SCIENCE-21

Method to Identify the Damage of Concrete due to Sodium Fire

n EXECUTIVE SUMMARY
Hot sodium coming in contact with structural concrete in case of sodium leak in Fast Breeder Reactor system cause damage as a result of thermo-chemical attack by burning sodium. A method has been developed to identify and quantify the damage caused by the sodium fire on concrete. The method involves determination of the Ca(OH)2 content in concrete samples using Differential Thermal Analysis technique. It is known that Ca(OH)2 decomposes in the temperature range of o o 480 C to 500 C. The peak area at this temperature corresponds to the quantity of Ca(OH)2. This compound is formed during the setting of the cement and it is present in the microscopic pores formed. Decomposition of this compound leads to increased porosity, which in turn leads to damage and loss of strength.

n OUTLINE
Accidental spillages or leakages of hot liquid sodium (~ 550C) used as the coolant in Liquid Metal Cooled Fast Breeder Reactors result in sodium fire and interaction with the structural concrete as well. The sodium-concrete interaction is initiated by the highly exothermic reaction between sodium and water reaction with the production of hydrogen. The major source of water for such interaction comes from the dehydration of concrete at high temperature. Water is present in concrete as free and bound. While the free water is the quantity present in the pores, the bound water is predominantly in the form of Ca(OH)2 which results from the hydration of two major components, i.e. tricalcium silicate and di-calcium silicate present in cement. The reactions take place as follows.
10.0 600 0.0 500

Ref. Temperature (oC)

400 300 200 100

-10.0

-20.0

-30.0

2(3CaO.SiO2 ) + 7 H 2 O 3CaO.2SiO2 .4 H 2 O + 3Ca (OH ) 2 2(2CaO.SiO2 ) + 5H 2 O 3CaO.2SiO2 .4 H 2 O + Ca (OH ) 2

Ca(OH)2 formed decomposes endothermically in the temperature range 480 C to 500 C. according to the reaction

-40.0 0 -50.0 0
500 1000 1500 2000 2500 3000 3500 4000 4500

Time(s)
Fig 1: Thermogram of unreacted sample

Ca (OH ) 2 ( s ) CaO ( s ) + H 2 O( g )
DTA is a convenient method to estimate the Ca(OH)2 content through its characteristic decomposition.
Ref. Temperature (oC)
600

400

300 Interacted concrete Reduction in Mass

(%) of Ca(OH)2:20 (%w/w)

-25.0

Fig.1 and Fig. 2 show the typical results of DTA on concrete samples with and without sodium interaction for the Ca(OH)2 content respectively. Measurement of the compressive strength of concrete samples with different degree of interaction with sodium is being carried out. Correlation of Ca(OH)2 content and compressive strength can thus quantify the damage caused by sodium interaction. This approach to quantify the damage caused by sodium interaction can be regarded as a scientific or technological breakthrough.

200

100

-50.0

0 0

500

1000 1500 2000 2500 3000 3500 4000

Time(s)
Fig. 2: Thermogram of reacted sample

42

DTA Signal (mV)

A state of the art Differential Thermal Analysis (DTA) system with all the necessary peripherals has been indigenously developed at SED, IGCAR, with the help of an Indian manufacturer, M/s BYSAKH, Kolkata. The system has been calibrated with suitable reference materials from 100 oC to 1000 oC.

500

0.0

DTA Signal (mV)

SCIENCE-21
n ADDITIONAL INFORMATION
The damage evaluation of concrete has also been done by measuring the penetrated sodium content using Atomic Absorption Spectrometry (AAS). This method involves digestion of the sample using acids and then submitting for sodium determination. In addition, the influence of other major cations, especially Calcium, will interfere with the quantitative determination of sodium. Thus the damage determination using DTA not only involves less time but also highly specific and quantitative.

n GENERAL EXPLANATION RELATED TO THE DESCRIPTION

Limestone concrete blocks with a square cavity to hold liquid sodium were exposed to sodium fire at 550C for a period of 30 minutes. Then the remaining unburnt liquid sodium was transferred by suction. Subsequently the surface of the cavity was cleaned with alcohol to remove left over sodium. Samples were collected from the interacted surface for a depth of 50 mm at 10 mm intervals. These samples were subjected to DTA as described above. The content of Ca(OH)2 at various depths as obtained from the peak area at 480 C from DTA (Fig.3) shows that the concentration is increasing linearly up to about 40 mm depth of interacted concrete. Thus it is clear that DTA is a sensitive means to obtain the Ca(OH)2 content, which in turn is an indicator of the concrete damage.
7.0 6.5 6.0

Amount of Ca(OH)2 (%)

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 10 20 30 40 50

Depth from the interacting surface (mm)

Fig. 3 : Variation of Ca(OH)2 content in one of the interacted blocks

n BRIEF DESCRIPTION OF THEORETICAL BACKGROUND

In the event of sodium fire on a concrete surface, the temperature at the interface may be about 500 C. At this temperature the Ca(OH)2 present in the concrete formed during the setting of cements will decompose . This compound provides strength to the concrete through binding the C-S-H (calcium silicate hydrate) gel with the aggregates. Thus an estimation of this compound will provide an insight into the degradation behaviour of the concrete exposed to high temperature sodium fire.

n ACHIEVEMENT
Thermal analysis of sodium interacted concrete specimens was carried out to determine the Ca(OH)2 content which is responsible for the strength of the concrete. The relative variation of this quantity in the specimens collected from a sodium interacted concrete block as a function of depth revealed that the concrete layer does not show appreciable degradation beyond 30 mm from the sodium-concrete interface. This has been used in deciding to provide a 50 mm sacrificial layer of special concrete in the Steam Generator Building of PFBR.

n PUBLICATIONS ARISING OUT OF THIS STUDY AND RELATED WORK

K. Sivasubramanian, V.Gopalakrishnan and F.C.Parida, Proc. of International Symposium on Material Chemistry, Dec.2006, Mumbai.

Further inquiries: Shri K. Sivasubramanian and Shri N. Kasinathan, Safety Engineering Division, Safety Group IGCAR, e-mail: nkasi@igcar.gov.in

43