CORROSION/ FRACTURE MECHANICS LAB WORK

An experimental study on corrosion and mechanical behaviour of Zircaloy-4 under oxidation. Presented by: SHUKEIR Malik RAI Ajit PALLA Harin Reddy BARI Md. Abdullah Al

INTRODUCTION
OBJECTIVE : Behaviour of Zr-4 alloy under LOCA oxidation conditions.

Environment: In LOCA usually steam environment. Possible air oxidation under severe accidents: - During shutdown when RCS is open to containment atmosphere. - During BDBA, core degrades and oxidation of outer core regions.
Current Experiment: Behaviour of Zr-4 under air oxidation. - Corrosion study: Oxidation of Zr-4 in air, corrosion kinetics, breakway oxidation. - Fracture Mechanics: Failure behaviour under mechanical loading.
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CORROSION STUDY
- Objective: The objective is to study the oxidation of Zircaloy4 under the effect of air. - Test conducted between 1273 K to 1473 K. - Parameters: Weight gain with respect to time and temperatures. Oxide thickness evaluation with respect time and temperature. - Conditions: Oxidation in air. - Experimental protocols: Measure the h, Di, Do of the samples. Degrease in acetone and clean in ethanol. Weigh each sample three times. Put samples in furnace for respective time and temperatures. Weigh the samples again after the furnace. Polish the samples and study oxidation thickness for Di and Do under SEM. 3

EXPERIMENTAL RESULTS
Sampl e No. 1 Tempe rature (C) Tim Weight e Gain (sec) (g/m2) 300 45.37584
500 700

600

y = -0,0003x2 + 0,8407x + 19,773

2
3 6 7 8 10 12 11 13

1000

900

59.35388
Weight Gain (g/m2) 400

1800 78.16846 120 94.82662 1150 300 900 120 1200 300 900 199.5630 479.2283

y = -0,0002x2 + 0,7336x + 3,4465

1000 300 1150 1200 200

134.287
100

y = 0,0373x + 17,724

255.7815 533.3813
0 0 500 1000 Time (sec) 1500 2000

1800 602.3297

KINETIC ANALYSIS
Equation for Oxidation of Zirconium alloys:

Instead of n= we are taking a variable as we will see later on that we dont follow just a parabolic trend but will also see linear and cubic trend of kinetics. Thus we get,

After getting the value of k, we can plot ln k v/s ln (1/T). The slope of this plot will give us the activation energy Ea as calculated from the following equation:

Which gives:

KINETIC ANALYSIS
6,5 6 5,5

y = 0,684x + 1,6315 y = 0,8039x + 0,7063

ln del M/S (g/m2)

5 4,5 4 3,5 1000 deg C 3 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 8 1150 deg C 1200 deg C

y = 0,2982x + 2,0978

ln t (s)

Temperature

Time

Inference

1200
1150 1000

900 s
900 s 1800 s

0.684
0.8039 0.2982

Between parabolic and linear: Mix Diffusion

Between parabolic and linear: Mix Diffusion Cubic: Diffusion
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KINETIC ANALYSIS
7 6,5

y = 0,5756x + 2,2141
6

ln del M/S (g/m2)

5,5 5 4,5

y = 0,2982x + 2,0978
4 3,5 3 3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 8

1000 deg C

1200 deg C

ln t (s)

Temperature 1200 1000

Time 1800 1800

n 0.3

Inference Cubic :Diffusion main phenomenon

0.5756 Almost parabolic

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KINETIC ANALYSIS
- Using the equation ln (del M/S)- n ln t = ln k given in the previous slide, we can calculate k.

Temp
1000 1150 1200

Time
1800 900 1800

Ln (delM/S)
4.358866 6.172177 6.400805

n
0.2982 0.8039 0.5756

Ln k
2.12369 0.70372 2.08637

k
8.3619 2.0212 8.055
2,5

1,5

ln k

3 points 2 points

0,5

-7,32

-7,3

-7,28

-7,26

-7,24

ln 1/T

-7,22

-7,2

-7,18

-7,16

0 -7,14

KINETIC ANALYSIS
CORROSION PHENOMENON Case 1: When n=1 : Linear Kinetic reaction takes place. Faster phenomenon. Catastrophic oxidation usually dominated by breakaway oxidation. In experiment observed around 1150 deg C.

Case2: When n= 0.5 : Parabolic. Diffusion is the main phenomenon. Slower kinetics. After 1200 deg C its observed value of n reaching parabolic limits.
Case 3: When n = 0.3: Cubic. Diffusion is the main phenomenon. Slowest kinetics. Observed around 1000 deg C.

Anomalies with experimental and theoretical results?? - Theoretical results say : From 700 deg C to 1000 deg C, big transition from subparabolic regime to linear fast kinetics. From 1100 deg C onwards, smoother kinetics. - These anomalies can be attributed to difference in the test setup and other important factors (to be discussed later).
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SEM images
Before oxidation After oxidation 1150C 120 sec

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SEM 1000 C 15 min

External side Internal side

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SEM-1150 C, 15 min
External side Internal side

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SEM 1200 C, 15min

External side Internal side

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SEM 1200C, 15min

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Comparison with Theory

In the paper three alloys were investigated for air oxidation at high temperatures namely M5, Zirlo and Zircaloy-4. The tests were conducted in a commercial thermal balance. The gases (Ar,O2,N2,air) were supplied via flow controllers. The samples were of different lengths than what we did. The temperature range was from 973k to 1853k. Also some of the samples were tested with preoxidation
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COMPARISON WITH THEORY

700 600 Weight Gain (g/m2) 500 y = -0,0002x2 + 0,7336x + 3,4465 400 300 200 100 0 0 500 1000 Time (sec) 1500 2000 y = 0,0373x + 17,724 1000 1150 y = -0,0003x2 + 0,8407x + 19,773

1200

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Comparison with Theory

Paper
There are strong differences between the three alloys and the curves show a transition from parabolic to linear or even faster kinetics. The transitions during the tests are caused by breakaway, i.e loss of the protective effect of the oxide scale allowing for nitrogen access to the metal and subsequent formation of ZrN

Experimental
The mass gain increases with Temperature. Oxidation kinetics at the highest Temperatures tends to be more linear than parabolic, which is most probably caused by oxygen starvation

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Mass gain vs Temperature Paper

0,06 0,05

Lab
Mass gain vs Temperature

M as s G ai n

0,04 0,03 0,02 0,01 0 1000 1150 1200 Mass gain vs Temperature

Temperature

The slightly lower oxidation rates in air at 50K/min, may be due to lower O2 concentration in air compared to pure O2. Significant differences between the behaviour in air and O2 were observed for lowest heating rate of 5K/min. After 1000 C, a significant acceleration of reaction of air is observed at a higher T, its assumed that N comes into play, leading to formation of ZrN and destabilization of oxide scale. 18

SEM Zr4
1273k 30min-paper
External layer,1273k 30 min lab, 55micrometer thickness

The degradation of the oxide scale is caused by formation of ZrN at the metal-oxide boundary which converts to oxide again with growing scale by fresh air flowing from external surface to metal. The region is mixed with ZrO2 and ZrN at the metal-oxide boundary, its thinner, but is porous and non protective. Dark area is ZrO2/ZrN mixture

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Fracture Mechanics study

Outlines
Objectives Our Sample Experimental Set-up Variation from ideal conditions Variation of oxidation thickness with temperature SEM observation of oxidized layer Load Vs Displacement curve Maximum energy Vs Load curve

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Objectives
Simulate LOCA (loss of coolant accident) tests on Zircaloy-4 cladding. Carry out mechanical tests after oxidation on same cladding. Mechanical property evaluations and compare. Analyse microstructure and evaluate the absorbed contents (oxygen).

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Our Sample:
Sample dimensions: Outer diameter: 9.5 mm, Thickness: 0.75 mm, Height: 15 mm (approx.) Materials: Zircaloy-4 (Zr-1.3Sn-0.2Fe-0.1Cr) Total 6 samples Total duration of time for each sample: 300 seconds Temperatures of Irradiation: 1000,1100,1125,1150,1175 and 1200 C

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Deviation from Ideal Conditions:

Temperature measurement method: No thermocouple used, no axial temperature recorded. Only the furnace temperature. Air oxidation only not the flowing steam oxidation. No intermediate temperature, only one temperature heated and then cooled. Air cooling instead of water quenching. Sample oxidizing at different temperatures but for same time (1-Dimensional failure evaluation only) no time variation. Only ring compression mechanical test no 3-points bend test. No gas analysis has done.
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Variation of oxidation thickness with temperature:

Here the thickness is measured from SEM observation

Oxide Layer Thickness

300 250 Oxide thickness(m) 200 150 100 50 0 950 1000 1050 1100 1150 1200 1250

Total Oxide thickness

Temperature(K)

Figure : Oxide layer thickness Vs temperature graph

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Similar types of trend we also found in mass gain before and after oxidation
Mass gain with temperatures
0,5 0,45 0,4 0,35 Mass in grams 0,3 0,25 0,2 0,15 0,1 0,05 0 950 1000 1050 1100 Temperature in deg C 1150 1200 1250

Figure : Mass difference Vs temperature graph

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SEM observation of oxidation layer

Figure: Fractography after compression test at 1125 C

Figure: Schematic illustrations of intermetallic precipitation in oxide layers

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At high temperature near 1200 C, the behviour of Zircaloy

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Mechanical test:
Failure behaviour under mechanical test. Ring Compression test. Roughly 15 mm each specimen, compressed at 1 mm/min. Three main curves:
Load Displacement curves. Absorbed Energy. Maximum Load.
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Mechanical Properties
Load Displacement Diagram
120 100 1000 C 80 Load (Kgf) 1100 C 1125 C 1150 C 40 1175 C 1200 C

60

20

0
0 1 2 3 Displacement (mm) 4 5 6

Cladding Oxidized at 1000 & 1100 C exhibited a ductile compression. Oxidation over 1100 C, cladding showed an abrubt load drop, then plastic deformation. This load drop is due to Fracture of the brittle oxide outside the cladding surface.
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Mechanical Properties
Load Displacement Diagram
120 100

Load (Kgf)

80 60 40 20 0 0 1 2 3 4 5 6 Displacement (mm)

1000 C 1100 C

When the load drop occured the prior B-layer was so stable and can sustain an additional compression load. Additional load after load drop decreased gradually with oxidation temperature for T=1000, 1100 C. Beyond 1125 C, the thickness of the prior- layer was so thin, and brittle; drop at the elastic region.

Load Displacement Diagram

60 50 1125 C 1150 C 30 20 10 0 0 0,5 1 Displacement (mm) 1,5 2 1175 C 1200 C

Load (Kgf)

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Note: Sawtooth patern, due to maintained cylindrical shape with deformation.

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Mechanical Properties
Machine Stiffness
0,7 0,6

0,5 Displacement (mm)

0,4

y = -2E-09x4 + 1E-06x3 - 0.0002x2 + 0.0107x + 0.2224

0,3 0,2

0,1

0 0 20 40 60 80 Load (Kgf) 100 120 140 160 180

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Mechanical Properties
Absorbed Energy
200 180

160
140 Energy (Kgf.mm) 120 100 80 60 Oxidized for 5 min

40
20 0 950 1000 1050 1100 Oxidation temperature (C) 1150 1200 1250

Absorbed Energy= Area under the curve. Abrubt decrease between 1100 1125. (for them 1100 1150) more precice. At 1200 C So high temperature that result in an accelerated Oxygen diffusion, O content increase cause Prior-B causing Embrittlement. 33

Mechanical Properties:
120

Maximum Load

100

80

DBTT

Load (N)

60 Oxidized for 5 min

40

20

0 950 1000 1050 1100 1150 Oxidation tamperature (C) 1200 1250

Load drop by fracture of Oxide surface occured at the plastic region when oxidized at T up to 1125 C. Load drop at Elastic region, when Oxidized at high temperature.
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Mechanical Properties:
Maximum Displacement
1,4 1,2 1 Displacement (mm) 0,8 0,6 0,4 0,2 0 950 1000 1050 1100 Oxidation temperature (C) 1150 1200 1250 Oxidized for 5 min

Maximum displacement decrease with increasing temperature.(at first load drop). In the paper, Max displacement is Contiuously decreasing not the same case, where a drop occured. 35

Conclusion:
Unable to compute the activation energy due to lack of samples, and anomalies between experimental and theoretical set up. Improper polishing due to brittle behaviour at high temperature. Oxidation thickness increase with temperature. Unability to observe the dissolved oxygen due to lack of facility. Ductile to brittle transition at around 1100 C.

Fracture at the elastic region for elevated temperatures.

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