Cladding selection criteria

Nuclear properties (low absorption) Metallurgical => physical properties Corrosion behavior Irradiation stability Economics Fabricability/availability Thermal conductivity Fuel/coolant compatibility

Major purposes of fuel cladding

Act as pressure boundary Act as heat-transfer medium Contain fission products

Nuclear Properties Thermal reactors: Mg: lowest neutron cross section, but highly reactive, and Tmelt = 650 C Zr: 2nd best neutronically. Common pollutant is Hf (Hf = 102 b). Al: good neutronically, but Tmelt = 660 C Stainless steel: ok, but usually contains B impurities (B = 3000 b). Fast reactors: V: high cost Co: reactive Fe Cr s.s. Ni Zr: reacts with Na Mo: difficult to process

Metallurgical and Physical Properties Strength and creep resistance Thermal stability against phase transformations Ductility Fracture toughness

Corrosion Resistance a) In thermal reactors: compatibility with water Mg reacts with water, but is used in gas-cooled reactors (CO2, Ar) Zr and stainless steel: form passive, protective oxide films in water (advantage!) Al performs nearly as well as Zr, but its mechanical strength is very low at elevated temperature (240 C = Tm/2). s.s. has the best overall high-temperature properties, but its high cross section is a serious disadvantage.
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Corrosion Resistance (cont.) b) In fast reactors: compatibility with sodium The corrosion rate of metals in Na is very sensitive to its oxygen concentration. At cO > 5 ppm, Ni, V and Nb alloys corrode significantly. Best alloys to use with Na are Mo, Co-based or s.s.

Properties of various candidate metals for nuclear fuel cladding

Zr has the best combination of strength and neutron transparency.

Crystal structure of -Zr

Pure zirconium exhibits two crystallographic phases: the alpha phase is anisotropic, with a hexagonal close-packed (hcp) structure that is stable from low temperatures up to 860oC. At this temperature, the alpha phase changes to the body-centered cubic (bcc) beta phase. The alloy additions in Zry change the transformation temperature and introduce a 150o temperature region in which the and phases coexist, but the - transformation is basically the same as in pure Zr. The transformation influences the microstructure of the final product and is exploited in the fabrication of tubing and plates. The anisotropic crystal structure of -Zr, coupled with nonrandom orientation of crystallites (grains) resulting from the fabrication process, produces Zry parts that have direction dependent properties. This feature causes cladding deformation under irradiation by growth (increasing length) and bowing.

Selected physical properties of hcp Zr metal

For -Zr c/a ratio of 1.593 (i.e. a slight compression in the c direction compared to the ideal ratio of 1.633). The melting point of Zr is 1860C, so that zirconium can be classified as a weak refractory metal. Note its strong anisotropic behavior.

Fuel CladdingThe Choice of Zircaloy

Release of gaseous fission products into the coolant system represents a significant hazard to the general public. Particularly radioactive isotopes of iodine which, as airborne contaminants, are readily absorbed in the body and may result in a significant dose to internal organs. To prevent the release of these fission products from the fuel, the fuel pellets are sealed in "pins" or tubes of zircaloy (Zry). Zirconium has the advantages of having high thermal conductivity, low neutron absorption cross-sections, good multiaxial rupture strength, good creep strength and ductility. The addition of alloying elements increases the corrosion resistance of the clad in high temperature aqueous environments over that of pure zirconium.

The Roles of Alloying Elements in Zircaloy

Tin, stabilizer. At a concentration of 1.2-1.8 %, it forms in the and phases a substitutional solid solution. Tin was originally used to improve corrosion resistance specially by mitigating the deleterious effect of nitrogen. Addition of Tin also increases the tensile yield strength. Niobium is a stabilizer. From pure -Zr to pure Nb there exists a complete substitutional solid solution at high temperature. Alloys that have high Nb concentration (>0.4%) tend to form beta Nb. Thus, alloys such as M5 and ZIRLO exhibit bcc beta Nb precipitates. Oxygen is considered an alloying element, rather than an impurity. It is added before melting as small additions of ZrO2 powder. The usual oxygen content is in the range of 800-1600 ppm and its purpose is to increase the mechanical properties by solution strengthening (a 1000 ppm oxygen addition increases the yield strength by 150 MPa at room temperature). Oxygen is an -stabilizer, expanding the region of the phase diagram by formation of an interstitial solid solution. Iron, Chromium and Nickel are -stabilizers. They were added to the early Sn-based alloys after an accidental pollution of a melting lot by stainless steel showed an enhancement in corrosion resistance, leading to the alloys Zircaloy-2 and 4. At common concentrations, these elements are fully soluble in the phase. The temperature of dissolution of those elements is in the range of 835-845C. Hydrogen is an impurity element. During waterside corrosion, hydrogen produced by the reduction of the water as well as hydrogen present for water chemistry control, can be absorbed to some extent into the bulk of the alloy. Hydrogen atoms are located at tetrahedral sites of the hcp cell of the Zr matrix up to the solubility limit (about 15 ppm at 200 C and 200 ppm at 400 C). Above the solubility limit, hydrogen precipitates as the equilibrium fcc phase (Zr H1.66). The hydrides are more brittle than the matrix.
Typical acceptable concentration limits for O, N, H are (in ppm by weight): O: 1400 200; N: < 80; H: < 25.

10

Zr M

11

The concentrations of the added elements exceed the solubility limits intermetallic precipitates are distributed in the alloys. These give Zircaloy its corrosion resistance -- which depends on their size distribution. The phases depend on the processing history. (hcp) plus precipitates are stable at room temperature. (bcc) can be quenched from high temperature. + can be obtained by subsequent anneal. The empirical annealing parameter determines the particle sizes and distributions, as well as strength, ductility and corrosion resistance:
A(T) = t i exp(E /Ti )
i

Where Ti and ti are the temperature (K) and duration (h) of the ith anneal. E=40,000.

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Sn results in adherent post-transition oxide

ln WO2

% Sn (Fe, Cr, Ni)

Zircaloy-1: 2.5% Sn for lowest corrosion rate (depends on N concentration in Zr)

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For each alloying element, the corrosion rate has a minimum for a certain concentration. This minimum is a function of the presence of other alloying elements. The Zircaloys were developed by optimizing the concentrations of the alloying elements to minimize the corrosion rate. The experiments were done out of pile!

750 F Steam 1500 psi 66 days Cr

Weight gain [mg/dm2]

680 F water 84 days

Fe

Ni

Cr Fe Ni

Fe, Ni or Cr content, % Corrosion of Zr-1.8% Sn-base ternary alloys with Fe, Ni and Cr

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ln WO2

ln t

Sn results in adherent post-transition oxide

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Two Forms of Zircaloy

Zircaloy is an alloy of zirconium and is used in two principal forms: Zircaloy-2 consists of a zirconium with 1.5 wt.% tin, 0.12 wt.% iron, 0.01 wt.% chromium and 0.05 wt.% nickel. Zircaloy-4 is similar to Zircaloy-2, but without nickel and has an iron content of 0.18 wt. % iron. The difference between Zicraloy-2 and Zircaloy-4 is primarily due to nickel content, which tends to absorb hydrogen so that Zircaloy-4 absorbs less hydrogen that Zircaloy-2 during high temperature water corrosion. The corrosion rate of Zircaloy-2 is low in steam, high in H2 used in BWR, incr. [O2]. The corrosion rate of Zircaloy- 4 is low high-T water, OK in H2, used in PWR.
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Zircaloy Fabrication

Chlorination with Cl2 to convert all oxides to chlorides Removal of silicon as volatile SiCl4 by distillation, removal of HfCl4 by sublimation Conversion of ZrCl4 to Zr metal by reaction with magnesium: ZrCl4 + 2Mg Zr + 2 MgCl2 Removal of Mg from the impure Zr by vacuum distillation, leaving chunks of pure Zr Crushing and blending results in sponge zirconium, so called because of its porous character.

Blending of the alloying elements (Sn, Fe, Cr, Ni) give the desired Zircaloy composition Triple-pass vacuum arc melting to produce a solid ingot of uniform composition Hot forging to reduce ingot diameter to ~ 20 cm. Cutting the ingot into shorter lengths called billets and drilling a central hole in each Induction heating to > 1000oC, which converts the phase to the phase, followed by rapid quenching, reversing the phase transformation. The beta quenching, produces a small-grained product () with a desirable microstructure for optimum mechanical properties. In addition, beta quenching reduces the size of the second phase precipitates, which improves the water corrosion resistance of the final product. Annealing at ~ 500oC to further tailor the microstructure Machining the outer surface produces the final product called a tubeshell

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Zircaloy Fabrication

18

Composition range of standard Zr alloys

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Microstructural Changes of Zircaloys under Irradiation

Point Defects in Zr alloys
Single vacancies and interstitials as well as vacancy and interstitial clusters are formed when the material is exposed to neutron irradiation. Under reactor operating temperatures, the point defects that escape immediate recombination can migrate to sinks, such as grain boundaries, free surfaces and dislocations. Dislocation Loops When network dislocations are not present in large quantities (i.e. in recrystallized material), the point defects can agglomerate into dislocation loops, contributing significantly to the dislocation density. Void Swelling Zircaloy does not exhibit significant void formation under neutron irradiation, but it does exhibit creep and growth.

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Hydrogen embrittlement during Zircaloy corrosion: a portion of the H released during the reaction with H2O is absorbed in the metal. When the solubility limit is exeeded, brittle hydride precipitates.
H-Zr Phase Diagram
1200 1100 K=1 1000 900 800 700 K=0 K = -1 K = -2
K Pressure: 1 x 10 atmosphere

Temperature (C)

+
600 500 400 300 200 100 0 0.2 0.4

K = -3 K = -4 K = -5 K = -6 K = -7 K = -8 K = -9 K = -10
K = -11
K = -12

+
0.6 0.8 1 1.2 H/Zr atom ratio 1.4 1.6

+
1.8 2

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Fuel Element Failure

Failure of cladding from Pellet-Cladding Interactions (PCI)
Mechanical interaction (different thermal expansion coefficient, swelling) in corrosive environment (contributed by Cs and I), thermal shock and change in pellet geometry result in cracking of the cladding.

Hydriding of the zircaloy cladding

Internal sources of hydrogen include: helium gas impurities, radiolytic decomposition of organic contaminants, hydrogen trapped in pores of the UO2 lattice and moisture absorbed in the fuel pellets. Hydrogen absorbed in the zircalloy leads to formation of zircalloy hydride, which is less dense and more brittle than the original material. Stresses can be established which nucleate blisters and cracks in the cladding which continue to grow under the formation of additional hydrided material until the cracks completely penetrate the clad. A more dramatic form of hydride failure is that of secondary hydriding. Primary clad defects caused by PCI or primary hydriding, allow water to enter the interior portions of the rod. The influx of water and steam erode the defect, increasing its size. Radiolysis of the steam produces hydrogen gas which is transported through the gap by differential pressures and gaseous diffusion, leading to more rapid hydriding until massive failure of the cladding occurs.

Failure due to rupture from plastic deformation and creep

Analysis of the mechanical behavior is a very complicated task due to the complicated relationships which exist between the mechanical, thermal, chemical, and structural properties. Additionally, not all of the individual mechanisms involved are completely understood.

Fuel-modeling codes
Have been developed which accept operational, geometric and mechanical parameters and return an estimate of the time to failure based on observed and predicted results for individual phenomena. The most sophisticated codes in used today are the LIFE (U. S. National Code) and COMETHE/CRASH (Belgo nucleaire) codes.

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There are two modes of corrosion in Zircaloys: Uniform Nodular

Nodular corrosion of Zircaloy

1 cycle 3 cycles

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Nodular corrosion can result in: Excessive thinning of the clad Loss of corrosion products to coolant Enhanced hydrogen pickup Increased clad temperature

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Conflicting requirements for resistance to uniform vs. nodular corrosion

Solute retention in matrix allows oxide to grow uniformly => prevents nodular corrosion Presence of solutes, e.g., when precipitates are dissolved under irradiation, leads to enhanced rate of uniform corrosion
Solute conc. Solute conc.

Local solute depletion leads to oxide break-down and formation of nodules

distance

distance

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Fixed composition

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Observations: Corrosion: uniform, nodular Matrix composition has little effect on corrosion resistance and + phases have higher corrosion resistance than Size distribution of precipitates affects both uniform and nodular corrosion resistance Irradiation leads to Fe dissolution into the matrix. This composition change results in amorphization of the intermetallic precipitates, at the interface. Resulting effect on corrosion: higher rate of uniform corrosion, lower rate of nodular corrosion Irradiation leads to deformation by channeling The dislocation microstructure of irradiated Zircaloys has been characterized extensively Oxide can display various phases and microstructures influenced by irradiation and microstructure of the metal. Irradiation -> precipitate coarsening ??? Use to high burnup values is limited by uniform corrosion.
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Irradiation induced changes of precipitates in Zircaloy-2

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Zr(Cr,Fe)2

200 nm 0.5 m

50 nm

ZrFe2

Fe-map
HCP-[111] FCC-[001]

100 nm

BF TEM micrograph and SA diffraction patterns of precipitates in as-received sample

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2 dpa

10 nm

5 dpa

10 nm

7 dpa

10 nm

Zr(Cr,Fe)2

Zr(Cr,Fe)2

Matrix

Matrix

Zr(Cr,Fe)2

HREM of Zr(Fe, Cr)2 precipitate and matrix at different damage levels

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100 nm

0 dpa

2 dpa

5 dpa

7 dpa

BF micrographs of the matrix showing the evolution of dislocation loops with dose
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Amorphous rim

20 nm

5 nm

amorphous

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33

Fe concentration

neutron

(schem.)

proton

Distance (nm)

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In situ Ne irradiation
600 keV (10-3 dpa/s) at 350 C
unirradiated

matrix

100 nm

precipitate

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In situ Ne irradiation (cont.)

0.2 dpa 0.4 dpa

100 nm

100 nm

0.8 dpa

100 nm

1.2 dpa

100 nm

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TEM images showing the microstructure of various zirconium alloys

Zircaloy-4

M5 Alloy

37

38

Radiation Damage in alpha-Zirconium

Transmission electron micrograph showing dislocation loops in pure Zr after irradiation to 1.5 x 1026 n.m-2 at 700 K.

39

Zr

40

ZrO2 phases: T < 1174 C 1174 C < T < 2293 C 2293 C < T < 2680 C

=5.68 g/cm3
6.10 g/cm3 6.27 g/cm3

Monoclinic Tetragonal Cubic

Zr:

6.49 g/cm3

HCP

How does one measure oxidation? Use weight gain when the oxide is adherent: The weight/(unit area) is normally measured in [mg/cm2] of added oxygen weight WO2. Also: WZrO2 = mg of ZrO2/(dm2 surface area). This corresponds to an oxide thickness tZrO2 = WZrO2/ ZrO2

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Design limits: Heat transfer Oxide spalling Hydrogen pickup Wastage (reduction in wall thickness) WO2 < 100-200 mg/dm2 WO2 < 600 mg/dm2 < 250 ppm (solubility limit)

< 10 % of wall thickness

Sample oxide calculation: Consider clad after 1000 days of operation at 680 F. Extrapolate weight gain curve to 103 days: obtain ~ 340 mg/dm2 oxygen, of which 30 mg/dm2 are pre-transition and 310 post transition. 1) Oxide thickness: WZrO M ZrO 2 2 (mass ratio of oxide to oxygen in the layer is Use the following relation: =

WO

equal to the ratio of molecular masses.

MO

MH = 1; MO2 = 32; MZr = 91.2; MZrO2 = 123.2

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WZrO WO
2

M ZrO MO
2

WZrO2 = 340 mg/dm2 x (123.2/32) x 10-3 g/mg x 10-2 dm2/cm2 = 1.31 x 10-2 g/cm2

The corresponding oxide thickness:

tZrO =
2

WZrO

ZrO

13.110 3 g /cm 2 = = 2.3110 3 cm 5.68 g /cm 3

Note: the clad thickess is ~ 0.0625 cm => the oxide thickness is ~ 3.7% of the total.

Calculate the temperature drop across the oxide:

T =

q" tZrO k ZrO

2

315 W /cm 2 2.3110 3 36 C 0.02 W /(cm C)

Add the temperature drop across the Zr (~ 15C) => total temperature drop of ~ 50C.

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Hydrogen absorption: Suppose that the % theoretical hydrogen pickup is

25% pre transition fH = 50% post transition

Then
4M H WH = WO fH 2 MO 2

Weight/unit area added hydrogen

M Zr WZr = Zr tZr W M O O2 2

Weight/unit area remaining clad

pre 4M pre post 4M post WO2 M H fH + WO2 M H fH O O WH 2 2 = WZr M Zr Zr t Zr WO MO 2 2

WO is the total 2
oxygen weight gain, pre- and post-transition

Total: 480 ppm (exceeds the solubility limit)

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New Zr-based alloys In the 1990s, extensive experiments were conducted in order to develop corrosionresistant alloys that can tolerate greater radiation damage. These included: In pile (up to 55 GWd/tU): corrosion, growth and creep Out of pile: corrosion, creep, stress-corrosion crackin, mechanical properties.

Beneficial effect of Sn is seen only out of pile! Alloys were developed with properties superior to those of Zircaloy-4:

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120 Maximum oxide thickness (m)

120 Maximum oxide thickness (m)

Zr-4 mean M4

Zr-4 mean M5

0 0

0 0

GWd/tU
Average fuel rod burnup

60

GWd/tU
Average fuel rod burnup

60

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