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Precipitation during continuous

casting

vorgelegt von

M. Sc.

Charles-Edouard Muller

geb. in Mulhouse (F)

von der Fakultät III - Prozesswissenschaften

der Technischen Universität Berlin

zur Erlangung des akademischen Grades

Doktor der Ingenieurwissenschaften

- Dr.-Ing. -

genehmigte Dissertation

Promotionsausschuss:
Vorsitzender: Herr Prof. Dr.-Ing. Manfred Wagner
Gutachter: Herr Prof. Dr. rer. nat. Walter Reimers
Gutachter: Herr Prof. Dr.-Ing. Karl-Hermann Tacke

Tag der wissenschaftlichen Aussprache: 1. Dezember 2015

Berlin 2015
2
Abstract

This work deals with the risk of surface cracking during continuous casting of thick
slabs. While surface cracks are traditionally related to losses in ductility and reduc-
tion of area, the current approach is to estimate the precipitation of carbonitrides as
source of cracking. Knowledge on precipitation in continuous casting - still limited
in the literature - is gathered through analysis of as-cast and heat-treated specimens.
Investigations are carried out by Gleeble testing, scanning electron and transmission
electron microscopy, partly using automated particle scans. This is complemented with
thermodynamic equilibrium computations as well as with kinetic numerical modelling
using a commercial package. The microalloying elements titanium, niobium, aluminium
and boron and their nitrides/carbides are considered. Three plate steels with different
micro-alloying concepts are studied. The population of precipitates is characterised by
measurements and model calculations, and related to the surface cracking behaviour
during slab casting.

3
Kurzfassung

Diese Arbeit befasst sich mit dem Risiko von Oberflächenrissen beim Stranggießen dicker
Brammen. Während Oberflächenrisse traditionell mit einer Verschlechterung der Duk-
tilität und der Brucheinschürung in Verbindung gebracht werden, wird hier die Aus-
scheidung von Mikrolegierungselementen als Ursache von Rissen betrachtet. Das in
der Literatur immer noch begrenzte Wissen über Ausscheidungen beim Stranggießen
wird anhand von Proben im gegossenen und wärmebehandelten Zustand erweitert. Die
Untersuchungen basieren auf Gleeble-Versuchen, Raster- und Rastertransmissionsmik-
roskopie; zum Teil auch mittels automatisierter Scan-Methoden. Dies wird durch ther-
modynamische Gleichgewichtsrechungen und einer numerischen Modellierung der Kin-
etik unter Verwendung eines kommerziellen Softwarepaketes ergänzt. Hierbei werden die
Mikrolegierungselemente Titan, Niob, Aluminium, Bor sowie deren Nitride und Karbide
berücksichtigt. Drei Grobblechstähle mit unterschiedlichen Mikrolegierungskonzepten
werden untersucht. Die Ausscheidungspopulationen werden anhand von Messungen und
Modellrechnungen charakterisiert und dem Oberflächenrissverhalten gegenüber gestellt.

4
Contents

1 Introduction 9

2 State of the Art 11


2.1 Phases and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Solubility products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.1 TiN and TiC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.2 NbC, NbN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.3 AlN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2.4 VC and VN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.5 BN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.3 Discussion on thermodynamic modelling using solubility products and its
alternatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4 Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.4.1 Literature data on precipitation kinetics . . . . . . . . . . . . . . . 23
2.4.2 European commission funded projects . . . . . . . . . . . . . . . . 25
2.4.3 Strain induced precipitation . . . . . . . . . . . . . . . . . . . . . . 27
2.4.4 Thermal cycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5 Solidification during continuous casting . . . . . . . . . . . . . . . . . . . 28
2.6 Classical theory of ductility loss . . . . . . . . . . . . . . . . . . . . . . . 29
2.6.1 Strain rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.6.2 Secondary cooling & thermal cycling . . . . . . . . . . . . . . . . 29
2.6.3 Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.6.4 Failure mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . 31

3 Investigation methods 33
3.1 Acid dissolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2 Thermomechanical testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2.1 Ductility testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2.2 Hold and quench trials (HQT) . . . . . . . . . . . . . . . . . . . . 38
3.3 SEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.3.1 Mechanical polishing . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.3.2 Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.3 Fracture surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.4 Automated particle analyses (APA) . . . . . . . . . . . . . . . . . 40
3.4 Scanning transmission electron microposcope (STEM) . . . . . . . . . . . 41
3.5 Energy and wavelength dispersive X-ray spectroscopy (EDS, WDS) . . . . 42

5
Contents

3.6 Comparison of the investigation methods in regard to resolution and in-


spection region . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

4 Modelling 45
4.1 Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.1.1 Basic calculations with solubility products . . . . . . . . . . . . . 45
4.1.2 Equilibrium model . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.1.3 CALPHAD based packages . . . . . . . . . . . . . . . . . . . . . . 49
4.1.4 Austenite to ferrite transformation . . . . . . . . . . . . . . . . . . 50
4.2 Modelling of kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.2.1 Dutta-Sellars model . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.2.2 MatCalc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

5 Al-Ti steel 53
5.1 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.2 Thermomechanical testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.2.1 Ductility trials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.2.2 Fracture facets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.2.3 Microstructure of Gleeble specimens . . . . . . . . . . . . . . . . . 56
5.2.4 Automated particle analysis APA on Gleeble specimens . . . . . . 56
5.2.5 STEM on quenched Gleeble specimens . . . . . . . . . . . . . . . . 61
5.2.6 Discussion APA & STEM vs. thermodynamics . . . . . . . . . . . 62
5.2.7 Particle profiles over the slab thickness (APA) . . . . . . . . . . . 62
5.3 MatCalc kinetic simulations . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.3.1 MatCalc simulations of Gleeble specimens . . . . . . . . . . . . . . 63
5.3.2 MatCalc simulations of TTP diagrams . . . . . . . . . . . . . . . . 64
5.3.3 MatCalc simulation for three positions in slab thickness . . . . . . 66
5.3.4 MatCalc simulation including periodic temperatures and strain . . 68
5.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

6 Nb-Ti steel 73
6.1 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.2 Thermomechanical testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.2.1 Ductility trials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.2.2 Hold and quench trials HQT . . . . . . . . . . . . . . . . . . . . . 75
6.2.3 Particle profiles over the slab thickness . . . . . . . . . . . . . . . . 80
6.3 MatCalc kinetic simulations . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.3.1 MatCalc simulations of HQT samples . . . . . . . . . . . . . . . . 80
6.3.2 MatCalc simulation for three positions in slab thickness . . . . . . 83
6.3.3 MatCalc simulation including periodic temperatures and strain . . 85
6.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

7 Al-Nb-B steel 89
7.1 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

6
Contents

7.2 Thermomechanical testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 91


7.2.1 Ductility trials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
7.2.2 Hold and quench trials HQT . . . . . . . . . . . . . . . . . . . . . 91
7.2.3 Particle profiles over the slab thickness . . . . . . . . . . . . . . . . 97
7.2.4 Reference analysis of narrow face specimens at KIMAB . . . . . . 97
7.3 MatCalc kinetic simulations . . . . . . . . . . . . . . . . . . . . . . . . . . 100
7.3.1 MatCalc simulations of HQT samples . . . . . . . . . . . . . . . . 100
7.3.2 MatCalc simulations of as-cast specimens . . . . . . . . . . . . . . 104
7.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

8 Summary and outlook 111

List of solubility products 113

List of abbreviations 116

List of symbols 117

7
8
1 Introduction

Continuous casting has become a significant alternative to ingot casting since the early
seventies due to its better yield. More recently the process has been extended to the
casting of high thickness heavy plates. With the improvement of the technology, thicker
slabs necessary for the production of high thickness heavy plates can be cast. As a
consequence of the increasing slab thickness and thus increasing deformation during
bending and straightening, the risk of transverse cracks on the slab surface rises. During
rolling, the absence of cracks is critical for the surface quality of heavy plates. Hence
crack sensitive qualities must undergo a time and cost intensive scarfing before rolling.
To improve the properties of heavy plates, the thermo-mechanical rolling (TM rolling)
was developed. It consists of controlled deformation steps at temperatures so that mi-
croalloying elements like titanium (Ti), niobium (Nb), aluminium (Al) and vanadium
(V) can precipitate in desired quantities and sizes. However, these elements precipitate
already during continuous casting and can be at the origin of the cracking problem.
The precipitation of these elements is influenced by the secondary cooling conditions.
Further factors like the intensive cooling at the rolls or the deformations at bending and
straightening have to be taken into account.
The first investigations were concerned with single phases like aluminium nitride and
used solubility products to describe the equilibria. The next step was to consider multiple
precipitating phases and their interaction. Complex equilibrium computations today use
thermodynamic databases in multiphase systems.
The next challenge is to consider the precipitation kinetics. This has been attempted
by several researches, but the problem, especially with multiple precipitation phases, is
so complicated that realistic predictions are not yet reliable, especially for microalloyed
high strength low alloy (HSLA) steels.
This work studies precipitations during continuous casting in three plate steels. The
steels are microalloyed with the elements Ti, Nb, B and contain different quantities of Al.
They form various nitrides and sometimes carbides. The steels have different cracking
risks during continuous casting. The first case mainly involves two precipitating phases,
while four different precipitating elements may interact in the third case.
A set of experimental techniques is used to analyse and quantify the precipitates. Clas-
sical ductility tests show the reduction of area as well as the precipitation state after
fracture. Hold and quench trials allow to assess the effect of strain and temperature
on the precipitation kinetics. These investigations are carried out on industrial samples
from as-cast slabs. Furthermore, slab specimens taken at various distances from the
surfaces were investigated.

9
1 Introduction

The analyses were performed using a scanning electron microscope with automatic
particle analysis. The empirical studies were complemented with equilibrium precip-
itation models: a self-written simple precipitation model and three commercial thermo-
dynamic models (Thermo-Calc, JMatPro, MatCalc). In addition the software package
MatCalc was used for kinetic calculations. Model results are compared to experimental
findings.

10
2 State of the Art

The precipitating phases of microalloying elements are described in manifold publica-


tions. This chapter will give an overview of the relevant phases in the case of continuous
casting of thick slabs and their properties. Further the solubility products will be com-
pared and the challenge of a modelling of the precipitation behaviour based on them will
be discussed. In addition the literature data on precipitation kinetics will be compiled
and discussed; as well as the effects of solidification on the precipitation. Finally the
classical theory of ductility loss will be discussed.

2.1 Phases and their properties


Thermodynamics covers several simulation methods. Solubility products determined
experimentally by holding of simple alloys at constant temperature and analysing the
precipitated phase fraction can be combined to calculate the phase amount of precipitates
of a more complex alloy. Another classical simulation method is the CALPHAD method
using thermodynamic data of binary and ternary systems in complex algorithms in order
to calculate phase diagrams of multicomponent systems. Here only the former will be
discussed.
The precipitating elements considered in these steels are Al, B, Mo, Nb, Ti and V. In low
carbon steels the alloying elements Al and B precipitate only as nitrides while Mo forms
only carbides. The microalloying elements Nb, Ti and V can precipitate as carbides,
nitrides or carbonitrides depending on the concentration of carbon and nitrogen. Further
the latter may form complex carbonitrides since the phases have all a cubic structure
and similar lattice spacings.
The thermodynamics of the different precipitating phases will be described in the fol-
lowing.

TiN and other Ti-containing precipitates

The main effect of Ti in microalloyed steels is the inhibition of grain boundary move-
ment, thereby providing grain refinement. Ti precipitates depending on the C and N
concentrations either as nitride, carbide or carbonitride. Its effect is very important since
it precipitates first and may consume all the N so that no other nitride can precipitate
during the subsequent cooling.

TiN Titanium is well known for its extremely low solubility in steel so that even modest
Ti additions are sufficient to induce precipitations of TiN [1]. The segregation occurring

11
2 State of the Art

during solidification leads to locally high Ti and N concentrations and allow in turn the
precipitation in both the liquid and delta ferrite. The authors of the RFCS-1 project [2]
estimated that a supersaturation of at least 10 should ensure a sufficient driving force
for TiN to precipitate before total solidification. In case no Ti precipitates as TiN in the
liquid, the precipitation will be stronger in the delta ferrite than in the austenite. This
can be explained by the lower solubility in ferrite.
If the steel contains 200 ppm Ti and 80 ppm N as typical of microalloyed steels, Kunze
et al. consider a TiN precipitation due to microsegregation as impossible [3]. How-
ever, they predict TiN precipitates in areas affected by supersaturations of more than
10 to 15 during a ferritic solidification [4]. An even higher segregation can be reached
during austenitic solidification. However, the cooling rate during the solidification con-
sidered is approximately 10 times higher than typical for continuous casting. Further
measurements were made by Secondary Ion Mass Spectrometry SIMS and showed a Ti
supersaturation of up to 9 [4].
TiN were for example observed at more than 10 nm from the slab surface in the form of
rosettes and small dendrites [5]. The size of the Ti(C,N) increases with the distance from
the as-cast surface because the cooling rate becomes lower with the distance from the
surface. A further reason for the increasing size is the macrosegregation that occurred
during solidification. All precipitates are distributed regularly, but cubic Ti(C,N) tended
to nucleate in bands parallel to the direction of solidification [5].
Further Zhou and Priestner [6] mention also the existence of Nb containing Ti(C,N).
Especially at low Ti contents manganese sulphides may act as nucleation site for Nb-
rich Ti-carbonitrides .

TiC and Ti(C,N) Titanium carbides are less stable than TiN. However complex Ti(C,N)
are prone to precipitate early and in great amounts.
Riaz et al. and Ludlow et al. [5, 7] investigated the precipitation of (Ti,Nb)(C,N). In the
steels used they were found to precipitate preferably at austenite grain boundaries or in
the form of strings of around 70 nm length. The size of the precipitates increases and their
number decreases with increasing distance from the slab surface or diminishing degree of
undercooling. However the precipitates have several different forms and corresponding
sizes from few nanometres up to several hundred of nanometres.

Nb and other Nb-containing precipitates

Niobium can remain in solid solution in austenite or precipitate in both the austenite and
ferrite domains. The strengthening effect of the solid solution is stronger than with Ti or
V while the grain refinement effect of the precipitate may also play a role. However the
most important effect of Nb is the retardation of recrystallisation [1]. Nb can precipitate
as nitride, carbide or carbonitride at dislocations, grain boundaries, sub-grain boundaries
and even heterogeneously at other precipitates like TiN or AlN [8].

12
2.1 Phases and their properties

NbC and NbN Wilson and Gladman [9] indicate that NbN is thermodynamically more
stable than NbC, the precipitation of NbN is however considered to be almost impossible
in commercial steels at higher C/Nb ratios. Hence the precipitates are mostly complex
carbonitrides whereby the N content is higher as they are formed at higher temperatures
due to the higher stability of NbN. Six et al. [10] have another point of view and consider
pure NbC to be the main precipitating phase in a HSLA steel with Nb addition. The
addition of a significant amount of N leads to the coexistence of pure nitrides and complex
Nb(C,N). Further the influence of Ti on the precipitation of NbC is discussed. It inhibits
the formation of the carbides and so delays the precipitation start time.

Nb(C,N) According to Gladman [1] Nb(C,N) precipitate mostly in string form. The
globular precipitates found near the surface and up to 5 mm inwards from the surface
were finer and greater in number than those found 10 mm to 40 mm inwards from the
surface.
Several authors expected the presence of Nb(C,N) but were not able to find them. It
is thought that they are too small to be found by energy dispersive X-ray spectroscopy
(EDS) [11, 12].

AlN

Aluminium is primarily used as deoxidiser. Nevertheless it also precipitates as a nitride


and is one of the most studied microalloying elements.
With an Al content of at least 0.02 mass percent (%) in the steel, AlN is considered stable
at low temperatures in the austenite range, while aluminium carbide is not stable in steel
[1]. According to Leslie et al. [13], the reduced solubility of AlN could be a consequence
of the local microsegregation of Al and N. Meyer et al. [14] confirm and state that
a reheating e.g. for normalising may also be sufficient for precipitation. Wilson and
Gladman [9] showed the solubility of N in the ferrite of Al-killed steels being vanishingly
small.
Depending on the chemical composition, on the grain size and on the annealing temper-
ature the precipitation of AlN in austenite can occur simultaneously at grain boundaries
and on dislocations. Due to the considerable volumetric misfit between the AlN precip-
itate and the austenite matrix, precipitation at the grain boundary is however preferred
[15].
Due to the hexagonal structure of AlN, any miscibility with the carbides and nitrides
of Ti, Nb and V with cubic structures can be excluded. However, Emenike et al. [16]
think that epitaxial growth on Ti or Nb precipitates is possible. Thus this would be an
additional nucleation site besides grain boundaries and dislocations.

Mox C

Molybdenum is added to steel to enhance the hardenability. Further it delays the form-
ation of ferrite, promoting by the way the formation of low-temperature phases like

13
2 State of the Art

bainite. Mo precipitates as carbide and is believed to form complex carbides by repla-


cing e.g. Nb atoms in Nb(C,N).
The precipitation of Mo has not been investigated intensively yet. It is known that Mo is
very soluble in austenite [17] and precipitates during the transformation to ferrite or first
in the ferrite phase [18, 19]. Further Mo in solution is known to delay the precipitation
of Nb(C,N) in microalloyed steels [20]. G\´{o}mez et al. [17] put this statement into
perspective by excluding only the presence of pure Mo(C,N) in austenite. As Ti and
Nb often form mixed carbonitride due to their cubic structure, they can also include
a certain amount of Mo. Molybdenum precipitates have been found in different forms,
e.g. combined with (Ti,Nb)(C,N) with a mean size of 25 nm [21]. In the same steel
G\´{o}mez et al. found also Ti free complex carbonitrides with Mo introduced in the
lattice with approximately 5 nm diameter. Pavlina et al. [19] reports of carbonitrides
containing Ti and Mo of about 7 nm diameter and needle-shaped Mo2 C particles. Further
he reports that the observed Mo concentration in Nb(C,N) increases with decreasing
temperature.
An alternative precipitation form would be a heterogeneous nucleation of Mo-rich car-
bonitrides on Nb(C,N) or Ti(C,N), but in both cases the amount of incorporated Mo
would be limited due to the high solubility in austenite [19].
In the frame of the RFCS-1 project [2], Sidenor made a more detailed analysis of a V-
Mo-Cr steel. Three specimens were taken in different depths of an ingot: at the surface,
in quarter depth and in the middle. In the centre specimen very large M6 C-type Mo
carbides of 100 to 200 µm were found in the zone of residual melt between equiaxed
grains. Smaller Mo-rich carbides were also found at the austenite grain boundaries and
in the matrix. In the specimen from a quarter of the ingot thickness some large Mo-rich
carbonitrides of approximately 100 µm were found agglomerated with V-rich carbides
and Ti-rich carbonitrides. Further 20 µm Mo-rich precipitates of the M6 C carbide type
with Cr and V and V-rich carbides of the MC-type of the same size with some Cr and
Mo were found. Lastly at the ingot surface some Mo-rich particles could be observed at
the grain boundaries.

VN and VC

Vanadium is often used in HSLA steels as microalloying element. It retards the austenite
recrystallisation by precipitating in the interphase between austenite and ferrite. V can
precipitate as nitride, carbide or carbonitride. The carbonitrides are also miscible with
carbonitrides of Nb or Ti.
Inoue et al. [22] believe that V will not form pure nitrides or carbides because a stable
three phase equilibrium may already exist when Ti and Nb have already precipitated.
Thus V will form complex carbides with Nb or more likely complex nitrides with Ti.
However a co-precipitation in TiN is more likely because the lattice constants are sim-
ilar and those of NbC are significantly larger. Zajac et al. [23] also indicate that the
precipitation of VN may be favoured by a foregoing precipitation of TiN since VN will
co-precipitate on them.

14
2.1 Phases and their properties

V has a very high solubility in austenite. The solubility product of V(C,N) is higher
than that of the carbonitrides of Nb or Ti. VC has a solubility product about two
orders of magnitude higher than VN. Due to the very high solubility of V in austenite,
the precipitation of carbides or nitrides is mostly negligible so that the hot deformation
process will hardly be influenced by V precipitates. However precipitates can be expected
in the ferrite [24]. Lagneborg et al. mention further the possible presence of V in TiN
and that V has already been detected in AlN.
Ludlow et al. [5] confirm the statements because they found complex (Nb,V,Ti) (C,N)
in the crack free surface and sub-surface areas of cracked billets. However the presence
in the crack free zones may indicate a weaker influence on cracking. The globular or
cubic precipitates get smaller and more numerous near the surface. But pure V(C,N)
with less than 40 nm in diameter were also found distributed uniformly. Thereby only
the surface and sub-surface layer up to 10 mm depth had less precipitates.

BN and other B-containing precipitates

Boron in solution is used to promote the formation of bainite and to increase the harde-
nability. Boron, when present as nitride, is also known to improve the strength of steel
whereby 5 ppm are already sufficient for BN precipitation [25]. In B containing low-alloy
steels three types of precipitates can be found: BN, Fe23 (CB)6 and Fe(CB)3 [11].
According to Wilson and Gladman [9], BN is indeed less stable than AlN but it still
precipitates in preference of AlN. This can be explained by the high diffusion rate of B
in austenite, similar to that of N, leading to a fast precipitation of BN.
The solubility of B in austenite is lower than those of V, Al or Si. The solubility of Ti and
Zr in austenite are lower than that of B i.e. they are stronger nitride formers [25]. Werner
states that besides a faster austenite to ferrite transformation, bigger grains are prone
to a higher B concentration at the grain boundaries and so facilitate the precipitation
of B phases [25].
Unfortunately BN can be detected by means of EDS only with difficulty so that only
few experimental data can be found. An experiment of Zajac et al. [26] with two similar
steels, one containing B, the other not, did not allow to find BN. However the reheating
at 1050 °C showed that the steel containing B had less particles and mostly particles over
30 nm diameter leading to an average particle diameter of 31 nm instead of 18 nm for the
B free steel. The same reheating made at 1125 °C or even higher temperatures showed a
decrease of more than 80 % in the particle number for both steels and particles average
diameter having raised to 51 nm and 71 nm for the B and B free steels respectively. This
is the consequence of the obvious dissolution of the particles below 20 nm diameter.
Tanino [27] states that B tends to segregate to high angle grain boundaries but even more
to the interfaces of incoherent particles like MnS, FeS or Al2 O3 . On this way complex
agglomerates of e.g. spherical MnS precipitates with a shell of BN can be formed.

15
2 State of the Art

Table 2.1: Temperature ranges of the phases considered in the calculation of solubility
products
phase Tmin [°C] Tmax [°C]
liquid 1500 1750
delta ferrite 1350 1500
austenite 800 1350
alpha ferrite 500 800

2.2 Solubility products

According to Palmi\‘{e}re et al. [28] the four principal techniques used for the determ-
ination of thermodynamic solubility data at the example of Nb(C,N) are the separation
techniques, the equilibration methods, the thermodynamic calculations and the hardness
techniques.
The separation techniques are problematic because very fine precipitates cannot be sep-
arated from the steel and the exact composition cannot be determined. The equilibration
methods are also sensitive to the inaccuracy in the determination of the composition,
because the determination of the C content is made by an assessment of a stoichiomet-
ric or non-stoichiometric compound. The equilibration methods, consisting in exposing
the Nb containing specimen to an hydrogen-methane atmosphere before measuring the
C content, neglect the effect of precipitate size on their solubility; as like as the two
methods described before. Thus the predicted solubility may be overestimated, i.e. the
precipitate would be predicted more stable than it is really. The hardness techniques
are also based on an assumption since the solubility products are calculated with the
assumed relation between the hardness and the Nb amount precipitated. Additionally
no hardening mechanism like solid solution or dislocation strengthening is taken into
account for the calculation [28].
In the following the solubility products found in the literature will be discussed phase by
phase in order to compare the stability of the different phases and to see the differences
between the different sources. The datasets considered to be the most reliable are plotted
using a broader line. The solubility products were calculated for the phases liquid, delta
ferrite, austenite and alpha ferrite for the temperature ranges listed in Table 2.1. The
solubility products are consecutively numbered and can be linked up to the corresponding
reference using the list at the end of this work.

2.2.1 TiN and TiC

Carbides and nitrides are considered separately for the precipitation of Ti. The solubil-
ity products of TiC in austenite (cf. Figure 2.1) are quite similar and show a slightly
lower solubility than those of ferrite. The austenite side of Figure 2.2 shows a very
high scattering over seven orders of magnitude for TiN at low temperatures. Almost
no difference is visible between the six solubility products for the liquid phases. Two
solubility products predict even a higher solubility in the austenite than in liquid which

16
2.2 Solubility products

is in contradiction with the observation of Gladman [1] and Ludlow et al. [2]. According
to this plot the solubility of TiN in austenite and ferrite is comparable.

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
no. 86
no. 87
0 no. 88
no. 89
no. 90
-2 no. 91
no. 92
no. 93
-4 no. 94

-6
log[Ti][C]

-8

-10

-12

-14

-16

0.0005 0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.1: Graphical representation of the solubility products found for TiC

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
no. 67 no. 76
no. 68 no. 77
0 no. 69 no. 78
no. 70 no. 79
no. 71 no. 80
-2 no. 72 no. 81
no. 73 no. 82
no. 74 no. 83
-4 no. 75 no. 84

-6
log[Ti][N]

-8

-10

-12

-14

-16

0.0005 0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.2: Graphical representation of the solubility products found for TiN

When comparing Figure 2.1 and Figure 2.2 it can be seen that TiN has lower values of

17
2 State of the Art

log[T i][N ] and thus a lower solubility than TiC in both phases. This is in accordance
with the common knowledge and observations that TiN precipitate earlier than TiC.

2.2.2 NbC, NbN

For Nb the carbides and nitrides are also considered separately and compared in a second
step. NbC has a relatively low scattering of two orders of magnitude in both phases as
can be seen in Figure 2.3. In average NbC should be more stable in ferrite than in
austenite. Solubility products for NbN from the literature are quite similar whereby
the difference between austenite and ferrite is not clearly distinguishable in Figure 2.4.
When comparing both plots, NbN is slightly more stable than NbC and this means that
it should precipitate at first.

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2

-2

no. 38
-4 no. 39
no. 40
no. 41
-6 no. 42
log[Nb][C]

no. 43
no. 44
-8 no. 45
no. 46
no. 47
-10 no. 48
no. 49
no. 50
-12 no. 51
no. 52
no. 53
-14 no. 54
no. 55
-16 no. 56
no. 57

0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.3: Graphical representation of the solubility products found for NbC

18
2.2 Solubility products

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
no. 25
no. 26
0 no. 27
no. 28
no. 29
-2 no. 30
no. 31
no. 32
-4 no. 33
no. 34
no. 35
-6 no. 36
log[Nb][N]

-8

-10

-12

-14

-16

0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.4: Graphical representation of the solubility products found for NbN

2.2.3 AlN

Figure 2.5 shows the solubility products of AlN. The scattering is negligible at high tem-
perature in the austenite range, but is much higher near the austenite-ferrite transition
temperature. The difference of solubility is of approximately four orders of magnitude
between lowest and highest estimation.

19
2 State of the Art

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
no. 3
no. 4
0 no. 5
no. 6
no. 7
-2 no. 8
no. 9
no. 10
-4 no. 11
no. 12
no. 13
-6 no. 14
log[Al][N]

no. 15
no. 16
-8

-10

-12

-14

-16

0.0005 0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.5: Graphical representation of the solubility products found for AlN

It should be noticed that the solubility product No. 16 according to Bergmann et al.
[29] has been specially designed to account for the delayed precipitation of AlN observed
during cooling under conditions similar to continuous casting.

2.2.4 VC and VN

For V also the carbides and nitrides will be considered separately. Figure 2.6 shows a
very high solubility product of VC. The spreading between the four solubility products in
the austenite is small, as like as in the ferrite. However the solubility in the ferrite phase
is slightly lower. Exactly the same observations can be made for VN in Figure 2.7. Here
the solubility product in the liquid shows a considerably higher solubility than those
for austenite. The comparison of both plots confirms the experimental observations, i.e.
that VN is less soluble than VC.

20
2.2 Solubility products

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
No. 108
No. 109
0 No. 110
No. 111
No. 112
-2 No. 113
No. 114
-4

-6
log[V][C]

-8

-10

-12

-14

-16

0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.6: Graphical representation of the solubility products found for VC

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
No. 97
No. 98
0 No. 99
No. 100
No. 101
-2 No. 102
No. 103
No. 104
-4 No. 105
No. 106
No. 107
-6
log[V][N]

-8

-10

-12

-14

-16

0.0005 0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.7: Graphical representation of the solubility products found for VN

2.2.5 BN

Only few solubility products for BN could be found in the literature. The reason may be
that the detection of B is not possible with all EDS detectors. The differences between

21
2 State of the Art

the three solubility products in the austenite are considerable but the small difference
between the solubility products in the austenite and in the ferrite are more noteworthy
(cf. Figure 2.8). This means that BN should have a similar solubility in both phases.

T [°C]
1700 1500 1300 1100 1000 900 800 700 600 500
2
no. 18
no. 19
0 no. 20
no. 21
no. 22
-2 no. 23

-4

-6
log[B][N]

-8

-10

-12

-14

-16

0.0005 0.0006 0.0007 0.0008 0.0009 0.001 0.0011 0.0012


1/T [K-1]

Figure 2.8: Graphical representation of the solubility products found for BN

2.3 Discussion on thermodynamic modelling using solubility


products and its alternatives

Thermodynamic calculation methods using solubility products are error-prone because


they are based on assumptions and simplifications. Examples therefore would be the
activity coefficients assumed to be unity and the activities themselves represented by
their mass percentages. Further it must be mentioned that the experimental data show
a high scattering, cf. Section 2.2.
An alternative approach would be to use the Wagner formalism [30]. In this case the
so called “first-order interaction parameters” take account of the interactions between
the diluted components and the solvent. This formalism allows a better description of a
solution but is however only valid in the case of infinite dilution [31]. This limitation was
lifted by Darken [32] for 2- and 3-component systems by a “quadratic formalism”. This
formalism allows to model simple binary solutions up to relatively large mole fractions
of the dilute component [31].
A further improvement is the CALPHAD methodology that will be described more in
detail later on.

22
2.4 Kinetics

2.4 Kinetics

The high discrepancies between the observed precipitations during e.g. laboratory testing
or continuous casting and the predictions of thermodynamic models require to consider
further factors. The two main parameters to be considered are the strong temperature
variations and the occurring deformations. Both are known to be responsible for faster
and stronger precipitations, especially of AlN and NbC. These effects can be taken into
account for a more realistic simulation of the precipitation processes.

2.4.1 Literature data on precipitation kinetics

The main parameters influencing the precipitation kinetics will be shortly discussed on
the basis of the work of Schwerdtfeger [33] on AlN. Further the three projects funded by
the Research Fund for Coal and Steel (RFCS) covering this topic will be summarized as
well as the literature data on strain induced precipitation and thermal cycling.

Main effects on the precipitation kinetics

Schwerdtfeger [33] has described the precipitation kinetics of AlN in-depth.


In the case of continuous cooling of castings, cooling rates of less than 0.01 Ks-1 are
reported to be necessary for full precipitation of AlN e.g. in a steel with 0.0143 % N
and 0.105 % Al. It should be considered that the cooling rate necessary for precipitation
depends on the concentration of N and especially of Al because Al is the kinetic de-
termining diffusion partner. According to this it can be concluded that the cooling rate
during continuous casting is too high for a normal (i.e. not strain-induced) precipitation
of AlN.
The case of strain-induced precipitation was also addressed. The exact description of
this phenomenon is however made difficult by the mutual effects of strain-induced precip-
itation and recrystallisation depending on the strain and especially strain rates applied.

AlN

The impossibility to simulate the continuous casting process by an isothermal holding


after solution treatment is also shown in the case of AlN. The precipitation curve has the
expected C-form with a maximum rate of precipitation at about 1100 °C. The precipita-
tion takes however six hours to complete [1]. Independently of the testing temperature,
three similar alloys with Al contents reaching from 190 to 600 ppm showed that the pre-
cipitation rate gets higher with increasing Al content. An influence of the temperature
was also measured and was analysed using the Johnson-Mehl-Avrami equation

fp = 1 − exp(−KT n ) (2.1)

where fp is the precipitated fraction, K is a variable depending on the activation energy


and T is the temperature. Comparing the value of n for the steels considered, it was

23
2 State of the Art

concluded that the precipitates growth mechanism is the same independently of the Al
content or temperature [34].
Wilson and Gladman [9] describe the precipitation rate of AlN as a function of five
factors: the chemical driving force, the lowest diffusion rate of both Al or N, the nuc-
leation energy barrier, the holding time at a given temperature and the solubility of
Al and N in austenite or ferrite. A particularity of AlN is the well demonstrated abil-
ity to nucleate selectively at the grain boundaries or at dislocations. The simulation
predicts nucleation at grain boundaries or at dislocations depending on the annealing
temperature, on the grain size and on the steel analysis [15].
Michel and Jonas [35] investigated the precipitation kinetics of AlN in plain C steels and
found out that the precipitation rate was increased by more than one order of magnitude
when compared with the static precipitation.

NbC, NbN and Nb(C,N)

Several studies were carried out on Nb microalloyed steels. The precipitation times
measured on as-cast slabs and on specimens exposed to different conditions confirm the
assumption that applying a deformation is not sufficient for simulating the continuous
cooling process. At the surface, in the centre of the wide face of the as-cast slab,
Nb(C,N) were measured to precipitate after about 200 seconds while at the corner the
precipitation began already after less than 15 seconds [7]. This shows that, besides the
straining, the temperature history is also important. It should be noted that in case
of static (i.e. without deformation) precipitation, i.e. during continuous cooling, the
precipitation of Nb(C,N) takes around one day [1]. This statement is confirmed by Xu
et al. [36] indicating also that the precipitation process is between two and four orders
of magnitude faster when a deformation typical for hot rolling is applied.
Park et al. [37] report several authors confirming the preferential precipitation of Nb(C,N)
at grain boundaries. The mechanism consists only in microalloying atoms near the grain
boundaries diffusing in it and precipitating as carbonitrides. The atoms remaining in the
grain precipitate there to precipitates finer than those on the grain boundaries. Further
it is reported that the austenite grain size is not relevant for the kinetics because the
precipitation fraction is small in comparison to the grain boundary surface. Experiments
made with strains of 0, 0.2 and 0.4 show that at the temperatures of 850, 900 and 950 °C
the precipitation is always accelerated by strain. Further it has been observed that the
precipitation end time is also shortened. This can be explained by a deformation induced
increase of nucleation sites like dislocations and sub-grain boundaries.
Measurements presented by Riaz et al. [7] show Nb(C,N) of some nanometres diameter
getting more numerous at the expense of bigger ones when 5 % straining was used.
Another trial made with different strain rates showed globular carbonitrides to be bigger
at a lower strain rate. It has been observed that at slower strain rates the precipitates
had also an elongated thin rod morphology and that at higher strain rates there was
additionally a noticeable precipitation of sulphides.

24
2.4 Kinetics

TiC, TiN and Ti(C,N)

Medina and Mancilla [38] made investigations on Ti microalloyed steels and demon-
strated that the incubation time is related to the Ti content of the steel.
The case of deformation induced precipitation has been studied by Kunze et al. [39]
on low-alloyed steels containing between 250 and 400 ppm Ti and around 100 ppm N.
Above 1100 °C at high strain the recovery and/or recrystallisation is faster than the
precipitates nucleation, but at temperatures lower than 1100 °C TiN precipitate. The
number of particles nucleated increases with decreasing temperature.

VC, VN and V (C,N)

V(C,N) as well as (Ti,V) (C,N) were found to become respectively more numerous and
finer when using a harder secondary cooling. Here again higher nucleation rates and
lower growth rates are the consequence of a faster cooling [7].
Mintz and Abushosha [40] state also that VN can precipitate at a rate similar to Nb(C,N)
at strain rates smaller than 0.1 s-1 .

BN

Boron nitride is a nitride without much kinetics data, which could be explained by the
fact that it is already detected in quenched specimens or after short rolling cycles at
rates close to equilibrium. This means in turn that the kinetics of precipitation of boron
nitride is very fast [9].

2.4.2 European commission funded projects

The precipitation of nitrides and carbides during solidification and cooling and the effects
on the mechanical behaviour of the strand during casting have been studied in two
projects. Both were funded by the European Commission. The more recent project
“Kinetics of Precipitation during Continuous Casting of Plate Steels - KinPCC” is also
funded by the RFCS. The present author has contributed to the latter.

RFCS-1: “Precipitation of nitrides and carbides during solidification and cooling“

The first project named in this work RFCS-1 [2] concentrated on the precipitation of
nitrides and carbides during both the solidification and the following cooling.
Specimens were taken from different industrial casters and from laboratory melts allow-
ing a wide range of cooling rates. The investigated steels are Ti alloyed ultra low carbon
steels and steels microalloyed with Nb, V, Nb+Ti, V+Nb+Ti or V+Ti. The thermo-
dynamic properties of these steels were reviewed and compared with experimental data.
So the solubility products of the precipitating nitrides and carbides were evaluated in
the liquid phase, in austenite and in ferrite.

25
2 State of the Art

It was concluded from the comparison of the different process routes that precipitates
get smaller when the specimen undergoes a fast solidification with high cooling rates.
Similarly this lead to a finer microstructure and less microsegregation. Nevertheless
exceptions were found and could not be explained.

RFCS-2: “Precipitation: Behaviour of microalloyed steels during solidification and


cooling”

The second project, RFCS-2 [7] continues the work undertaken in the earlier one. This
time the aim is to understand the precipitation of the carbides, nitrides and carboni-
trides during solidification and cooling. Further it should allow to modify the microalloy
composition so as to reduce the risk of cracking during bending or cooling.
Specimens originated from both industrial plants and laboratory melts. The focus was
set on analysis of as-cast semis under different casting conditions. The influence of the
casting conditions were also investigated on a pilot plant. Thermodynamic and kinetic
modelling were used to model the effects of modified compositions or casting parameters.
It was found out that when using a soft cooling strategy, i.e. bending at temperatures
well above 900 °C, the precipitates were less detrimental to the surface quality of the
strand. However other experiments on the pilot plant and using hot ductility laboratory
measurements showed that a hard cooling gives better results. In this case the bending
is carried out at temperatures below Ar3 , so the sample is outside the ductility trough
and the alpha ferrite may also have a positive effect on the hot ductility.
Using thermodynamic modelling a laboratory melt was optimised by replacing V with
Nb. A transfer to an industrial slab caster was successful thanks to small changes in the
secondary cooling strategy. The thermodynamics was modelled using Thermo-Calc and
DICTRA. Further models developed in the frame of the project allowed also to model
the kinetics of the precipitation of AlN, TiN, Nb(C,N) and VN and the precipitation of
TiN directly after solidification. Scheil-Gulliver simulations were also performed in order
to calculate the precipitation in the microsegregated and non-microsegregated regions
at different cooling rates.
A Round Robin test was carried out in order to assess the quality of the models. Differ-
ences of more than 100 °C emerged for example in the precipitation start temperature of
Nb(C,N). At the end of the project it was concluded by the authors that the kinetic mod-
elling has still potential for improvements. The handling of the interfacial energies, the
effect of the phase transformations and of the deformation could be implemented. Fur-
ther they consider the hard cooling as very promising on industrial scale for warranting
good hot ductility.

RFCS-3: “Kinetics of Precipitation during Continuous Casting of Plate Steels -


KinPCC”

This third project, named RFCS-3 [41], on the precipitation of carbides, nitrides and
carbonitrides during continuous casting of plate steels is based on the two first RFCS

26
2.4 Kinetics

projects discussed above. It aims on the reduction of cracking that is known to be


induced by precipitates using an ameliorated prediction of the precipitation process.
This necessitates to assess the effect of stresses and strains on the precipitation kinetics
to further understand the mechanisms of slab cracking.
Samples were taken from industrial slabs and were either investigated directly or used for
further experiments. In contrast to the first RFCS projects, all steels are microalloyed
HSLA steels for heavy plate rolling. The results of the experimental laboratory work
are of empirical nature and can be used to ameliorate the kinetic modelling software
MatCalc. Further on the simulation results can be compared to the investigations of the
slab specimens.
The laboratory work proved that the sharp temperature variations and the strain en-
countered at the slab surface have an influence on the precipitating populations. A
possible explanation for the different mechanisms is proposed. Experiments carried out
on the as-cast specimens allowed to assess and to improve the model so that MatCalc
delivered satisfactory simulation results.

2.4.3 Strain induced precipitation

Studies [7, 9, 42, 43, 44] were carried out with the aim to compare the kinetics of strain
induced precipitation with the static precipitation. One should notice that the dynamic
precipitation can be influenced by the strain rate, the temperature of deformation and
the chemical composition [9]. The presumed mechanism is based on an increase of
nucleation sites i.e. of the dislocation density and an increased solute diffusivity, both as
consequences of the plastic deformation. Riaz et al. [7] limit the effect of an increase of
nucleation sites to the precipitation of Nb(C,N), V(C,N) and AlN; the effects for Ti(C,N)
being lower due to the precipitation start at higher temperatures. It should be noted
that the deformation strain applied in this study was higher than during continuous
casting.
Herman et al. [42] showed that plastic deformation accelerates the precipitation kinetics
especially around 900 °C and that the acceleration effect becomes saturated at strains
greater than 0.4. The saturation is explained by the nearly constant dislocation density,
i.e. number of potential nucleation sites, with further applied strain. Dutta et al. [43]
gives also further consequences of the presence of dislocations, besides the enhanced rate
of nucleation, namely growth and coarsening of all precipitates.
Medina and Quispe [44] point out that the effect of the strain on the precipitation
depends only on the microalloy content. Investigations were made with steels containing
Ti, V or Nb and strains of 0.2 and 0.35. The strain rate was 3.63 s-1 so that both
the strain and strain rate are not comparable with continuous casting conditions. The
precipitates induced by strain were NbN, VN, TiC and to lower extent NbC. It should
be noted that TiN had already precipitated at higher temperatures and the titanium
carbides were the only titanium precipitates being strain induced. Using an equation of
Dutta and Sellars for the time necessary for 5 % precipitation, the authors could prove

27
2 State of the Art

that the time necessary for precipitation is a function of the microalloy content and of
the strain.

2.4.4 Thermal cycling

Changing only the cooling rate proved to be insufficient since no noticeable difference
in distribution and size of Ti-, Nb- and V-carbonitrides was detected [7]. Thus more
complex temperature profiles are necessary. For example a temperature cycle similar
to that imposed by the secondary cooling and the rolls during the continuous casting
can be used and may allow to simulate more accurately the continuous casting process.
The thermal variations allow probably higher precipitation rates by alternating high
nucleation periods with high growth periods [41].
The combination of 1.5 % strain and thermal cycling led to a precipitation level com-
parable to 16 hours of isothermal holding, to large deformation or to the surface of an
as-cast slab [7]. This shows that the combination of low strain and thermal cycling could
be a good experimental method to simulate continous casting (CC) in the laboratory.

2.5 Solidification during continuous casting

During continuous casting the steel solidifies with local changes of composition and
mechanical properties. Changes of composition on the microscopic scale are commonly
designated as microsegregation. It occurs during a cooling fast enough to avoid the dif-
fusion of elements between liquid and solid phases when the solubility of solute elements
is lower in the solid phase. The solidification of steel occurs in a dendritic process begin-
ning at the mould and progressing up to the core. Almost all elements are rejected by the
solid phase in the surrounding liquid because of the comparatively low solubility of solute
elements in the solid. With ongoing solidification the remaining liquid volume between
the dendrites gets smaller and the concentration of alloying elements gets higher. The
result is a repetitive pattern of solute depleted dendrites and solute rich interdendritic
areas.
Another phenomenon occurring during solidification is macrosegregation. It can have
multiple causes: for example strand bulging between rolls due to ferrostatic pressure
or solidification shrinkage. These phenomena can however be largely suppressed on
modern continuous casters respectively by narrow roll pitches and the appropriate use
of soft reduction shortly before completion of the solidification.
A further characteristic of the continuous casting process are the oscillation marks on
the strand surface. They appear already in the mould as a consequence of its oscillation
during formation of the solidified shell. Because of their notch effect they may also
influence the cracking behaviour [45].

28
2.6 Classical theory of ductility loss

2.6 Classical theory of ductility loss

Surface cracks on continuously cast slabs can be induced by the precipitation of mi-
croalloying elements. Traditionally the cracking risk is associated to the reduction of
the hot ductility. The reduction of the hot ductility is influenced by the temperature or
temperature variations of the slab corner during the bending and unbending processes
[7, 46] and especially by the chemical composition of the steel [47]. Barber and Perkins
[48] state that transverse facial and corner cracking may occur when the slab surface
temperature is in the range of approximately 700 to 1000 °C.
Brimacombe and Sorimachi [49] also mention the importance of strain induced precip-
itation for cracking, especially at the tension-loaded top surface of the strand in the
straightening zone.

2.6.1 Strain rate

Yue et al. [50] indicate that a higher strain rate improves the hot ductility. The reason
given is that higher strain rates reduce the time available for the precipitation and for
the diffusion assisted void nucleation.
The contrary effect is however also mentioned: e.g. a decrease in the strain rate by
one order of magnitude at high cooling rates of 3 °Cs-1 having an important effect on
the ductility. The minimum reduction of area was decreased and the high temperature
ductility shifted to higher temperatures. Several reasons were proposed by Chown [11]
like enhanced precipitation of Nb(C,N), increased grain boundary sliding or increased
formation and growth of voids.

2.6.2 Secondary cooling & thermal cycling

The influence of the temperature is mentioned by several authors, e.g. in the RFCS-2
project [7]. The authors report of the so-called hard cooling leading to a low bending
temperature that causes surface cracking on the continuous casters considered. However
the softer cooling causes in the same study also more corner cracks due to a higher
Nb precipitation. This phenomenon is explained by the fact that in the case of softer
cooling the precipitation begins already before bending while in the case of a harder
cooling the precipitation begins only after the bending. The faster cooling leads also
to corner temperatures below the trough temperature, i.e. temperature range of low
ductility.
According to Chung and Cho [51] the hot ductility of an Al-killed steel with B additions
of 12 to 29 ppm is improved by decreasing the cooling rate and by increasing the strain
rate. Possible explanations are less precipitates at the austenite grain boundaries and a
change in the deformation mechanism from grain boundary sliding to grain deformation,
respectively.
Similar investigations for Nb containing low alloy steels were done by several authors
cited by Chown [11]. A decrease of the cooling rate from 3 to 0.3 °Cs-1 at a low strain rate

29
2 State of the Art

showed an increased ductility. The authors agree on the favoured static precipitation of
NbC. On that way only coarse NbC can precipitate, Nb being removed from solution
even before fine strain-induced Nb(C,N) can precipitate dynamically on dislocations.
It has also been shown that temperature oscillations have an effect on the hot ductility.
Cardoso et al. [46] found out that temperature oscillations influence in general adversely
the ductility by encouraging, in the considered steels, the precipitation of AlN. Tem-
perature cycling has been introduced by Comineli et al. [47] in order to better simulate
the commercial cooling conditions. They showed that while Ti free steels are relatively
unaffected by such temperature oscillations, all Ti containing steels tested invariably
gave worse ductility. More generally El-Wazri et al. [52] investigated the influence of os-
cillated cooling on the hot ductility trough and found out that increasing the oscillation
amplitude increases the depth and width of the trough. Schwerdtfeger and Spitzer [45]
also claimed that especially transverse corner cracks are influenced by thermal cycles.
Cardoso and Yue [53] investigated the influence of the temperature history and found out
that the ductility decreases when the temperature drops below the final testing temper-
ature. The proposed explanation is based on higher precipitation rates and thus smaller
precipitates at the lower temperature. This observation is confirmed by the investigations
in the RFCS-3 project [41] based on thermomechanical cycling and scanning electron
microscope (SEM) observations. Here the evolution of the precipitate populations was
described by alternating phases of high nucleation rate and high growth rate.

2.6.3 Chemical composition

It is well known that the chemical composition has a great influence on the steel proper-
ties. First of all the C content influences the temperature at which the austenite-ferrite
transformation occurs. Further the microalloying elements Al, B, Nb and V influence
again the austenite-ferrite transformation temperature and also the temperature do-
main of the ductility trough. As a rule of thumb it can be said that an increase in the
concentration of these elements will widen and deepen the trough [50].
Many studies concentrated on the role of Al and AlN precipitation on hot ductility. For
example Cardoso et al. [46] studied the microstructure and fracture facets of steels with
low and high Al content. In low Al steels no AlN precipitations were observed, however
a thin film of several micrometres thickness of ferrite formed at the austenite grain
boundaries. The film contained MnS inclusions leading to intergranular ductile failures in
the ductility trough. On the other side high Al steels contained among MnS particles also
AlN precipitates. The missing grain boundary ferrite inhibited any inclusion controlled
failure at the testing temperatures of 800 to 900 °C.
Comineli et al. [47] studied also the influence of Ti and registered a diminishing ductility
when adding N to a steel containing Ti because more Ti containing nitrides precipitated.
However, an even higher addition of N improved again the ductility whereby the authors
suspect the higher N level to permit already a precipitation at higher temperature and
so the formation of coarser precipitates with a less detrimental effect on the hot ductility.
Ti containing steels have also shown not to be influenced by a Nb or Al addition, quite

30
2.6 Classical theory of ductility loss

contrary to Ti free steels showing a decreasing hot ductility even though the volume
fraction of precipitates increases. Thus Ti is sometimes considered being an element
capable to alleviate the problem of transverse cracking [46].
Ma et al. [54] state that most of the slabs considered containing between 80 and 270 ppm
Nb were likely to crack.
Poor ductility was found in peritectic steels with less than 20 ppm B at temperatures
in the range of 700 to 900 °C. Yamamoto et al. [55] found also BN precipitates on the
austenite grain boundaries. They assume that BN are presumably responsible for the
intergranular cracking and hence low ductility. Two methods were elaborated in order
to prevent cracking: either limiting the available N by TiN precipitation or keeping the
cooling rate in the secondary cooling zone at less than 0.5 °Cs-1 . On this way coarse BN
precipitate in the matrix allowing a better hot ductility.

2.6.4 Failure mechanisms

Apart from the temperature and the influence of some alloying elements, four main
mechanisms for the low ductility have been described by Cardoso et al., Ma et al.,
Patrick et al. and Yue et al. [46, 50, 54, 56]:
1. Precipitates of microalloyed elements arranged in a chain-like way at the austenite
grain boundaries weaken the grain boundary binding forces. This suppresses the
movement along the grains and so contributes to the reduction of ductility [54].
2. The second mechanism explained by Ma et al. [54] is a consequence of the precip-
itation of carbides at the austenite grain boundaries. The decrease in C content
at the boundaries causes the austenite-ferrite transformation to happen preferen-
tially there. The consequence is a thin layer of ferrite around the austenite grains.
Other authors believe the ferrite to be deformation-induced. In all cases the softer
ferrite layer enables the MnS inclusions and microalloy precipitates to concentrate
the strain so that the particles are sites for void initiation, coalescence and crack
propagation [46, 50].
3. Grain boundary sliding in austenite, that normally occurs at high temperatures,
is a mechanism leading to increased ductility. Cracks initiate in grain boundaries
and can propagate easily, but their growth is then inhibited by the motion of the
grain boundaries. The probably most important mechanism responsible for the
grain boundary movement is the dynamic recrystallisation. So, as well as for the
ferrite film, the precipitates are also here the encouraging factor because they are
able to retard the dynamic recrystallisation and to pin the grain boundaries [50].
4. Yue et al. [50] explained the low ductility by the existence of precipitate free zones
at the austenite grain boundaries. These zones are depleted from microalloying
elements because e.g. Nb has already precipitated. These zones are not ferritic
but are nevertheless soft compared to the adjacent grain boundaries so they con-
centrate strain. This leads in turn to the formation of microvoids by decohesion
of the precipitate-matrix interface and eventually to void coalescence and crack

31
2 State of the Art

propagation along the grain boundaries.

32
3 Investigation methods

Observation techniques should allow the determination of morphological parameters of


precipitates like diameter and roundness and ideally allow a chemical analysis. The
assessment of all precipitating phases whatever the particle size and the chemistry is of
particular importance.

3.1 Acid dissolution

A method for particle characterisation is the matrix dissolution, either with acids,
halogen-based mildly alcoholic solutions or electrolytic solutions [57]. This method con-
sists in dissolving a bulk specimen or swarfs in the given solution. After filtering and, as
the case may be, centrifuging, the obtained particles can be analysed by means of SEM
and EDS.
For the particular case of the determination of the Nb content at different depths of the
slab, the dissolution has been carried out by dissolving approximately 10 g of steel in
a solution of iodine (I) in methanol. This solution has been filtered on polycarbonate
filters with pore sizes comprised between 800 and 200 nm in diameter. By weighing the
filters before and after use, one can precisely estimate the amount of precipitates in the
investigated steel. However it should be noted that this solvent is not very selective since
the undissolved phases are as well nitrides as oxides and oxysulphides [57].
Nevertheless a gradient in the precipitated phase fraction over the thickness of the slab
could be measured. An analysis of the particles using the SEM and EDS was carried out
to get a particle size distribution. Therefore the filters were applied to adhesive carbon
tabs or alternatively particles were brushed off the filter on tabs. The particles found
were mostly conglomerates with diameters of 50 µm or more. They contained Al, Si, Nb,
P and I, whereby the iodine can be considered to be an impurity from the solvent (cf.
Figure 3.1). Additionally, smaller spherical particles of less than 100 nm diameter were
found on the surface of the conglomerates and are considered to be some of the expected
precipitates (cf. Figure 3.2). This hypothesis can be made since weak signals of Al, Nb
or Ti were detected when trying to determine their chemical composition.
Despite allowing to determine the exact chemistry, the experiments permitted to de-
termine a phase amount profile of Nb containing precipitates over the thickness at the
narrow side of a slab. Figure 3.3 shows that the phase amount in the specimens taken
near the surface (blue curve) was higher than in the specimens taken 10 mm below the
surface (red curve).

33
3 Investigation methods

Figure 3.1: Particle of approximately 100 µm diameter found on the filter and correspond-
ing EDS spectrum showing Nb, Al, Si, P and traces of I from the solvent

34
3.1 Acid dissolution

Figure 3.2: Scanning electron micrographs showing sub-millimetre structures (above) and
particles smaller than 100 nm on their surface (below, probably Nb(C,N))
found on the filters after dissolution in iodine methanol

35
3 Investigation methods



VXUIDFH


1EFRQWHQW



PPEHORZVXUIDFH




  
UHODWLYHGHSWKLQWKHVODE

casting
direction
wide face

relative depth
narrow face -
near surface
narrow face -
inner

Figure 3.3: Graphical representation of the phase amount measured by dissolution in


iodine methanol of specimens taken in two depths of a slab narrow face

36
3.2 Thermomechanical testing

The unsuccessful SEM observations make it necessary to search for alternatives for this
dissolution method as the filters do not necessarily contain the expected particles.
A literature study from Lu et al. [57] on matrix dissolution shows that for example
hydrochloric acid HCl should be particularly adapted for the analysis of Nb containing
particles in steel. It could even allow to find exclusively Nb(C,N) on the filter and to
get a size distribution. Further this method should not be prone to conglomeration of
dissolved particles. In reality it looked different and the particles conglomerated on the
filter. The dissolved steel was filtered subsequently on three filters with pore sizes of
800, 450 and 200 nm. An increase of the filter weight could only be measured for the
800 nm filter. All filters were analysed by SEM. By this way the presence of few large
conglomerates on the first filter and the total absence of particles on the finer filters was
confirmed. Better results may be obtained either by centrifuging the solute or by using
other analysis methods. Filters could also be analysed by small angle neutron scattering
SANS that would also give the possibility to get information on the size distribution of
the precipitates.

3.2 Thermomechanical testing

The conditions encountered during continuous casting like thermal variations of up to


300 °C or fast cooling and heating rates hardly allow high accuracy simulations using
classical hot tensile machines with infrared or induction heating. These experimental
simulations necessitate to use a resistance heated tensile machine like a Gleeble 3500
that allows a fast and precise control of the temperature and of the mechanical strain.
Some restrictions have however to be accepted, like the missing oscillation marks on the
specimens surface or the differences in the austenite grain size and morphology [11].
Two types of thermomechanical trials were done: ductility tests and hold and quench
trials.

3.2.1 Ductility testing

In the first case tensile specimens are tested at different temperatures up to failure. From
the measurement of the initial and final cross section A0 and A, one can calculate the
reduction of area as

A0 − A
RA = (3.1)
A0
obtaining a value between 0 and 1. When the fracture is brittle the reduction of area
tends to 0 while a ductile fracture is characterised by a reduction of area near unity (cf.
Figure 3.4). This data allows to plot the reduction of area versus temperature as it is
currently used in production for the assessment of the cracking risk during continuous
casting. It also allows to obtain clean unoxidised fracture surfaces for subsequent SEM
analyses.

37
3 Investigation methods

Figure 3.4: Example of ductile (top and bottom) and brittle (middle) fracture of Gleeble
specimens

Numerous experiments with the Gleeble allowed different authors to establish a correla-
tion between the reduction of area and metallurgical factors like the precipitation extent
or the austenite to ferrite transformation [12, 29, 55, 58, 59, 60].

3.2.2 Hold and quench trials (HQT)

Beside the classical ductility testing, the Gleeble machine allows also to produce samples
with a known temperature and strain history. This is necessary for investigating the in-
fluence of strain and temperature on precipitates and microstructure. These hold and
quench trials consist in a dissolution of previous precipitates at high temperature, con-
trolled cooling to the test temperature and subsequent holding. Different precipitation
states can be simulated by changing the holding time and applying or not a mechanical
deformation. A high cooling rate typical for quenching is applied at the end of the heat
treatment in order to guarantee the aimed precipitation state in the final specimen. Test
series applying this method are described in the following.

3.3 SEM

Optical microscopy cannot be used for the investigation of sub-micrometre precipitates


because of insufficient depth of field and insufficient resolution. On the other side, a
SEM has a high depth of field allowing the observation of fractured specimens and also
a higher resolution allowing the analysis of particles of some nanometres diameter.
The SEM investigations were made on a Zeiss Supra 55 equipped with a secondary
electrons detector, an InLens detector and a backscatter detector. Additionally a silicon
drift EDS detector from EDAX was in use.

3.3.1 Mechanical polishing

As the surface quality is important for scanning electron microscopy and especially for
an automated particle analysis (APA), several methods have been tested in this work.
All specimens were first polished with diamond sprays up to a grain size of 0.25 µm.
Comparisons were then made with specimens additionally polished in a last step with a

38
3.3 SEM

suspension of colloidal SiO2 or with a suspension of 0.05 µm Al2 O3 particles. Differences


could be seen at high magnification but not at the magnification relevant for the APA.
Nonetheless comparative particle analyses were made with the three types of specimen
preparation but only differences smaller than those due to the local enrichments in the
steel could be found. Hence the most simple and less error prone method was chosen,
namely polishing with 0.25 µm diamond spray.
Preparation artefacts can however not be excluded. They are mostly difficult to detect
and so to quantify. The most important artefact occurring during mechanical polishing
is the tearing out of particles. In fact it is possible to detect the holes in a polished
specimen however without having any possibility to determine the size and chemistry of
the particle torn out.

3.3.2 Microstructure

The microstructure is investigated on polished specimens. Two preparation methods


were taken into consideration: the classic mechanical polishing followed by etching with
e.g. nital and electropolishing after a coarser polishing. In both cases the aim is to etch
preferentially a phase, here ferrite, in order to get a phase contrast.
These methods does not only allow to characterise the phases present, but also to reveal
precipitates especially if the etching process lasted too long. The longer etching process
let most of the precipitates emerge from the surface, making them particularly easy to
find. The drawback is that small particles may fall off the surface so that this method
may only works for bigger particles.

3.3.3 Fracture surfaces

Fracture surfaces allow not only to estimate the ductility by determining the fracture
mode, but also to observe precipitates. A clear difference is found between brittle and
ductile fractures. They show respectively a rock-candy and a cup-and-cone shaped
failure surface. On the brittle fracture surface the origin of the fracture, in most cases an
inclusion or a precipitate, can be found. This fracture type is called intergranular because
the crack propagates preferentially along the austenite grain boundaries. Thus it is
highly probable to find the precipitates that nucleated at the austenite grain boundaries
like AlN and Nb(C,N). Ductile fractures are characterised by an intragranular crack
propagation. The fracture surface runs through the grains so all type of precipitates are
potentially visible. The number of precipitates found on these surfaces are however very
small due to the low particle density.
Fracture surfaces can be prepared on two ways. Thin specimens can be cooled down
to liquid nitrogen temperature and then broken apart. The fracture surfaces are then
typical for the brittle fracture mode. The second method consist in a simple tensile
testing at any temperature up to failure; preferentially under vacuum in order to avoid
any oxidation of the fracture surface.

39
3 Investigation methods

Figure 3.5: Schematic position of the polished surface using the example of a ductility
specimen

The investigation is however tricky because precipitates are not necessarily present on
the fracture surface, not even on intergranular fracture surfaces. Chemical analysis by
EDS was also difficult due to the relatively large interaction volume of the EDS compared
to the particle size. Further the jagged surface lead to shadowing effects impeding even
more the EDS analyses.

3.3.4 Automated particle analyses (APA)

Particle characterisation is carried out on polished specimens by automated particle de-


tection using the Genesis software from EDAX in combination with SEM and EDS. The
working principle is as follows: first a picture is collected, then an image analysis determ-
ines the morphological parameters of the interesting particles so that finally the chemical
composition can be determined by EDS. The important parameters for a particle ana-
lysis are the surface preparation of the specimen and the image contrast adjustment in
the software. Contrast is believed to have little effect as long as similar adjustments
are used in comparative studies. The surface preparation is also kept constant over
all the investigations to guarantee the reproducibility. The specimens of ductility tests
and HQT were cut as close to the fracture surface or thermocouple as possible. The
transversal cut and polished surfaces are symbolised in Figure 3.5 by an arrow using the
example of a fractured ductility specimen.
All particle analyses were made using similar parameters. An accelerating voltage of
10 kV turned out to be adapted because all elements of interest can be detected and
the interaction volume is still reasonably small. The probe current was approximately
2 nA and the detector used was an angle selective backscatter detector from Zeiss. The
settings in Genesis, e.g. a collection time of 4 s so as to get around 6000 counts per
second, were also kept constant for comparable results. The influence of the particle size
on the EDS measurement was neglected since most particles were significantly smaller
than the interaction volume, i.e. the characteristic spectrum was superimposed with that
of the steel matrix.

40
3.4 Scanning transmission electron microposcope (STEM)

Oxidic and sulphidic inclusions were not evaluated because their number and their effect
on the slabs properties are considered to be negligible. This is due to the very low level of
elements like calcium (Ca) and magnesium (Mg) and especially the deliberately reduced
level of S and P.

3.4 Scanning transmission electron microposcope (STEM)

To overcome the problem of insufficient lateral resolution of SEM and EDS measure-
ments due to a large interaction volume, the idea is to cut off the lower part of the
volume considered. As can be seen in Figure 3.6, the specimen needs therefore to be
appropriately thin.

Figure 3.6: Schematic view of the interaction volume in a SEM bulk specimen and a
TEM thin foil

A thin specimen does not backscatter enough electrons but therefore the electrons trans-
mitting through the sample can be detected in sufficient number. The samples electron
transmission can be further improved either by increasing the accelerating voltage or by
using a thinner, i.e. electron transparent specimen.
The two forms of specimens commonly used for observation in transmission mode are
thin foils and carbon replicas. Thin foils are challenging to produce but allow to observe
particles in the matrix and other features like grain boundaries, subgrain boundaries or
dislocations.
Carbon replicas are manufactured in a three step process. First the polished surface of
the specimen is shortly etched to uncover the particles. Then the specimen is coated
with a thin layer of carbon. This film is etched from the surface with particles adhering
at it. Small film pieces can finally be collected on a TEM grid and observed in a SEM
or TEM. On that way one can observe single particles adhering on a carbon film with a
very good EDS lateral resolution, however without any possibility to know their original
position in the microstructure.
The STEM investigations in this work were made on a Zeiss FEG-SEM Merlin with in-
tegrated STEM detector and the same detectors as the last-mentioned Supra (cf. Section
3.3).

41
3 Investigation methods

3.5 Energy and wavelength dispersive X-ray spectroscopy


(EDS, WDS)

The chemical composition can be determined on different ways, e.g. by optical emission
spectrometry on bulk samples or by energy dispersive X-ray diffraction in the case of
a point analysis. The interaction of electrons with the sample leads to the emission
of secondary electrons, backscatter electrons and X-rays. Most SEMs and TEMs are
equipped with an EDS detector allowing the elemental characterisation with a precision
of a few mass percent for light elements like B, C, N and O and of some tenth of mass
percent for heavier elements. The characterisation is based on the fact that each element
has a unique set of peaks in its X-ray spectrum.
The mechanism involved is easy: the high energy electron beam from the microscope
excites an electron in an inner shell of an atom and ejects it creating an electron hole.
When an electron from an outer shell fills the hole, a photon with an energy proportional
to the energy difference between the two shells is emitted. The energy of the photon is
then measured and assigned to a chemical element.
EDS has some limitations, e.g. when peaks overlap or in the low energy range where
peaks may be difficult to distinguish from the underground signal. These drawbacks can
be overcome with a WDX detector. The X-rays emitted from the specimen are collimated
and deviated on a known single crystal. When Braggs’s law is fulfilled, the photons are
diffracted and collected by a proportional counter. On this way only a single element
can be measured at a time, but in return the determination of the chemical composition
is better than for EDS.

3.6 Comparison of the investigation methods in regard to


resolution and inspection region

The aim of all discussed investigation methods should be to obtain the morphological
parameters and chemical composition of all precipitates. The smallest precipitates have a
size around five to ten nanometres while the biggest have diameters of some micrometres.
This makes it difficult to find a method suitable for all sizes and types of precipitates
which allows at once to find a statistically relevant number of particles and to determine
the chemical composition.
The advantages and drawbacks of all methods as they were used in this work are sum-
marised in Table 3.1. Only the acid dissolution allows an investigation of a volume.
However the solute must be filtered to allow a subsequent SEM analysis and the ap-
propriate filters have a minimum pore size of 200 nm. Moreover precipitates may also
be partly etched influencing maybe their form and more certainly their diameter [61].
Optical microscopy is not suitable because both the resolution and the depth of field are
not sufficient.
SEM was the standard method used for 2-dimensional investigations of particles with
more than 20 nm diameter on surfaces of some square millimetres. STEM has the highest

42
3.6 Comparison of the investigation methods in regard to resolution and inspection region

resolution so that particles of less than five nanometres diameter could be obesrved. The
production of samples, carbon replicas or thin foils, was laborious and prone to artefacts.
The detection of phases like AlN and BN was limited by a lack of contrast on carbon
replicas and the investigated surfaces were very small so that the acquisition of statistical
relevant data was very time consuming. EDS analyses were made at SEM and STEM
but were limited by a low signal to background ratio when analysing small particles.
On the basis of Table 3.1 it can be concluded that actually no investigation method
allows the measurement of all precipitating populations in the whole size range from
few nanometres to some micrometres. Thus only combinations of the described methods
were used to get the maximum information on the precipitate populations.

43
44
investigation investigated dimension of chemical position in
lateral resolution particle type comments
method zone the zone analysis microstructure
3 Investigation methods

particles may
acid here: mainly
volume some mm³ ≈ 200 nm possible unknown partly be
dissolution Nb(C,N)
etched
resolution not
adapted for
optical mostly precipitates
surface some mm² ≈ 5 µm no yes
microscopy inclusions of
microalloying
elements
SEM surface µm² to mm² ≈ 20 nm all possible yes -
carbon replica:
carbon replica: laborious and
carbon film is a
STEM surface µm² ≈ 2 nm possible no prone to
limiting factor
thin foils: yes artefacts
thin foil: all
bulk: ≈ 50 nm dependant on
spot or cf. SEM and all elements
EDS replica / foil: n/a n/a beam tension
surface STEM heavier than B
≈ 10 nm and current
Table 3.1: Comparison of the investigation methods used in this work
4 Modelling

This chapter reviews modelling approaches for precipitates, starting with single phases
precipitating under equilibrium conditions. Then a case of multiple precipitates in equi-
librium is embraced, using a solubility product based equilibrium model and, further
more, CALPHAD based multicomponent commercial codes. Finally kinetic approaches
are addressed, the Dutta-Sellars method and the MatCalc simulation software.

4.1 Equilibrium

4.1.1 Basic calculations with solubility products

In the simplest case a microalloying element M is reacting with an interstitial element


X forming a compound M X. This reaction can be described thermodynamically by the
mass action law
a[M ] a[X]
K= (4.1)
a[M X]
where K is the equilibrium constant and a[..] are chemical activities. When the product
MX is present, its activity is equal to one. The start of precipitation is commonly written
in terms of percent concentrations of the solutes as

kS = [%M ] × [%X] (4.2)

, where ks is known as the solubility product. It is often expressed in the following form:

B
log10 kS = A − (4.3)
T
where T is the temperature in Kelvin and A and B are parameters which are determined
empirically.
To give an example Figure 4.1 shows the solubility curve for Al and N in low C steels
at 1000 °C according to Equations 4.2 and 4.3. Following Leslie et al. [13] values of
A = 1.03 and B = 6670 K have been used.
Above the curve AlN will precipitate. All points beneath the curve correspond to com-
positions where both components stay dissolved.
When AlN precipitates, one mole of N reacts with one mole of Al forming one mole of
AlN. Using molar masses means that 14 g of N react with 27 g of Al. Figure 4.2 shows a
concentration pair of 0.007 % N and 0.06 % Al. Precipitation follows the stoichiometric

45
4 Modelling

log[Al][N]=1.03-6770/T
0.14

0.12

0.1
Al content [mass-%]

0.08

precipitation
0.06

0.04

0.02 dissolved

0
0 0.002 0.004 0.006 0.008 0.01
N content [mass-%]

Figure 4.1: Solubility curve of Al and N with coefficients A and B after Leslie et al. [13]
at 1000 °C

line with slope


27
a= = 1.93 (4.4)
14
Finally, for equilibrium at 1000 °C, approximately 0.0015 % N and 0.050 % Al stay dis-
solved in the matrix.

log[Al][N]=1.03-6770/T
0.14

0.12

0.1
Al content [mass-%]

0.08

AlN precipitation
0.06

0.04

0.02 dissolved

0
0 0.002 0.004 0.006 0.008 0.01
N content [mass-%]

Figure 4.2: Solubility curve for Al and N and precipitation curve of AlN according to
Leslie et al. [13] at 1000 °C

When the temperature decreases the solubility curve shifts to lower concentrations, and

46
4.1 Equilibrium

larger amounts of precipitates appear. Figure 4.3 shows the increase of precipitated phase
as a function of temperature in a similar case. Such computations are, of course, only
applicable to an ideal cooling with the assumption that the cooling rate is sufficiently
low for the system to stay at equilibrium. Nevertheless this method allows an estimation
of the precipitation start temperature and indicates the temperature at which the full
phase fraction can be attained.

0.04
AlN

0.035

0.03
phase mass fraction [mass-%]

0.025

AlN
0.02

0.015

0.01

0.005

0
600 700 800 900 1000 1100 1200 1300 1400 1500
temperature [°C]

Figure 4.3: Calculation made for AlN with 0.06 % Al and 0.007 % N, using solubility
products listed in Table 4.1

The situation changes when other elements are present which can also form nitrides, for
example Ti. TiN precipitates at higher temperatures than AlN and thereby consumes
N which is not available for forming AlN. The phase amounts in an alloy containing
the same concentrations of Al and N but with the addition of 0.015 % Ti are shown in
Figure 4.4. The precipitation of AlN is delayed to 650 °C.

47
4 Modelling

0.04
AlN
TiN
0.035

0.03

phase mass fraction [mass-%] 0.025

TiN
0.02

0.015

0.01

AlN
0.005

0
600 700 800 900 1000 1100 1200 1300 1400 1500
temperature [°C]

Figure 4.4: Calculation made for AlN and TiN with 0.06 % Al, 0.015 % Ti and 0.007 %
N using solubility products listed in Table 4.1

4.1.2 Equilibrium model

Based on solubility products an equilibrium model was developed for precipitation of


multiple phases in both austenite and ferrite. For each precipitating compound coeffi-
cients of the solubility products have been evaluated in Section 2.2. Table 4.1 lists the
coefficients used in the computations of this thesis.

Table 4.1: Solubility products used in the model


A B [K] phase number reference
AlN 0.568 -5517 austenite 16 [29]
5.24 -13970 austenite 20 [62]
BN
4.63 -13680 ferrite 23 [62]
2.96 -7510 austenite 39 [63]
NbC
5.43 -10960 ferrite 51 [64]
4.04 -10230 austenite 26 [65]
NbN
4.96 -12230 ferrite 35 [64]
5.12 -10300 austenite 89 [66]
TiC
4.4 -9575 ferrite 94 [67]
3.82 -15020 austenite 73 [68]
TiN
4.65 -16310 ferrite 83 [69]

By applying Newton’s method and the law of conservation of mass, the mass fraction of
all phases for all temperatures can be computed. A computation for a more complex case
of an Al-Nb-B steel is shown in Figure 4.5. It should be noted that such computations
rely on coefficients measured in alloys with only a few elements and therefore more
complex interactions between the components are ignored.

48
4.1 Equilibrium

AlN
BN
NbC
NbN
TiC
TiN
0.01 VC
VN
phase mass fraction [mass-%]

0.001

0.0001
600 700 800 900 1000 1100 1200 1300 1400
temperature [°C]

Figure 4.5: Plot of the precipitated phase fractions during cooling of the Al-Nb-B steel
(0.17 % C, 0.0066 % N, 0.0685 % Al, 0.0027 % Ti, 0.029 % Nb, 0.0016 % V,
0.002 % B) using the solubility products listed in Table 4.1 and limiting the
precipitation to the austenite phase

4.1.3 CALPHAD based packages

Another approach for multicomponent systems, the CALPHAD method is used in many
commercial software packages. This method became more and more important in the
eighties with the emergence of thermodynamic database systems. The thermodynamic
properties are described by models of the phases of the system based on empirical data.
Numerical minimisation of Gibbs energies results in equilibrium states. The models
take into account all elements involved and all possible phases. This method allows
extrapolated predictions in regions without experimental information. It is not always
clear how well the models are adapted to the present low alloyed microalloyed steels.
Nowadays several commercial implementations of the CALPHAD method are available:
Thermo-Calc, JMatPro, MatCalc, FactSage and PANDAT. Each of these packages has
its individual strength and some have additional components allowing kinetic computa-
tions.
Three of these models are used in the following, JMatPro, ThermoCalc and MatCalc.
They will be compared with the equilibrium model.
Thermo-Calc for Windows version 5 was used with the TCFE 6 database. The JMatPro
release 8.0.1 with the database for general steels was applied. This software also offers
the possibility to plot time-temperature-precipitation diagrams (TTP) that will be dis-
cussed later on. MatCalc, a software still in development at the Technical University
Vienna, was used in the version 5.53. The particularity of this software is to use an

49
4 Modelling

open CALPHAD-type database which allows an adaptation of the thermodynamic data.


MatCalc in particular is designed for kinetic calculations.

4.1.4 Austenite to ferrite transformation

The modelling of the phase evolution during cooling necessitates to calculate also the
temperature of austenite to ferrite transformation. All commercial thermodynamic mod-
els of this study use TAe3 , the transformation temperature for equilibrium conditions.
A more realistic, although still not fully accurate, value would be TAr3 , the temperat-
ure experimentally determined during cooling with cooling rates typical for continuous
casting. This is not available in most cases. Fortunately Mintz et al. [70] have published
regression equations for TAr3 , which will be used in our equilibrium computations. The
dataset “Reference 7” of “Table 7” in [70] was adopted.

4.2 Modelling of kinetics

The Dutta-Sellars and MatCalc models consider not only the thermodynamics but also
the kinetics and are for that reason also adapted for the use of temperature curves like
those typical of the surface slab temperature during continuous casting.
In addition to the total deformation and deformation rate, further parameters like the
nucleation rate, the diffusivity of normal and fast diffuser and a differentiation of the
possible nucleation sites are needed.
The diffusivity is essential to determine the growing rate of a nucleus or particle. The
diffusivity depends in turn on several factors. The most important factors are the tem-
perature, the size of the atom, the concentration and concentration gradients and the
dislocations. Higher diffusion rates can be attained at higher temperatures, with smaller
atoms like C, N or B and at dislocations. The ratios of diffusion at grain boundaries or
dislocations compared to the diffusion in the bulk is assumed to be in the range of 104
to 107 in austenite and ferrite [71].
Possible nucleation sites are in the bulk, at dislocations, at grain boundaries, at grain
boundary corners or at sub-grain boundaries. The number of possible nucleation sites
depends on several factors, amongst others the dislocation density and the austenite
grain size. Unfortunately the determination of both parameters is not straightforward.
The values used in MatCalc are assessed values taken from the literature that could not
be verified and could be possible sources of discrepancies between the simulation results
and the microscopical observations.
A remaining problem is non-uniformity of concentration due to microsegregation (cf.
Subsection 2.5). Since microalloying elements such as Nb can segregate, their concen-
trations and thus their conditions for precipitation can vary significantly in the inter-
dendritic space. This effect can be taken into account using microsegregation models as
Scheil-Gulliver [72] but was neglected in the current work.

50
4.2 Modelling of kinetics

4.2.1 Dutta-Sellars model

The Dutta-Sellars model [73] describes strain induced precipitation of Nb(C,N). The
model is based on semi-empirical laws for precipitation and the kinetics is taken into
account by the application of the additivity rule. No precipitate size distribution can be
calculated. The model was fitted using a limited set of experimental data.
Due to the fact that the model has been primarily developed in order to determine the
time for 5 % precipitation with or without strain, it is particularly reasonable to use
it for TTP-plots. For undeformed austenite and austenite with deformation respect-
ively only few constants are necessary, thus making the adjustment of the model quite
simple. Unfortunately, experimental data from the literature cannot be used for adjust-
ing the model for the conditions of this study because such experiments were made with
deformations and deformation rates typical for hot rolling.
The nucleation process is described by the classical nucleation theory. The model takes
the effect of the strain and of the strain rate into account by using the Zener-Hollomon
parameter. The model has been optimised by Dutta and Sellars using seven publica-
tions on Nb(C,N) in austenite. The time for 5 % precipitation is described by following
equation:
270000 B
t0.05 = A [N b] −1 ϵ−1 Z −0.5 exp exp (4.5)
RT T (ln κs )2
3

A and B are constants allowing an adaptation of the model to the experimental data.
ϵ is the deformation, R is the universal gas constant, T the absolute temperature in
Kelvin. Z is the Zener-Hollomon parameter defined as

Qdef
( )
Z = ϵ̇ exp (4.6)
RT
where Qdef is the activation energy for deformation. The supersaturation ratio κs is
defined as
[N b] [C + 12/14N ]solution
κs = (4.7)
102.26−6670/T

4.2.2 MatCalc

MatCalc is a computer simulation software package of transformations in metallic sys-


tems using the CALPHAD method and a kinetic based on the classical nucleation the-
ory. MatCalc uses a mean field approach and allows the description of precipitate sizes,
number densities and chemical composition. The nucleation rate J is described by the
multi-component nucleation theory according to
G∗ τ
J = N0 Zβ ∗ e− kT e− t (4.8)

N0 is the number of possible nucleation sites, Z the Zeldovich factor describing the
influence of thermal vibrations, β ∗ the atomic attachment rate, G∗ the critical nucle-
ation energy, k the Boltzmann constant, τ a time constant and t the time in seconds.

51
4 Modelling

The two exponential terms describe respectively the probability of nucleation and the
characteristic period of time for reaching equilibrium.
The numerical implementation is based on the Kampmann-Wagner model. On this way
the evolution of several precipitation classes is computed simultaneously allowing the
determination of precipitate size distributions.

52
5 Al-Ti steel

The Al-Ti steel is a modified grade 50 of the API 2Y specification [74] from the American
Petroleum Institute and has the composition shown in Table 5.1. It has a high Al content,
only a low Ti content and residual contents of Nb and B. This steel showed to be
crack sensitive during continuous casting when cast as 450 mm thick slab with a casting
speed of 0.24 m min-1 . The minimum yield strength after quenching and tempering is
approximately 380 MPa.
First samples were cut out of specimens after Gleeble testing. For this test three char-
acteristic temperatures were chosen. The Gleeble specimens were strained in vacuum
after several purging with argon. Fracture facets and polished surfaces were studied in
the SEM to find precipitates by manual and APAs and to characterise the microstruc-
ture. Smaller particles could be found on carbon replicas observed with help of a STEM
detector.
Furthermore three different slab specimens were investigated. The specimens were taken
near the surface, in quarter depth and near the centre of the slab, but not in the segreg-
ation zone. All of them were analysed by APA at the SEM.
Simultaneously the phase fractions and size distributions of particles were calculated
with the MatCalc simulation software.

5.1 Thermodynamics

The stoichiometric reaction of Ti with N leads to a full consumption of Ti and almost


14 ppm of N are left over. These 14 ppm N could react preferentially with Al because all
other nitride forming elements are residuals.
The four thermodynamic models are used to determine which phases may be able to
precipitate. According to Figure 5.1 TiN precipitates first, followed by AlN. Nb(C,N)
and BN should, if at all, precipitate in smaller amounts and at much lower temperature.
This gives a hint for the precipitation sequence whereby it should be taken into account
that, in reality, all precipitation processes can be kinetically constrained or, on the
contrary, for example strain induced.

Table 5.1: Chemical composition of the Al-Ti steel


element C N Al Nb Ti B
content [%] 0.085 0.0043 0.052 0.0005 0.01 0.0002

53
5 Al-Ti steel

-4 MatCalc JMatPro
2.0·10
AlN
TAe3 TAe3 BN
-4 Nb(C,N)
1.5·10 TiN
phase fraction

1.0·10-4

5.0·10-5

0.0·100
ThermoCalc equilibrium model
2.0·10-4
TAe3 TAr3 according to Mintz et al.
-4
1.5·10
phase fraction

1.0·10-4

5.0·10-5

0.0·100
100
reduction of area [%]

80

60

40

20

0
600 800 1000 1200 1400 600 800 1000 1200 1400
temperature [°C] temperature [°C]

Figure 5.1: Equilibrium precipitation (four models) and results of ductility trials of the
Al-Ti steel

Besides the simulation results the figure also shows the evolution of the reduction of area
with the temperature. This will be discussed later on. The phases are colour coded to
improve the comparability of figures. AlN, BN, Nb(C,N) and TiN are respectively drawn
in blue, yellow, green and brown. If a differentiation is made between AlN nucleating at
grain boundaries or at dislocations, the latter will be drawn in light blue.

Comparing the four models, the precipitation start temperatures of AlN differ by up
to 150 °C. The precipitated phase fraction at 500 °C varies between 0.003 and 0.008 %.
The phase fractions of BN and Nb(C,N) are negligible according to all models. The low
precipitation of AlN in the equilibrium model is explained by a solubility product for a
delayed precipitation (cf. Subsection 2.2.3).

54
5.2 Thermomechanical testing

1400

300s, 1350 °C
- 4 °Cs-1
1200

- 0.5 °Cs-1
1000
deformation with
3·10-5 s-1
temperature [°C]

800

600

400 - 57 °Cs-1

200

0
0 200 400 600 800 1000 1200
time [s]

Figure 5.2: Exemplary temperature profile during a Gleeble ductility testing

5.2 Thermomechanical testing

5.2.1 Ductility trials

The ductility was tested in the Gleeble at defined temperatures between 1100 and 500 °C.
The specimens were heat treated and tested as described in Figure 5.2. The diameters
measured before and after fracture allow the determination of the reduction of area as
described in Subsection 3.2.
The bottom graphs of Figure 5.1 show a very low ductility in a wide trough between
975 and 750 °C. The reduction of area can be compared with the thermodynamic sim-
ulation results plotted above. There seems to be coincidence between the decrease of
the reduction of area and the precipitation of AlN. Below 750 °C the phase fraction con-
tinues however to increase while the reduction of area rises again rapidly. This may be
explained by the presence of ferrite at this temperature.

5.2.2 Fracture facets

From the series of ductility tests three temperatures were chosen for further investiga-
tions. Three new specimens were tested at characteristic temperatures under vacuum
after flooding the chamber with argon, so that the fracture facets could not oxidise. One
specimen was tested at a high temperature above the ductility trough (1050 °C), one at
the lowest ductility (850 °C) and one at a low temperature, possibly in the austenite-
ferrite domain, where the ductility has improved again (700 °C). Figure 5.3 shows the
fracture facets. At 1050 and 700 °C they are representative for a ductile crack while on

55
5 Al-Ti steel

the 850 °C specimen single grains are visible, i.e. the fracture was intergranular.
Using a higher magnification, Figure 5.4 allows to find inclusions and precipitates on
the fracture facets. On the 1050 °C specimen TiN of different forms and sizes between
approximately 50 nm and some micrometres, along with calcium sulphides CaS, were
found.
The 850 °C specimen, showing distinct austenite grains, contained some TiN of sev-
eral micrometres with the well known cubic form but also AlN. The AlN were evenly
distributed on some austenite grains (see Figure 5.5).
Figure 5.6 shows the 700 °C specimen where only globular CaS of some micrometres
diameter could be found.
Intergranular failure allows to find the precipitates that nucleated on the austenite grain
boundaries while all precipitates that nucleated inside the grain, e.g. on dislocations are
difficult to find. This explains that almost only AlN were found on the 850 °C specimen.
Similarly TiN will be found preferentially on ductile fracture surfaces like the ones of
the 1050 and 700 °C specimens.

5.2.3 Microstructure of Gleeble specimens

For microstructure analysis the surface orthogonal to the direction of tension directly
beneath the fracture surface was chosen, cf. Figure 3.5. The surfaces were polished
mechanically to 1 µm and electropolished. The electropolishing allows to get a flat and
smooth surface and reveals the microstructure. Pictures were taken at different magni-
fications between 100 and 10 000x. A set of pictures taken at the same magnification
can be compared in Figure 5.7.
It can be seen that at 1050 and 850 °C the microstructure is very similar. This micro-
structure, namely intragranular ferrite, is typical for specimens cooled rapidly from a
high temperature in the austenite range to room temperature. The specimen strained
at 700 °C contains ferrite and martensite.

5.2.4 Automated particle analysis APA on Gleeble specimens

On surfaces similar to those previously used for microstructure analyses, APAs were
made at different magnifications with pixel sizes of 40 and 12 nm . This allows to search
for particles over 80 nm diameter on surfaces of around 10 mm², and over 24 nm diameter
on smaller surfaces. The results are summarised in Table 5.2 and displayed in Figure 5.8
and Figure 5.9. Due to the negligible phase amounts of BN and Nb(C,N) both phases
are not shown in the APAs. Hence they will not be taken into account in the simulations
to follow.
As observed on the fracture facets, AlN occurred mainly on the intergranularly fractured
850 °C specimen, while TiN is omnipresent on the other two specimens.
An interesting observation that can be made when comparing both magnifications relates
to the TiN. At high magnification the surface density is six to ten times higher on

56
5.2 Thermomechanical testing

Figure 5.3: Fracture facets of the Gleeble specimens tested at 1050 °C, 850 °C and 700 °C

57
5 Al-Ti steel

Figure 5.4: TiN on the Gleeble specimen tested at 1050 °C

Figure 5.5: AlN on an austenite grain of the Gleeble specimen tested at 850 °C

58
5.2 Thermomechanical testing

Figure 5.6: CaS on the Gleeble specimen tested at 700 °C

Figure 5.7: Microstructure of Gleeble specimens at 1050 °C, 850 °C and 700 °C (from left
to right and from top to bottom) quenched after testing

59
5 Al-Ti steel

Table 5.2: Surface densities and mean diameters according to the APAs at both magni-
fications for the three Gleeble specimens

40 nm pixel size 12 nm pixel size


surface density [cm-2 ]
AlN TiN AlN TiN
1050 °C 0 52 0.85 6347
850 °C 10 15 94 650
700 °C 1.05 70 0 1172
(a) surface densities

40 nm pixel size 12 nm pixel size


mean diameter [µm]
AlN TiN AlN TiN
1050 °C - 0.22 0.025 0.056
850 °C 0.16 0.21 0.077 0.058
700 °C 0.16 0.19 - 0.068
(b) mean diameters

10000
AlN
TiN
surface density [1/mm ]
2

1000

100

10

0.1
700 850 1050

250
equivalent circle diameter [nm]

200

150

100

50

0
700 850 1050
temperature [°C]

Figure 5.8: Surface densities and equivalent circle diameters for all phases in the three
Gleeble specimens according to the APAs with a pixel size of 40 nm i.e. for
particles with more than 80 nm diameter

60
5.2 Thermomechanical testing

10000

surface density [1/mm2]


1000

100
AlN
TiN
10

0.1
700 850 1050

250
equivalent circle diameter [nm]

200

150

100

50

0
700 850 1050
temperature [°C]

Figure 5.9: Surface densities and equivalent circle diameters for all phases in the three
Gleeble specimens according to the APAs with a pixel size of 12 nm i.e. for
particles with more than 24 nm diameter

the 1050 °C specimen than on both other specimens. The lower surface density at low
magnification would indicate that a high number of small TiN precipitated at high
temperature. During cooling they have probably grown to bigger precipitates.

TiN are again interesting when considering the equivalent circle diameter (ECD) because
particles with more than 80 nm diameter (40 nm resolution) show a smaller ECD at lower
temperatures. However the particles over 24 nm diameter are growing with sinking
temperature. Only the latter correlates the conclusions made on the surface density
plots. The surface densities well below one particle per square millimetre of AlN at
some temperatures do not allow any conclusion to be made.

5.2.5 STEM on quenched Gleeble specimens

Investigations were made on carbon replicas extracted from the previously described
sections of the three specimens. TiN were found in sizes between ca. 10 nm and some
100 nm length and contained often magnesium. TiN were more numerous but slightly
smaller on the 850 and 700 °C replicas. Additionally few AlN of approximately 200 nm
length were found on the 850 °C specimen. Further numerous particles containing Si, O
and C were found. The carbon signal comes most probably from the carbon film, so the
particles can only be silicon oxides. The origin of these particles is not clarified yet.

61
5 Al-Ti steel

casting
direction
wide face

narrow face
relative depth

Figure 5.10: Schematic position of the specimens in the slab

5.2.6 Discussion APA & STEM vs. thermodynamics

The very low surface density of AlN at 1050 °C is in accordance with all thermodynamic
calculations (see Figure 5.1). According to this figure almost all TiN should have precip-
itated at 1050 °C. This may explain the almost constant mean diameter of TiN over the
considered temperature range observed by APA with the pixel size of 40 nm. However
the evolution of the surface density cannot be explained by these data.
According to the thermodynamic calculations at 850 °C an average of approximately
50 % of the maximum AlN content should already have precipitated at 850 °C. At 700 °C
nearly all AlN should have precipitated.
The measurements made with pixel sizes of 12 nm are not easily correlated with the
thermodynamic calculations. For example the higher TiN content measured on the
1050 °C specimen compared with the 850 °C, despite a constant mean diameter, is in
contradiction with the thermodynamic models.

5.2.7 Particle profiles over the slab thickness (APA)

Specimens were cut from the slab at defined positions, i.e. far from the narrow side and
at three depths, namely near the surface, in quarter thickness and near the centre of the
slab (see Figure 5.10). Further preparation is done by grinding and polishing with an
abrasive grain size of 0.25 µm. Approximately 10 mm² of each specimen was investigated
by APAs. This allows to find a statistically relevant number of precipitates in the size
range of 80 nm to some micrometers. All morphological parameters of the particles were
measured and their chemical composition determined by EDS. Images were taken with
the backscatter detector at a 1500x magnification and 10 kV acceleration tension. The
spectra were collected with the same parameters and a collection time of 4 s allowing
approximately 6000 counts per second.
The results of the particle analyses in Figure 5.11 show that the particle density and the
average diameter depend on the depth in the slab. Near the surface the particle density
is high and the particles are small. A minimum in particle density and a maximum in
particle diameter is found in quarter depth.

62
5.3 MatCalc kinetic simulations

AlN
100 TiN
surface density [mm-2]

10

0.1
0 0.25 0.5

1400
equivalent circle diameter [nm]

1200
1000
800
600
400
200
0
0 0.25 0.5
relative depth in the slab

Figure 5.11: Results of the APAs on as-cast specimens taken in three different depths

5.3 MatCalc kinetic simulations

5.3.1 MatCalc simulations of Gleeble specimens

MatCalc was used to calculate the phase fractions, volume densities and mean radiuses
after Gleeble testing at the three temperatures. Calculations were made for the three
specimens using the real temperature profiles and strains determined during the Gleeble
tests (see top graph of Figure 5.12). The two possible parent phases (i.e. the phase in
which another phase precipitates), austenite and ferrite, were taken into account for the
simulations with a temperature of austenite to ferrite transformation Ae3 estimated in
an equilibrium simulation to be 828 °C. The cooling to room temperature was simulated
using the maximum cooling rate attainable in the Gleeble machine by air cooling.
In Figure 5.12 one can see the volume densities and the mean diameters for the three
Gleeble testing temperatures. It can be observed that the phases precipitating in ferrite
have high volume densities. AlN at dislocations precipitate only at 850 °C in significant
number. TiN in austenite have a volume density staying almost constant at the three
temperatures while the mean diameter has a minimum at 850 °C. In the ferrite the TiN
have a growing diameter but decreasing volume density when the temperature decreases
from 850 to 700 °C. Considering the mean diameter it can be concluded that all phases
beside AlN at dislocations have a constant or growing diameter at sinking temperature.
To make a comparison with the APA easier, the size distribution of the three phases
for each specimen have been plotted (see Figure 5.13). The nucleation site is coded: a

63
5 Al-Ti steel

1400

temperature [°C]
1200
1000 AlN at gb (aust)
800 AlN at d (aust)
600 TiN (aust)
400 AlN (ferr)
200 TiN (ferr)
0
0 200 400 600 800 1000 1200
time [s]
1020
volume density [m ]
-3

1019
18
1017
1016
1015
1014
1013
1012
10
700 850 1050

140
mean diameter [nm]

120
100
80
60
40
20
0
700 850 1050
temperature [°C]

Figure 5.12: MatCalc simulation of Gleeble testing considering the austenite and ferrite
domains: temperature profile of trial at 850 °C, volume densities and mean
diameters at the three temperatures according to MatCalc

plain line corresponds to austenite while a dashed line corresponds to ferrite. For AlN a
differentiation must be made between nucleation at grain boundaries and at dislocations.
The latter is symbolised by a lighter colour. The vertical thin lines delimit the size range
detectable in the particle analyses with low and high magnification, i.e 40 nm radius at
low magnification and 12 nm at high magnification.
According to Figure 5.13 the AlN at 700 and 850 °C and parts of the austenite pop-
ulations of TiN should be detected at low magnification. At the higher magnification
some additional AlN and TiN should be detected in both the austenite and the ferrite.
MatCalc predicts detectable AlN precipitates in the 700 and 850 °C specimens while the
predicted particles at 1050 °C are below the detection limit of even the finest resolution.
MatCalc computes volume densities while the measurement yield surface densities. The
direct comparison is thus not possible. The mean diameters are in the same order of
magnitude, but are not identical, probably because too small particles are not captured
by the APA measurement.

5.3.2 MatCalc simulations of TTP diagrams

Time-temperature-precipitation (TTP) diagrams were calculated with MatCalc for AlN


and (Nb,Ti)(C,N) and are displayed in Figure 5.15. The temperature profile used for
the simulation is shown in Figure 5.14. The times necessary for 5 and 50 % of the total
precipitation are shown without strain and with 4 % strain at temperatures between 750
and 1050 °C. The strain of 4 % is exaggerated in order to make sure to detect a difference

64
5.3 MatCalc kinetic simulations

22 700 °C 850 °C 1050 °C


10
AlN,gb AlN,gb AlN,gb
20 AlN,d AlN,d AlN,d
10 AlN,ferr AlN,ferr AlN,ferr
volume density [m-3]

18
10

1016

1014

1012

1010
1022
TiN,aust TiN,aust TiN,aust
TiN,ferr TiN,ferr TiN,ferr
1020
volume density [m-3]

1018

1016

1014

1012

1010
1 10 100 1 10 100 1 10 100
diameter [nm] diameter [nm] diameter [nm]

Figure 5.13: Size distribution of the three phases of Figure 5.12 for each specimen ac-
cording to MatCalc, vertical lines indicate the APA resolution limit

in the analysed specimens. A normal deformation in a CC process is in the range of 1 to


2.5 %. The calculation has been made limiting the precipitation to the austenite domain
without consideration of the austenite to ferrite transformation temperature.
According to Figure 5.15a no AlN will precipitate without strain. With 4 % strain
precipitation can only be expected at temperatures below 900 °C. After only 1000 s at
800 °C more than 50 % of the phase will have precipitated.
Figure 5.15b shows that the fastest precipitation of the titanium rich phase will occur
at 1000 °C. The precipitation should start after 700 s without strain and already after
350 s when 4 % strain is applied.
For this steel no hold and quench trials could be made. Therefore the MatCalc simula-
tions cannot be compared with empirical data. Such comparisons will be postponed to
the next two steel grades.

CC temperatures in TTP diagrams

The strand surface temperature passes through complex patterns. This cannot be rep-
resented in a isotherm TTP diagram. Fortunately the idealisation of assuming constant
surface temperature over a long time interval (in the secondary cooling zone) is not
entirely unrealistic. This can be depicted as a temperature corridor in the TTP dia-
gram. Figure 5.16 shows two examples of idealised surface temperatures of two different
continuous casters. The points represent the time after which the strand is deformed

65
5 Al-Ti steel

1400
300s, 1350°C

1200
- 4°Cs-1

1000 1000 s holding and 4 % strain

temperature [°C]
800

600

-1
400 - 57°Cs

200

0
0 200 400 600 800 1000 1200 1400
time [s]

Figure 5.14: Exemplary temperature profile of a TTP simulation for a holding of 1000 s
with an applied deformation of 4 %

during the bending and straightening processes. In this manner a TTP diagram helps
to determine if the precipitation of a phase may be possible after a given time. After
exiting the secondary cooling zone the strand still encounters few cooling rolls so that
the strand surface temperature slowly decays.
Assuming the conditions of CC 1 with constant surface temperatures AlN precipita-
tion will be completed while more than 50 % of (Nb,Ti)(C,N) will precipitate. No AlN
precipitation will occur assuming the conditions of CC 2, but (Nb,Ti)(C,N) will also
precipitate to more than 50 %.

5.3.3 MatCalc simulation for three positions in slab thickness

MatCalc was run with temperature profiles corresponding to the three depths studied in
Subsection 5.2.7. The assumed temperature profiles are plotted in Figure 5.17 together
with the resulting number densities, mean diameters and phase fractions. The number
densities are generally higher at the surface, but the profiles over the thickness are by
far not as pronounced as on the slab samples. If this may be a consequence of neglecting
the periodic temperature dips caused by the rolls in the MatCalc assumptions, it will
be checked in the next subsection. The empirical profiles of diameter and density are
not reproduced. The diameters differ by an order of magnitude. It is interesting to note
that, according to MatCalc, AlN only precipitate at dislocations near the surface.
An explanation for these discrepancies is possible by considering the computed size
distributions shown in Figure 5.18 for the three precipitation phases. In all plots a
vertical line symbolises the detection limit of the APA. The predicted sizes of AlN
are similar in the three cases, although much smaller than from the particle analyses.
Noteworthy is the narrow peak in TiN size distribution near the surface with precipitates
between 10 and 70 nm, which should not be detectable by the lower resolution APA

66
5.3 MatCalc kinetic simulations

1050
t5 % with 4 % strain
t50 % with 4 % strain
t5 % without strain
1000 t50 % without strain

950
temperature [°C]

t5 % t50 %
t5 %
900

t50 %
850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(a) TTP-plot for AlN

1050
t5 % without strain
t5 % with 4 % strain
t50 % without strain
1000 t50 % with 4 % strain
t5 % t50 %

950
temperature [°C]

900

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(b) TTP-plot for (Nb,Ti)(C,N)

Figure 5.15: TTP-plots of the Nb-Ti steel according to MatCalc showing the times ne-
cessary for 5 % and 50 % precipitation

67
5 Al-Ti steel

1050

1000 CC 2, Vg = 1 m/s

950

temperature [°C] 900

850

800 CC 1, Vg = 0.3 m/s

750
10 100 1000 10000 100000 1e+006
time [s]

Figure 5.16: Corridors displaying the approximate temperatures and times of the bending
and straightening processes for two continuous casters

underlying Figure 5.11 while many much larger TiN were actually found in the CC
specimens. At the two other positions the precipitates have diameters between 1 and
220 nm partly detectable by APA but much smaller than observed. All populations could
be detected by APA but not AlN at dislocations and TiN near the surface. At least the
latter does not correspond to the SEM observations summarised in Subsection 5.11.

5.3.4 MatCalc simulation including periodic temperatures and strain

Another simulation was carried out with a temperature profile with the sharp temper-
ature dips to check the significance of this effect. Additionally the strain occurring
at the bending and unbending was also taken into account and is symbolized by two
vertical lines in Figure 5.19a. It shows the assumed slab surface temperature profile.
Figure 5.19b shows the calculated size distributions of AlN and TiN. The vertical line
at 80 nm marks the detection limit of the APA. Thus it can be seen that AlN are clearly
over the size limit and could all be detected. TiN show a larger size distribution with
diameters between 20 and 90 nm so that only few of them should be detectable by APA.

5.4 Conclusions

This steel is characterised by high Al, low Nb and Ti. B is present only in traces.
The thermodynamic calculations reflect this fact by predicting only TiN and AlN as
noteworthy precipitating phases.
Experiments were made with Gleeble specimens heat-treated and strained at different
temperatures and with as-cast specimens taken in three different depths.
The Gleeble specimens were investigated by SEM. Numerous AlN were found on the

68
5.4 Conclusions

1600
temperature [°C]

slab inner
1400 slab 1/4 thickness
1200 slab surface
1000
800
600
0 1000 2000 3000 4000 5000 6000 7000 8000
time [s]

10-4
phase fraction

10-6

10-8

10-10

1020
volume density [m-3]

1018
AlN at gb
16 AlN at dislocations
10 TiN

1014

1400
mean diameter [nm]

1200
1000
800
600
400
200
0
0 0.25 0.5
relative depth in the slab

Figure 5.17: Temperature profiles, phase fraction, volume density and mean diameter
according to MatCalc in the three as-cast specimens using idealised temper-
ature profiles without deformation

69
5 Al-Ti steel

surface quarter depth inner


1018 AlN, gb AlN, gb AlN, gb
AlN,d
volume density [m-3]

1016

1014

1012

1010

1018 TiN TiN TiN


volume density [m-3]

1016

1014

1012

1010
1 10 100 1 10 100 1 10 100
diameter [nm] diameter [nm] diameter [nm]

Figure 5.18: Size distribution of the phases of Figure 5.17 (i.e. without deformation) for
the three depths according to MatCalc, vertical lines indicate limits of APA
detection

70
5.4 Conclusions

1400 strain
temperature [°C]

1300
1200
1100
1000
900
800
700
600
0 1000 2000 3000 4000
time [s]
(a) Slab surface temperature, vertical lines indicate bending and unbending

1018 AlN at grain bound. 1018 TiN


volume density [m-3]

volume density [m-3]

1016 1016

1014 1014

1012 1012

1010 1010
1 10 100 1 10 100
diameter [nm] diameter [nm]
(b) Histograms of the diameter distributions of the calculated phases after 4200 s, vertical lines indicate
limit of APA detection; to be compared with Figure 5.18 left column

Figure 5.19: MatCalc results of the simulation of the surface cooling taking the deform-
ation into account

71
5 Al-Ti steel

fracture surface of the specimen strained at 850 °C and failing with an intergranular
failure. The APAs on cross-sections showed AlN only at 850 °C. Why they were not
found at 700 °C is not clear. It is supposed that AlN are found at 850 °C because
the specimen broke intergranularly i.e. along the austenite grain boundaries where the
AlN precipitated. The specimen that broke intragranularly at 700 °C contains very
probably still these AlN but the fracture surface does not show necessarily austenite
grain boundaries and so only few AlN. TiN were detected on all Gleeble specimens. They
precipitate at temperatures much higher than the temperature drop and are therefore
not associated with the cracking risk.
CC samples from the slab surface also showed elevated amounts of AlN of relatively
small size with a more or less constant amount of TiN particles.
It is concluded that the cracking risk of this steel is mainly due to AlN precipitation
which is likely to occur already about 850 °C.

72
6 Nb-Ti steel

The Nb-Ti steel conforms to the norm API 5L X70 [75] and reaches a minimum yield
strength of 420 MPa after thermomechanical rolling and accelerated cooling. The com-
position is shown in Table 6.1 and is characterised by Nb and Ti contents besides low
contents of Al, C, N and traces of B. No problems were encountered during the casting
of this steel.

6.1 Thermodynamics

With only 33 ppm N and 140 ppm Ti, approximately 27 ppm Ti would remain when all
the nitrogen is consumed in the case of a stoichiometric reaction of both elements. Hence
it can be expected that Al and B will most likely form no nitrides. Nb can precipitate,
mostly as carbide, since the carbon content is high enough.
Thermodynamic calculations of the three commercial models JMatPro, Thermo-Calc
and MatCalc and of the equilibrium model were carried out and are compared in Fig-
ure 6.1. JMatPro and the equilibrium model give very similar results. MatCalc and
Thermo-Calc differ from both other models by the occurrence of AlN at about 800 °C
which may be due to the transfer of N from TiN to AlN. Further Thermo-Calc predicts
the presence of small amounts of BN.

6.2 Thermomechanical testing

6.2.1 Ductility trials

Ductility tests were carried out as described in Subsection 5.2.1. The results are shown
in the bottom of Figure 6.1. The reduction of area indicates that the ductility is low at
temperatures between 1000 and 700 °C. Overall the ductility is better than for the Al-Ti
steel. This may explain that the steel caused no problems during continuous casting.
The shape of the reduction of area curve can be compared to the simulation results. The
decrease of ductility at 1000 °C corresponds to the incipient precipitation of Nb(C,N).

Table 6.1: Chemical composition of the Nb-Ti steel


element C N Al Nb Ti B
content [%] 0.051 0.0033 0.035 0.035 0.014 0.0002

73
6 Nb-Ti steel

MatCalc JMatPro
7·10-4
AlN
6·10-4 TAe3 TAe3 BN
Nb(C,N)
5·10-4 TiN
phase fraction

4·10-4
3·10-4
2·10-4
1·10-4
0·100
ThermoCalc equilibrium model
7·10-4
6·10-4 TAe3 TAr3 according to Mintz et al.
-4
5·10
phase fraction

4·10-4
-4
3·10
2·10-4
-4
1·10
0·100
100
reduction of area [%]

80

60

40

20

0
600 800 1000 1200 1400 600 800 1000 1200 1400
temperature [°C] temperature [°C]

Figure 6.1: Equilibrium precipitation (four models) and results of ductility trials of the
Nb-Ti steel

74
6.2 Thermomechanical testing

1400

300 s, 1350°C

1200
-1
- 30°Cs

1000 1000 s, 950°C


temperature [°C]

800

600
- 57°Cs-1

400

200

0
0 200 400 600 800 1000 1200 1400
time [s]

Figure 6.2: Plot of the temperature during hold and quench trials with a holding time of
1000 s at 950 °C

6.2.2 Hold and quench trials HQT

Hold and quench trials (HQT) were carried out in order to investigate the influence of the
three parameters temperature, time and deformation on the precipitation kinetics. The
influence of the temperature was determined by holding specimens at 850 and 950 °C.
Specimens were first heated to 1350 °C and held there in order to dissolve all precipitates
remaining from the continuous casting (cf. Figure 6.2). The specimens were then cooled
to the test temperature of 950 or 850 °C and held for 100, 1000 or 5000 s. In each case
a second specimen was strained to 4 % deformation during holding in order to simulate
the bending. The deformation encountered during the CC process is in the range of 1 to
2.5 %. Thus the deformation was exaggerated to make sure that the difference between
the two sets of specimens is pronounced. The specimens were finally quenched at a
cooling rate of over 30 °Cs-1 to freeze the microstructure. Specimens cut in the vicinity
of the thermocouple as sketched in Figure 3.5 were prepared for metallographic analysis
according to the standard preparation method.

Automated particle analyses APA on HQT samples

APAs at the SEM allow to determine the number of precipitates as well as their size and
chemistry. Particles of more than 80 nm diameter could be found with a pixel size of
40 nm on surfaces of approximately 10 mm² per specimen. The chemistry is determined
by means of EDS measurements and the particles are classified as AlN, BN, NbC and
TiN. The corresponding phase fractions are calculated from the surface density with
the assumption of ideally round and evenly distributed particles according to following
formula

75
6 Nb-Ti steel

Table 6.2: Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for AlN
at 850 °C and 950 °C; values in italic being questionable
AlN at 950 °C 850 °C
held 100 s 1000 s 5000 s 100 s 1000 s 5000 s
only holding 0.23 7.39 6.42 0 2.87 3.57
strain + holding 0.81 2.06 0.86 1.20 10.2 2.39

Table 6.3: Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for BN
at 850 °C and 950 °C; values in italic being questionable
BN at 950 °C 850 °C
held 100 s 1000 s 5000 s 100 s 1000 s 5000 s
only holding 0.08 0.60 0.67 0.04 2.17 18.7
strain + holding 0.11 0.28 0.11 3.44 1.00 0.50

Aphase × ρphase/Mphase
fphase = (6.1)
Atotal × ρtotal/Mtotal

where f is the phase fraction, A the surface area, ρ the density and M the molar mass.
Table 6.2 shows the phase fractions of AlN at 950 and 850 °C. It can be seen that the
phase fraction generally increases with the holding time. Without strain the phase
fraction is higher at 950 °C, but is clearly smaller at this temperature when strain is
applied. The specimens held 100 s contain no or almost no AlN of more than 80 nm
diameter.
It should be taken into account that the detection of AlN is error prone. First the Al
peak in the EDS spectra is difficult to find automatically because of a very low peak to
background ratio. This is exacerbated by the fact that AlN precipitates are particularly
small so that the signal of the precipitate is strongly overlaid by the signal of the matrix.
Further the differentiation between an aluminium oxide and an aluminium nitride can
be difficult because the specimens are always contaminated to a greater or lesser extent
with oxygen.
Table 6.3 shows the phase fractions of BN at both temperatures. Without straining a
trend to higher phase fractions with longer holding times can be seen. When strain is
applied the phase fraction stays almost constant or decreases with longer holding times.

Table 6.4: Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
(Nb,Ti)(C,N) at 850 °C and 950 °C; values in italic being questionable
(Nb,Ti) (C,N) at 950 °C 850 °C
held 100 s 1000 s 5000 s 100 s 1000 s 5000 s
only holding 17.6 19.9 24.5 5.91 27.0 32.2
strain + holding 27.9 24.1 27.9 136 14.6 66.8

76
6.2 Thermomechanical testing

Table 6.5: Comparison of the phase fractions calculated from the APA with the phase
fractions from the thermodynamic simulations in Figure 6.1
×10−4 thermodynamics APA
AlN 0..2 6
BN 0 0.2
Nb(C,N) 4..5
0.7
TiN 0.5..1.7

This may be due to a preferential strain induced precipitation of another phase. It can
also be concluded that the phase fractions of BN are higher at 850 °C.
It should also be taken in consideration that the determination of BN during an APA is
delicate. B is the lightest element that can be detected by the EDS but its quantification
is of limited accuracy. Further several BN were found to have coprecipitated on oxidic or
sulphuric inclusions. Hence these particles cannot be distinguished automatically from
pure inclusions.
Table 6.4 shows the phase fractions of the (Nb,Ti)(C,N) at 950 and 850 °C. Here the
longer holding time leads clearly to increased phase fractions. It can also be observed
that the phase fractions are higher when strain is applied at 850 °C.
Some values in the tables are abnormally high. They are marked in italic. This could be
due to APA made in zones of microsegregation. Unfortunately this cannot be assessed.
A much larger number of APA scans is necessary to limit this effect.
A question is how well the phase fraction calculated from APA compare with the the-
oretical thermodynamic values from Figure 6.1. Table 6.5 shows this comparison. The
APA phase fraction for AlN is much higher than the equilibrium value. This could be
due to the detection of Al in oxides, but the reasons are not fully clear. The higher
amount of APA detected BN may be due to the detection problem mentioned above and
the possibly rapid early precipitation of BN. The detected Nb(C,N) and TiN are below
the thermodynamic results which may be due to incomplete precipitation.
The results of the HQT study are further graphically represented in Figures 6.3 to 6.6.

Estimation of TTP diagrams

The measured phase fractions were used to approximate the start of precipitation. For
this the first time with relevant precipitation was estimated from the precipitation curves.
This times were marked in Figure 6.7 both for the experiments with and without strain.
AlN precipitates fastest with strain at 850 °C after 100 s, but only after approximately
1000 s at 950 °C without applied strain.
The precipitation of BN needs at least 10 000 s to begin at 950 °C. However the precipit-
ation is faster at 850 °C with precipitation start times lower than 1000 s both with and
without strain.
At 950 °C the precipitation of (Nb,Ti)(C,N) needs around 100 s to start. This is compar-
able to the time needed at 950 °C with strain, while around 1000 s are necessary without

77
6 Nb-Ti steel

without deformation at 850°C with 4% deformation at 850°C


AlN
600 BN
NbCN
TiN

500
surface density [1/mm2]

400

300

200

100

0
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 6.3: Comparison of surface densities for the specimens held at 850 °C according
to the APA limited to particles over 80 nm diameter

without deformation at 950°C with 4% deformation at 950°C


AlN
600 BN
NbCN
TiN

500
surface density [1/mm2]

400

300

200

100

0
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 6.4: Comparison of surface densities for the specimens held at 950 °C according
to the APA limited to particles over 80 nm diameter

78
6.2 Thermomechanical testing

without deformation at 850°C with 4% deformation at 850°C


700
AlN
BN
NbCN
600 TiN

500
equivalent circle diameter [nm]

400

300

200

100

0
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 6.5: Comparison of the mean equivalent circle diameters for the specimens held
at 850 °C according to the APA limited to particles over 80 nm diameter

without deformation at 950°C with 4% deformation at 950°C


700
AlN
BN
NbCN
600 TiN

500
equivalent circle diameter [nm]

400

300

200

100

0
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 6.6: Comparison of the mean equivalent circle diameters for the specimens held
at 950 °C according to the APA limited to particles over 80 nm diameter

79
6 Nb-Ti steel

Table 6.6: Surface densities and equivalent circle diameter of particles over 80 nm dia-
meter according to the APAs for the specimens taken in three slab depths

surface density [mm-2 ] AlN BN Nb(C,N) TiN

near surface 0.94 0.94 5.58 73.81


quarter depth 0 12.51 2.11 146.1
near centre 0.27 13.61 8.98 31.64
(a) surface densities

equivalent circle diameter [µm] AlN BN Nb(C,N) TiN

near surface 0.59 0.12 0.10 0.24


quarter depth - 0.26 0.14 0.24
near centre 0.53 0.22 0.13 0.24
(b) equivalent circle diameters

strain.
This method is of course very rough but gives first indications of the time scale relevant
for precipitation. Only a limited number of HQT samples could be analysed.

6.2.3 Particle profiles over the slab thickness

The specimens were investigated in the same manner as described in Subsection 5.2.7.
Three specimens were cut out of the slab near the surface, in quarter thickness and
near the centre. The mean values determined from at least three measurements on total
surfaces of 2 mm² to 4 mm² are displayed in Table 6.6.
These results are graphically represented in Figure 6.8. The TiN densities and particle
diameters are almost constant over the thickness. AlN are very rare on the surface with
one particle per cubic metre (much less than for the Al-Ti steel) and are almost non-
existent on the other positions. Nb(C,N) throughout have a more remarkable volume
density of 3 to 9 m-3 and an almost constant diameter of 100 nm. The graphs show
also certain amounts of BN between 100 and 250 nm in diameter, although this must be
interpreted with care since boron is present only in trace quantities.

6.3 MatCalc kinetic simulations

6.3.1 MatCalc simulations of HQT samples

Time-temperature-precipitation TTP-plots were calculated with MatCalc separately for


each phase without deformation and with a deformation of 4 % applied with a strain rate
typical for CC. The deformation of 4 % is exaggerated for the simulation of a CC process
but allows nevertheless to ensure that the influence on the precipitation is detectable.

80
6.3 MatCalc kinetic simulations

1050

1000

950
temperature [°C]

900 no strain
with strain

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(a) Estimation of the start of AlN precipitation

1050

1000

950
temperature [°C]

900 no strain
with strain

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(b) Estimation of the start of BN precipitation

1050

1000

950
temperature [°C]

no strain
900
with strain

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(c) Estimation of the start of (Nb,Ti)(C,N) precipitation

Figure 6.7: Rough estimation of the start of all precipitation phases in the Nb-Ti steel
according to hold and quench trials

81
6 Nb-Ti steel

100
surface density [m-2]

10

0.1

1400
AlN
equivalent circle diameter [nm]

1200 BN
Nb(C,N)
1000 TiN

800

600

400

200

0
0 0.25 0.5
relative depth in the slab

Figure 6.8: Graphical representation of the surface densities and equivalent circle dia-
meters according to the APAs of particles over 80 nm diameter for specimens
taken in three slab depths

82
6.3 MatCalc kinetic simulations

The calculation has been made limiting the precipitation to the austenite domain without
consideration of the austenite to ferrite transformation temperature.
TTP diagrams have been calculated for AlN and (Nb,Ti)(C,N) with MatCalc. The
plotted curves in Figure 6.9 show the times necessary for the precipitation of 5 % and
50 % of the maximal possible phase fraction of the given phase at equilibrium.
Figure 6.9a displays the case of AlN. Without applying any deformation, 5 % precipit-
ation will be attained after approximately 12 000 s and 50 % even not before 400 000 s
holding at 850 °C. At other temperatures the times needed are longer. When apply-
ing 4 % strain the temperatures with the fastest precipitation sinks to 800 °C. In this
case, 5 % of the maximum phase fraction should have already precipitated after less
than 2000 s. For the precipitation of 50 % of the maximum phase fraction, a holding of
approximately 6000 s is necessary.
Figure 6.9b shows the TTP plots for (Nb,Ti)(C,N). Without applied deformation, hold-
ing times of respectively 3500 and 100 000 s are necessary to obtain a precipitation of
5 and 50 % of the maximum phase fraction at 875 °C, respectively. When applying 4 %
strain the nose is reached at 875 °C after 1000 s.
Looking at the corridor of Figure 5.16 for CC 1 shows that both AlN and (Nb,Ti)(C,N)
are likely to have precipitated between bending and unbending or during unbending for
this steel. The corridor of the other machine CC 2 lies above the curves and precipitation
happens only at later stages of cooling.
The TTP-plots can be compared to the phase fractions of Table 6.2 and Table 6.4
that were calculated on the basis of the APA measurements. According to the TTP-
plots the phase fraction should be higher at 850 °C for both phases without and with
deformation. However it is only the case for AlN with deformation and for Nb(C,N)
without deformation. Thus the experiments confirm the simulation only in half of the
cases. It is also interesting to note that the surface densities of some phases decrease
already after 100 or 1000 s of holding. This observation cannot be brought in line with
the TTP plots.

6.3.2 MatCalc simulation for three positions in slab thickness

The slab specimens taken in three different depths can be simulated with MatCalc using
typical CC surface temperatures as shown in the top of Figure 6.10. The phase fractions
of the four phases AlN, BN, Nb(C,N) and TiN were calculated as well as the number
densities and the mean diameters. The phase fractions near the surface are higher than
deeper in the slab, especially for AlN and BN. The computed number densities and mean
diameters can be compared with the empirical values shown in Figure 6.8. The number
densities of BN are higher near the surface, opposite to the experiments. In agreement
with the experiments, the densities of TiN and Nb(C,N) are almost constant through
the thickness. The densities of AlN are very low in both cases. There are differences in
diameters. BN are predicted far too large. Nb(C,N) are predicted to be 50 nm diameter
in the calculations and were about 100 nm in the measurements.

83
6 Nb-Ti steel

1050
t5 % without strain
t5 % with 4 % strain
t50 % without strain
1000 t50 % with 4 % strain

950
temperature [°C]

900

850
t5 % t50 %

800

t50 %
750
10 100 1000 10000 100000 1e+006
time [s]
(a) TTP-plot for AlN

1050
t5 % without strain
t5 % with 4 % strain
t50 % without strain
1000 t50 % with 4 % strain

950
temperature [°C]

900
t5 % t50 %

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(b) TTP-plot for (Nb,Ti)(C,N)

Figure 6.9: TTP-plots of the Nb-Ti steel according to MatCalc showing the times neces-
sary for 5 % and 50 % precipitation

84
6.3 MatCalc kinetic simulations

temperature [°C] 1600


slab inner
1400 slab 1/4 thickness
1200 slab surface
1000
800
600
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
time [s]

10-4
10-6
phase fraction

10-8
10-10
10-12
10-14
10-16
10-18
10-20

18
volume density [m ]

10
-3

1016
1014
1012
1010
8
10
106

1400
mean diameter [nm]

1200
1000
800
600
400
200
0
0 0.25 0.5
relative depth in the slab

Figure 6.10: Temperature profiles, phase fraction, volume density and mean diameter
according to MatCalc in the three as-cast specimens using idealised temper-
ature profiles without deformation

It should be taken into considerations that APA is size limited and therefore neglects
fine particles which shifts mean diameters to higher values.

6.3.3 MatCalc simulation including periodic temperatures and strain

As in previous chapter the computation was repeated with temperature variations at the
rolls and strain during bending and unbending. The temperature profiles and results
are shown in Figure 6.11a.
The mean diameters show at short times an influence of the oscillating temperature. The
temperature drops lead to fast nucleations and so to reductions of the mean diameters.
Once the temperature increases again, all nuclei and precipitates grow so that the mean
diameters increase again. The same mechanism is transferable to the phase fractions
and to the number densities but can hardly be seen because of the logarithmic vertical
scale.

85
6 Nb-Ti steel

1400 -4
10
1300
10-5
temperature [°C] 1200

phase fraction
1100 10-6
1000 10-7
900
10-8
800
700 10-9

600 10-10

1018

volume density [m-3]


mean diameter [nm]

100 1016

1014

10 1012
AlN at grain bound.
1010 AlN at dislocations
BN
108 NbC
1 TiN
106
0 1000 2000 3000 4000 0 1000 2000 3000 4000
time [s] time [s]
(a) Plot of the temperature, phase fractions, mean diameters and number densities; vertical lines indicate
bending and unbending

1022 1022
AlN at grain bound. BN
1020 AlN at dislocations 1020
volume density [m-3]

volume density [m-3]

1018 1018

1016 1016

1014 1014

1012 1012

1010 1010

1022 1022
NbC TiN
1020 1020
volume density [m-3]

volume density [m-3]

1018 1018
16 16
10 10
14 14
10 10

1012 1012

1010 1010

1 10 100 1000 1 10 100 1000


diameter [nm] diameter [nm]
(b) Histograms of the size distributions of the calculated phases after 4200 s, vertical lines indicate limit of
APA detection

Figure 6.11: MatCalc results of the simulation of the surface cooling taking the deform-
ation into account

86
6.4 Conclusions

As in the last simulation NbC and TiN have the highest phase fractions and number
densities. The mean diameters are relatively small, i.e. in the range of 20 to 40 nm.
As a consequence of the applied deformation of 4 % at bending and straightening, AlN
are also able to precipitate at dislocations. This population of AlN consists, in com-
parison to the population that precipitates on grain boundaries, of numerous very small
precipitates. The volume density is six orders of magnitude higher while the mean dia-
meter is only a tenth of the one on the grain boundaries. All together it leads to a phase
fraction three orders of magnitude higher, so that the value is comparable to those of
the other nitrides and carbides.
BN have a comparably low volume density but a high mean diameter in the range of
500 nm.
Size distributions are plotted in Figure 6.11b. The vertical lines symbolise the resolution
limit of the APAs. The final mean diameters shown before are of course the averages
of the distribution curves. The predicted population of AlN nucleated at dislocations
could not be detected by APA because all precipitates are well below the detection limit.
The AlN at grain boundaries as well as the BN should be detectable. The maximum
predicted diameters of Nb(C,N) and TiN correspond to the APA findings. This does,
however, not apply to BN. In view of the low B contents such results have no great
significance.

6.4 Conclusions

The Nb-Ti steel is a steel with relatively high Nb and Ti contents of respectively 0.035
and 0.014 %. The Al and N contents are in contrast rather low with 0.035 and 0.0033
%. This explains that the thermodynamic simulations predict strong precipitations of
TiN and NbC but neither AlN nor BN in relevant amount. This has been confirmed by
experiments.
The Gleeble testing proved the steel to have very low ductilities at the temperatures of
550 and 750 °C. At all other temperatures the reduction of area was better than 40 %.
Holding and testing experiments were carried out in the Gleeble at 850 and 950 °C in or-
der to determine the effect of time, temperature and strain on the precipitation kinetics.
An effect of the holding time could clearly be seen for all specimens. Rough approxim-
ations of the TTP diagrams were constructed. The influence of the 4 % deformation on
the precipitation kinetics is however not so explicit when considering the experimental
results. However also the simulations do not show significant differences between both
temperatures.
Specimens taken from the slab in different depths were analysed by APA. High phase
fractions of TiN and NbC were found. The phase fractions of BN were also high, though
not near the surface. Only few AlN were found so that the measured ECDs have only a
negligible signification. The measured ECDs of the three other phases are very similar.

87
88
7 Al-Nb-B steel

This Al-Nb-B steel represents a high-strength fine grained structural steel S690 according
to the EN 10025-6 norm. It contains 19 ppm of B which enhances the yield strength by
30 to 40 MPa. The steel is commonly delivered in water-quenched state and attains a
minimum yield strength of 690 MPa. The composition (see Table 7.1) is characterised
by comparatively high contents of all elements except Ti. The steel was found to be
sensitive to transverse crack formation during continuous casting.

7.1 Thermodynamics

If all the available Ti reacts with the N, 58 ppm of N will be left over. Therefore other
nitrides such as AlN, BN and Nb(C,N) can be expected. The mass fractions of all phases
can only be calculated taking into account the interactions between them. Calculations
were done with the assumption of thermodynamic equilibrium with JMatPro, Thermo-
Calc, MatCalc and the equilibrium model.
The results are plotted in Figure 7.1 and show only slight differences in the precipitation
behaviour of Nb(C,N) and Ti(C,N). It should be noted that MatCalc does not distin-
guish Nb(C,N) and TiN and predicts therefore a complex (Nb,Ti)(C,N). The differences
in the calculated phase fractions are important for AlN and Nb(C,N). According to the
commercial simulations BN precipitates very early, even before Nb(C,N) or AlN. Thus
the commercial models differ from the equilibrium model and from the expected precip-
itation sequence TiN-NbC-AlN-BN. Note that according to JMatPro and Thermo-Calc
the phase will disappear at temperatures below 750 °C.
The precipitation start temperature and precipitated phase amounts of the four phases
were compared. Huge discrepancies could be found, especially for AlN and BN with
approximately 250 °C difference between the lowest and highest predicted precipitation
start temperatures. These differences are shown in Table 7.2.
Besides these discrepancies it should also be noted that even the precipitated phase
amount of simple phases like AlN and BN are different depending on the model. Similar
differences for the complex phases Nb(C,N) and Ti(C,N) could be a consequence of the
different compositions of this phases. Depending on the model they have for example

Table 7.1: Chemical composition of the Al-Nb-Ti steel


element C N Al Nb Ti B
content [%] 0.17 0.0066 0.0685 0.0291 0.0027 0.0019

89
7 Al-Nb-B steel

-4 MatCalc JMatPro
7·10
AlN
-4 TAe3 TAe3
6·10 BN
Nb(C,N)
5·10-4 TiN
phase fraction

4·10-4
3·10-4
2·10-4
1·10-4
0·100
ThermoCalc equilibrium model
7·10-4
6·10-4 TAe3 TAr3 according to Mintz et al.
-4
5·10
phase fraction

4·10-4
-4
3·10
2·10-4
-4
1·10
0·100
100
reduction of area [%]

80

60

40

20

0
600 800 1000 1200 1400 600 800 1000 1200 1400
temperature [°C] temperature [°C]

Figure 7.1: Equilibrium precipitation (four models) and results of ductility trials of the
Al-Nb-B steel

Table 7.2: Precipitation start temperatures of the four phases and models considered us-
ing the example of the Al-Nb-B steel
precipitate start temperature
precipitate phase
JMatPro Thermo-Calc MatCalc equilibrium model
AlN 1350 °C 1100 °C 1200 °C 1125 °C
BN 1100 °C 1300 °C 1350 °C 1100 °C
Nb(C,N) 1200 °C 1150 °C 1150 °C
1250 °C
Ti(C,N) 1350 °C 1350 °C 1250 °C

90
7.2 Thermomechanical testing

Figure 7.2: AlN on the etched surface of a low ductility Gleeble specimen with corres-
ponding EDS spectrum from [41]

different C to N ratios and may also contain other additional elements like Mo or Cr.

7.2 Thermomechanical testing

7.2.1 Ductility trials

Ductility tests were performed as in the cases before. Results are shown on the bottom
of Figure 7.1. A ductility trough is visible between 1000 and 700 °C. It is more severe
than for the Nb-Ti steel.
The shape of the ductility trough can be compared with the thermodynamic simulations.
The ductility loss at 1000 °C seems to be related to the increase of the AlN and Nb(C,N)
phase fractions.
Fracture surfaces of specimens with low ductility were extensively analysed by SEM, but
particles were only found rarely in dips and could not be analysed by EDS. For further
investigations some specimens taken near the fracture surface were polished and etched.
Very small precipitates in the size range of approximately 50 nm diameter were found
and EDS measurements proved them to be AlN (see Figure 7.2).

7.2.2 Hold and quench trials HQT

Specimens were submitted to the hold and quench trials as described in Subsection 6.2.2.
The number and sizes of precipitates were measured by means of APA with a pixel
size of 40 nm on a total surface of approx. 10 mm² per specimen. Particles of more
than 80 nm diameter were found, measured, and their chemistries determined by EDS
measurements. The determined mean values for the surface densities and the equivalent
circle diameters are converted into phase fractions to facilitate the comparison with the
equilibrium simulations. To facilitate the conversion, it is assumed that all particles are
ideally round and evenly distributed so that the surface density is equal to the volume
density.

91
7 Al-Nb-B steel

Table 7.3: Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for AlN
at 850 °C and 950 °C; values in italic being questionable
AlN at 950 °C 850 °C
held 100 s 1000 s 5000 s 100 s 1000 s 5000 s
only holding 0.62 5.78 1.91 6.73 26.3 8.23
strain + holding 0.77 8.65 7.66 0.12 8.81 8.90

Table 7.4: Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for BN
at 850 °C and 950 °C; values in italic being questionable
BN at 950 °C 850 °C
held 100 s 1000 s 5000 s 100 s 1000 s 5000 s
only holding 0.08 2.53 74.4 60.6 62.3 48.3
strain + holding 91.8 53.5 53.7 88.3 81.2 78.4

Table 7.3 shows the evolution of the phase fraction of AlN with the holding time at the
temperatures of 950 and 850 °C. The phase fractions are slightly higher at 850 °C and
when strain is applied.
The situation is similar for BN, see Table 7.4. Noticeable is that in this case the phase
fraction tends to stay constant with longer holding time. For this reason and because of
the problematic detection of B (cf. Subsection 6.2.2), it is difficult to make any conclusion.
Table 7.5 shows similarly the phase fraction for (Nb,Ti)(C,N). Also in this case an
increase of the phase fraction with longer holding time can be seen. A trend to higher
phase fraction at 850 °C and with applied strain can also be seen.
The discussion in Subsection 6.2.2 on the reliability of the measurements is also valid
here.
Table 7.6 shows a comparison of the phase fractions calculated from the APA with the
phase fractions from the thermodynamic simulations in Figure 7.1. The phase fractions
of AlN according to the APA is lower than according to the thermodynamic calculations
so that the phase has either not fully precipitated within 5000 s or was not found. The
same consideration can be made with the nitrides or carbonitrides of Ti and Nb. BN
was however found with a noticeable higher phase fraction. This may be explained by
the very fast precipitation of BN in comparison with all other phases.
The surface densities of all phases in the specimens tested at 950 °C are plotted in
Figure 7.3. The difference with the phase fractions is mainly that the number densities

Table 7.5: Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
(Nb,Ti)(C,N) at 850 °C and 950 °C; values in italic being questionable
(Nb,Ti)(C,N)at 950 °C 850 °C
held 100 s 1000 s 5000 s 100 s 1000 s 5000 s
only holding 0.00 0.07 6.00 8.88 29.0 10.2
strain + holding 8.81 1.28 1.83 33.8 11.5 54.5

92
7.2 Thermomechanical testing

Table 7.6: Comparison of the phase fractions calculated from the APA with the phase
fractions from the thermodynamic simulations in Figure 7.1
×10−4 thermodynamics APA
AlN 1..2 0.6
BN 0..0.5 3
Nb(C,N) 3..6
0.9
TiN 0..0.2

without deformation at 950 °C with 4% deformation at 950 °C

100
surface density [1/mm2]

10

AlN
BN
NbCN
TiN
0.1
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 7.3: Comparison of surface densities for the specimens held at 950 °C according
to the APA limited to particles over 80 nm diameter

contain no information on the size of the precipitates. The consequence is a partly


contrary influence of increasing temperature or strain.
At 950 °C the surface densities increase with the holding time both without and with
deformation (cf. Figure 7.3). The surface densities of BN and Nb(C,N) with deformation
show however a contrary behaviour. In the case of Nb(C,N) the surface density after
5000 s is even lower than in the case without deformation.
The same consideration is done for the specimens tested at 850 °C beginning with the
surface densities plotted in Figure 7.4. First of all it can be observed that the surface
densities are higher than after the holding at 950 °C. The surface density of Nb(C,N)
decreases between 1000 and 5000 s with and without deformation after attaining a max-
imum at 1000 °C. The surface density of TiN remains constant in this time period. The
surface density of BN is the highest and increases with the application of strain with a

93
7 Al-Nb-B steel

without deformation at 850 °C with 4% deformation at 850 °C

100
surface density [1/mm2]

10

AlN
BN
NbCN
TiN
0.1
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 7.4: Comparison of surface densities for the specimens held at 850 °C according
to the APA limited to particles over 80 nm diameter

tendency to decrease with the holding time. The case of AlN is more complex due to the
fact that the surface density decreases with the time without deformation and increases
when a strain is applied.
Figure 7.5 shows the evolution of the mean ECDs of all phases with increasing holding
time and deformation. The diameters tend to be higher after application of a strain.
It is however difficult to find any correlation between the ECD and the time or the
deformation. A general trend to decreasing ECDs with the holding time for all phases
but BN can be seen.
Compared to the results of the 950 °C specimens, the plotted mean ECDs of the 850 °C
specimens in Figure 7.6 are slightly higher. Without and with deformation the mean
diameters are decreasing after having attained a maximum after 1000 s of holding time.
Only Nb(C,N) after 1000 s holding with 4 % deformation is an exception. The influence
of the deformation and that of the holding period with a strain applied cannot be merged
succinctly.

Estimation of TTP diagrams

TTP diagrams were estimated using the method described in Subsection 6.2.2 and are
shown in Figure 7.7. The comparison with the estimation in the previous chapter shows
that BN precipitates earlier here. This can easily be explained by the higher B content.

94
7.2 Thermomechanical testing

without deformation at 950 °C with 4% deformation at 950 °C

AlN
1200 BN
NbCN
TiN

1000
equivalent circle diameter [nm]

800

600

400

200

0
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 7.5: Comparison of mean equivalent circle diameters for the specimens held at
950 °C according to the APA limited to particles over 80 nm diameter

without deformation at 850 °C with 4% deformation at 850 °C

AlN
1200 BN
NbCN
TiN

1000
equivalent circle diameter [nm]

800

600

400

200

0
100 1000 5000 100 1000 5000
time [s] time [s]

Figure 7.6: Comparison of mean equivalent circle diameters for the specimens held at
850 °C according to the APA limited to particles over 80 nm diameter

95
7 Al-Nb-B steel

1050

1000

950

temperature [°C]
900 no strain
with strain

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(a) Estimation of the start of AlN precipitation

1050

1000

950
temperature [°C]

900 no strain
with strain

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(b) Estimation of the start of BN precipitation

1050

1000

950
temperature [°C]

no strain
900
with strain

850

800

750
10 100 1000 10000 100000 1e+006
time [s]
(c) Estimation of the start of (Nb,Ti)(C,N) precipitation

Figure 7.7: Rough estimation of the start of all precipitation phases in the Nb-Ti steel
according to hold and quench trials

96
7.2 Thermomechanical testing

casting
direction
wide face

relative depth
narrow face -
near surface
narrow face -
inner

Figure 7.8: Schematic view of a slab cross-section showing the position of the specimens

7.2.3 Particle profiles over the slab thickness

As-cast specimens were analysed in the same manner as in Subsection 5.2.7. At least
three measurements of surfaces of approximately 4 mm² were necessary in order to get
enough data to make statistics and take the local enrichments of the steel into account.
These measurements confirmed the presence of AlN besides BN, Nb(C,N) and TiN.
Additional investigations showed that the size and number of precipitates is dependent
on the depth in the slab, i.e. of the cooling rate and/or strain rate during casting.
Specimens were taken from the wide face and from the narrow face both directly at the
surface and some centimetres beneath. The position of the specimens in the slab are
sketched in Figure 7.8. In each case specimens were taken near the wide face surface, in
quarter thickness and near the centre of the slab, though preferably not in the segregation
zone. Thus it is possible to compare the cooling conditions on the two faces and also at
different depths inside the slab.
Figures 7.9 to 7.11 show the surface densities and ECDs of all phases at the three
positions considered.
When compared to the observations of the previous chapters, the AlN found at the
surface of the wide face are relatively small. The surface density is smaller than for the
Al-Ti steel but higher than for the Nb-Ti steel. Further much more Nb(C,N) were found.
The distribution over the slab thickness is noteworthy. Directly underneath the narrow
face only few Nb(C,N) and even no AlN were found, while the surface fractions of BN
was similar to those of the other slab positions. The reason is possibly that the edges
are considerably colder so that the precipitation can only occur after long times when
the precipitation nose is finally stroke.

7.2.4 Reference analysis of narrow face specimens at KIMAB

A combined SEM and TEM particle analysis was commissioned to the KIMAB in Stock-
holm, Sweden in order to have a benchmark to confirm the SEM results obtained in this
work. It consisted in a SEM analysis with a FEG-SEM Jeol 7000F and a X-Max EDS
silicon drift detector controlled by the software Inca Feature from Oxford. Particles

97
7 Al-Nb-B steel

100
surface density [mm-2]

10

0.1
1400
equivalent circle diameter [nm]

1200

1000

800

600

400

200

0
0 0.25 0.5
relative depth in the slab

Figure 7.9: Results of the APAs on as-cast specimens taken in three different depths on
the wide face

100
surface density [mm-2]

10

0.1
1400
equivalent circle diameter [nm]

1200

1000

800

600

400

200

0
0 0.25 0.5
relative depth in the slab

Figure 7.10: Results of the APAs on as-cast specimens taken in three different depths in
the inner of the narrow face

98
7.2 Thermomechanical testing

100
surface density [mm-2]

10

0.1
1400
equivalent circle diameter [nm]

1200

1000

800

600

400

200

0
0 0.25 0.5
relative depth in the slab

Figure 7.11: Results of the APAs on as-cast specimens taken in three different depths on
the narrow face near the surface

were found automatically using the backscatter detector at 10 kV, measured and their
chemistry determined by means of EDS. At the end the particles found on a surface of
approximately 6 mm² were classified by their chemistry and additionally size distribu-
tion curves were plotted. Due to the pixel size of approximately 41 nm only particles of
more than 100 nm diameter were taken in account. A TEM analysis was made using a
HAADF detector on carbon replicas.
The specimen considered here corresponds to the relative depth of 0 in Figure 7.11. In
total 19 AlN were found by SEM (Figure 7.12). The size distribution may be considered
to be bimodal with a first maximum around 800 nm and a second at a diameter of
150 nm or less. Further 15 ALN with an average diameter of 15 nm were found by TEM
analysis. This could confirm the hypothesis of a second maximum at a diameter of less
than 150 nm.
More than 1000 BN were found during the automated SEM scanning, showing by the way
that most of them are more than 100 nm in diameter with a maximum at approximately
600 nm. The absence of BN on carbon replicas may confirm that BN are clearly bigger
than e.g. AlN. It should however be borne in mind that BN may be difficult to detect
on a carbon film using a HAADF detector.
During SEM scanning no differentiation was made between Nb(C,N) and Ti(C,N). The
size distribution shows that more than 100 particles were found. The size distribution
could also be bimodal with a maximum at 150 nm or less and a second possible one

99
7 Al-Nb-B steel

100 AlN 100 BN

particle number

particle number
10 10

1 1
1 10 100 1000 1 10 100 1000
equivalent circle diameter [nm] equivalent circle diameter [nm]

100 (Nb,Ti)(C,N)
particle number

10

1
1 10 100 1000
equivalent circle diameter [nm]

Figure 7.12: Size distribution of AlN, BN and (Nb,Ti)(C,N) by APA at the SEM at
KIMAB on a specimen taken near the narrow face

around 1000 nm. On carbon replicas 13 (Nb,Ti)N with diameters between 3 and 30 nm
were found and also 4 pure TiN with sizes between 90 and 145 nm.
These results are in good accordance with the results of the APAs carried out in this
work.

7.3 MatCalc kinetic simulations

7.3.1 MatCalc simulations of HQT samples

Simulations of HQT samples were carried out as described in Subsection 6.3.1.


Figure 7.13a shows the TTP-plots for AlN. Without deformation the precipitation of
5 % of the maximum phase fraction occurs fastest at approximately 1000 °C after nearly
100 000 s. With applied strain the precipitation is much faster and a minimum time of
about 200 s is necessary at 900 °C.
Figure 7.13b shows the calculated precipitation times for BN. The precipitation is very
fast irrespective of the deformation, attaining for example 50 % of the precipitation at
1000 °C after less than 600 s. At 800 °C the precipitation is slower but begins nevertheless
already after 400 s.
Figure 7.13c shows similar plots for (Nb,Ti)(C,N). Without deformation the precipitation
of 5 % of the maximum phase fraction is fastest at 900 °C with around 5000 s. With an

100
7.3 MatCalc kinetic simulations

applied deformation of 4 % a minimum precipitation time of 1100 s is reached at 875 °C.


The holding temperature of the first trial was set at 950 °C where high phase fractions
of AlN, BN and (Nb,Ti)(C,N) could be expected. A second trial was made at a lower
temperature where lower AlN phase fractions and higher (Nb,Ti)(C,N) phase fractions
were expected. BN is expected to precipitate rapidly during the cooling or the first
seconds at the holding temperature.
Each pair of points in Figure 5.16 symbolise typical times needed for the strand to reach
the bending and unbending positions. As was already described in the foregoing chapters
it can be seen that both precipitates can be expected at the CC 1 as a consequence of
the applied strain.
The comparison of the TTP-plots with the SEM results of the hold and quench trials
shows disparities. The higher phase fractions at 850 °C can only hardly be explained for
BN and (Nb,Ti)(C,N). According to the experiments the strain does not always lead to
higher phase fractions. This observation could only be explained by the TTP-plot for
BN, even when considering the possible scattering of an APA.
Further MatCalc simulations were carried out using the temperature and deformation
profiles of the hold and quench trials. The results of the simulations at 800, 850 and
900 °C without and with the applied deformation are shown in Figure 7.14.
Figure 7.14 shows the evolution of the volume densities, mean diameters and phase frac-
tions as a function of the temperature. Four phases, namely AlN nucleated at grain
boundaries, AlN nucleated at dislocations, BN and (Nb,Ti)(C,N) are taken into con-
sideration. Without deformation the phase fraction of AlN at dislocations is negligible.
The volume density of (Nb,Ti)(C,N) is increasing with sinking temperature while the
mean diameter is decreasing. Both the volume density and mean diameter of BN are
almost constant over the whole temperature range, probably because all the boron has
precipitated. AlN nucleated at grain boundaries have a constant volume density but get
smaller with sinking temperature.
The precipitation state after holding and 4 % deformation shows a clear difference to
the one without deformation. Although the volume density of AlN nucleated at grain
boundaries is only slightly smaller, AlN nucleated at dislocations have now the highest
volume density of all considered phases. Compared to the case without deformation, AlN
nucleated at the grain boundaries are also smaller and those at the dislocations have a
higher diameter. It should be noted that with deformation all phases have decreasing
mean diameter with decreasing temperature. Higher volume densities of (Nb,Ti)(C,N)
are also predicted.
Figure 7.15 compares the evolution of the predicted volume density with the time for
the four phases considered. The time in second corresponds to the holding time at the
testing temperature, with additional points at higher temperature in order to estimate
the equilibrium phase fraction. The phase with the highest volume density when no de-
formation is applied is (Nb,Ti)(C,N) followed by the AlN nucleated at grain boundaries,
BN and AlN nucleated at dislocations. This order is independent of the temperature.
BN and AlN nucleated at dislocations reach both their equilibrium values after a very

101
7 Al-Nb-B steel

1050
t5 % without strain
t5 % with 4 % strain
t50 % without strain
1000 t50 % with 4 % strain

950

temperature [°C]
t5 % t50 %

900

850

800

750
10 100 1000 10000 100000 1e+006
time [s]

(a) TTP-plot for AlN

1050
t5 % without strain
t5 % with 4 % strain
t50 % without strain
1000 t50 % with 4 % strain
t5 % t50 %

950
temperature [°C]

900

850

800

750
10 100 1000 10000 100000 1e+006
time [s]

(b) TTP-plot for BN

1050
t5 % without strain
t5 % with 4 % strain
t50 % without strain
1000 t50 % with 4 % strain

t5 % t50 %
950
temperature [°C]

900

850

800

750
10 100 1000 10000 100000 1e+006
time [s]

(c) TTP-plot for (Nb,Ti)(C,N)

Figure 7.13: TTP-plots of the Al-Nb-B steel according to MatCalc showing the time ne-
cessary for 5 % and 50 % precipitation

102
7.3 MatCalc kinetic simulations

22 without deformation with 4 % deformation


10
volume density [m-3] 10
20
18
10
1016
1014
1012
1010

10-4
10-6
phase fraction

10-8
10-10
AlN at grain boundaries
10-12 AlN at dislocations
10-14 BN
10-16 (Nb,Ti)(C,N)

1000
mean diameter [nm]

100

10

800 850 900 950 800 850 900 950


temperature [°C] temperature [°C]

Figure 7.14: MatCalc simulation for a holding time of 5000 s at different temperatures
without and with strain

without deformation with 4% deformation


1022
950°C 950°C
1020
volume density [m-3]

18
10
16
10

1014
12 AlN at grain boundaries
10 AlN at dislocations
BN
1010 (Nb,Ti)(C,N)

22
10
850°C 850°C
1020
volume density [m-3]

1018
16
10

1014

1012

1010

102 103 104 105 106 102 103 104 105 106
holding time [s] holding time [s]

Figure 7.15: MatCalc results for volume densities at different temperatures and holding
times with and without strain

103
7 Al-Nb-B steel

short time.
The volume densities after 4 % deformation are plotted on the right side of Figure 7.15.
A clear influence of strain on the precipitation is visible for some phases at given tem-
peratures. Hence the AlN nucleated at the dislocations have the highest volume density
at short times. The volume density of (Nb,Ti)(C,N) is increased by the deformation at
all temperatures. The volume densities of BN and AlN nucleated at grain boundaries
remain constant over the time.

7.3.2 MatCalc simulations of as-cast specimens

MatCalc was used to simulate the precipitation processes during continuous casting.
Real temperature profiles were used and the number densities, mean diameters and phase
fractions of AlN nucleating at dislocations and grain boundaries, BN and (Nb,Ti)(C,N)
were calculated.
Figure 7.16 shows a MatCalc comparison of the specimens taken in three different slab
depths. The phase fractions, mean diameters and number densities of AlN at grain
boundaries, BN and (Nb,Ti)(C,N) are almost constant at the three depths. AlN at dis-
locations are however only able to precipitate due to deformation or strong temperature
variations. Given that these simulations were done without strain, the AlN at disloca-
tions growing and getting more numerous is a consequence of the strong temperatures
variations encountered near the surface of the slab. The simulation corresponds well to
the SEM investigations of the slab specimens from the wide face that are presented in
Figure 7.9.
Figure 7.17 shows the distribution of the diameters for the four phases at the three slab
depths. The vertical lines mark the lower resolution limit of the APA and allow to make
a better comparison of experiments and simulations. Thus it can be concluded that AlN
nucleating at dislocations cannot be found by APA. The same applies for the whole or
part of the (Nb,Ti)(C,N) populations. All BN should be detectable.
Figure 7.18 shows all calculated parameters for the MatCalc simulation of the cooling
of a slab surface taking in consideration the bending and unbending strain. The phase
fraction of AlN nucleated at the grain boundaries is low whereby they are around 100 nm
in diameter. AlN nucleating at the dislocations begin to precipitate first between 800 and
900 °C. The volume density stays low until the deformation is applied. Then the increase
of the volume density is very fast and lead to a high phase fraction. The phase fractions
of BN and (Nb,Ti)(C,N) are also high. They have mean diameters of respectively around
1400 and 40 nm.
Figure 7.18b allows to get more detailed information on the precipitated populations.
According to the histograms the AlN populations have very low spreading in their
size distributions. On the contrary BN have sizes between 400 and 1400 nm and the
(Nb,Ti)(C,N) precipitates are between 3 and 100 nm in diameter.

104
7.3 MatCalc kinetic simulations

1600
temperature [°C]

slab inner
1400 slab 1/4 thickness
1200 slab surface
1000
800
600
0 1000 2000 3000 4000 5000 6000 7000
time [s]
10-4
10-6
phase fraction

10-8
10-10
10-12 AlN at grain boundaries
10-14 AlN at dislocations
10-16 BN
10-18 (Nb,Ti)(C,N)
10-20

1018
volume density [m-3]

1016
1014
1012
10
10
8
10
106

2500
mean diameter [nm]

2000
1500
1000
500
0
0 0.25 0.5
relative depth in the slab

Figure 7.16: Temperature profiles, phase fractions, volume densities and mean diameters
according to MatCalc in the three as-cast specimens using idealised temper-
ature profiles without deformation

105
7 Al-Nb-B steel

surface quarter depth inner


18
10 AlN, gb AlN, gb AlN, gb
AlN, d AlN, d AlN, d
volume density [m-3]

1016

1013

1011

1 10 100 1000 1 10 100 1000 1 10 100 1000

1018 BN BN BN
volume density [m-3]

1016

1013

11
10

1 10 100 1000 1 10 100 1000 1 10 100 1000

18
10 (Nb,Ti)(C,N) (Nb,Ti)(C,N) (Nb,Ti)(C,N)
volume density [m-3]

1016

13
10

11
10

1 10 100 1000 1 10 100 1000 1 10 100 1000


diameter [nm] diameter [nm] diameter [nm]

Figure 7.17: Size distribution of the phases of Figure 7.16 (i.e. without deformation) for
the three depths according to MatCalc, vertical lines indicate limits of APA
detection

106
7.3 MatCalc kinetic simulations

-3
1400 10
1300 10
-4

1200
10-5
temperature [°C]

phase fraction
1100
10-6
1000
10-7
900
800 10-8

700 10-9
600 10-10

1000
1018
1016

volume density [m-3]


mean diameter [nm]

1014
100
1012
1010
10 108
106 AlN at grain bound.
104 AlN at dislocations
BN
1 102 (Nb,Ti)(C,N)
100
0 1000 2000 3000 4000 0 1000 2000 3000 4000
time [s] time [s]
(a) Plot of the temperature, phase fractions, mean diameters and volume densities, vertical lines indicate
bending and unbending

1022 1022
AlN at grain bound. BN
1020 AlN at dislocations 1020
volume density [m-3]

volume density [m-3]

1018 1018

1016 1016

1014 1014

1012 1012

1010 1010

22
10
(Nb,Ti)(C,N)
20
10
volume density [m-3]

18
10
16
10

1014

1012

1010

1 10 100 1000
diameter [nm]
(b) Histograms of the size distribution after 4200 s of the calculated phases, vertical lines indicate limit of
APA detection; to be compared with Figure 7.17 left column

Figure 7.18: MatCalc results of the simulation of the surface cooling taking the deform-
ation into account

107
7 Al-Nb-B steel

7.4 Conclusions

The thermodynamic calculations of the four models for the Al-Nb-B steel predict strong
precipitations of AlN and NbC or (Nb,Ti)(C,N) beginning at temperatures between 1300
and 1100 °C. According to these calculations the precipitation of BN is almost negligible
but existent.
Ductility trials were carried out in order to determine the reduction of area at the pos-
sible bending and unbending temperatures and showed that this steel has poor ductility
between 725 and 925 °C. Some of these specimens were analysed by means of SEM and
EDS. They proved to contain AlN that could however only be found with great difficulty
on polished surfaces. The low number of particles found and the impossibility to de-
termine their chemistry on fracture surfaces makes it impossible to establish a relation
with the low ductility.
The experimental procedure was improved for a more effective detection of precipitates
and ongoing correlation with the mechanical properties. Hold and quench trials were
carried out in order to assess the influence of temperature, time and strain on the
precipitation kinetics. It was found out that both the time period and the deformation
have different effects depending on the temperature and the phase considered so that
any generalisation is challenging. As like as the surface density, the mean diameter
grows in the majority of cases with higher strains and with longer time periods. Further
at 850 °C, i.e. the lower temperature, both the surface density and the diameter were
higher. Correlations with the mechanical properties were not possible.
These observations were compared with time-temperature-precipitation plots calculated
with MatCalc. They show that longer time periods and a deformation lead to higher
precipitated phase amounts. When comparing both temperatures, it can be seen that the
precipitation is faster for AlN at 950 °C and for (Nb,Ti)(C,N) at 850 °C. Unfortunately no
indications can be made on the mean precipitate diameters using these plots. Therefore
other simulations were carried out confirming that with sinking temperature the volume
densities raise and the mean diameters sink.
The transition to the industrial case, i.e. to continuously cast specimens, was made
with specimens taken from the slab in three different depths. Further specimens taken
in different distances from the narrow face were compared to them. All phases but
especially AlN proved to be very sensible to the position in the slab and in this way to the
temperature history. This effect is visible when comparing both the surface densities and
the mean diameters of the precipitates. These investigations were successfully controlled
by a combined SEM / TEM study of the KIMAB. Additionally simulations were made
with MatCalc and showed that the depth in the slab has virtually only an influence
on the AlN precipitating at the dislocations. These results are consistent with the
observations. Finally a simulation of the continuous casting taking into account the
temperature oscillations at the slab surface and the deformation due to bending and
unbending was carried out. The calculated phase fractions and particle size distributions
are also consistent with the experiments.

108
7.4 Conclusions

The simulations allow to conclude that the high cracking risk and low ductility of this
steel may be due to BN. An influence of the AlN can be virtually excluded by the low
phase fraction. Thus the high phase fractions of BN found on austenite grain boundaries
are the most probable explanation.

109
110
8 Summary and outlook

Three plate steels with various microalloying components have been investigated with
respect to the formation of precipitates during continuous casting. The steels were cast
as thick slabs with intensive cooling and bending / unbending after final solidification.
Precipitations were studied on as-cast slab samples taken at different distances from the
slab surface, on samples after ductility testing at various temperatures, and on samples
after hold and quench trials. The empirical studies were accompanied by computations
under the assumption of thermodynamic equilibrium and by kinetic calculations using
the MatCalc package.
The measurement techniques have limitations. Automatic particle analyses (APA) may
not fully capture the spectrum of particles on the low end due to resolution limits of
SEM/EDS, and on the high end due to the rareness of large particles and because they
may be truncated at the edges of the image. STEM yields finer resolution, but it is
even more unclear how representative a selected scan section is. The computational
methods are limited, too. Thermodynamic equilibria, depending on the component, are
only known to certain degree of accuracy. Furthermore, the knowledge on the kinetic
behaviour of various precipitating phases is still partial at present.
This work has combined several investigation techniques to reach a rather complete
picture of the precipitation population of the three steels.
The first steel is characterized by AlN precipitates due to its relatively high content of
Al. AlN particles precipitate below about 1000 °C according to equilibrium models, and
their presence at 850 °C in significant magnitudes was confirmed by Gleeble testing. At
the surface of the slab, AlN particles are frequent and of relatively small diameter. AlN
precipitates are the likely origin of the surface cracking under these casting conditions.
TiN particles are present, but precipitate significantly above the ductility trough and so
probably do not contribute to cracking.
The second steel has enough Ti to absorb almost all N. The phase precipitating when
the ductility decays is a C-rich Nb(C,N). Quantities of such particles are much lower
than AlN for the first steel, but the particles are smaller. This combination does not
seem to imply surface cracking for the current casting conditions. TTP diagrams for
(Nb,Ti)(C,N) and AlN precipitation of this steel could be estimated (with and without
strain) by hold and quench trials.
The third steel contains only traces of Ti, which leaves significant amounts of N in
solution. The other microalloying elements of this steel, namely B, Nb and Al, compete
for the remaining nitrogen. To identify a dominating compound is more difficult than in
the other cases since precipitation start temperatures are not very distant and roughly

111
8 Summary and outlook

coincide with the upper end of the ductility trough. Slab samples as well as hold and
quench trials indicate the presence of BN, AlN and (Nb,Ti)(C,N). Hold and quench trials
were applied to estimate TTP diagrams. The particularly large amount of BN identified
on the slab as well as predicted by equilibrium models indicate that BN on austenite
grain boundaries is the most probable explanation of transverse surface cracking in this
case.
These complex plate steels have never been studied in the previous literature in such
depth and with such an array of methods. The techniques have provided a mosaic of
information, from which the dominant factors of precipitation and potential causes of
surface cracking could be identified for the first time in this work.
Future work should aim at the characterisation of precipitation without the extensive
arsenal of methods of this study, and preferably at an a-priori prediction of precipitation.
This requires robust and validated modelling. So far, equilibrium model calculations -
in combination with ductility trials - were found to provide first and useful basic in-
formation on the general sequences of precipitation. Accurate predictions of the times
of precipitation as during the thermal and mechanical history of continuous casting are
of interest, especially for the critical moment of unbending. As a precondition, TTP
diagrams should be predicted reasonably. MatCals’s kinetic precipitation modelling is
on the road of reaching this criterion, although there are still some limitations as shown
in this work. The real situation is even more complicated than for a TTP diagram due
to the variable surface temperature. Current European research projects contribute sig-
nificantly to this theme, but extensive work still lies ahead. Crucial for the advancement
of modelling is the availability of empirical results, such as provided in this thesis.

112
List of solubility products

This list merges the solubility products used in the Figures 2.5 to Figure 2.8 and in the
equilibrium model with their source. The parameters A and B of the solubility products
with the form log [%M ] [%X] = A − B T (cf. Section 4.1.1) can be found in the rows “A”
and “B”. The row “phase” indicates for which phase of the steel matrix the data set is
valid. The column “number” corresponds to the number used in the said figures.

phase A B [K] phase number reference


6.05 -14140 liquid 3 [68]
5.58 -12950 liquid 4 [76]
1.95 -7400 austenite 5 [77]
1.79 -7184 austenite 6 [78]
1.03 -6770 austenite 7 [13]
1.8 -7750 austenite 8 [79]
0.73 -6180 austenite 9 [80]
AlN
1.48 -7500 austenite 10 [81]
2.92 -9200 austenite 11 [82]
0.309 -6015 austenite 12 [80]
1.48 -7500 austenite 13 [81]
4.382 -11085 austenite 14 [83]
6.4 -14356 austenite 15 [81]
0.568 -5517 austenite 16 [29]
4.64 -10030 liquid 18 [76]
4.45 -9870 liquid 19 [83]
5.24 -13970 austenite 20 [62]
BN
4 -11690 austenite 21 [83]
0.06 -6950 austenite 22 [84]
4.63 -13680 austenite 23 [62]
2.8 -8500 austenite 25 [68]
4.04 -10230 austenite 26 [65]
1.71 -7000 austenite 27 [66]
3.79 -10150 austenite 28 [85]
3.7 -10800 austenite 29 [26]
NbN 6.63 -12500 austenite 30 [24]
5.09 -11880 austenite 31 [22]
4.2 -10000 austenite 32 [86]
4.03 -10790 austenite 33 [83]

113
List of solubility products

4.96 -12230 alpha ferrite 34 [64]


4.9 -11030 alpha ferrite 35 [8]
NbN0.87 2.86 -7927 austenite 36 [87]
3.42 -7900 austenite 38 [68]
2.96 -7510 austenite 39 [63]
3.36 -7167 austenite 40 [24]
2.81 -7019 austenite 41 [24]
3.04 -7290 austenite 42 [88]
2.783 -7407 austenite 43 [8]
2.9 -7500 austenite 44 [89]
3.7 -9100 austenite 45 [65]
NbC
4.37 -9290 austenite 46 [90]
1.18 -4880 austenite 47 [91]
1.74 -5600 austenite 48 [91]
3.89 -8030 austenite 49 [92]
3.42 -7900 austenite 50 [93]
5.43 -10960 alpha ferrite 51 [64]
3.9 -9930 alpha ferrite 52 [67]
4.93 -12000 alpha ferrite 53 [8]
3.18 -7700 austenite 54 [85]
3.11 -7520 austenite 55 [63]
NbC0.87
3.4 -7200 austenite 56 [63]
3.4 -7920 austenite 57 [94]
2.26 -6770 austenite 59 [95]
1.54 -5860 austenite 60 [63]
3.97 -8800 austenite 61 [96]
Nb(C,N)
4.12 -9454 austenite 62 [85]
4.09 -10500 austenite 63 [63]
4.46 -9800 austenite 64 [63]
5.9 -16586 liquid 67 [68]
6.4 -17040 liquid 68 [3]
4.46 -13500 liquid 69 [69]
5.97 -16130 liquid 70 [83]
5.56 -17205 delta ferrite 71 [97]
6.4 -18420 delta ferrite 72 [83]
3.82 -15020 austenite 73 [68]
0.32 -8000 austenite 74 [98]
5.4 -15790 austenite 75 [83]
TiN
4.35 -14890 austenite 76 [69]
5.19 -15490 austenite 77 [24]
5 -14400 austenite 78 [24]

114
6.75 -19470 austenite 79 [24]
3.84 -8990 austenite 80 [24]
6.63 -12500 austenite 81 [24]
5 -15400 austenite 82 [24]
4.65 -16310 delta + alpha ferrite 83 [69]
4.95 -12228 alpha ferrite 84 [68]
3.25 -6160 liquid 86 [83]
2.75 -7000 austenite 87 [95]
5.33 -10475 austenite 88 [99]
5.12 -10300 austenite 89 [66]
TiC 5.22 -10475 austenite 90 [68]
2.75 -7000 austenite 91 [83]
4.81 -10220 austenite 92 [83]
4.45 -10230 alpha ferrite 93 [83]
4.4 -9575 alpha ferrite 94 [67]
6.01 -9110 liquid 97 [100]
3.46 -8330 austenite 98 [95]
2.27 -7070 austenite 99 [24]
3.02 -7840 austenite 100 [99]
3.63 -8700 austenite 101 [68]
VN 2.86 -7701 austenite 102 [83]
3.84 -8990 austenite 103 [24]
2.21 -6680 austenite 104 [101]
4.38 -9680 austenite 105 [83]
6.63 -12500 alpha ferrite 106 [24]
2.45 -7830 alpha ferrite 107 [79]
6.72 -9500 austenite 108 [68]
7.06 -10800 austenite 109 [99]
5.65 -9407 austenite 110 [102]
VC 4.45 -6560 austenite 111 [103]
4.33 -6151 austenite 112 [83]
8.05 -12265 alpha ferrite 113 [104]
5.95 -9407 alpha ferrite 114 [24]

115
List of abbreviations

AlN aluminium nitride


APA automated particle analysis
BN boron nitride
CALPHAD calculation of phase diagrams
CC continuous casting
Cr chromium
ECD equivalent circle diameter
EDS energy dispersive X-ray spectroscope or spectroscopy
HAADF high angle annular dark field
HSLA high strength low alloy
HQT hold and quench trial
Mox C molybdenum carbide
MnS manganese sulphide
n/a not available
NbC niobium carbide
NbN niobium nitride
Nb(C,N) niobium carbonitride
RFCS research fund for coal and steel
SANS small angle neutron scattering
SEM scanning electron microscope or microscopy
SIMS secondary ion mass spectroscopy
STEM scanning transmission electron microscope or microscopy
TEM transmission electron microscope or microscopy
TiN titanium nitride
Ti(C,N) titanium carbonitride
TM thermo-mechanical
TTP time-temperature-precipitation
VC vanadium carbide
VN vanadium nitride
V(C,N) vanadium carbonitride
WDS wavelength dispersive X-ray spectroscope or spectroscopy

116
List of symbols

ppm part per million


% mass percentage
µm micrometer
nm nanometer
kV kilovolt
nA nanoampere
keV kiloelectronvolt
MPa megapascal
A surface
RA reduction of area
K equilibrium constant
a[x] activity of element x
ks solubility product
f phase fraction
fp phase fraction precipitated
ρ density
M molar mass
T temperature
TAe3 austenite-ferrite transformation temperature at equilibrium
TAr3 austenite-ferrite transformation temperature during cooling
ϵ deformation
ε̇ deformation rate
R universal gas constant
Qdef activation energy for deformation
Z Zener Hollomon parameter
κs supersaturation ratio
J nucleation rate
β∗ atomic attachment rate
G∗ critical nucleation energy
k Boltzmann constant
τ time constant

117
List of Figures

2.1 Graphical representation of the solubility products found for TiC . . . . . 17


2.2 Graphical representation of the solubility products found for TiN . . . . . 17
2.3 Graphical representation of the solubility products found for NbC . . . . 18
2.4 Graphical representation of the solubility products found for NbN . . . . 19
2.5 Graphical representation of the solubility products found for AlN . . . . . 20
2.6 Graphical representation of the solubility products found for VC . . . . . 21
2.7 Graphical representation of the solubility products found for VN . . . . . 21
2.8 Graphical representation of the solubility products found for BN . . . . . 22

3.1 Particle of approximately 100 µm diameter found on the filter and corres-
ponding EDS spectrum showing Nb, Al, Si, P and traces of I from the
solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.2 Scanning electron micrographs showing sub-millimetre structures (above)
and particles smaller than 100 nm on their surface (below, probably Nb(C,N))
found on the filters after dissolution in iodine methanol . . . . . . . . . . 35
3.3 Graphical representation of the phase amount measured by dissolution in
iodine methanol of specimens taken in two depths of a slab narrow face . 36
3.4 Example of ductile (top and bottom) and brittle (middle) fracture of
Gleeble specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.5 Schematic position of the polished surface using the example of a ductility
specimen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.6 Schematic view of the interaction volume in a SEM bulk specimen and a
TEM thin foil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

4.1 Solubility curve of Al and N with coefficients A and B after Leslie et al.
[13] at 1000 °C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.2 Solubility curve for Al and N and precipitation curve of AlN according to
Leslie et al. [13] at 1000 °C . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.3 Calculation made for AlN with 0.06 % Al and 0.007 % N, using solubility
products listed in Table 4.1 . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4 Calculation made for AlN and TiN with 0.06 % Al, 0.015 % Ti and 0.007 %
N using solubility products listed in Table 4.1 . . . . . . . . . . . . . . . . 48
4.5 Plot of the precipitated phase fractions during cooling of the Al-Nb-B steel
(0.17 % C, 0.0066 % N, 0.0685 % Al, 0.0027 % Ti, 0.029 % Nb, 0.0016 % V,
0.002 % B) using the solubility products listed in Table 4.1 and limiting
the precipitation to the austenite phase . . . . . . . . . . . . . . . . . . . 49

118
List of Figures

5.1 Equilibrium precipitation (four models) and results of ductility trials of


the Al-Ti steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
5.2 Exemplary temperature profile during a Gleeble ductility testing . . . . . 55
5.3 Fracture facets of the Gleeble specimens tested at 1050 °C, 850 °C and 700 °C 57
5.4 TiN on the Gleeble specimen tested at 1050 °C . . . . . . . . . . . . . . . 58
5.5 AlN on an austenite grain of the Gleeble specimen tested at 850 °C . . . . 58
5.6 CaS on the Gleeble specimen tested at 700 °C . . . . . . . . . . . . . . . . 59
5.7 Microstructure of Gleeble specimens at 1050 °C, 850 °C and 700 °C (from
left to right and from top to bottom) quenched after testing . . . . . . . . 59
5.8 Surface densities and equivalent circle diameters for all phases in the three
Gleeble specimens according to the APAs with a pixel size of 40 nm i.e.
for particles with more than 80 nm diameter . . . . . . . . . . . . . . . . . 60
5.9 Surface densities and equivalent circle diameters for all phases in the three
Gleeble specimens according to the APAs with a pixel size of 12 nm i.e.
for particles with more than 24 nm diameter . . . . . . . . . . . . . . . . . 61
5.10 Schematic position of the specimens in the slab . . . . . . . . . . . . . . . 62
5.11 Results of the APAs on as-cast specimens taken in three different depths . 63
5.12 MatCalc simulation of Gleeble testing considering the austenite and ferrite
domains: temperature profile of trial at 850 °C, volume densities and mean
diameters at the three temperatures according to MatCalc . . . . . . . . 64
5.13 Size distribution of the three phases of Figure 5.12 for each specimen
according to MatCalc, vertical lines indicate the APA resolution limit . . 65
5.14 Exemplary temperature profile of a TTP simulation for a holding of 1000 s
with an applied deformation of 4 % . . . . . . . . . . . . . . . . . . . . . . 66
5.15 TTP-plots of the Nb-Ti steel according to MatCalc showing the times
necessary for 5 % and 50 % precipitation . . . . . . . . . . . . . . . . . . . 67
5.16 Corridors displaying the approximate temperatures and times of the bend-
ing and straightening processes for two continuous casters . . . . . . . . . 68
5.17 Temperature profiles, phase fraction, volume density and mean diameter
according to MatCalc in the three as-cast specimens using idealised tem-
perature profiles without deformation . . . . . . . . . . . . . . . . . . . . 69
5.18 Size distribution of the phases of Figure 5.17 (i.e. without deformation)
for the three depths according to MatCalc, vertical lines indicate limits
of APA detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.19 MatCalc results of the simulation of the surface cooling taking the de-
formation into account . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

6.1 Equilibrium precipitation (four models) and results of ductility trials of


the Nb-Ti steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.2 Plot of the temperature during hold and quench trials with a holding time
of 1000 s at 950 °C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.3 Comparison of surface densities for the specimens held at 850 °C according
to the APA limited to particles over 80 nm diameter . . . . . . . . . . . . 78

119
List of Figures

6.4 Comparison of surface densities for the specimens held at 950 °C according
to the APA limited to particles over 80 nm diameter . . . . . . . . . . . . 78
6.5 Comparison of the mean equivalent circle diameters for the specimens held
at 850 °C according to the APA limited to particles over 80 nm diameter . 79
6.6 Comparison of the mean equivalent circle diameters for the specimens held
at 950 °C according to the APA limited to particles over 80 nm diameter . 79
6.7 Rough estimation of the start of all precipitation phases in the Nb-Ti steel
according to hold and quench trials . . . . . . . . . . . . . . . . . . . . . . 81
6.8 Graphical representation of the surface densities and equivalent circle dia-
meters according to the APAs of particles over 80 nm diameter for speci-
mens taken in three slab depths . . . . . . . . . . . . . . . . . . . . . . . 82
6.9 TTP-plots of the Nb-Ti steel according to MatCalc showing the times
necessary for 5 % and 50 % precipitation . . . . . . . . . . . . . . . . . . . 84
6.10 Temperature profiles, phase fraction, volume density and mean diameter
according to MatCalc in the three as-cast specimens using idealised tem-
perature profiles without deformation . . . . . . . . . . . . . . . . . . . . 85
6.11 MatCalc results of the simulation of the surface cooling taking the de-
formation into account . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

7.1 Equilibrium precipitation (four models) and results of ductility trials of


the Al-Nb-B steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.2 AlN on the etched surface of a low ductility Gleeble specimen with cor-
responding EDS spectrum from [41] . . . . . . . . . . . . . . . . . . . . . 91
7.3 Comparison of surface densities for the specimens held at 950 °C according
to the APA limited to particles over 80 nm diameter . . . . . . . . . . . . 93
7.4 Comparison of surface densities for the specimens held at 850 °C according
to the APA limited to particles over 80 nm diameter . . . . . . . . . . . . 94
7.5 Comparison of mean equivalent circle diameters for the specimens held at
950 °C according to the APA limited to particles over 80 nm diameter . . . 95
7.6 Comparison of mean equivalent circle diameters for the specimens held at
850 °C according to the APA limited to particles over 80 nm diameter . . . 95
7.7 Rough estimation of the start of all precipitation phases in the Nb-Ti steel
according to hold and quench trials . . . . . . . . . . . . . . . . . . . . . . 96
7.8 Schematic view of a slab cross-section showing the position of the speci-
mens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
7.9 Results of the APAs on as-cast specimens taken in three different depths
on the wide face . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
7.10 Results of the APAs on as-cast specimens taken in three different depths
in the inner of the narrow face . . . . . . . . . . . . . . . . . . . . . . . . 98
7.11 Results of the APAs on as-cast specimens taken in three different depths
on the narrow face near the surface . . . . . . . . . . . . . . . . . . . . . . 99
7.12 Size distribution of AlN, BN and (Nb,Ti)(C,N) by APA at the SEM at
KIMAB on a specimen taken near the narrow face . . . . . . . . . . . . . 100

120
List of Figures

7.13 TTP-plots of the Al-Nb-B steel according to MatCalc showing the time
necessary for 5 % and 50 % precipitation . . . . . . . . . . . . . . . . . . . 102
7.14 MatCalc simulation for a holding time of 5000 s at different temperatures
without and with strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
7.15 MatCalc results for volume densities at different temperatures and holding
times with and without strain . . . . . . . . . . . . . . . . . . . . . . . . . 103
7.16 Temperature profiles, phase fractions, volume densities and mean diamet-
ers according to MatCalc in the three as-cast specimens using idealised
temperature profiles without deformation . . . . . . . . . . . . . . . . . . 105
7.17 Size distribution of the phases of Figure 7.16 (i.e. without deformation)
for the three depths according to MatCalc, vertical lines indicate limits
of APA detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
7.18 MatCalc results of the simulation of the surface cooling taking the de-
formation into account . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

121
List of Tables

2.1 Temperature ranges of the phases considered in the calculation of solubil-


ity products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

3.1 Comparison of the investigation methods used in this work . . . . . . . . 44

4.1 Solubility products used in the model . . . . . . . . . . . . . . . . . . . . 48

5.1 Chemical composition of the Al-Ti steel . . . . . . . . . . . . . . . . . . . 53


5.2 Surface densities and mean diameters according to the APAs at both
magnifications for the three Gleeble specimens . . . . . . . . . . . . . . . 60

6.1 Chemical composition of the Nb-Ti steel . . . . . . . . . . . . . . . . . . . 73


6.2 Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
AlN at 850 °C and 950 °C; values in italic being questionable . . . . . . . . 76
6.3 Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
BN at 850 °C and 950 °C; values in italic being questionable . . . . . . . . 76
6.4 Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
(Nb,Ti)(C,N) at 850 °C and 950 °C; values in italic being questionable . . 76
6.5 Comparison of the phase fractions calculated from the APA with the phase
fractions from the thermodynamic simulations in Figure 6.1 . . . . . . . . 77
6.6 Surface densities and equivalent circle diameter of particles over 80 nm
diameter according to the APAs for the specimens taken in three slab
depths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

7.1 Chemical composition of the Al-Nb-Ti steel . . . . . . . . . . . . . . . . . 89


7.2 Precipitation start temperatures of the four phases and models considered
using the example of the Al-Nb-B steel . . . . . . . . . . . . . . . . . . . . 90
7.3 Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
AlN at 850 °C and 950 °C; values in italic being questionable . . . . . . . . 92
7.4 Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
BN at 850 °C and 950 °C; values in italic being questionable . . . . . . . . 92
7.5 Phase fractions (×10−6 ) measured by APA with a pixel size of 40 nm for
(Nb,Ti)(C,N) at 850 °C and 950 °C; values in italic being questionable . . 92
7.6 Comparison of the phase fractions calculated from the APA with the phase
fractions from the thermodynamic simulations in Figure 7.1 . . . . . . . . 93

122
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