Zirconium hydride precipitation and dissolution kinetics in - - PowerPoint PPT Presentation

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Zirconium hydride precipitation and dissolution kinetics in - - PowerPoint PPT Presentation

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Zirconium hydride precipitation and dissolution kinetics in zirconium alloys E. Lacroix 1,2 , P.-C. Simon 2 , A. T. Motta 2 and J. D. Almer 3 1 : Framatome, Lynchburg, VA, USA 2 : Pennsylvania State University, PA, USA 3 : Argonne National

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SLIDE 1

Zirconium hydride precipitation and dissolution kinetics in zirconium alloys

  • E. Lacroix1,2, P.-C. Simon2, A. T. Motta2 and J. D. Almer3

1

1: Framatome, Lynchburg, VA, USA 2: Pennsylvania State University, PA, USA 3: Argonne National Laboratory, Lemont, IL, USA

19th International Symposium on Zirconium in the Nuclear Industry Manchester, UK, May 22nd, 2019

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SLIDE 2
  • Background
  • Experiments
  • Model development
  • Conclusions

Outline

2 – Hydride hysteresis understanding – How can hydrogen behavior be studied? – How can we incorporate the experimental data obtained to create the HNGD model

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SLIDE 3

Background: Hydride hysteresis understanding

3 Conclusions Model Experiments Background

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SLIDE 4

Zirconium / zirconium hydride hysteresis

4

50 100 150 200 250 50 100 150 200 250 300 350 400 450

Hydrogen content in solid solution (wt.ppm) Temperature (°C)

Hydride precipitation behavior by region

TSSD TSSP

Precipitation Dissolution if hydrides are present Precipitation Hydride nucleation and growth

  • E. Lacroix, A. T. Motta, J.D. Almer "Experimental determination of zirconium hydride precipitation and

dissolution in zirconium alloy", Journal of Nuclear Materials, 509 (2018) 162-167.

Conclusions Model Experiments Background

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SLIDE 5

z

5

Terminal solid solubility for precipitation and dissolution

  • E. Lacroix, A. T. Motta, J.D. Almer "Experimental determination of zirconium hydride precipitation and dissolution in zirconium alloy", Journal
  • f Nuclear Materials, 509 (2018) 162-167.

603 wt.ppm 400 wt.ppm 541 wt.ppm

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SLIDE 6

z

6

hydrides Dissolved Hydrogen Dissolution Temperature

  • E. Lacroix, A. T. Motta, J.D. Almer "Experimental determination of zirconium hydride precipitation and

dissolution in zirconium alloy", Journal of Nuclear Materials, 509 (2018) 162-167.

Conclusions Model Experiments Background

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SLIDE 7

7

Dissolved hydrogen Precipitation Temperature hydrides

  • E. Lacroix, A. T. Motta, J.D. Almer "Experimental determination of zirconium hydride precipitation and

dissolution in zirconium alloy", Journal of Nuclear Materials, 509 (2018) 162-167.

Conclusions Model Experiments Background

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SLIDE 8

How was the hydride behavior studied?

8 Conclusions Model Experiments Background

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SLIDE 9

Experimental Setup at Beamline 1 at APS

Load Frame Clam shell furnace Sample 9 Conclusions Model Experiments Background

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SLIDE 10

z

Diffraction patterns 10 Peak intensity Peak position Peak width volume fraction Stress Size of the crystal size

Integration of diffraction data

Raw data Conclusions Model Experiments Background

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SLIDE 11

Differential Scanning Calorimetry (DSC)

Cooling System Heating system and sample holder 11 Conclusions Model Experiments Background

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SLIDE 12

Nucleation and Dissolution kinetics measurement using Synchrotron X-ray diffraction

12 Conclusions Model Experiments Background

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SLIDE 13

Nucleation and Dissolution kinetics: hypothesis

13

  • First order kinetics in the form:

𝑒𝐷𝑇𝑇 𝑒𝑢 = −𝐿 ⋅ 𝐷𝑇𝑇 − 𝐷𝑓𝑟

  • Differentiating:

𝐿 = − Δ𝐷𝑇𝑇 (𝐷𝑇𝑇−𝐷𝑓𝑟)Δ𝑢

  • K is the kinetic constant, following an Arrhenius law:

𝐿 = 𝐿0 ⋅ exp − 𝐹𝑞 𝑙𝐶𝑈

𝐷𝑇𝑇 is the hydrogen content in solid solution (wt.ppm) 𝐷𝑓𝑟 is the hydrogen content in solid solution at equilibrium (wt.ppm) 𝐿0 is the pre-exponential factor (𝑡−1) 𝐹𝑞 is the activation energy of the process (eV/atom) 𝑙𝐶 is the Boltzmann constant 𝑈 is the temperature (K)

Conclusions Model Experiments Background

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SLIDE 14

Studying hydrogen behavior in Zr

14

  • I:

𝑈𝑇𝑇P, 𝑈𝑇𝑇𝐸 (dynamic)

  • II:

𝑈𝑇𝑇D (equilibrium)

  • III:

Dissolution rate Nucleation rate

Conclusions Model Experiments Background 𝐿 = − Δ𝐷𝑇𝑇 (𝐷𝑇𝑇−𝐷𝑓𝑟)Δ𝑢

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SLIDE 15

Studying hydrogen behavior in Zr

15

  • Nucleation Kinetics
  • 𝑒𝐷𝑇𝑇

𝑒𝑢 = −𝐿𝑂(𝐷𝑇𝑇 − 𝑈𝑇𝑇𝑄)

  • 𝐿𝑂 =

−Δ𝐷𝑇𝑇 Δ𝑢 𝐷𝑇𝑇−𝑈𝑇𝑇𝑄

Conclusions Model Experiments Background

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SLIDE 16

Studying hydrogen behavior in Zr

16

  • Dissolution Kinetics
  • 𝑒𝐷𝑇𝑇

𝑒𝑢 = −𝐿𝐸(𝐷𝑇𝑇 − 𝑈𝑇𝑇𝐸)

  • 𝐿𝐸 =

−Δ𝐷𝑇𝑇 Δ𝑢 𝐷𝑇𝑇−𝑈𝑇𝑇𝐸

Conclusions Model Experiments Background

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SLIDE 17

Growth kinetics measurement using DSC

17 Conclusions Model Experiments Background

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SLIDE 18

Differential Scanning Calorimetry

18 Conclusions Model Experiment Background

350 ℃ 320 ℃ 305 ℃ 300 ℃ 290 ℃ 280 ℃

𝑦(𝑢) = Δ𝐼 𝑢 Δ𝐼𝑢𝑝𝑢 = 𝐷𝑄𝑄(𝑢) 𝐷0 − 𝑈𝑇𝑇𝐸(𝑢)

𝑦 = 1 − exp − 𝐿𝐻𝑢 𝑞

Growth Kinetics Parameter Depends on the growth regime 𝐿𝐻 = 𝐿𝐻

0 ⋅ exp − 𝐹𝐻

𝑙𝐶𝑈 Avrami Parameter Dimensionality of the growth.

  • 2.5 for platelets
  • 3 for spheres, 1 for

needles ASTM standard E2070

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SLIDE 19

19 Conclusions Model Experiment Background

Differential Scanning Calorimetry

99% (𝑦, 𝑢) (𝑦, 𝑢) (𝑦, 𝑢) ASTM standard E2070

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SLIDE 20

20 Conclusions Model Experiment Background

Time Temperature Transformation diagram

Temperature Time to reach 99% of reaction Diffusion reaction, 𝐿𝐻

𝑆

Phase transformation reaction, 𝐿𝐻

𝐸

𝑈𝑒 1 𝐿 = 1 𝐿𝐻

𝐸 + 1

𝐿𝐻

𝑆

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SLIDE 21

21 Conclusions Model Experiment Background

Experiment repeated to obtain TTT

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SLIDE 22

Model development

22 Conclusions Model Experiment Background

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SLIDE 23

23 Conclusions Model Experiment Background

Model Summary

50 100 150 200 250 50 100 150 200 250 300 350 400 450

Hydrogen content in solid solution (wt.ppm) Temperature (°C)

Hydride precipitation behavior by region

TSSD TSSP

Dissolution if hydrides are present Hydride nucleation and growth 𝑦 = exp −𝐿𝐸𝑢 Nucleation: 𝑦 = 1 − exp(−KNt) Growth: 𝑦 = 1 − exp − 𝐿𝐻𝑢 𝑞

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SLIDE 24

24 Conclusions Model Experiment Background

Model Results

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SLIDE 25

25 Conclusions Model Experiment Background

Synchrotron Experiment Simulation

  • E. Lacroix, A. T. Motta, J.D. Almer "Experimental determination of zirconium hydride precipitation and

dissolution in zirconium alloy", Journal of Nuclear Materials, 509 (2018) 162-167.

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SLIDE 26

z

Hold time: 41 days 26 157⁰C 454⁰C 1” 64 wt.ppm of Hydrogen Conclusions Model Experiment Background

  • A. Sawatzky, Hydrogen in Zircaloy-2: its distribution and heat of transport,

Journal of Nuclear Materials 2 (1960) 321{328.

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SLIDE 27

Conclusions

▪ Synchrotron X-ray diffraction was successfully used to

measure nucleation, and dissolution kinetics of hydrides.

▪ DSC was successfully used to measure hydride growth

kinetics and to obtain a Time-Temperature-Transformation diagram for hydride precipitation.

▪ A hydrogen precipitation and dissolution model was created

based on a new approach and showed good agreement with experimental data.

27 Conclusions Model Experiment Background

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SLIDE 28

Acknowledgement

▪ DOE-NEUP ▪ Argonne National Laboratory ▪ Penn State Nanofab ▪ Penn State MCL

28

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SLIDE 29

Questions

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SLIDE 30

Furnace Roughing Pump Diffusion Pump Gas tank Control Volume

Vacuum chamber

  • 1. Remove oxide from sample using an acid solution
  • 2. Deposit Nickel to prevent further oxidation
  • 3. Introduce hydrogen using gaseous charging method

30

Introducing Hydrogen in the zirconium metal

Conclusions Model Experiment Background

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SLIDE 31

sugar

  • 1. T0 = Room temperature (RT)
  • 2. T1 > Room temperature

→ less solid sugar in the water → more dissolved sugar

  • 3. T2 > T1 → Dissolution Temperature

→ Only dissolved sugar

  • 4. T3 < T2 → Precipitation Temperature

→ first occurrence of solid sugar

  • 5. T3 hold → Growth of sugar crystals
  • 6. T4 = Room temperature

T time

T1 T2 T3

32

T4

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SLIDE 32

z

33 157⁰C 454⁰C 1” 64 wt.ppm of Hydrogen

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SLIDE 33

Differential Scanning Calorimetry

34

  • Low temperature to

measure only diffusion- driven process

  • 1

𝐿𝐻 = 1 𝐿𝐻

𝐸 +

1 𝐿𝐻

𝑆

  • High temperature was

implemented using free energy curves

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SLIDE 34

z

35

Terminal solid solubility for precipitation and dissolution

  • E. Lacroix, A. T. Motta, J.D. Almer "Experimental determination of zirconium hydride precipitation and dissolution in zirconium alloy", Journal
  • f Nuclear Materials, 509 (2018) 162-167.

603 wt.ppm 400 wt.ppm 541 wt.ppm

✓ Show that hydrogen continues to precipitate below TSSP

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SLIDE 35

z

36

Terminal solid solubility measurement using DSC

300 Temp H content TD TP

  • K. Une and S. Ishimoto, “Dissolution and precipitation behavior of hydrides in Zircaloy-2 and high Fe Zircaloy,” Journal of Nuclear

Materials, vol. 322, pp. 66–72, 2003.

  • K. Colas, A. Motta, D. M.R., and J. Almer, “Mechanisms of hydride reorientation in Zircaloy-4 studied in situ,” Zirconium in the Nuclear Industry:

17th International Symposium, vol. ASTM STP 1543, pp. 1107–1137, 2014.

TSSP TSSD

100 200 300 400 500 600 100 200 300 400 500 600 CSS (wt.ppm) Temperature (°C)

TSSP (APS) [5] TSSD (APS) [5] TSSP (DSC) [3] TSSD (DSC) [3]

✓ Show that the TSSP is the nucleation temperature

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SLIDE 36

Studying hydrogen behavior in Zr

37

  • Sample A: 0 MPa
  • Sample B: 200 MPa