ML22271A816
| ML22271A816 | |
| Person / Time | |
|---|---|
| Site: | Orano USA |
| Issue date: | 06/27/2009 |
| From: | AREVA |
| To: | Division of Fuel Management |
| Garcia-Santos N | |
| Shared Package | |
| ML22271A128 | List:
|
| References | |
| A33010, EPID L-2022-DOT-0007 | |
| Download: ML22271A816 (9) | |
Text
TN International NOTE ON THE CHARACTERIZATION OF RESIN FS 69
[PACKAGE FS 69 RESIN]
Names Signatures Dates Prepared by Verified by Réf.
NTC 00118662E-NPV Rév 1E Approved by Form : PM04-3-MO-3E rév. 1 Page 1/9 Non-proprietary version TABLE OF CONTENTS 1.
PURPOSE.......................................................................................................................... 2 2.
DESCRIPTION OF THE RESIN.................................................................................... 2 3.
CHEMICAL COMPOSITION........................................................................................ 2 4.
NEUTRON ABSORPTION EFFICIENCY <3>............................................................ 5 5.
PHYSICAL CHARACTERISTICS................................................................................ 6 6.
MECHANICAL CHARACTERISTICS......................................................................... 7 7.
THERMAL BEHAVIOR................................................................................................. 7 8.
REFERENCES.................................................................................................................. 9 REVISION STATUS Revision Date Modifications Prepared by /
Verified by 0
27-05-08 Translation to English New Address for TN International 1E 27-06-09 Update A
AREVA I
I I
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 2 / 9 Non-proprietary version
- 1. PURPOSE The purpose of this note is to make available a variety of useful information regarding the resin used in the FS 69 package. Henceforth, the aforementioned resin will be called Resin FS 69.
At first, people are reminded that the resin is the property of TN International.
This note is intended for use by AREVA-NP within the framework of the resin supply agreement for the concept of the modified FCC package. It has been used as basis for the setting of the AREVA-NP note TFX.DC.2116, in the framework of the redaction of the safety analysis report of the FCC packaging.
This document also includes a bibliography of literature describing the qualifications and qualities of Resin FS 69.
- 2. DESCRIPTION OF THE RESIN It acts as a polyester resin, composed of approximately 60% aluminum hydrate, glass fibers, and zinc borate <1>. Before polymerization, the resins viscosity allows it to flow through complex piping structures. After polymerization, the resin has a white color and is solid, machinable, and fire resistant. Interest in this resin lies in its neutron absorption capacity.
- 3. CHEMICAL COMPOSITION 3.1 Pre-Fired Composition Chemical analysis of the resin is shown below in weight percentage:
ELEMENTS H
O C
Al B
Zn Si Mg
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 3 / 9 Non-proprietary version The contents of H and B given are the minimal median values in a casting.
They are affected locally and have the following uncertainties:
H: +/- 0,1 B: +/- 0,2 3.2 Post-Fire Composition The resin was subjected to various fire tests in order to determine the evolution of its hydrogen and boron content.
3.2.1 Furnace Fire Test <2>
The conditions of this test were the following: a sample of Resin FS 69 was contained in a cylinder 60 mm in diameter and 60 mm tall and was subjected to fire between 600°C and 800°C for 1/2 an hour (corresponding to the increase in temperature of the furnace due to its being opened to introduce the sample), then another 1/2 hour at 800°C. This fire test is very penalizing.
The sample was then placed in a stainless steel cup with a thickness of 1mm so that the top face of the sample exposed to heat was protected by the steel.
This test affected the first mm of the resin but the remaining mm retained their pre-fire properties.
The resin lost between 90% and 0% of its hydrogen content in the first mm. Taking into account the resins hydrogen content gradient, this loss is equivalent to losing 100% of the hydrogen content in the first mm (thus allowing the statement that the resin was unperturbed after mm).
A boron gradient was also established in the material. The average boron loss after the fire test was %.
3.2.2 Direct Flame Fire Test <11>
The resin was subjected to the direct flame of a blowtorch. The conditions of the test were as follows: three cylindrical samples of Resin FS 69 (diameter of 240 mm, height of 60 mm) were prepared, subjects were placed in the 800°C flame for 1/2 an hour, and analysis was then performed.
The flame was applied on the axis of each sample, with temperature measured by three 20 mm diameter thermocouples at 10, 25, and 50 mm away from the exposed face.
Whatever the sample tested and for the whole term of the test or beyond, the temperature remains below 85°C at the distance of mm of the exposed surface.
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 4 / 9 Non-proprietary version Analyses of B, H and Zn contents have been performed for different thicknesses. The Zn content can be considered as constant regarding to its melting temperature so the content of B and H, in a same section, could have been quite precisely estimated.
The first sample was subjected to the direct action of the flame. The flame created a crater of charred, crumbling resin mm in diameter with a maximum depth of mm.
Hydrogen content was found to vary in the first mm: 86% of hydrogen content was lost on the burned surface, but there was no more than 19% loss mm from the surface. This loss of hydrogen is equivalent to a 100% loss to a thickness of mm from the surface.
The average boron content loss was found to be %.
The second sample was protected from the flame by a steel sheet 1 mm thick. The impact of the flame left a charred, crumbling crater mm in diameter with a maximum depth of mm. The steel sheet bent during the test because of the large amount of heat, obviously inducing a concentration of heat straight to the flame.
Therefore, the elemental analysis results were less favorable than for the first sample. For depths from 0 to mm from the burned surface, 83% of the hydrogen content vanished, which is equivalent to 100% of hydrogen content at a depth of mm. The average boron content loss was found to be %.
The third sample was protected by two 1 mm steel sheets separated by a 5 mm gap at the center of the sample. The impact of the flame left a charred, crumbling crater mm in diameter and mm in depth.
For depths from 0 to mm from the burned surface, 81% of the hydrogen content vanished, equivalent to 100% at a depth of mm.
The average boron content loss was found to be %.
During these tests, the thermocouples placed in the samples made it possible to obtain variations in temperature in each sample. It was therefore possible to establish a correlation between the maximum percentage loss of hydrogen and the maximum temperature of the resin.
Several examples are displayed in the table below:
Resin Temperature
% Hydrogen Loss 810°C (External layer in direct contact with heat source)
< 86%
200°C (Internal layer of material)
< 23%
125°C (Internal layer of material)
< 10%
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 5 / 9 Non-proprietary version The values of the table above are not exact values, but are conservative estimates. These values are usable whatever the fire test carried out.
The conclusions of the elementary comparatives analyses are recapitulated in the table below:
Element Resin only Resin protected by a sheet of steel Resin protected by a split sheet of steel H
loss 100%
over e = mm loss 100%
over e = mm loss 100 %
over e = mm B
Average loss Average loss Average loss These values are envelope values, which have to be used in the safety demonstrations and particularly in the criticality analyses.
The values shown above are not directly representatives of physics phenomena because there is actually a content gradient of B and H in the thickness of the resin. These values can not be used to establish a relation with values obtained via thermal calculations in accidental transport conditions.
- 4. NEUTRON ABSORPTION EFFICIENCY <3>
Resin FS 69 is used to attenuate neutron radiation coming from the contents of the package. Neutron shielding calculations were carried out for various thicknesses of the resin placed around fresh, combustible PWR fuel (UO2, the uranium from reprocessing).
The unit dose rates due to neutron radiation by both the (,n) reaction and spontaneous fission according to resin thickness considerations are given below.
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 6 / 9 Non-proprietary version Unit Neutron Response for (alpha-neutron) and (spontaneous fission) vs. Resin Thickness
- 5. PHYSICAL CHARACTERISTICS 5.1 Density The minimal density of Resin FS 69 is g/cc.
The nominal density is +/- g/cc (measured according to the NFT 51 063 standard in water at 22°C) <4><5>.
5.2 Thermal Conductivity The thermal conductivity of Resin FS 69 between 20 and 150°C is as follows <6>:
Temperature (°C)
Thermal Conductivity (W/(m.K))
30
+/- 0,035 100
+/- 0,03 150
+/- 0,04
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 7 / 9 Non-proprietary version 5.3 Heat Capacity The heat capacity of Resin FS 69 between 20 and 160°C is as follows <6>:
Temperature (°C)
Cp (J/(g.°C))
20 40 60 80 100 120 140 160 5.4 Thermal Expansion Coefficient The maximum thermal expansion coefficient is:
= mm/(mm.K) <1>
- 6. MECHANICAL CHARACTERISTICS Compression tests were also carried out on tubes 19,85 mm in diameter and 40 mm in height. Between the three samples tested, the compression modulus had an average value of MPa at 20°C (average value for 3 samples tested) <7>.
It should be noted, though, that Resin FS 69 does not contribute to the packaging structural resistance in the modes in which it has be implemented to date. This information, therefore, is of a secondary nature.
- 7. THERMAL BEHAVIOR 7.1 Temperature in Normal Use 7.1.1 Thermal Aging of Resin F Tests have been carried out on a resin known as Resin F, which is made up of the same components as Resin FS 69 but in different proportions. Resin F does not have glass fibers but its allotment of aluminum hydrate is larger than that of Resin FS 69.
Temperature aging kinetics is one of the attributes of resins that is closely tied to the chemical degradation of aluminum hydrate.
Tests have made it possible to define the evolution of the loss of mass and loss of hydrogen after 10 years at 155°C <8>.
It appears that the total hydrogen loss in Resin F does not exceed 5% after one 10 year period in the normal usage mode.
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 8 / 9 Non-proprietary version 7.1.2 Thermal Aging in Resin FS 69 Thermal aging without containment appears most particularly by a loss of mass <1>.
Below 90°C, the permanent loss of mass mode can be taken as stationary.
Beyond, loss of mass can be broken up into two successive phases in time:
an initial transitory phenomenon, lasting approximately a few tens of days, of fast, pseudo-exponential evolution a permanent evolutionary mode which is quasi-linear <9>
At a temperature of 125°C, the permanent mode stabilizes at a loss of mass of 0,7% after 100 days.
It is important to note that the loss of mass in Resin FS 69 is less important than in Resin F, because it has less aluminum hydrate. Accordingly, it is possible to deduce that the hydrogen loss of Resin FS 69 over time matches at most, the hydrogen loss of Resin F.
Therefore, we consider 155°C a valid temperature for permanent mode calculations, for hydrogen loss of Resin FS 69 will not exceed that of Resin F, which is approximately 5% after 10 years.
7.2 Behavior in Fire 7.2.1 Automatic Extinguish-ability The tests carried out for the qualification of Resin FS 69 <1> showed that it is self-extinguishable when it was subjected to a direct flame at 950°C.
7.2.2 Carbonized Test The first test followed the framework of the regulatory first test for Resin FS
- 69. The examination of the resin samples in both the bench and doors showed that:
the resin thickness (initially 50 mm) had remained intact in the central portion of the bench the charred resin thickness in the doors did not exceed 5 mm (at the portion near the bench) 7.2.3 Degasification Due to Temperature An analysis of gas production by a sample of Resin FS 69 heated at 125°C was carried out <1> in order to both highlight the nature and quantity of produced gas emissions as well as identify, if required, any toxic components.
TN International Réf. NTC-08-00118662E-NPV ; Rév. 1E Page 9 / 9 Non-proprietary version Analysis highlighted that the major gas released was styrene ( µg/g of resin). Also released was a concentration of very weak (less than g/g of resin total) hydrogen, nitrogen, oxygen, carbon monoxide, xylene type compositions and methyl-ethyl-benzenes.
Steam was also produced by the heating of the sample, depending on the amount of chemical degradation of aluminum hydrate. This lead to a loss of mass of the sample and a loss of hydrogen content, additionally quantified within the framework of the aforementioned entire life tests (see paragraph 7.1.2 above).
- 8. REFERENCES The documents quoted below are maintained in the data bases of the establishment producing this note. These documents are confidential and are property of TN International.
<1>
"Rapport de qualification de la résine FS 69" - 9856-R-9 Rév. 0 du 27.05.88.
<2>
<< Evolution de la composition chimique de la résine FS 69 aprs un essai de feu sur maquette >> - 10556-B-3 Rév. 0 du 29/04/98.
<3>
<< Efficacité décran de la résine FS 69 >> - 10373-B-2 Rév. 0 du 28/04/98.
<4>
Rapport du Ple de Plasturgie de lEst - n° FS 69-P2 Rév. A.
<5>
"Mesures de densité de D.S.C. sur échantillons de coulée" - 96/08/FJ Rév. 0.
<6>
Rapport dessais << Caractérisation de la conductivité thermique >> - bon de commande n° 162 - UMR CNRS 6607 du 7 mai 1998
<7>
Essais de compression - Laboratoire National dEssais - 05/05/98
<8>
"Evolution de la perte de performance en blindage neutronique due au vieillissement. Cas des compound F" - 1001-B-01 Rév. 0 du 05.04.93.
<9>
"Bilan sur R & D résines - vieillissement des résines polyesters" - 1001-B-02 Rév. 0 du 29.11.96
<10>
"Rapport dexamen de la résine du banc aprs essai de feu réglementaire" -
9856-R-5 Rév. 0 de 06.05.87.
<11>
Evolution de la composition chimique de la résine du banc aprs un essai de feu sur échantillons. 10556-B-8 Rév. 0 du 12/01/99.
The consultation of the above documents is possible at our office, located 1 Rue des Hérons, 78180, Montigny le Bretonneux - France, by written request addressed to TN International, subject to our acceptance.