Assessment of Degradation Mechanisms of Primary Components

in Water Cooled Nuclear Reactors: Current Issues and Future Challenges

Corrosion and basic chemistry in primary circuits

in Pressurized Water Reactors

Dolores Gmez-Briceo
Structural Materials Division
CIEMAT

IAEA Training Workshop TR 47184, Madrid, September 2014

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 CORROSION OF PRIMARY CIRCUITS MATERIALS

General corrosion

Influence of Zn additions

Boric acid corrosion

Flow accelerated corrosion ( FAC)

Stress corrosion cracking ( next talk)

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 TYPES OF PRESSURISED WATER REACTORS

PHWR

WWER
PWR

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MAIN MATERIALS IN THE PRIMARY SYSTEM OF PRESSURISED WATER REACTORS

Main materials in the primary system of pressurized water reactors

PWR PWR WWER PHWR
(W / EDF) (Siemens-KWU) 440/1000

Carbon steel
Austenitic steels
Stabilised austenitic steels

Alloy 600/ 690

A600/690
A 800 NG
SG tubes
Stabilised SS

All the materials show low corrosion rates the in primary water conditions
of the different types of pressurized water reactors

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The optimization of primary water chemistry is aimed at :

Control materials degradation

Avoid fuel performance issues

Minimize radiation effect

Primary water chemistry has to be reducing and alkaline

H2 injection to suppress oxygen produced by radiolysis

Li or K to raise the acidic pH produces by boric addition

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The optimum pH chemistry is consequence of a balance among the three goals

Radiation field control has lower priority than pressure boundary integrity and
fuel performance

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 Materials corrosion of primary systems

Release of corrosion products (CP)

Activation of corrosion products in the core

Deposition of activated corrosion products out of core

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 Pressure
PWR primary water chemistry High enough to prevent boiling
Local boiling may occur and cause
Typical formation of deposits that lead to
Pressure(MPa) 14.2 Axial Offset Anomaly (AOA)
Temperature(C) 286-323
Boric Acid
Oxygen(ppm) <0.1 Controls nuclear reactions
Conductivity(S/cm) 1-40 Decreases throughout fuel cycle

LiOH
H2 (ml/kg) at STP 20-50
Controls pH; from 2.1-3.5 ppm to reduce
Li(ppm) as LiOH 0.1-3.5 activity in the circuit
B(ppm) as H3BO3 0-2300
Hydrogen
Chloride(ppm) <0.15
To prevent radiolysis( oxygen>0.1ppm)
Fluoride(ppm) <0.15
SiO2 (ppm) <0.20 Natural Li is not used to avoid the tritium formation from 6Li.
pHT 6.8-7.4 Li enriched in 7Li (99%) is used

Natural B only contains about 20% of 10B, the useful isotope for
neutron absorption.
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Options for PWR primary chemistry

Constant chemistry: Li, B coordination Modified chemistry: Li, B coordination

300C 300C

Elevated chemistry: The coolant pH is maintained at or above pHT =7.2 for the entire cycle
This strategy can be carried out following a Constant chemistry or a Modified Chemistry

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In the early times, it was thought that the main CP was magnetite, at pH300C= 6.9
magnetite solubility is at a minimum.

Later, it was identified that nickel ferrite is the major constituent of CP,at pH300C=
7.4 nickel ferrite solubility is at a minimum

Magnetite solubility an Fe corrosion rate

300C

Sweeton, 1968

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Options for WWER primary chemistry

KOH as pH control agent pH260C = 7.1-7.3 2.2-4.5ppm H2

Reducing environment H2 produced by NH3 injection 3 ppm ammonium
direct gas H2 injection

VVER 440 VVER 1000

After Zmitko, 2004

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 Primary water chemistry for Pressurized Heavy Water Reactors (PHWR)

Heavy water (D2O) is used both as coolant in the primary heat transport system (PHTS)
and moderator of the nuclear reaction.

PHTS Chemistry Specification in Normal Operation

specified desired

Dissolved deuterium 3-10 ml/kg 3-7 ml/kg

Dissolved oxygen < 10mg/kg
pHRT 10.2-10.8 10.2-10.4
Lithium 0.4-1.1 mg/kg 0.5-0.7 mg/kg
IAEA TECDOC 1666

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 GENERAL CORROSION OF PRIMARY LOOP MATERIALS

Corrosion metals in aqueous environment involves various electrochemical and

chemical reactions at the material /environmental interface.

Primary loop materials undergo general corrosion in high temperature, neutral or

alkaline water to form thin oxides, with low corrosion rates.

288C
M + H2O Maq z+ + ze-

M + H2O MOnn- + 2nH+ + ne-

M + H2O MO + 2 H2O + 2e- (1)

Maq z+ + H2O MO + H+ (2)

(1)Oxidation
(2)Dissolution/precipitation

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 OXIDE LAYERS OF MATERIALS IN PRIMARY LOOP COMPONENTS

The composition and characteristics of the oxide layers formed in high temperature water
depend on the type of materials.
Carbon steels
Double oxide layer formed by Fe3O4

Tomlinson, 1981

Austenitic stainless steels

Outer layer: NiFe2O4
Inner layer: FeCr2O4

Nickel base alloys

Outer layer: Fe-Ni spinel ( Ni Fe2O4)
Inner layer: Ni (Cr,Fe)3O4 spinel
Terachi, 2005

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 OXIDE LAYERS OF MATERIALS IN PRIMARY LOOP COMPONENTS
Fe2+ Fe2+
Ni2+
Fe2+
Anions Ni2+ Double oxide layers is a consequence of different
diffusion coefficients and different transport rates
Outer layer NiFe2O4 + Fe3O4
of alloy elements.
Inner layer FeCr2O4
Fe and NI exhibit much higher transport rates than Cr.

Austenitic Alloy
Outer layer is porous and loosely adherent,
316L in PWR primary water, 320C formed by cristallites (from hundres nm-few m).

Inner layer is non porous and thightly adherent

It is the protective layer ( 200-500 nm)

Terachi, 2005 Terachi, 2005

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 OXIDE LAYERS OF MATERIALS IN PRIMARY LOOP COMPONENTS

Temperature and water chemistry ( B, Li, pH) have influence on thickness an properties of
oxide layer, but the influence of surface state is more accused

T and Cr content effect

Polished surface

Polished surface: Internal layer Cr rich, 50 nm

Ground surface : Internal layer Cr rich, 10 nm

Ground surface
Cisse, 2012
 Influence of Zn additions on general corrosion of primary loop materials

Zn additions inhibit the cobalt incorporation into the oxide layer of ex-core
regions (mainly iron and nickel chromites FeCr2O4, NiCr2O4and nickel ferrites
NiFe2O4) reduce activation

Zn2+ + CoCr2O4 Co2+ + ZnCr2O4

Zn2+ + FeCr2O4 Co2+ + ZnCr2O4

Substitute the cobalt ions already incorporated in the oxide structures.

Diminish the corrosion release from primary circuit material.

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Stability regions of spinel oxides in primary water

NI- base alloys Fe- base alloys

Miyajima, CORROSION 2001

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Reduction of corrosion rates and corrosion products release by Zn additions

Corrosion Corrosion release

Alloy (mg/dm2/month) (mg/dm2/month)
With Zinc Without With Zinc Without
Zinc Zinc
304 SS 1.1 3.5 0.1 1.3
316SS 1.3 3.5 0.1 1.4
600MA 1.5 2.6 0.3 0.8
600TT 0.5 2.1 0.2 0.9
690TT 0.2 1.3 0.1 0.6
X-750 0.6 2.6 0.2 1.2
Stellite 0.4 14.7 0.1 12.0

Corrosion product generation and transport to the core is reduced

In addition to this, PWSCC susceptibility of nickel alloys decreases

Zinc is added to the primary loop as Zinc acetate ( Zn(CH3COO)2 2H2O by

Its high solubility ( 430 g/l at 25C) and its high purity.
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 B0RIC ACID CORROSION

Corrosion of carbon and low-alloy steel (C&LAS) components by leaking borated

water has posed significant maintenance problems for PWR plants:
gasketed joints, valve packing, mechanical seals, CRDMs

The water can become oxygenated and the boric acid can concentrate as the water
boils off or evaporates.

Oconee 1

David Besse RPV

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 BORIC ACID CORROSION

The mode of corrosion of greatest concern due to leakage of borated water is

uniform corrosion, often called "wastage, of C&LAS

pH and oxygen influence

Corrosion rates are a function of oxygen concentration, pH, boron concentration

temperature and flow velocity.

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 Corrosion rates of C&LAS in environmental conditions postulated in the
CRDM nozzle/head crevice

In the absence of moisture , no corrosion was observed for any of the materials in
H-B-O environments at 150, 260 and 300C

In aerated saturated solution of boric acid at 97,5C and ambient pressure,

a corrosion rate of 40mm/y was measured in A533 Gr.-B

In deaerated solutions, corrosion rates were 40% lower

than in aerated one.

Corrosion rates up to 150 mm/y were measured at 150C

Typical values of Corrosion rates of C&LAS

in primary water are 0.025 mm/y.

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 FLOW ACCELERATED CORROSION (FAC) IN THE PRIMARY LOOP OF PHWR

PHWRs use carbon steels for the primary heat transport system (PHTS) piping that
connects the fuel channels to the rest of the PHTS circuits.

At the conditions of primary water at CANDU-6 reactor, pH ~ 10, magnetite is stable

and the corrosion rates of carbon steels are low.

But in particular locations as the outlet feeders with

Turbulent flow of Fe-unsaturated water

High mass transfer at tight radius bend

Corrosion rates of 175 m/y are been measured

The low Cr content of the outlet feeder materials Slade, 2005

promote this high corrosion rates

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 FLOW ACCELERATED CORROSION (FAC) OF C & LAS

Flow accelerated corrosion (FAC) is a degradation mechanism affecting metallic materials

(carbon steels) that not form tightly adherent passive surface films when the materials are
exposed to fluid flow environments in power reactor systems.

Water Single phase FAC

Steam + water Two-phases FAC
FAC does not occur in dry steam

FAC is a consequence of a flow-accelerated increase in mass transfer of

dissolving and reacting species at a high flow or highly turbulent location.

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 The surfaces experiencing single-phase FAC often look like "orange-peeled" and have
small cavities in them.
Areas with very high FAC rate can have a polished appearance with no cavities.
In certain areas, in which the rate of FAC is slow, pit-like features are encountered on the
surface.

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 Factors influencing rate of flow accelerated corrosion

Flow accelerated corrosion ( FAC) is an electrochemical corrosion process dependent:

Hydrodynamic factors : fluid velocity, pipe configuration, roughness pipe,.

FAC rate is controlled by mass transfer ( low fluid velocity) or by chemical reaction
water/ oxide ( high fluid velocity)

Corrosion rate increases when flow

increase. A maximum is found around 130C

The roughness of the surface increase the

dependence of mass transfer of the fluid
velocity.

Hydrodynamic disturbances, such as

elbows, tees, reductions in the pipes or
downstream of valves or control orifices
increase the FAC rate
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 Factors influencing rate of flow accelerated corrosion

Metallurgical factors: Chromium content

Cr concentration is critical for FAC resistance.

For concentrations < 0.04-0.05% there is not protection
Cr contents >0.2% are recommended
Alternative materials to the carbon steelsP11(1.25Cr-0.5Mo)
P22 (2.25Cr- 1Mo)
Single- phase FAC

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 Factors influencing rate of flow accelerated corrosion

Environmental factors: Temperature

Higher temperatures lower ferrous ion concentrations

Higher temperatures faster mass transfer

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 Factors influencing rate of flow accelerated corrosion

Environmental factors: pH and ECP

E-JAM Vol1, N4
Sturla, 1973

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