Abstract:

There is uncertainty on the physical significance of models applied to the coarsening of

austenite grains in nuclear pressure vessel steels. As a result, new data are generated and analysed
by adapting standard theory to account for the initial austenite grain size generated when the steel
becomes fully austenitic, and any growth during heating to the annealing temperature. The
experimental data reflect two regimes of isothermal grain coarsening, with grain boundary pinning
dominating the kinetics at temperatures below about 940°C. The precipitates responsible for this
pinning have been identified using thermodynamics, high-energy X-rays, transmission electron
microscopy and microanalysis as aluminium nitrides.

Introduction:
There are only a few steels that have been sufficiently tested for approved use in the
construction of nuclear pressure vessels, partly because the qualification of such materials requires
an enormous amount of time-consuming work. The reactor pressure vessels (RPV) in particular have
demanding requirements for tensile strength, toughness and resistance to irradiation embrittlement
over the projected service life [1, 2]. One of the popular alloys in this context is the ASME SA-508,
used in a variety of reactor facilities, such as pressure vessels, steam generators and pressurisers. The
steel is generally given multiple heat-treatments involving austenitising followed by water
quenching, and tempering at temperatures as high as 650°C. The tempering treatment produces a
variety of substitutionally–alloyed carbides and can relieve stresses generated by fabrication
operations [3]. Within the broad specification of SA-508, there is a particular variant, Grade 3, which
exhibits better mechanical properties than earlier versions, and is the material of choice for pressure
vessels in Gen III plants. There have been many studies of the microstructure obtained after the series
of heat treatments described above, with the conclusion that the quenching produces bainite,
whereas the tempering leads to the formation of molybdenum rich M2C precipitates in addition to
residual cementite [1, 2, 4]. However, there is a lack of information on the austenitising process of
SA-508 Gr.3 steels, a key feature of the multiple heat treatments. An understanding of this is
important in achieving the optimum austenite grain size, which in turn influences the hardenability
and consequently determines the final properties of the steel.

Experimental Procedure:
The chemical composition of the steel is given as:
C Mn Ni Mo Cr Si Cu P S
0.17 1.315 0.785 0.53 0.27 0.22 0.04 0.004 0.002
Co Al Nb Ti Sb As Sn N H
0.01 0.0145 0.004 0.002 0.002 0.005 0.006 0.007 0.65
(ppm)

The steel in its as received state had been subjected to multiple heat treatments:
austenitisation between 860 and 880◦C for approximately 12h, water quenched and tempered
between 635 and 655◦C for 10h. The range in temperatures is due to the thermal gradients in thick
samples, which makes the temperature in a particular location uncertain.
 Specimens from the as-received condition were reheated at a total of 48 different
austenitising conditions at temperatures from 840◦C to 990◦C, and held between 12 h and 13h. Heat
treatments were carried out using a Thermecmaster thermomechanical simulator. Cylindrical
samples (8mm× 12mm) each with a 5mm wide metallographically–polished flat surface parallel to
the long axis were heated under vacuum (≈ 1Pa) in order to avoid excessive oxidation [5].

Figure: Transmission Electron Micrograph of as-received Steel

The austenite grain boundaries were revealed on the flat surface by the formation of thermal
grooves due to the balancing of surface tension forces. The heating and cooling rates used were ±5
◦Cs−1. The grain sizes were measured using the linear intercept method with data obtained from four
different fields of the sample and a total of 72 linear intercept lines. High-energy X-ray diffraction
experiments on as-received specimens were performed at the PETRA III facility in Hamburg. Disk like
samples, 8mm×1mm, were tested in the P02 beam line with a wavelength of 0.20812˚A, 60keV and
a beam size of 1.2 × 1.0mm. Transmission diffraction patterns were recorded using a flat 2D solid–
state detector, mounted perpendicular to the incident beam behind the sample.
The sample to detector distance was 1300mm to optimise the spatial resolution.
Microstructural features were identified using a range of techniques including transmission electron
microscopy. Thin foils for this purpose were prepared by electro-polishing with a solution of 5% per-
chloric acid, 25% glycerol and 70% ethanol. The voltage, current and temperature during
electropolishing were, 37V, 26mA and 10°C respectively. Thermodynamic calculations were carried
out with MTDATA version 4.73 with, PLUS v.3.02, TFCE v.1 and SUB SGETE v.10 as databases.

Results and Analysis:

The heat treatments given to the as–received steel led to the microstructure consisting of
severely tempered bainite platelets, fine needle shaped molybdenum-rich M2C carbides, and some
coarser cementite particles located at the bainitic ferrite plate boundaries. The structure is important
to note because it is the starting condition for the austenitisation experiments described below;
previous work has indicated that the initial microstructure can influence the development of
austenite during heating [6,7].
Austenite grain growth behaviour:
There is a moderate increase of grain size for temperatures up to 910°C, e.g. ∼13µm increase
after 12h at 910°C. However, at 940°C the size increases significantly, doubling when compared with
the lower temperature results.

Figure: Iso-thermal grain growth behaviour of austenite

The sudden change in grain growth behaviour observed at 940°C is typical of cases where a
distribution of pinning particles dissolves, permitting a reduction in Zener drag. These particles, if
they exist, have not been reported in the nuclear pressure vessel steel of the type studied here in the
context of the austenitisation heat treatment.

Activation energy for grain growth:

In theory, the activation energy for the transfer of atoms across a general grain boundary
should be about half that for self-diffusion [8]. The activation energy for iron diffusion in austenite is
286 kJmol−1 [9] so that the expected Q should be about 143 kJmol−1, unlike the 310 kJmol−1 deduced
above. Large activation energies are also reported in many studies. There is a dearth of explanations
in the past, but one possibility is that there is a nonlinear relationship between driving force and
boundary velocity [10, 11], but as stated previously, the driving force for grain growth is very small,
much smaller than for example in solid–state phase transformations in steels, where the linear
relationship applies well, for example [12]. It was felt instead that the usual analysis methods do not
account sufficiently for uncertainties, which may lead to over-fitting of the experimental data.
Table: Measured and Calculated Grain Sizes
Conclusions:
Austenite grain growth in a nuclear pressure vessel steel, SA-508 Gr.3, has been studied with
the aim of deriving a physically reasonable expression which generalises well. The essential
conclusions can be summarised as follows:

 The kinetics of the isothermal growth of austenite grains can be categorised into two
temperature regimes, one in which the boundaries experience a pinning force due to
precipitates so that the grain size rapidly reaches a limiting value. In contrast, at higher
temperatures where the precipitates are expected to dissolve, not only is the rate of grain
growth dramatically increased, but also does not reach a limiting value within the time scale
of the experiments reported here.
 It has been established using thermodynamic calculations, high-energy X-ray diffraction,
transmission electron microscopy and microanalysis, that the pinning particles at the
temperatures of interest are aluminium nitrides.
 The standard theory for grain growth has been adapted to account for the initial grain size
generated as the steel reaches its fully austenitic state, and for the evolution of this size as
the sample is heated continuously to the isothermal annealing temperature.
 It is demonstrated that the activation energy for grain growth is, as expected, about half that
for the self-diffusion of iron in austenite, once the data are interpreted to avoid over-fitting.
The activation energy is thus found to be about 190kJmol−1, a value much smaller than most
reported data on nuclear pressure vessel steels.

Figure: Effects of austenitising condition in grain size of SA-508 Gr.3 steel. a) 840°C for 30min; b) 940°C for
30min; c) 840°C for 5h; d) 940°C for 5h; e) 840°C for 12h; f) 940°C for 12h
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