects additional alloy elements, Figure 5.9. It represents molten weld metal of high alloy steels and determines the developed microstructures after cooling down from very high temperatures. The diagram was always prepared considering identical cooling conditions, the influence of different cooling speeds is here disregarded. The areas 1 to 4 in this diagram limit the chemical compositions of steels, where specific defects may occur during welding. Depending on the composition, purely ferritic chromium steels have a tendency to embrittlement by martensite and therefore to hot cracking (area 2) or to embrittlement due to strong grain growth (area 1).
Nickel-equivalent = %Ni + 30x%C + 0,5x%Mn
30 28 26 24 22 20 18 16 14 12 10 8 6 4 2 00

A cause for this strong grain growth during welding is the greatly increased diffusion speed in the ferrite compared with austenite. After reaching a diffusion-start Figure 5.10 temperature, have a

0%

t rri Fe 5%
10

austenite

%
20 %

A+F A +M

40%
80 %

100%

martensite F + M
2 4 6 8 10

A+M+F M+F ferrite

12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

Chromium-equivalent = %Cr + %Mo + 1,5x%Si + 0,5x%Nb

shows that ferritic steels considerably

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hardening crack susceptibility (preheating to 400C!) hot cracking susceptibility above 1250C

sigma embrittlement between 500-900C grain growth above 1150C

ISF 2002

stronger grain growth than austenites. Therefore high alloyed ferritic steels are to be considered as of limited weldability. The area 3 marks a possible embrittlement of the material
4000 6000
m

Schaeffler Diagram With Border Lines of Weld Metal Properties to Bystram

Figure 5.9

5000

grain size

due to the development of -phase. As explained in 5.6, this risk occurs with increased increased ferrite contents, conchromium

3000

2000

austenitic steel

1000
ferritic steel

tents, and sufficiently slow cooling speed.

0
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200

400

600 temperature

800

1000

1200

ISF 2002

Grain Size as a Function of Temperature

Figure 5.10

5. Welding of High-Alloy Steels, Corrosion

63

Finally, area 4 marks the strongly increased tendency to hot cracking in the austenite. Reason is, that critical elements responsible for hot cracking like e.g. sulphur and phosphorous have only very limited solubility in the austenite. During welding, they enrich the melt residue, promoting hot crack formation (see also chapter 9 - Welding Defects). There is a Z-shaped area in the centre of the diagram which does not belong to any other endangered area. This area of chemical composition represents the minimum risk of welding defects, therefore such a composition should be adjusted in the weld metal. Especially when welding austenitic steels one tries to aim at a low content of -ferrite, because it has a much greater solubility of S and P, thus minimising the risk of hot cracking. The Schaeffler diagram is not only used for determining the microstructure with known chemical composition. It is also possible to estimate the developing microstructures when welding different materials with or without filler metal. Figures 5.11 and 5.12 show two examples for a determination of the weld metal microstructures of so-called 'black and white' joints.

28 28 24 A 20 10 20 24 A A+M 16 12 8 : =1:1 4 0 0 4 8 12 16 20 24 28 32 36 0 0 4 8 12 16 20 24 Chromium-equivalent 28 32 36 Chromium-equivalent

S235JR (St 37) Welding consumable

10 20 40

Nickel-equivalent

20

Nickel-equivalent

40 80

A+M 16 12 8 4 F M+F M 20% : =1:1 +

123

3 1 20%
3
A+F

80 A+F 100 % F

A+M+F M+F

100 % F

A+M+F

X8Cr17 (W.-Nr. 1.4510)

21% Cr, 14% Ni, 3% Mo

S235JR (St 37) Welding consumable

X10CrNiTi18-9 (W.-No. 1.4541)

21% Cr, 14% Ni, 3% Mo

Weld metal under 30 % dilution (= base metal amount)

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ISF 2002

Weld metal under 30 % dilution (= base metal amount)

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ISF 2002

Application Example of Schaeffler - Diagram

Application Example of Schaeffler - Diagram

Figure 5.11

Figure 5.12

5. Welding of High-Alloy Steels, Corrosion

64

The ferrite content can only be measured with a relatively large dispersal, therefore DeLong proposed to base a measurement procedure on standardized specimens. Such a system makes it possible to measure comparable values which don't have to match the real ferrite content. Based on these measurement values, the ferrite content is no longer given in percentage, but steels are grouped by ferrite numbers. In addition to ferrite numbers, DeLong proposed a reworked Schaeffler diagram where the ferrite number can be determined by the chemical composition, Figure 5.13. Moreover, DeLong has considered the influence of nitrogen as a strong austenite developer (effects are comparable with influence of carbon). Later on, nitrogen was included into the nickel-equivalent of the Schaeffler diagram.
21

Nickel-equivalent = %Ni + 30 x %C + 30 x %N + 0,5 x %Mn

20 19 18 17 16 15 14 13 12 11 10 16 austenite

te rri fe d re su ea ym all .-% tic vol e n in ag s m nt 0% ly te er con 2% rm fo rrite 4% Sc e f ha effl 6% % er6 au 7, 2% ste nite 9, 7% , -m art 10 ,3% en site 12 ,8% -lin 13 e

nu

r be m 0 2 4 6 8 10 12 14 16 18

The most important feature of high alloy steels is their corrosion resistance starting with a Cr content of 12%. In addition to the problems during welding
austenite + ferrite

described by the Schaeffler diagram, these steels can

26 27

17
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18

25 19 20 21 22 23 24 Chromium-equivalent = %Cr + %Mo + 1,5 x %Si + 0,5 x %Nb

ISF 2002

be negatively affected with view to their corrosion resistance caused by the

De Long Diagram

Figure 5.13

welding process.

Figure

air O 2Fe+++O+H2O 2Fe++++2OHOHFe+++ water

5.14 shows schematically the processes of electrolytic corrosion under a

O2 OH H2O cathode 4eFe(OH)3

drop of water on a piece of iron. In such a system a potential difference is a precondition for the development of a local element consisting of an anode and a cathode. To develop

2Fe++

anode 2Fe 2Fe+++4eiron

O2+2H2O+4e 4OH

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ISF 2002

Corrosion Under a Drop of Water

Figure 5.14

5. Welding of High-Alloy Steels, Corrosion

65

such a local element, a different orientation of grains in the steel is sufficient. If a potential difference under a drop of water is present, the chemically less noble part reacts as an anode, i.e. iron is oxidised here and is dissolved as Fe2+-ion together with an electron emission. Caused by oxygen access through the air, a further oxidation to Fe3+ takes place. The cathodic, chemically nobler area develops OH- ions, absorbing oxygen and the electrons. Fe3+and OH--ions compose into the water-insoluble Fe(OH)3 which deposits as rust on the surface (note: the processes here described should serve as a principal explanation of electrochemical corrosion mechanisms, they are, at best, a fraction of all possible reactions). If the steel is passivated by chromium, the corrosion protection is provided by the development of a very thin chromium oxide layer which separates the material from the corrosive medium. Mechanical surface damages of this layer are completely cured in a very short time.

passive layer

passive layer

active dissolution

gap tensile stress

active dissolution of the crack base pitting corrosion passive layer stress corrosion cracking passive layer activly dissolved grain boundary chromium depleted zones active dissolution of the gap crevice corrosion grain boundary carbides intergranular corrosion

incorrect

correct

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ISF 2002

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ISF 2002

Figure 5.15

Figure 5.16

The examples in Figure 5.15 are more critical, since a complete recovery of the passive layer is not possible from various reasons.

5. Welding of High-Alloy Steels, Corrosion

66 If crevice corrosion is present, corrosion products built up in the root of the gap and oxygen has no access to restore the passive layer. Thus narrow gaps where the corrosive medium can accumulate are to be avoided by introducing a suitable design, Figure 5.16.

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Pitting Corrosion of a Steel Storage Container

With pitting corrosion, the chemical composition of the attacking medium causes a

Figure 5.17

local break-up of the passive layer. Especially salts, preferably Clions, show this behaviour. This local attack causes a dissolution of the material on the damaged points, a depression develops. Corrosion products accumulate in this depression, and the access of oxygen to the bottom of the hole is obstructed. However, oxygen is required to develop the passive layer, therefore this layer cannot be completely cured and pitting occurs, Figure 5.17. Stress-corrosion cracking occurs when the material displaces under stress and the passive layer tears, Figure 5.18. Now the unprotected area is subjected to corrosion, metal is dissolved and the passive layer redevelops (figures 13). The repeated displace1 2 3 4 5 6

ment tion.

and

repassivation corrosion mainly

causes a crack propagaStress takes cracking

10

11

12

offset;

passive layer;

metal surface;

dislocation

place in chloride solutions. The crack propagation is transglobular, i.e. it does

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Model of Crack Propagation Through Stress Corrosion Cracking

not

follow

the

grain

boundaries.

Figure 5.18

5. Welding of High-Alloy Steels, Corrosion

67

Figure 5.19 shows the expansion-rate dependence of stress corrosion cracking. With very low expansion-rates, a curing of the passive layer is fast enough to arrest the crack. With very high expansion-rates, the failure of the specimen originates from a ductile fracture. In the intermediate range, the material damage is due to stress corrosion cracking. Figure 5.20 shows an example of crack propagation at transglobular stress corrosion cracking. A crack propagation speed is between 0,05 to 1 mm/h for steels with 18 - 20% Cr and 8 20% Ni. With view to welding it is important to know that already residual welding stresses may release stress corrosion cracking.

Sensitivity to stress corrosion cracking

complete cover layer

tough fracture

T=RT

SpRK

e 2

e 1

Elongation speed e

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ISF 2002

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ISF 2002

Influence of Elongation Speed on Sensitivity to Stress Corrosion Cracking

Transgranular Stress Corrosion Cracking

Figure 5.19

Figure 5.20

The most important problem in the field of welding is intergranular corrosion (IC). It is caused by precipitation of chromium carbides on grain boundaries. Although a high solubility of carbon in the austenite can be expected, see Fe-C diagram, the carbon content in high alloyed Cr-Ni steels is limited to approximately 0,02% at room temperature, Figure 5.21.

5. Welding of High-Alloy Steels, Corrosion

68 The reason is the very high affinity of chro-

to Bain and Aborn 1200 C 1100 1000 900 800 700 600 0 0.05 0.1 0.15 0.2 Carbon content 0.25 % 0,3 A

mium to carbon, which causes the precipitation of chromium carbides Cr23C6 on grain boundaries, Figure 5.22. Due to these precipitations, the austenite grid is depleted of chromium content along the grain boundaries and the Cr content drops below the parting limit. The diffusion speed of chromium in austenite is considerably lower than that of carbon, therefore the chromium reduction cannot be compensated by late diffusion. In the depleted areas along the grain boundaries (line 2 in Figure 5.22) the steel has become susceptible to corrosion.

Heat treatment temperature

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ISF 2002

Carbon Solubility of Austenitic Cr - Ni Steels

Only after the steel has been subjected to sufficiently long heat treatment, chromium will diffuse to the grain boundary and increase the

Figure 5.21

C concentration along the grain boundary (line 3 in Figure 5.22). In this way, the complete corrosion resisChromium content of austenite
resistance limit 3 1 - homogenuous starting condition 2 - start of carbide formation 3 - start of concentration balance 4 - regeneration of resistance limit 1 2 4

tance can be restored (line 4 in Figure 5.22). Figure 5.23 explains why the IC is also described as intergranular disintegration. Due to dissolution of depleted areas along the grain boundary, complete grains break-out of the steel.

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Distance from grain boundary

ISF 2002

Sensibility of a Cr - Steel

Figure 5.22

5. Welding of High-Alloy Steels, Corrosion The precipitation and repassivation mechanisms described in Figure 5.22 are covered by intergranular corrosion diagrams according to Figure 5.24. Above a certain temperature carbon remains dissolved in the austenite (see also Figure 5.21). Below this temperature, a carbon precipitation takes place. As it is a diffusion controlled certain process, the time
3
Reciprocal of heat treatment temperature 1/T
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69

Grain Disintegration

Figure 5.23

precipitation occurs after a incubation

unsaturated austenite austenite chromium carbide (M23C6) no intergranular disintegration

which depends on temperature (line 1, precipitation characteristic curve). During stoppage at a constant temperature, the parting limit of the steel is

2
austenite + chromium caride (M23C6) sensitive to intergranular disintegration

oversaturated austenite

Heat treatment time (lgt)

regained by diffusion of chromium.

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1 incubation time 2 regeneration of resistance limit 3 saturation limit for chromium carbide

ISF 2002

Area of Intergranular Disintegration of Unstabilized Cr - Steels

Figure 5.24

Figure 5.25 depicts characteristic precipitation curves of a ferritic and of an austenitic steel. Due to the highly increased diffusion speed of carbon in ferrite, shifts the curve of carbon precipitation of this steel markedly towards shorter time. Consequently the danger of intergranular corrosion is significantly higher with ferritic steel than with austenite.

5. Welding of High-Alloy Steels, Corrosion

70

As carbon is the element that triggers the intergranular corrosion, the intergranular corrosion diagram is relevantly influenced by the c content, Figure 5.26. By decreasing the carbon content of steel, the start of carbide precipitation and/or the start of intergranular corrosion are shifted towards so-called than 0,03% During welding, the considerable influence of
cooling curve

lower temperatures ELC-steels

and

longer

quench temperature precipitation curves for 17% Cr steel 18-8-Cr-Ni steel

times. This fact initiated the development of where the C content is decreased to less
Tempering temperature

(Extra-Low-Carbon)

carbon is also important for the selection of the shielding gas, Figure 5.27. The higher the CO2-content of the shielding gas, the
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Tempering time

stronger is its carburising effect. The Ccontent of the weld metal increases and the steel becomes more susceptible to intergranular corrosion.
Figure 5.25

Precipitation Curves of Various Alloyed Cr Steels

1000 C 900 800

An often used method to avoid intergranular corrosion is a stabilisation of the

0.07%C

700

steel by alloy elements like

0.05%C 0.03%C

Temperature

niobium and titanium, Fig0.025%C

600

ure 5.28. The affinity of these elements to carbon is significantly higher than that of chromium, therefore

500

400 1 10
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102

103 Time

104

105

106
ISF 2002

carbon is compounded into Nb- and Ti-carbides. Now carbon cannot cause any chromium depletion. The

Influence of C-Content on Intergranular Disintegration

Figure 5.26

5. Welding of High-Alloy Steels, Corrosion

71

proportion of these alloy elements depend on the carbon content and is at least 5 times higher with titanium and 10 times higher with niobium than that of carbon. Figure 5.28 shows the effects of a stabilisation in the intergranular corrosion diagram. If both steels are subjected to the same heat treatment (1050 C/W means heating to 1050 C and subsequent water quenching), then the area of intergranular corrosion will shift due to stabilisation to significantly longer times. Only with a much higher heat treatment temperature the intergranular corrosion accelerates again. The cause is the dissolution of titanium carbides at sufficiently high temperature. This carbide dissolution causes problems when welding stabilised steels. During welding, a narrow area of the HAZ is heated above 1300 C, carbides are dissolved. During the subsequent cooling and the high cooling rate, the carbon remains dissolved.

700
Heat treatment temperature

600 550

M2 M1

0.018 % C 0.57 % Nb Nb/C = 32

Heat treatment temperature

0.058 % C 0.53 % Nb Nb/C = 9

0.030 % C 0.51 % Nb Nb/C = 17

800 C 700 650 600 550 500 450 0,3 1 3 10 30 100 Time W.-No.:4301 (0,06%)

1050C /W

500 450 400 0,2 0,5 1 2,5 5 10 25 50 100 250 h

S1

300

1000

10000

1000

Heat treatment time

X5CrNi18-10
Heat treatment temperature
800 C 700 650 600 550 500 450 0,3

unstabilized

C o m p o sitio n S hie ld ing g a s S 1 M 1 M 2 A r [% ] 99 90 82 C O2 / 5 18 O2 1 5 /

1300C /W 1050C /W

1 3 W.-No.:4541

10

30

100 Time

300

1000

10000

X5CrNiTi18-10

stabilized

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Influence of Shielding Gas on Intergranular Disintegration

Influence of Stabilization on Intergranular Disintegration

Figure 5.27

Figure 5.28

If a subsequent stress relief treatment around 600 C is carried out, carbide precipitations on grain boundaries take place again. Due to the large surplus of chromium compared with niobium or titanium, a partial chromium carbide precipitation takes place, causing again inter-

5. Welding of High-Alloy Steels, Corrosion

72

granular susceptibility. As this susceptibility is limited to very narrow areas along the welded joint, it was called knife-line attack because of its appearance. Figure 5.29. In stabilised steels, the chromium carbide represents an unstable phase, and with a sufficiently long heat treatment to transform to NbC, the steel becomes stable again. The stronger the steel is over-stabilised, the lower is the tendency to knife-line corrosion. Nowadays the importance of Nickel-Base-Alloys increases constantly. They are ideal materials when it comes to components which are exposed to special conditions: high temperature, corrosive attack, low temperature, wear rebr-er-06-29e.cdr

sistance, or combinations hereof. Figure 5.30 shows one of the possible grouping of nickel-base-alloys.
Figure 5.29

Knife-Line Corrosion

Materials listed there are selected examples, the total number of available materials is many times higher. Group A consists of nickel alloys. These alloys are
Alloy Group A Nickel 200 Nickel 212 Nickel 222 Group B Monel 400 Monel 450 Ferry Group C Inconel 600 Nimonic 75 Nimonic 86 Incoloy 800 Incoloy 825 Inco 330 Ni 66.5, Cu 31.5 Ni 30.0, Cu 68.0, Fe 0.7, Mn 0.7 Ni 45.0, Cu 55.0 Ni 76.0, Cr 15.5, Fe 8.0 Ni 80.0, Cr 19.5 Ni 64.0, Cr 25.0, Mo 10.0, Ce 0.03 Ni 32.5, Fe 46.0, Cr 21.0, C 0.05 Ni 42.0, Fe 30.0, Cr 21.5, Mo 3.0, Cu 2.2, Ti 1.0 Ni 35.5, Fe 44.0, Cr 18.5, Si 1.1 Ni 99.6, C 0.08 Ni 97.0, C 0.05, Mn 2.0 Ni 99.5, Mg 0.075 Chem. composition Alloy Group D1 Duranickel 301 Ni 94.0, Al 4.4, W 0.6 Incoloy 925 Ni 42.0, Fe 32.0, Cr 21.0, Mo 3.0, W 2.1, Cu 2.2, Al 0.3 Ni-Span-C 902 Y2O3 0.5, Ni 42.5, Fe 49.0, Cr 5.3, W 2.4, Al 0.5 Group D2 Monel K-500 Inconel 718 Ni 65.5, Cu 29.5, Al 2.7, Fe 1.0, W 0.6 Ni 52.0, Cr 22.0, Mo 9.0, Co 12.5, Fe 1.5, Al 1.2 Chem. Composition

characterized by moderate mechanical strength and high degree of toughness. They can be hardened only by cold working. The alloys are quite gummy in the annealed or hot-worked condition, and cold-drawn material is recommended

Inconel X-750 Ni 61.0, Cr 21.5, Mo 9.0, Nb 3.6, Fe 2.5 Nimonic 90 Ni 77.5, Cr 20.0, Fe 1.0, W 0.5, Al 0.3, Y2O3 0.6 Nimonic 105 Incoloy 903 Incoloy 909 Inco G-3 Inco C-276 Group E Monel R-405 Ni 66.5, Cu 31.5, Fe 1.2, Mn 1.1, S 0.04 Ni 76.0, Cr 19.5, Fe 112.4, Al 1.4 Ni 39.0, Fe 34.0, Cr 18.0, Mo 5.2, W 2.3, Al 0.8 Ni 58.0, Cr 19.5, Co 13.5, Mo 4.25, W 3.0, Al 1.4 Ni 38.4, Fe 42.0, Cu 13.0, Nb 4.7, W 1.5, Al 0.03, Si 0.15 Ni 38.4, Fe 42.0, Cu 13.0, Nb 4.7, W 1.5, Al 0.03, Si 0.4

br-er-06-30e.cdr

ISF 2002

Typical Classification of Ni-Base Alloys

for best machinability and smoothest finish.

Figure 5.30

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Group B consists mainly of those nickel-copper alloys that can be hardened only by cold working. The alloys in this group have higher strength and slightly lower toughness than those in Group A. Cold-drawn or cold-drawn and stress-relieved material is recommended for best machinability and smoothest finish. Group C consists largely of nickel-chromium and nickel-iron-chromium alloys. These alloys are quite similar to the austenitic stainless steels. They can be hardened only by cold working and are machined most readily in the cold-drawn or cold-drawn and stress-relieved condition. Group D consists primary of age-hardening alloys. It is divided into two subgroups: D 1 Alloys in the non-aged condition. D 2 Aged Group D-1 alloys plus several other alloys in all conditions. The alloys in Group D are characterized by high strength and hardness, particularly when aged. Material which has been solution annealed and quenched or rapidly air cooled is in the softest condition and does machine easily. Because of softness, the non-aged condition is necessary for trouble free drilling, tapping and all threading operations. Heavy machining of the age-hardening alloys is best accomplished when they are in one of the following conditions: 1. Solution annealed 2. Hot worked and quenched or rapidly air cooled Group E contains only one material: MONEL R-405. It was designed for mass production of automatically machined screws. Due to the high number of possible alloys with different properties, only one typical material of group D2 is discussed here: Material No. 2.4669, also known as e.g. Inconel X-750. The aluminium and titanium containing 2.4669 is age-hardening through the combination of these elements with nickel during heat treatment: gamma-primary-phase (') develops which is the intermetallic compound Ni3(Al, Ti). During solution heat treatment of X-750 at 1150 C, the number of flaws and dislocations in the crystal is reduced and soluble carbides dissolve. To achieve best results, the material

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should be in intensely worked condition before heat treatment to permit a fast and complete recrystallisation. After solution heat treatment, the material should not be cold worked, since this would generate new dislocations and affect negatively the fracture properties. The creep rupture resistance of X-750 is due to an even distribution of the intercrystalline ' phase. However, fracture properties depend more on the microstructure of the grain boundaries. During an 840 C stabilising heat treatment as part of the triple-heat treatment, the fine ' phase develops inside the grains and M23C6 precipitates onto the grain boundaries. Adjacent to the grain boundary, there is a ' depleted zone. During precipitation hardening (700 C/20 h) ' phase develops in these depleted zones. ' particles arrest the movement of dislocations, this leads to improved strength and creep resistance properties. During the M23C6 transformation, carbon is stabilised to a high degree without leaving chromium depleted areas along the grain boundaries. This stabilisation improves the resistance of this alloy against the attack of several corrosive media. With a reduction of the precipitation temperature from 730 to 620 C as required for some special heat treatments additional ' phase is precipitated in smaller particles. This enhances the hardening effect and improves strength characteristics. Further metallurgical discussions about X-750, can be taken from literature, especially with view to the influence of heat treatment on fracture properties and corrosion behaviour.

The recommended processes for welding of X-750 are tungsten inert gas, plasma arc, electron beam, resistance, and pressure oxy arc welding. During TIG welding of INCONEL X-750, INCONEL 718 is used as welding consumable. Joint properties are almost 100% of base material at room temperature and about 80% at 700 820 C. Figure 5.31 shows typical strength properties of a welded plate at a temperature range between -423 and 1500 F (-248 820 C). Before welding, X-750 should be in normalised or solution heat treated condition. However, it is possible to weld it in a precipitation hardened condition, but after that neither the seam nor the heat affected zone should be precipitation hardened or used in the temperature range of precipitation hardening, because the base material may crack. If X-750 was precipitation hardened and then welded, and if it is likely that the workpiece is used in the temperature range of precipitation hardening, the weld should be normalised or once again precipitation hardened. In any case it must be noted that heat stresses are minimised during assembly or welding.

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X-750 welds should be solution heat treated before a precipitation hardening. Heating-up speed during welding must be from the start fast and even touching the temperature range of precipitation hardening only as briefly as possible. The best way for fast heating-up is to insert the welded workpiece into a preheated furnace. Sometimes a preheating before welding is advantageous if the component to be welded has a poor accessibility, or the welding is complex, and especially if the assembly proves to be too complicated for a post heat treatment. Two effective welding preparations are: 1. 1550 F/16 h, air cooling 2. 1950 F/1 h, furnace cooling with 25 -100 F/h up to 1200 F, air A repair welding of already fitted parts should be followed by a solution heat treatment (with a fast heating-up through the temperature range of precipitation hardening) and a repeated precipitation hardening. A cleaning of intermediate layers must be carried out to remove the oxide layers which are formed during welding. (A complete isolation of the weld metal using gas shielded processes is hardly possible). If such films are not removed on a regular basis, they can become thick enough to cause material separations together with a reduced strength. Brushing with wire brushes only polishes the surface, the layer surface must be sand-blasted or ground with abrasive material. The frequency of cleaning depends on the mass of the developed oxides. Any sand must be removed before the next layer is welded. X-750 can be joined also by spot-, projection-, seam-, and flash butt welding. The welding equipment must be of adequate performance. X-750 is generally resistance welded in normalized or solution heat treated condition.
Figure 5.31