2.

TTA / TTT - Diagrams

2. TTA / TTT Diagrams

9 An essential feature of low alloyed ferrous materials is

a -Iron body-centered

g -Iron face-centered

the crystallographic transformation of the bodycentred cubic lattice which is stable at room temperature (-iron, ferritic structure) to the face-centred cubic lattice (-iron, aus ISF 2002

Lattice constant 0.286 nm at room temperature

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Lattice constant 0.364 nm at 900 C

tenitic 2.1.

structure), The

Figure

Body- and Face-Centered Lattice Structures

temperature,

where this transformation occurs, is not constant but depends on factors like

Figure 2.1

alloy content, crystalline structure, tensional status, heating and cooling rate, dwell times, etc.. In order to be able to understand the basic
L1 S TsA T1 T2 S+ a 3 2 5 So 4 Li TsB L1

processes it is necessary to have a look at the basic processes occuring in an Figure 2.2 shows the state of a binary system with
a 1

Temperature T

a - ss
b

complete solubility in the liquid and solid state. If the melting of the L1 alloy is cooling down, the first crystals of the composition c1 are formed with reaching the temperature T1. These crystals are depicted as mixed crystal , since they consist of a compound of the components A (80%) and of B (20%). Further, a melting with the composition c0 is present at the temperature T1. With dropping temperature, the remaining melt is enFigure 2.2
A (Ni) c1 c2 c0
c3

c4

Concentration c

B (Cu)

Temperature T

idealized

binary

system.

Time t

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ISF 2002

Binary System With Complete Solubility in Liquid and Solid Phase

2. TTA / TTT Diagrams

10

riched with component B, following the course of line Li (liquidus line, up to point 4). In parallel, always new and B richer -mixed crystals are forming along the connection line So (solidus line, points 1, 2, 5). The distribution of the components A and B in the solidified structure is homogeneous since concentration differences of the precipitated mixed crystals are balanced by diffusion processes. The other basic case of complete solubility of two components in the liquid state and of complete insolubility in the solid state shows Figure 2.3 If two components are completely insoluble in the solid state, no mixed crystal will be formed of A and B. The two liquidus lines Li cut in point e which is also designated as the eutectic point. The isotherm Te is the eutectic line. If an alloy of free composition solidifies according to Figure 2.3, the eutectic line must be cut. This is the temperature (Te) of the eutectic transformation: S A+B (T = Te = const.). This means that the melt at a constant temperature Te dissociates in A and B. If an alloy of the composition L2 solidifies, a purely eutectic structure results. On account of the eutectic reaction, the temperature of the alloy remains constant up to the completed transformation (critical point) (Figure 2.2). Eutectic structures are normally fine-grained and show a characteristic orientation between the constituents. The alloy L1 will consist of a compound of alloy A and eutectic alloy E in the solid state. You can find further inL1 TsA S 2 1 TsB Li Li L2 L1 L2

formation on transformation behaviour in relevant specialist literature. The definite use of the principles occurs in the iron-iron carbide diagram.

Temperature T

S+A

So Te

S+B 3 4

A+E

B+E

A
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c1 Concentration c

ce

Temperature T

Time t
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Transformation behaviour of carbon containing iron in the equilibrium condition is described by the

Binary System With Complete Solubility in Liquid Phase and Complete Unsolubility in Solid Phase

Figure 2.3

2. TTA / TTT Diagrams

11

stable phase diagram iron-graphite (Fe-C). In addition to the stable system Fe-C which is specific for an equilibrium-close cooling, there is a metastable phase diagram iron cementite (Fe-Fe3C). During a slow cooling, carbon precipitates as graphite in accord with the stable system Fe-C, while during accelerated cooling, what corresponds to technical conditions, carbon precipitates as cementite in agreement with the metastable system (Fe-Fe3C). Per definition, iron carbide is designated as a structure constituent with cementite although its stoichiometric composition is identical (Fe3C). By definition, cementite and graphite can be present in steel together or the cementite can decompose to iron and graphite during heat treatment of carbon rich alloys. However, it is fundamentally valid that the formation of cementite is encouraged with increasing cooling rate and decreasing carbon content. In a double diagram, the stable system is shown by a
dmelt + d - solid solution melt melt + graphite

dashed, the metastable by a solid line, Figure 2.4.

solid sol.

d -+gsolid sol. melt + austenite

Fe3C (cementite)

Temperature C

austenite

melt + cementite

The

metastable

phase

austenite + graphite austenite + cementite

diagram is limited by the formation of cementite with a carbon content of 6,67 mass%. The of strict the
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austenite + ferrite

ferrite ferrite + graphite ferrite + cementite

perlite

stable equilibrium metastable equilibrium

Mass % of Carbon
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stoichiometry

formed carbide phase can be read off at the top Xcoordinate of the molar
Figure 2.4

Stable and Metastable Iron-Carbon-Diagram

carbon content. In accordance with the carbon content of Fe3C, cementite is formed at a molar content of 25%. The solid solutions in the phase fields are designated by Greek characters. According to convention, the transition points of pure iron are marked with the character A - arrt (stop point) and distinguished by subjacent indexes. If the transition points are determined by cooling curves, the character r = refroidissement is additionally used. Heat-up curves get the supplement c - chauffage. Important transition points of the commercially more important metastable phase diagram are:

1536 solidification temperature (melting point) -iron, C: 1392 A4- point - iron, C:

ledeburite

2. TTA / TTT Diagrams 911 A3- point non-magnetic - iron, C: 723 A1- point (perlite point). C:

12

with carbon containing iron: The corners of the phase fields are designated by continuous roman capital letters. As mentioned before, the system iron-iron carbide is a more important phase diagram for technical use and also for welding techniques. The binary system iron-graphite can be stabilized by an addition of silicon so that a precipitation of graphite also occurs with increased solidification velocity. Especially iron cast materials solidify due to their increased silicon contents according to the stable system. In the following, the most important terms and transformations should be explained more closely as a case of the metastable system. The transformation mechanisms explained in the previous sections can be found in the binary system iron-iron carbide almost without exception. There is an eutectic transformation in point C, a peritectic one in point I, and an eutectoidic transformation in point S. With a temperature of 1147 and a carbon concentration of 4.3 mass%, the eutectic phase called LeC deburite precipitates from cementite with 6,67% C and saturated -solid solutions with 2,06% C. Alloys with less than 4,3 mass% C coming from primary austenite and Ledeburite are called hypoeutectic, with more than 4,3 mass% C coming from primary austenite and Ledeburite are called hypereutectic.

If an alloy solidifies with less than 0,51 mass percent of carbon, a -solid solution is formed below the solidus line A-B (-ferrite). In accordance with the peritectic transformation at 1493 melt (0,51% C) and -ferrite (0,10% C) decompose to a -solid solution (austenite). C,

The transformation of the -solid solution takes place at lower temperatures. From -iron with C-contents below 0.8% (hypoeutectoidic alloys), a low-carbon -iron (pre-eutectoidic ferrite) and a fine-lamellar solid solution (perlite) precipitate with falling temperature, which consists of -solid solution and cementite. With carbon contents above 0,8% (hypereutectoidic alloys) secondary cementite and perlite are formed out of austenite. Below 723 tertiary cementite C, precipitates out of the -iron because of falling carbon solubility.

2. TTA / TTT Diagrams

13

The most important distinguished feature of the three described phases is their lattice structure. - and -phases are cubic body-centered (CBC lattice) and -phase is cubic facecentered (CFC lattice), Figure 2.1. Different carbon solubility of solid solutions also results from lattice structures. The three above mentioned phases dissolve carbon interstitially, i.e. carbon is embedded between the iron atoms. Therefore, this types of solid solutions are also named interstitial solid solution. Although the cubic face-centred lattice of austenite has a higher packing density than the cubic body-centred lattice, the void is bigger to disperse the carbon atom. Hence, an about 100 times higher carbon solubility of austenite (max. 2,06% C) in comparison with the ferritic phase (max. 0,02% C for -iron) is the result. However, diffusion speed in -iron is always at least 100 times slower than in -iron because of the tighter packing of the -lattice.

Although - and -iron show the same lattice structure and properties, there is also a difference between these phases. While -iron develops of a direct decomposition of the melt (S ), -iron forms in the solid phase through an eutectoidic transformation of austenite ( + Fe3C). For the transformation of non- and low-alloyed steels, is the transformation of ferrite of lower importance, although this -phase has a special importance for weldability of high alloyed steels. Unalloyed steels used in industry are multi-component systems of iron and carbon with alloying elements as manganese, chromium, nickel and silicon. Principally the equilibrium diagram Fe-C applies also to such multi-component sysAc3

tems. Figure 2.5 shows a schematic cut through the

Ac1e

three phase system Fe-M-C. During precipitation, mixed carbides of the general composition M3C develop.
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In contrast to the binary

Description of the Terms Ac1b, Ac1e, Ac3

system Fe-C, is the three

Figure 2.5

2. TTA / TTT Diagrams

14

phase system Fe-M-C characterised by a temperature interval in the three-phase field + + M3C. The beginning of the transformation of + M3C to is marked by Aclb, the end by Acle. The indices b and e mean the beginning and the end of transformation. The described equilibrium diagrams apply only to low heating and cooling rates. However, higher heating and cooling rates are present during welding, consequently other structure types develop in the heat affected zone (HAZ) and in the weld metal. The structure transformations during
Figure 2.6
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ISF 2002

TTA Diagram for Isothermal Austenitization

heating and cooling are described by transformation diagrams, where a temperature change is not carried out close to the equilibrium, but
ASTM4; L=80m ASTM11; L=7m

at different heating and/or cooling rates. A representation during of the transformation austenitizing processes isothermal

shows Figure 2.6. This figure must be read

20m 20m

exclusively along the time axis! It can be recognised 800 C. that several transformations austenite means during isothermal austenitizing occur with e.g. Inhomogeneous both, low carbon containing austenite is formed in areas, where ferrite was present before transformation, and carbon-rich austenite is formed in areas during transformation, where carbon was present before

Temperature

Time
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transformation. During sufficiently long annealing times, the concentration differences are balanced by diffusion, the border to a ho-

TTA-Diagram for Continuous Warming

Figure 2.7

2. TTA / TTT Diagrams

15

mogeneous austenite is passed. A growing of the austenite grain size (to ASTM and/or in m) can here simultaneously be observed with longer annealing times.

The influence of heating rate on austenitizing is shown in Figure 2.7. This diagram must only be read along the sloping lines of the same heating rate. For better readability, a time pattern was added to the pattern of the heating curves. To elucidate the grain coarsening during austenitizing, two microstructure photographs are shown, both with different grain size classes to ASTM. Figure 2.8 shows the relation between the TTA and
Ac3

the Fe-C diagram. It's obvious that the Fe-C diagram is only valid for infinite long dwell times and that the TTA diagram applies only for one individual alloy. Figure 2.9 shows the dif-

Ac1e Ac1b

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ISF 2002

Dependence Between TTA-Diagram and the Fe-M-C System

ferent and down.

time-temperature subsequent cooling

passes during austenitizing

Figure 2.8

The heating period is comAc3 continuous Ac1e

posed of a continuous and an isothermal section.

Ac1b

isothermal

During cooling down, two different ways of heat control can be distinguished: 1. : During continuous temperature control a

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ISF 2002

Heating and Cooling Behaviour With Several Heat Treatments

cooling is carried out with a constant cooling rate out of

Figure 2.9

2. TTA / TTT Diagrams the area of the homogeneous and stable austenite down to room temperature.

16

2. : During isothermal temperature control a quenching out of the area of the austenite is carried out into the area of the metastable austenite (and/or into the area of martensite), followed by an isothermal holding until all transformation processes are completed. After transformation will be cooled down to room temperature. Figure 2.10 shows the

time-temperature diagram of a isothermal transformation of the mild steel Ck 45. Read such diagrams only along the time-axis! Below the Ac1b line in this figure, there is the area of the metastable austenite, marked
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with

an

A.

The

areas

Isothermal TTT-Diagram of Steel C45E (Ck 45)

marked with F, P, B, und M represent areas where ferrite, perlite, Bainite and martensite are formed. The

Figure 2.10

lines which limit the area to the left mark the beginning of the formation of the respective structure. The lines which limit the area to the right mark the completion of the formation of the respective structure. Because the ferrite formation is followed by the perlite formation, the completion of the ferrite formation is not determined, but the start of the perlite formation. Transformations to ferrite and perlite, which are diffusion controlled, take place with elevated temperatures, as diffusion is easier. Such structures have a lower hardness and strength, but an increased toughness.

Diffusion is impeded under lower temperature, resulting in formation of bainitic and martensitic structures with hardness and strength values which are much higher than those of ferrite and perlite. The proportion of the formed martensite does not depend on time. During quenching to holding temperature, the corresponding share of martensite is spontanically formed. The present rest austenite transforms to Bainite with sufficient holding time. The right

2. TTA / TTT Diagrams

17

detail of the figure shows the present structure components after completed transformation and the resulting hardness at room temperature. Figure 2.11 depicts the graphic representation of the TTT diagram, which is more important for welding techniques. This is the TTT diagram for continuous cooling of the steel Ck 15. The diagram must be read along the drawn cooling passes. The lines, which are limiting the individual areas, also depict the beginning and the end of the respective transformation. Close to the cooling curves, the amount of the formed structure is indicated in per cent, at the end of each curve, there is the hardness value of the structure at room temperature. Figure 2.12 shows the TTT diagram of an alloyed steel containing
27 19 40

approximately

the same content of carbon as the steel Ck 15. Here you can see that all transformation processes are strongly postponed in relaTime

370

235 220

170

tion to the mild steel. A

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Continuous TTT-Diagram of Steel C15E (Ck 15)

completely transformation

martensitic is carried

Figure 2.11

out up to a cooling time of about 1.5 seconds, comC 0,13 Si 0,31 Mn 0,51 Al P S 0,023 0,009 0,010 Cr 1,5 Mo 0,06 Ni 1,55 V < 0,01

Chemical composition %
1000 C 900 800 700
Temperature

pared with 0.4 seconds of Ck 15. In addition, the completely diffusion controlled transformation processes of the perlite area are postponed to clearly

austenitizing temperature 870C (dwell time 10 min) heated in 3 min

Ac3 Ac1
75 75 75
25

600 500
MS

A+C

F
5

47

55 67

10 22

75 75 25 25

25 23

B
60 72 55 37

400
M

30

300 200 100

417 400 396

22 9
2

longer times.
167 152 151

314 304 287 268 251 224 192

0 10
-1

10

10

10

10 Time

104

10

s
ISF 2002

106

The hypereutectoid steel C 100 behaves completely different, Figure 2.13. With this carbon content, a pre-

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Continuous TTT-Diagram of Steel 15 CrNi 6

Figure 2.12

2. TTA / TTT Diagrams

18 eutectoid ferrite formation cannot still be car-

Chemical composition %
1000 C 900 800

C Si Mn P S Cr Cu Mo Ni V 1,03 0,17 0,22 0,014 0,012 0,07 0,14 0,01 0,10 traces
austenitizing temperature 790C dwell time 10 min, heated in 3 min

ried out (see also Figure 2.3). The term of the figures 2.9 to 2.11 "austenitizing temperature means the temperature, where the workpiece transforms to an austenitic microstructure in the course of a heat treatment. Dont mix up this temperature with the AC3 temperature, where above it there is only pure austenite. In addition you can see that only martensite is formed from the austenite, provided that the cooling rate is sufficiently high, a formation of any other

AC1e

700

A+C 100 P

Temperature

100

100

100

100

100

100

100 AC1b

600 500 400 300 200 100 0

1000 C 900 800
MS M RA30

2 15 180

914 901 817 366

351

283

236

215

214

177

austenitizing temperature 860C dwell time 10 min, heated in 3 min

AC1e

700

C A P 100 100 100

100

100

100

100

100

AC1b

Temperature

600
500 400 300

100
5

194

200
100

MS RA40 M 876 887 867 496 457 442 347 289 246 227 200

microstructure is completely depressed. With this type of transformation, the steel gains the highest hardness and strength, but loses its toughness, it embrittles. The slowest cooling rate where such a transformation happens, is called critical cooling rate.
Low number of nuclei due to melting, high temperature, long dwell time, coarse austenite grain, C-increase up to 0,9%, Mn, Ni, Mo, Cr
100 101 102 103 104 s 105

0
10-1
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Time

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Continuous TTT-Diagram of Steel C100U (C 100 W1)

Figure 2.13

1000 C 800 900C 1300C

Ar3 Ar1 Perlite 100%

Temperature

Cr, V, Mo

High number of nuclei, low hardening temperature, C-increase above 0,9%

A F 600 MS 400 M B P

Cr, V, Mo

C, Cr, Mn, Ni, Mo, high temperature, ferrite precipitation in perlite Bainite

Low hardening temperature (special carbides), austenite above bainite

200 100

Temperature

Structure distribution

% 75 M M

Ms Martensite C, Mn, Cr, Ni, Mo, V, high hardening temperature, preprecipitation in bainite Co, Al, deformation of austenite, low hardening temperature

50 25 0 10-1 1 10 102 s 103

Transition time
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Cooling time (A3 to 500C)

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Influence of Alloy Elements on Transformation Behaviour of Steels

Temperature Influence on Transformation Behaviour of Steels

Figure 2.14

Figure 2.15

2. TTA / TTT Diagrams

19

Figure 2.14 shows schematically how the TTT diagram is modified by the chemical composition of the steel. The influence of an increased austenitizing temperature on transformation behaviour shows Figure 2.15. Due to the higher hardening temperature, the grain size of the austenite is higher (see Figure 2.6 and 2.7). This grain growth leads to
S355J2G3 (St 52-3) Chemical composition % C 0,16 Max. temperature 1350 C Si 0,47 Welding heat cycle Cu 0,17 Ni 0,06 Mn P S Al N Cr 1,24 0,029 0,029 0,024 0,0085 0,10

an extension of the diffusion lengths which must be passed during the transformation. As a result, the "noses" in the TTT diagram are shifted to longer times. The lower part of the figure shows the proportion of

900 C 800

700
48

Temperature

600
500
B
55

75

400
300

222

215

200
449 420 400 363 334 324 270 253 251 249 243

100

8 10

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20 Time

40

60 80 100

200

400

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formed

martensite

and

Welding TTT-Diagram of Steel S355J2G3 (St 52-3)

Figure 2.16

Bainite depending on cooling time. You can see that with higher austenitizing temperature the start of

15 Mo 3 Chemical composition %
900 C 800

Max. temperature 1350 C C 0,16 Si 0,30 Mn P S Mo 0,68 0,012 0,038 0,29

Welding heat cycle

Bainite formation together with the drop of the martensite proportion is clearly shifted to longer times. As Bainite formation is not so much impeded by the coarse austenite grain as with the completely diffu-

Ac3=861C Ac1=727C F
32 8 4 45 17 53 32

700
1

19

Temperature

600
500

MS 14

B
74 87 95

99

83

77

60

38

15

400

M
300

208

200

178

200
440

HV30

431

338

285

255

234

224

210

100

8 10

20 Time

40

60 80 100

200

400

sion controlled processes of ferrite and perlite formation, the maximum Bainite proportion is increased from about 45 to 75%.

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ISF 2002

Welding TTT - Diagram of Steel 15Mo3 (15 Mo 3)

Figure 2.17

2. TTA / TTT Diagrams

20

Due to the strong influence of the austenitizing temperature to the transformation behaviour of steel, the welding technique uses special diagrams, the so called Welding-TTT-diagrams. They are recorded following the welding temperature cycle with both, higher austenitizing temperatures (basically between 950 and 1350 and shorter austenitizing times. C) You find two examples in Figures 2.16 and 2.17. Figure 2.18 proves that the
%C 1 1000 C 800 0 1000 C 800 F 600 400 MS B M 200 200 0 10-1 10
0

0,45 0,5

iron-carbon diagram was developed as an equilibrium diagram for infinite long cooling time and that
Temperature

Temperature

600

a TTT diagram applies always oy for one alloy.

400

10

10 Time

10

10

0
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Relation Between TTT-Diagram and Iron-Carbon-Diagram

Figure 2.18