Deliverable D3.3 MATTER

MATTER
MATERIALS TESTING AND RULES – Grant agreement for collaborative Project
Co-funded by the European Commission under the

Euratom Research and Training Programme on Nuclear Energy
within the Seventh Framework Programme
Grant Agreement no. 269706

Start date: 01/01/2011 Duration: 48 Months
D3.3 Creep test guidelines for cladding tubes

and miniaturized specimens
Authors: M. Serrano García (CIEMAT), R. Hernandez Pascual
(CIEMAT), M. Yurechko (KIT).
MATTER – Deliverable D3.3
EURATOM FP7 Grant Agreement no.269706
Table of contents
1. SCOPE ..........................................................................................................6
1.1 Reference documents ................................................................................................................ 6
2. EQUIPMENT ................................................................................................6
3. SPECIMENS ..................................................................................................9
4. PROCEDURE ..............................................................................................11
5. CALCULATIONS .........................................................................................12
1.2 Characteristics of the creep curve .......................................................................................... 13
6. Effect of specimen geometry ...................................................................16

1.3 MATERIAL.................................................................................................................................. 16
7. EFFECT OF LBE...........................................................................................21
1.4 Background ............................................................................................................................... 21
1.5 Experimental............................................................................................................................. 21
8. references .................................................................................................32
3
List of tables
Table 1.- T91 chemical composition ...................................................................................................... 16

Table 2.- Specimen geometry................................................................................................................. 17
Table 3.- CIEMAT creep tests results in air and liquid PbBi.................................................................. 22
Table 4.- KIT test matrix .......................................................................................................................... 23
4
List of figures
Figure 1.- Testing capsule ......................................................................................................................... 6

Figure 2.- CIEMAT testing capsule ........................................................................................................... 7
Figure 3.- CRISLA testing rings and schema of the elongation measurements outside the
capsule(KIT) ............................................................................................................................................... 7
Figure 4.- CRISLA capsule with uniaxial creep-to-rupture specimen built-in(KIT)................................ 8
Figure 5.- Rod-in-tube extensometer [Zwick-Roell] ............................................................................... 9
Figure 6.- Specimen for uniaxial tests.................................................................................................... 10
Figure 7.- Cylindrical creep specimens with collars [Zwick-Roell] ....................................................... 10
Figure 8.- Laser scanner with a specimen by measuring of the gauge length Lc and the distance Lo
and a measuring principle of the laser scanner (KIT) ........................................................................... 11
Figure 9.- Profile of a specimen measured with a laser scanner before the test (KIT) ..................... 12
Figure 10.- Strain and strain rate in creep regime. [4] ......................................................................... 14
Figure 11.- Manson-Haferd relationship for different materials [] ..................................................... 15
Figure 12. Specimen tested .................................................................................................................... 17
Figure 13.- Creep rupture time for different specimen sizes............................................................... 17
Figure 14.- Strain.vs.time for different specimen sizes ........................................................................ 18
Figure 15.- Fractographic examination.................................................................................................. 19
Figure 16.- Variation of ductility properties and average void diameter with strain rate of austenitic
304L. [Dass et al] ..................................................................................................................................... 19
Figure 17.- Creep tests in liquid PbBi and in air. CIEMAT ..................................................................... 22
Figure 18.- Creep strain.vs.time for CIEMAT tests ................................................................................ 23
Figure 19 – Apparent strain, temperature and oxygen output obtained in the running test carried
out with T91 in LBE with 10-7 mass.-% at 450°C and 390 MPa. ........................................................... 25
out with T91 in LBE bubbled with Ar-H2 mixed gas at 450°C and 390 MPa........................................ 26
out with T91 : (a) immerged in LBE bubbled with Ar-H2 mixed gas and (b) in air at 500°C and 310
MPa. ......................................................................................................................................................... 26
Figure 22 – Apparent strain, temperature and oxygen output obtained in the test carried out with
T91: (a) in LBE bubbled with Ar-H2 mixed gas and (b) in air at 550°C and 200 MPa.......................... 27
Figure 23 – Transversal cross-section of T91 tested in LBE with low oxygen concentration at 550°C
.................................................................................................................................................................. 28
Figure 24 – T91 tested in LBE at low co and 550°C. EDX- analysis across into the steel infiltrated LBE
(open circles illustrate steel/liquid metal interfaces)........................................................................... 29
Figure 25 – Surface of T91 oxidized in air at 550°C and 200 MPa. ...................................................... 29
Figure 26 – Surface of T91 oxidized in air at 550°C. ............................................................................. 30
5
1. SCOPE
The scope of this deliverable is to provide recommendations and guidance for uniaxial creep test
of miniature specimen in air and in contact with LBE. The experimental results to support the
guidelines are also included. Results and analysis of the tubular specimens are included on D3.7
1.1 Reference documents

• ASTM Designation: E 139 Standard Test Methods for Conducting Creep, Creep-Rupture,
and Stress-Rupture Tests of Metallic Materials
• ISO 204:2009 Metallic materials -- Uniaxial creep testing in tension -- Method of test
• ECCC RECOMMENDATIONS - VOLUME 2 Part V [Issue 1] Terms and terminology used for
the generation and assessment of multi-axial feature specimen and component test data,
PREPARED BY ECCC – WG4, EDITED BY: S R HOLDSWORTH & T B BROWN, 2005
• ECCC RECOMMENDATIONS - VOLUME 3 Part V [Issue 1] Testing practices for the
generation of multi-axial feature specimen and component test data, PREPARED BY ECCC –
WG4, EDITED BY: S R HOLDSWORTH & T B BROWN, 2005
2. EQUIPMENT
The equipment required for conducting creep tests consists primarily of a loading device, a
furnace or heating chamber equipped with sensitive temperature regulating controls, and
accurate extensometer of LVDT to measure strain during the test, in case of testing in contact with
LBE, a sealed testing capsule with the necessary equipment to control the oxygen concentration in
the LBS and the usual time measuring, recording, and supporting instrumentation
The most common loading is of a standard lever arm design, where a dead load is applyed to the
specimen once the testing temperature is reached.
When the creep tests are performed under a selected atmosphere, as is the case of liquid metals,
the specimen has to be fitted inside a sealed testing capsule. In order to accommodate the
elongation of the specimen maintaining, the testing capsule can consist on a bellow and two
flanges with the correspondent sealing gaskets, see figure 5 . The capsule is filled with solid lead-
bismuth and then sealed.
Figure 1.- Testing capsule
6
CIEMAT testing capsule can be seen in Figure 2
(a) (b)
Figure 2.- CIEMAT testing capsule
A CIEMAT capsule consists of an inner container of AISI 310 and an external bellow to
accommodate the displacement during the test. This capsule is mounted in a conventional creep
testing machine, as can be seen in Figure 3(b). The upper and lower parts of the capsule are
threaded to the loading train of the machine.
The CRISLA facility used for the creep-to-rupture tests provides eight rigs for creep-to-rupture
testing at elevated temperature (up to 650°C), three for air and five for liquid lead (Figure 3). Each
rig consists of a steel container (capsule) that encloses the specimen in the respective
environment, and an external system for imposing a static tensile load (Figure 3). A pull rod
conducted through the lid of the capsule forms the connection between the external loading
system and the specimen, and simultaneously transmits the deformation of the specimen to a
displacement transducer residing outside the capsule (Figure 3, right). The movement of the pull
rod is accommodated by a flexible bellows. The lever arm that is connected to the pull rod (and to
a weight pan on the opposite end) has a load-train factor of ten, which was verified for each
system using a load cell. The results differed by 2% using the same load frame and the different
lids for experiments in air and lead including the impact of the bellows etc. The measurements of
all test stands resulted in difference of 7% in the load factor using the lid for the experiments with
lead and showed good reproducibility.
Figure 3.- CRISLA testing rings and schema of the elongation measurements outside the
capsule(KIT)
7
The capsules for the tests in air and LBE at KIT are made of 17-12 Cr-Ni steel (DIN W.-Nr. 1.4571).
Additionally, the inner surface and internals of these capsules are provided with an aluminide
coating (FeAl), so as to minimize Ni dissolution from the austenitic construction material. The
capsules for tests in LBE contain approximately 9kg (900 ml) of the liquid metal. The volume of the
capsules for tests in stagnant air is smaller (~230 ml).
Figure 4.- CRISLA capsule with uniaxial creep-to-rupture specimen built-in(KIT)
The lower specimen mount is accomplished via an anchor screwed on the end of the specimen
and a bayonet connector in the bottom plate of the capsules (Figure 3, left). The other end of the
specimen is screwed on the pull rod. The bayonet connector allows for mounting the specimen
after melting the LBE in the open capsule (at ~140°C), which is performed in an extractor hood
without conditioning of the atmosphere. After sealing, the capsule is transferred to the test stand.
One filling of LBE is used for several experiments, if necessary, after removing slag that
accumulated on the liquid-teal surface in the course of the previous test. The tests in air are
performed using the same type of specimen mount for improved comparability.
Electrical resistance furnaces are the most common heating systems used. In general three
thermocouples are used to control the testing temperature. The system of heating the specimens
should provide a uniform temperature within a defined range over the test section of the
specimen. A tolerance band of ±2ºC for temperatures up to 1000ºC and ±3ºC for temperatures
from 1000ºC to 1350ºC are recommended in ref 1. In the case of the tests performed in contact
with LBE, the specimen capsule temperature should be also be maintained within a defined limit.
When a testing capsule is using to contain the liquid LBE, the temperature should be measured at
the outer and the inner surface of the capsule, at least at the beginning of the test campaign to
assure that the temperature control is adequate.
The temperature inside the capsule is controlled at KIT via heating sleeves and monitored using a
NiCr-Ni thermocouple residing close to the specimen. Measuring the temperature profile at 650°C
(what was done for other test array) in the capsule for tests in air showed variations ≤±1°C along
the gauge length of the specimen. Due to higher thermal conductivity of lead alloy in comparison
to air the temperature gradient along the gauge length in LBE is probably less than ±1°C
determined in air. The maximum temperature deviation at the centre of the specimens is ±2°C at
450°C for a running experiment.
8
The temperature inside the capsules at CIEMAT is not measured; it is only measured and
controlled outside the capsule, by using three thermocouples are used to control the temperature,
one in the lower part of the furnace, one in the middle part and the other in the upper part. Nobel
metal thermocouples type S or R are recommended. A calibration of the temperature difference
between the outside part of the capsule and the specimen submerged in liquid leas is made prior
to the tests for the liquid metal used and testing temperature.
Elongation of the specimen in creep tests are done usually by rod-in-tube type extensometers
attached to the specimen gage length, see Figure 5. The extensometer tubes extended align the
load train and down to the bottom of the closed furnace. A linear variable differential
extensometer (LVDT) is located at the lower end of the extensometer assembly outside the
furnace.
Figure 5.- Rod-in-tube extensometer [Zwick-Roell]
When the extension of the specimen is not measured at the gage length, displacements also can
be caused by creep of the fixtures, compliance of the machine, and other factors. Large-diameter,
highly creep resistant materials are recommended for the fixtures. Strain measurement is made
at CIEMAT at the upper and lower parts of the testing capsule, by mounting a classical rod-in-tube
extensometer. At KIT the strain is measured by a displacement transducer outside the capsule
(Figure 3¡Error! No se encuentra el origen de la referencia., right)
3. SPECIMENS
Testing standards recommend the use of cylindrical or square section specimens. The use of the
same specimen type, size and shape used for tensile testing can be suitable for creep tests, with
some modifications : tighter dimensional tolerances, larger ration of length to diameter (or width)
to increase the accuracy of strain measurement and for coarse-threaded specimens, the size of
the thread should be at least 7/4 the diameter of the reduced section. Some specimen designs
include collars to attach the extensometer.
The specimen geometry used by KIT and CIEMAT for the tests in liquid LBE and air is cylindrical
specimens with a adjusted length of 18 mm and a diameter of 3 mm, see figure 4
9
Figure 6.- Specimen for uniaxial tests
Testing standards recommend the use of cylindrical or square section specimens. The use of the
same specimen type, size and shape used for tensile testing can be suitable for creep tests, with
some modifications1: tighter dimensional tolerances, larger ration of length to diameter (or width)
to increase the accuracy of strain measurement and for coarse-threaded specimens, the size of
the thread should be at least 7/4 the diameter of the reduced section. Some specimen designs
include collars to attach the extensometer.
Figure 7.- Cylindrical creep specimens with collars [Zwick-Roell]
Following the ECCC recommendations2 creep specimen can be grouped by size as:
- Full-size specimen having gauge diameter d0≥5 mm and reference length Lr≥ 3d0.
- Sub-size specimen having 3≤d0<5 mm
- Miniature specimens having do<3 mm
When miniature specimens are used, the strain measurement is usually made by a double-sided
displacement measurement system measuring the relative displacement between a machine part
fixed to the upper end of the specimen and another machine part fixed to the bottom end of the
test piece. In these cases a machine compliance correction would be needed, to subtract the
elongation/displacements of the machine parts. The machine compliance can be calculated
assuming that the machine behaves as a linear spring with a constant compliance factor. The axial
stiffness, or compliance, of miniature specimens can be very high compared to bulk specimens,
thereby increasing the effect of the compliance of the machine frame and load train on the
experimental data.
1
ASTM E139 Standard
10
4. PROCEDURE
Prior to the tests, a metrology control should be made on the specimens. In particular the
following measurements should be made:
- Cross-section area (A0): measure the cross section area of the specimen at the centre of
the reduced section
- Gauge length (L0): measure de original length where the extension of the specimen will be
measured during the test.
- Reference length (Lr). This dimension is used to calculate the strain when the extension of
the specimen is not measured at the reduced section. The testing standards recommend
that the reference length is determined by [3]:
Where Lc is the parallel length, L0 is the gauge length, d0 is the diameter of the parallel length,
di is the mean diameter of the ith length increment li, between the end of the parallel length
and the gauge length and n is the Norton exponent. As the value of the Norton exponent is not
know at the beginning of the tests, this type of calculation would need a iterative procedure to
calculate the value of Lr assuming a initial n value of 5 and then calculate the real one and
adjust the strain measurement.
The characteristic dimensions of each specimen, before and after the test can be measured using a
laser scanner with spatial resolutions of 0.1 µm and 0.1 mm vertical to and along the long
specimen axis, respectively, as is included on the KIT testing procedure. Each vertical section is
proposed to measure four times after turning the specimen by 90° (Figures 3 and 4).
Figure 8.- Laser scanner with a specimen by measuring of the gauge length Lc and the distance Lo
and a measuring principle of the laser scanner (KIT)
11
Figure 9.- Profile of a specimen measured with a laser scanner before the test (KIT)
The diameter D is to specify as arithmetic average of all Dc-values of the profile curve with a
continual Dc (e.g., all Dc between (-27.500; 2.994) and (-9.900; 2.996) in Fig. 4).
After this metrology step, place the specimen into the grip and attach the LVDT or other strain
measurement devices. Once the specimen is mounted on the testing device, set the testing
temperature and when the temperature is considered stable, measure the initial gage length of
the test specimen. Apply the dead-weight mass and start the test.
Similar to the measurements of specimens before tests, the same parameter (the gauge length at
rupture Lc;R, diameter at rupture DR, and the distance at rupture Lo;R) are measured. Comparison
the parameters before and after the tests allows to characterise creep-rupture properties of the
material.
5. CALCULATIONS
Stresses re-calculated in load on the surface of cross-section have to be defined in the range of
interest, so that failure of the material can be extrapolate for other stresses, temperatures and
longer service/exposure time. Data is plotted log σ-log t. A straight line or best fit curve is usually
obtained at each temperature of interest. Change in the slope of the curve illustrates changes in
the material at definite stress due to changes in degradation mechanism (e.g., changes of
deformation mode from diffusion-controlled dislocation climb to thermally activated dislocation
glide, LME etc.).
The characteristics of the creep behavior of the tested material are retrieved from the recorded
displacement X as a function of time, t. It is assumed that the ideal curve can be described by
1
τ
Xo is a constant displacement of the pull rod that adjusts immediately after the mechanical load
becomes effective (e.g., elastic deformation of the specimen, but also of the loading system). For
the chosen procedure, Xo=0. Assuming that only the specimen, i.e., the part between the
12
specimen shoulders (Lo), is subject to creep, the second term on the right-hand side represents the
primary creep domain of the tested material, with final elongation X1 at the transition from
primary to secondary (steady) creep (t=t1,2). τ is a time constant characteristic for the decay of
primary creep with time. s denotes the temporarily constant elongation rate in the secondary
creep domain that is effective until the transition from secondary to tertiary creep (t=t2,3). The
tertiary domain that ends with rupture of the specimen at t=tR is not regarded in Eq. (4). Eq. (4)
allows for a computer-based numerical evaluation of X1, t1,2, s and t2,3 that was tried in addition
to the graphic method, i.e., finding the straight line with slope s that approximates the
experimental curve in the secondary creep domain. The corresponding strain-based characteristics
ε1 and εs follow from X1 and s, respectively, as
100 and ∗ 100

with reference length L. Choosing L=Lr gives the best approximation, while L=Lc overestimates the
actual values.
By definition of the strain with time, εo and strain at rupture, εR, the sampling length Lr is to use.
∆ ∆ ;#
100 and ! 100
where ∆Lo is the total elongation of the specimen between the shoulders measured with
displacement transducer residing outside the capsule and ∆Lo;R is the total elongation of the
specimen between the shoulders measured on the ruptured specimen with laser scanner.
According to DIN EN ISO 204:2009-10 the sampling length Lr is calculated as:

* -.
$ % 2 ∑0[) , /0 ]
* +
n is the material-specific stress exponent from the Norton (power) law, li and Di denote the length
increments and corresponding diameters, respectively
1.2 Characteristics of the creep curve

A typical, schematic plot of the strain is shown in Figure 10 which also shows the strain rate
versus the time and the strain. Initially, the specimen show a time-independent strain ε0 which
consists of an elastic and a plastic part. The strain increases further with time, with the strain rate
changing strongly, usually decreasing continuously. This region (region I) of the creep curve is
called primary creep or transient creep. Following this is a region (region II) of steady-state creep
or secondary creep with approximately constant strain rate. After most of the life time has passed,
the creep rate strongly increases until final fracture ensues. In this region of tertiary creep (region
III), massive inner damage that strongly reduces the load-bearing cross section and thus explains
the strong increase of [4]
13
Figure 10.- Strain and strain rate in creep regime. [4]
The minimun strain rate, at the secondary creep regime ( ε&min ) is related to the time to rupture
Monkman-Grant:
t r = K ⋅ ε&min
−r
Ln(t r ) = ln K − rLn(ε&min )
Where tr is the rupture time and K and r are material constants. The stress dependence of
minimum or steady-state creep rate is usually expressed by the Norton law, as
ε&S = A σ n
or
 QC 
ε& = Aσ n exp  − 
 RT 
where n is the stress exponent, Qc the activation energy for creep, R the gas constant and T the
absolute temperature. The parameter A′ includes microstructure parameters such as grain size
and so on.
Estimation of rupture time for long term operation can be done by using different extrapolation
techniques:
2 3 4 5 3 log $ 9:; <;=:> ?@// ;
14
CH
2A * /:B $ D. 3G4 9:; I;; Jℎ ;LM N:;>
log log P
$
23O 9:;?<>=:> Q<9 ;R
4 4P
where tr is the time to rupture, T is the absolute temperature and CLM , log ta and Ta are constants
and Q is the activation energy and R is the gas constant
Figure 11.- Manson-Haferd relationship for different materials [5]
15
6. EFFECT OF SPECIMEN GEOMETRY
1.3 MATERIAL
The T91 heat was produced within the DEMETRA project and distributed by SCK CEN. The material
was delivered as hot rolled and heat treated plates with a thickness of 15 mm by Industeel, Arcelor
group. The chemical composition of T91-D heat is illustrated in Table 1. In addition to the chemical
analysis of the producing company, chemical analysis was also performed by the laboratory for
iron and steel making at Ghent University and OCAS n.v. The heat treatment was normalizing
1050ºC/1 minute and tempering 770ºC/45 minutes (3 min/mm thickness).
Table 1.- T91 chemical composition
Three different specimen geometries are used, see Table 2 and Figure 12.
16
Figure 12. Specimen tested
Table 2.- Specimen geometry
gauge length, Lc (mm) gauge diameter, d0 (mm)

M12 50 8
M8 25 5
M5 18 3
The test are performed at 550ºC in air and stress levels between 225 and 320 MPa. Results from
the tests are seen in Figure 13.
Figure 13.- Creep rupture time for different specimen sizes
In this figure an effect of specimen size can be observed, especially for low stress tests. A
comparison of the strain-time curves at 225 MPa is shown in Figure 14. In this figure a reduced
rupture time can be observed for the smaller specimens.
17
5L4 T91 M5 ‫؛‬550 C 250MPa

18 8L3 T91 M8 ‫؛‬550 C 250MPa
12LR6 T91 M12 ‫؛‬550C 250MPa
16
3 mm diameter
14
5 mm diameter
12
Strain (%)
10
4
8 mm diameter
2
0
0 100 200 300 400 500 600 700 800 900
Time (h)
Figure 14.- Strain.vs.time for different specimen sizes
The effect of specimen size on creep properties of P91 was also studied by Olbritch et al [6] by
testing small specimens of gauge length of 17.5 and gauge diameter of 3 mm, similar to the M5
specimens presented here. No clear rend of specimen size on rupture time is found by the
authors. Miniature specimens give longer rupture times at 650ºC, but in contrast at 675ºC the
miniature specimens gives shorter time to rupture that the stardard ones. At 700ºC no effect of
specimen size is seen. It should be noted that rupture times where in most of the cases less that
50 hours and thus no clear conclusion can be done.
Segle et al [7] performed a very interesting analysis of the effect of specimen siza on creep
properties by finite element analysis of the stress distribution during a creep tests. The differences
observed on in minimum creep strain rate result in stress enhancements due to local stress re-
distribution and, depending on the creep ductility and creep rupture strength of the constituents,
the time to failure will be more or less reduced. They propose a time to rupture model that
depends inversely with the maximum principal stress and maximum Von Misses stress. The model
predicts larger time to rupture times for larger specimen diameter, mainly due to a higher
maximum principal stress of the smaller specimens. The experimental data with 1Cr0.5Mo welds
show the same trend, and also the location where the first damage appears moves from the
outside to the inside of the specimen with increasing size.
Krompholz et al show also a dependence on the creep properties with specimen size for a reactor
pressure vessel steel [8]. The effect depends on temperature and stress. At 700 C for the lowest
stress (15 MPa) these times are considerably larger by a factor of 10 and 6 for the small specimen,
while for the higher stresses the situation is reversed, but differences are much less (a factor of 1.6
and less for the highest stress of 30 MPa). The authors suggest that some diffusion processes may
be responsible for the observed size effect, and these processes are more important in small
specimens than in large ones. Thus, if sufficient time is available, such processes become
important and size influences due to diffusion may show up. Since creep tests at lower stress
levels have longer test duration than at higher stresses, diffusion induced size effects should be
more pronounced at the low stress level.
18
A preliminary fractographic examination shows that all the fracture surface are characterized by
ductile dimples. However, an effect of the specimen size on the size and distribution of dimples
could be observed, see Figure 15, where for the smallest specimens the dimple size seems to ba
larger than for the bigger ones.
Figure 15.- Fractographic examination
Dass et al [9] correlate ductile fracture features can be related to mechanical properties, in
particular ductility. Larger dimple size is correlated with lower ductility, see Figure 16. So it is
expected that larger ductile dimples can be correlated with less creep strength, as it is the case of
the smaller specimens
Figure 16.- Variation of ductility properties and average void diameter with strain rate of
austenitic 304L. [Dass et al]
Size effect and correspondence with fractography is also reported by Srivastava et al [10] by
testing Ni-based single-crystal superalloy. Although the fracture and damage mechanism can be
different to T91, a transition from homogeneous dimple fracture due to void nucleation, growth
and coalescence to a mixed mode of void nucleation, growth and coalescence together with
cleavage was observed with decreasing specimen thickness.
19
20
7. EFFECT OF LBE
1.4 Background
The open literature on the effect of heavy liquid metals on creep properties of F/M steels is not
easy to found. One of the first papers were published on 2004 by Gamaoun et al. [11], were a
significant acceleration of the plastic strain, by three orders of magnitude, and in parallel the
formation of cavities in the near surface region, was reported for 4-point bent T91 specimens
under an initial equivalent stress of 135 MPa at 525 ºC, in both reducing and oxidising lead, by
comparison with reference tests in air.
Jianu et al tested T91 steel in flowing LBE at 550ºC, with 10-6 wt% oxygen content [12]. The
analysis of their test results show that the time-to-rupture of specimens tested in LBE is
significantly smaller compared to the one of specimens tested in air. In particular under high
stress, and therefore high strain, the crack propagation process is mostly controlled by the
reduction of the surface energy due to Pb and Bi adsorption on the steel surface. Under low stress
(140 and 160 MPa) and low strain, this process is delayed due to the competing mechanism of
healing the oxide scale cracks.
Yurechko et al [13] show indications for a degradation of mechanical properties in stagnant Pb

with 10−6 mass% dissolved oxygen are conﬁned to comparaXvely low stress of <100 MPa or long
exposure to the liquid metal of >10,000 h, where this particular conditions resulted in brittle
fracture with significantly reduced necking and strain at rupture. The likely cause for this
exceptional behavior is the accumulation of liquid Pb underneath the thick oxide scale formed,
getting in intimate contact with Cr depleted steel. While the decrease in creep strength of P92 was
significant in this long-term test in Pb, T91 exhibited only a comparatively slight reduction of
necking in a test performed in Pb at 100 MPa or tR = 19,500 h. However, cracks were observed in
the necking region of the steel, in contrast to the other tests performed in either Pb or air.
1.5 Experimental
The material is the T91 heat was produced within the DEMETRA project and distributed by SCK
CEN. see Table 1. Two different experiments were carried out within MATTER project, CIEMAT
tests were performed at 500ºC with on-controlled oxygen atmosphere, thus the oxygen content of
the LBE is not know. On the contrary KIT performed the experiment under oxygen controlled
conditions and the measurement of the oxygen content is done by an oxygen sensor.
CIEMAT tests were performed at 500ºC with stress levels between 300-320 MPa. The obtained
time to rupture comes up to 3500 hours in air and 1000 hours in a liquid Pb-Bi. The specimen were
used for the creep test are according to DIN 50125, with a gage length of 18mm and gage
diameter of 3mm (same as KIT tests). Results of the tests are seen in Table 3
21
Table 3.- CIEMAT creep tests results in air and liquid PbBi
Reference Stress (MPa) t (h) Min. creep strain rate (1/h) Conditions
r
5L5 320 918 2,27E-6 Air
5L6 320 959 4,00E-6 Air
5L7 300 885 1,27E-5 Air
5L8 310 888 2,01E-5 Air
5L9 320 7 3,95E-3 Pb-Bi
5L11 300 448 8,81E-5 Pb-Bi
5L12 300 4 1,16E-2 Pb-Bi
5L13 300 88 4,61E-4 Pb-Bi
5L14 310 479 2,60E-5 Pb-Bi
5L15 320 4 1,69E-2 Pb-Bi
CIEMAT results point out a reduction on the creep rupture time for the teste performed in LBE in
comparison with the ones performed in air, see Figure 17 and Figure 18.
Figure 17.- Creep tests in liquid PbBi and in air. CIEMAT
22
Figure 18.- Creep strain.vs.time for CIEMAT tests
KIT test matrix can be seen in Table 4. Since T91 is still intact after 22.400 h at 10-7 wt% and after
7,600 h at lower Co (see Figure 19 and Figure 20), they changed the experimental program to
more degradative conditions. Tests in stagnant LBE were performed at 450 and 550°C and low Co
(under flowing Ar-H2 gas – see Table 4). At 550°C three simultaneous tests in LBE and air were
performed. Tests in stagnant LBE with low Co and air at 500°C are running (Figure 21) similar to
scheme that were used at 550°C .
Table 4.- KIT test matrix
23
Since tests at 450°C and 500° are running, no post-test analysis is still possible. F/M T91 steel was
studied in LBE of 10-7 wt./% oxygen concentration at 450°C, i.e. under conditions when
thermodynamically stable oxides have to form on the steel surface so that they can prevent
dissolution of steel elements in LBE and penetration of liquid metal into the steel. From
thermodynamic point of view a stable bi-layer scale that consists of magnetite (Fe3O4) grown on
the top of Cr-rich spinel ((Fe,Cr)3O4) have to form 14 like it was observed for the same material in
flowing LBE under similar conditions after 2,015 h [2]. In spite of thermodynamic stability of
magnetite under conditions reported in [2] only Cr-rich spinel was defined on the specimens
tested longer than 3,750 h proving dissolution of Fe at the scale surface outweighing magnetite
formation. It is very probable that similar formation kinetic of oxide scale is expected for T91
tested in stagnant LBE. Furthermore, it is confident that after 22,400 h creep-corrosion test the
steel did not ruptured (Figure 19). One can presume that the specimen did not reach a critical
thickness due to metal loss and necking as well as other factors like LME did not affect
detrimentally the steel up to 22,400 h.
In the test with decreasing oxygen activity in LBE (at 450°C) from 1.6×10-6 up to 3.2×10-13 wt.% it is
very possible that magnetite formed during first 1,000 h becomes unstable with a following
dissolving in liquid metal similar to T91 tested in flowing LBE after 500, 3749 and 8766 h with some
Fe-O protrusions [15]. Furthermore, at co=1×10-13 mass.-% stable Cr2O3 oxide that prevents
dissolution of steel elements in LBE and liquid metal penetration into the steel can form instead
Cr-rich spinel existed on the steel. But local liquid attack is not excluded at defects in the spinel or
Cr2O3 oxide scale/layer.
Change of the oxygen concentration from 5×10-10 up to 8.6×10-13 wt.% in LBE during the running
test at 500°C suspects an oxide scale formation/dissociation similar to the above mentioned
oxidation behaviour at 450°C.
24
T91 - 390 MPa - LBE

L (mm) = 21.6
LC (mm) = 18.1
Lr (mm) = 19.34
DC (mm) = 2.9925
Apparent Strain (%)

1,0
0,8
0,6
0,4
0,2
0,0
Oxygen-sensor output (V)
1,1
1,0
0,9
0,8
500
Temperature (°C)
400
300
200
0 5000 10000 15000 20000

Time /h
out with T91 in LBE with 10-7 mass.-% at 450°C and 390 MPa.
25
T91 - 390 MPa - LBE

L0 (mm) = 21.7
LC (mm) = 18.3
Lr (mm) = 19.6
DC (mm) = 2.9979
1,0
Apparent Strain (%)

0,8
0,6
0,4
0,2
0,0
-0,2
1,5
1,4
1,3
1,2
1,1
1,0
0,9
0,8
500
Temperature (°C)
400
300
200
0 1000 2000 3000 4000 5000 6000 7000 8000

Time /h
out with T91 in LBE bubbled with Ar-H2 mixed gas at 450°C and 390 MPa.
T91 - 310 MPa - LBE T91 - 310 MPa - air

L (mm) = 21.5 L0 (mm) = 21.5
LC (mm) = 17.9 LC (mm) = 18.0
Lr (mm) = 19.2 Lr (mm) = 19.3
DC (mm) = 2.9971 DC (mm) = 2.9890
5
Apparent Strain (%)
5
Apparent Strain (%)
4 4
3 3
2 2
1 1
0 0
1,5
1,5
1,4 1,4
1,3 1,3
1,2 1,2
1,1 1,1
1,0 1,0
0,9 0,9
0,8 0,8
Temperature in capsule (°C)
500 500
Temperature (°C)
400 400
300 300
200 200
0 500 1000 1500 2000

0 500 1000 1500 2000
Time (h)
(a) Time /h (b)
out with T91 : (a) immerged in LBE bubbled with Ar-H2 mixed gas and (b) in air at 500°C and 310
MPa.
26
To observe accelerated kinetic of detrimental effect of LBE on the steel, low (decreasing) oxygen
activity in the liquid metal and higher temperature, e.g. 550°C, was selected for the creep-rupture
test. Technical problems occurred with a heating during the test is observed on the apparent
strain, temperature, oxygen-sensor output and temperature-near-transducer curves as a sudden
decrease of values measured (Figure 22a). All three tests (one in LBE and two reference tests in
air) were stopped simultaneously after ∼1,400h when the test in LBE was broken for the 4th time.
It can be seen that primary creep area for both specimens differs strongly. Whether this effect
comes from media is doubted. Nevertheless, it is certain that T91 is still intact after 1,400 h creep
at 200 MPa and low oxygen concentration in LBE (1.6×10-3 wt.% for the first 300 h and up to
7.1×10-11 wt.% at the end of the experiment), while T91 tested in flowing LBE at co=10-6 wt.% was
ruptured after 120-150 h [12].
T91 - 200 MPa - LBE T91 - 200 MPa - air

L0 (mm) = 21.5 L0 (mm) = 21.5
LC (mm) = 18.2 LC (mm) = 18.0
Lr (mm) = 19.4 Lr (mm) = 19.3
DC (mm) = 2.9950 DC (mm) = 2.9927
0,5 0,5
Apperent Strain (%)
Apparent Strain (%)
0,4 0,4
0,3 0,3
0,2 0,2
0,1 0,1
0,0 0,0
1,4 1,4
1,2 1,2
1,0 1,0
0,8 0,8
0,6 0,6
0,4 0,4
0,2 0,2
Temperature near transducer (°C) Temperature in capsule (°C)
Temperature near transducer (°C) Temperature in capsule (°C)
800 800
700 700
600 600
500 500
400 400
300 300
200 200
100 100
0 0
60 60
50 50
40 40
30 30
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400
(a) Time /h (b) Time /h
Figure 22 – Apparent strain, temperature and oxygen output obtained in the test carried out with
T91: (a) in LBE bubbled with Ar-H2 mixed gas and (b) in air at 550°C and 200 MPa.
27
Polished cross-section provides evidence of an internal oxidation zone (IOZ) formed on the surface
from chromium oxides and liquid metal attack (LMA) areas (Figure 23a). Specimen surface that
was contacting directly to LBE during the experiment and finally was etched chemically from
solidified LBE is characterized by Fe3O4-protrusions grown on top of thin Cr-rich spinel layer (Figure
23b). From thermodynamic point of view stable magnetite can form during first 4 h with following
dissolution in Fe. Actually, iron oxides protrusions observed on the surface may contain mixture of
Fe3O4 and Fe. Therefore, formation of thin layer of the chromium containing spinel does not
protect the steel completely from degradation due to LMA. EDX-Analysis of the transversal cross-
section detects an increased content of chromium in the steel areas joined to liquid metal (Figure
24). Cr -Peaks measured with EDX-detector are well observed on the LBE/steel interface. On the
one hand, it is very probable that LMA occurred in places where chromium content was not high
enough to form stable oxides so that they can protect the steel elements from dissolution and
infiltration of Pb and Bi into the steel like it was found in the necking area of 9Cr conventinal steel
where oxide scale ruptures and provides Pb and Bi adsorption on the steel surface [16, 12]. On the
other hand, an increased chromium content at Pb-Bi/steel interface can decelerate LMA due to
chroimum-rich oxides formed in front of liquid metal dissolution areas.
Figure 23 – Transversal cross-section of T91 tested in LBE with low oxygen concentration at 550°C
The average thickness of an IOZ and LMA observed in the cross-section is 3.6U .V UX.
T . and 7.0TV.V µm,
respectively. Material loss was detected to be 8.82% or 67.6 µm estimated on the specimen radius
of 1.5 mm. IOZ/LMA ratio analyzed from the specimen surface with every 15° rotating angle is
estimated to be 0.375:0.625. In spite of LMA is the main degradation factor (>2/3 of the specimen
material is weakened due to LMA the specimen is still intact after 1,400 h direct contact to LBE
under stress.
T91 exposed to air at 550°C and 200 MPa for the same term shows a thin oxide layer that covered
the whole steel surface and particular areas of oxide(s) grown on the top (Figure 25). Chemical
composition of the oxide layer and the areas measured with EDX-detector (O:Fe:Cr = 27:49:24
wt.% and 35:65:0 wt.%, respectively) detect Cr-rich spinel as underlayer and hematite and/or
magnetite on the top.
28
Figure 24 – T91 tested in LBE at low co and 550°C. EDX- analysis across into the steel infiltrated LBE
(open circles illustrate steel/liquid metal interfaces).
Figure 25 – Surface of T91 oxidized in air at 550°C and 200 MPa.
Reference test with T91 in air without loading results in an oxide scale that is significantly thicker
than under loading and coloured red, that indicates hematite as outer oxide layer (Figure 26).
Nevertheless, formation of magnetite cannot be excluded. Stable oxides observed in SEM on the
29
transversal cross-section can be separated in two oxide layers with clearly observed interphase
boundary (Figure 26c). Splitting between the steel and the oxide scale is a feature of the polished
cross-sections. It is reasonable to assume that the oxide scale tends to split forming fresh steel
surface that starts to oxidize again (accelerated oxidation) with a corresponding material loss.
Formation of the (Fe,Cr)3O4-phase under hematite is similar for T91 in air in both “air”-tests.
Figure 26 – Surface of T91 oxidized in air at 550°C.
The thickness of the oxide layers formed on T91 in air under loading is 2.0U-. U .V
T . and 1.9T .V µm for
magnetite/hematite and Cr-rich spinel, respectively. These values are higher for T91 tested in air
without load: 5.3U .\ U-._
T .[ and 4.6T-.^ µm. Material loss in both cases is in the range of the
measurement error (up to 6 µm or 0.2% calculated on ∅3 mm).
30
All creep(-rupture) tests obtained by KIT and presented here resulted in much higher service time
of T91 in comparison to other data obtained by CIEMAT at 500°C and reported in technical
literature for T91 in LBE with co=10-6 wt.% at 550°C [12].
Discrepancy in rupture time can be looked in technical differences of the creep-to-rupture

experiments. For instance, CIEMAT container for LBE is much smaller than KIT capsule and is not
covered with an anticorrosive coating. Furthermore, LBE in CIEMAT experiments joins a flowing Ar-
atmosphere, while Ar-H2 gas mixture is bubbled through liquid metal in KIT capsule. Gas flowing
above LBE can lead to significant change in oxygen concentration/activity in liquid metal with
container height and correspondingly to various conditions of oxidation of the steel studied. Non-
coated steel container can oxidize removing oxygen from LBE and/or degrade dissolving elements
like Fe, Cr, Ni etc. depending on oxygen activity in liquid metal changing thereby chemical
equilibrium of the whole system. Flow direction of liquid metal relative to specimen in Jianu’s
experiment [12] is an additional factor why rupture time can differ from KIT results despite that
oxygen concentration in LBE was reported to be higher than in KIT test.
Nevertheless, creep data obtained in LBE at 450°C results in service time >22,400 h at co=10-7 wt%
and >7,600 h at low oxygen concentration in liquid metal, i.e. low oxygen concentration might be
an uncritical factor for the steel as long as chromium content at liquid metal/steel interface high
enough to protect the steel from LMA.
31
8. REFERENCES
1 ECCC Recommendations Volume 3 - Recommendations for data acceptability criteria and the generation of creep
data Part I - Data acceptability criteria and data generation: Generic recommendations for creep, creep rupture, stress
rupture and stress relaxation data, ed. Merckling, G., Calvano, F. & Bullough, C.K., publ. ERA Technology Ltd,
Leatherhead, 2001
2 ECCC RECOMMENDATIONS - VOLUME 3 Part III [Issue 4]
3 ECCC RECOMMENDATIONS - VOLUME 3 Part I [Issue 5], DATA ACCEPTABILITY CRITERIA AND DATA GENERATION:
GENERIC RECOMMENDATIONS FOR CREEP, CREEP RUPTURE, STRESS RUPTURE AND STRESS RELAXATION DATA, 2001
4 J. Rösler, H. Harders and M. Bäker, « Mechanical Behaviour of Engineering Materials » Springer-Verlag Berlin
Heidelberg 2007
5 Jie Zhao, Dong-Ming Li and Yuan-Yuan Fang Application of Manson–Haferd and Larson–Miller Methods in Creep
Rupture Property Evaluation of Heat-Resistant Steels, J. Pressure Vessel Technol. 132(6), Oct 22, 2010
6 J. Olbricht et al. / Materials Science & Engineering A 585 (2013) 335–342
7 P. Segle et al Int J. Pres. Ves. & Piping 66 (1996) 199-222
8 K. Krompholz, D. Kalkhof / Journal of Nuclear Materials 305 (2002) 112–123
9 A. Das, S. Tarafder / Scripta Materialia 59 (2008) 1014–1017
10 A. Srivastava et al. / Acta Materialia 60 (2012) 5697–5711
11 F. Gamaoun, M. Dupeux, V. Ghetta, D. Gorse, Scripta Mater. 50 (2004) 619–623.
12 A. Jianu, G. Müller, A. Weisenburger, A. Heinzel, C. Fazio, V.G. Markov, A.D. Kashtanov, Creep-to-rupture tests of
T91 steel in flowing Pb–Bi eutectic melt at 550 °C, Journal of Nuclear Materials 394 (2009) 102-108.
13 M. Yurechko et al. / Nuclear Engineering and Design 280 (2014) 686–696
14 C. Schroer, J. Konys, Physical Chemistry of Corrosion and Oxygen Control in Liquid Lead and Lead-Bismuth Eutectic,
in: Wissenschaftliche Berichte, Forschungszentrum Karlsruhe GmbH, Karlsruhe, Germany, 2007.
15 V. Tsisar, C. Schroer, O. Wedemeyer, A. Skrypnik, J. Konys, Compatibility of ferritic/martensitic steel T91 with
flowing LBE containing 10-7 mass% dissolved oxygen at 450 and 550°C in: 22nd International Conference of Nuclear
Engineering ICONE22, ASME, Prague, Czech Republic, 2014
16 M. Yurechko et al. / Nuclear Engineering and Design 280 (2014) 686–696
32

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MATTER

MATERIALS TESTING AND RULES – Grant agreement for collaborative Project

Co-funded by the European Commission under the

Grant Agreement no. 269706

D3.3 Creep test guidelines for cladding tubes

6. Effect of specimen geometry ...................................................................16

Table 1.- T91 chemical composition ...................................................................................................... 16

Figure 1.- Testing capsule ......................................................................................................................... 6

1.1 Reference documents

Figure 1.- Testing capsule

CIEMAT testing capsule can be seen in Figure 2

Figure 4.- CRISLA capsule with uniaxial creep-to-rupture specimen built-in(KIT)

Figure 5.- Rod-in-tube extensometer [Zwick-Roell]

Figure 6.- Specimen for uniaxial tests

Figure 7.- Cylindrical creep specimens with collars [Zwick-Roell]

100 and ∗ 100

According to DIN EN ISO 204:2009-10 the sampling length Lr is calculated as:

1.2 Characteristics of the creep curve

Figure 10.- Strain and strain rate in creep regime. [4]

Figure 11.- Manson-Haferd relationship for different materials [5]

6. EFFECT OF SPECIMEN GEOMETRY

Table 1.- T91 chemical composition

Figure 12. Specimen tested

Table 2.- Specimen geometry

gauge length, Lc (mm) gauge diameter, d0 (mm)

Figure 13.- Creep rupture time for different specimen sizes

5L4 T91 M5 ‫؛‬550 C 250MPa

Figure 14.- Strain.vs.time for different specimen sizes

Figure 15.- Fractographic examination

Yurechko et al [13] show indications for a degradation of mechanical properties in stagnant Pb

Figure 17.- Creep tests in liquid PbBi and in air. CIEMAT

Figure 18.- Creep strain.vs.time for CIEMAT tests

Table 4.- KIT test matrix

T91 - 390 MPa - LBE

Apparent Strain (%)

0 5000 10000 15000 20000

T91 - 390 MPa - LBE

Apparent Strain (%)

0 1000 2000 3000 4000 5000 6000 7000 8000

T91 - 310 MPa - LBE T91 - 310 MPa - air

0 500 1000 1500 2000

T91 - 200 MPa - LBE T91 - 200 MPa - air

(a) Time /h (b) Time /h

Figure 25 – Surface of T91 oxidized in air at 550°C and 200 MPa.

Figure 26 – Surface of T91 oxidized in air at 550°C.

Discrepancy in rupture time can be looked in technical differences of the creep-to-rupture

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