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ANRCP-1999-30 October 1999

Amarillo National Resource Center for Plutonium


A Higher Education Consortium of The Texas A&M University System, Texas Tech University, and The University of Texas System

Modeling of Beryllium Corrosion

Juan Sanchez, Sheldon Landsberger, and Li Zhao Mechanical Engineering Department The University of Texas at Austin

This report was prepared with the support of the U.S. Department of Energy (DOE) Cooperative Agreement No. DEFC04-95AL85832. However, any opinions, findings, conclusions, or recommendations expressed herein are those of the author(s) and do not necessarily reflect the views of DOE. This work was conducted through the Amarillo National Resource Center for Plutonium.

Edited by Angela L. Woods Technical Editor

600 South Tyler Suite 800 Amarillo, TX 79101 (806) 376-5533 Fax: (806) 376-5561 http://www.pu.org

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ANRCP-1999-30

AMARILLO NATIONAL RESOURCE CENTER FOR PLUTONIUM/ A HIGHER EDUCATION CONSORTIUM

A Report on

Modeling of Beryllium Corrosion

Juan Sanchez, Sheldon Landsberger, and Li Zhao Department of Mechanical Engineering The University of Texas at Austin Austin, Texas 77812

Submitted for publication to

ANRC Nuclear Program

October 1999

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Modeling of Beryllium Corrosion


Juan Sanchez, Sheldon Landsberger, and Li Zhao Department of Mechanical Engineering The University of Texas at Austin

Abstract
This research examined whether experiments concerning beryllium corrosion can be conducted at room temperature with no adverse affects. Because corrosion depends on the respiratory environment, mechanisms and parameters associated with corrosion must be identified. There are 3 stages in the evolution of storage conditions. The ability to identify beryllium corrosion at various stages would be ideal.

Actual temperature for beryllium metal cladding is approximately 50C. In calculating the Pourbaix diagram of beryllium at room temperature (50C) by Nerst equations, the diagram indicated a passivity range between pH 4 and pH 11. Comparing the passivity region at room temperature, almost no change at 50C could be seen; in effect, room temperature did not affect the passivity of beryllium in aqueous solutions.

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TABLE OF CONTENTS

1. INTRODUCTION ................................................................................................................... 1 2. IDENTIFICATION OF BERYLLIUM CORROSION....................................................... 2 3. THERMODYNAMIC CALCULATIONS FOR BERYLLIUM WITHIN CHLORINATE SOLVENTS ................................................................................................ 5 4. POURBAIX DIAGRAM OF BERYLLIUM AT 50C ...................................................... 11 5. CONCLUSIONS ................................................................................................................... 13 REFERENCES ........................................................................................................................... 15

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LIST OF FIGURES

Figure 1: Property Diagram of BeO in TCA ............................................................................... 6 Figure 2: Property Diagram of BeO in TCE ................................................................................ 6 Figure 3: BeCl2 in Solvents with Different Ratios of H/Cl.......................................................... 8 Figure 4: BeCl2 in Solvents with H/CL of Zero........................................................................... 8 Figure 5: The Property Diagram of BeO in CCl4 ......................................................................... 9 Figure 6: Pourbaix Diagram of Beryllium at Room Tempera*ture ........................................... 12 Figure 7: Pourbaix Diagram of Beryllium at 50C .................................................................... 12

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LIST OF TABLES Table 1: Product of BeCl2 in Different Solvents ......................................................................... 7

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1. INTRODUCTION In 1998, the research on a study of the corrosion of beryllium was performed in three areas: (1) mechanisms and parameters associated with corrosion have been identified by a literature review; (2) the

effects of the chlorinated solvents used in the cleaning process on beryllium corrosion have been considered by thermodynamic calculations; and, (3) the effect of temperature on the passivity of beryllium was described by Pourbaix diagrams.

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2. IDENTIFICATION OF BERYLLIUM CORROSION There are many published papers available about the corrosion of stainless steel, but just a few about beryllium corrosion. Because corrosion depends on the repository environment, such as temperature, and aggressive anions such as Cl-, mechanisms and parameters associated with corrosion must be identified. There are three stages in the evolution of storage conditions, called Phase 0, Phase 1, and Phase 2. The first stage, called Phase 0, is during the storageoperating period. During this period, dry

general corrosion and pitting corrosion may occur at ambient temperature because of the existence of sufficient oxygen and aggressive anions such as Cl-. The second stage, called Phase 1, occurs immediately after the containers have been sealed. In this stage, either dry or aqueous general corrosion may occur depending on the humidity in the container. Also oxygen is still available to cause pitting corrosion although oxygen is also consumed by the general corrosion. The third stage, called Phase 2, occurs after oxygen has been consumed. In this period, general corrosion becomes dominant and slow, and pitting corrosion does not happen.

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3. THERMODYNAMIC CALCULATIONS FOR BERYLLIUM WITHIN CHLORINATE SOLVENTS When beryllium is exposed in air at room temperature, a film of beryllium oxide forms quickly on the surface. Because beryllium alloys contain about 0.2% impurities of carbon, these carbon atoms can react with the water from air to form beryllium oxide as follows: Be2 C + 2 H 2 O 2 BeO + CH 4 Chloride ions are suspected to cause the beryllium pitting corrosion. These chloride ions can potentially come from three sources. First, beryllium metal contains chlorides; second, the Celotex packaging material contains chlorine and thus may be liberated as a chloride under the right environmental conditions; and third, chloride arises from the chlorinated solvents 1,1,1-trichloroethylene (TCA), and 1,1,2trichloroethane (TCE) during the process for cleaning weapons components. Given property diagrams of beryllium oxide in TCA, TCE, and carbon tetrachloride, one can predict the beryllium corrosion. These property diagrams were generated by simulating the interaction of beryllium oxide with TCA, TCE, and carbon tetrachloride by the computer program Thermo-Calc. Thermo-Calc is a powerful and flexible software for all kinds of thermodynamic parameters and phase

diagram calculations. It is used to predict properties of materials and processes. A system including BeO, CO2 , O2 , H 2 O, and the solvent at room temperature and at 1 atm pressure is used in Thermo-Calc. Although the operating temperature is about 50C in the actual cleaning processes, there are almost no differences at a temperature of 25 or 50C when comparing the property diagrams of BeO in TCA or TCE. Therefore, all calculations in this study were done at room temperature. The property diagrams of BeO in TCA and TCE are shown in Figures 1 and 2. These figures show that beryllium chloride is formed by exposing beryllium oxide to TCE, but not on exposing it to TCA. Therefore, the ratio of the hydrogen to chloride (H/Cl) in the solvents may play an important role to form the corrosion product, beryllium chloride. In order to reveal the influence of H/Cl ratio on the beryllium corrosion, the property diagrams for 20 chlorinated solvents having the ratio of H/Cl from 0 to 5 were done by Thermo-Calc. The results are shown in Table 1. These results suggest that (a) carbon is essential to form beryllium chloride from beryllium oxide, and (b) a ratio of H/Cl <1 in the solvent is essential for beryllium chloride to be formed. With a ratio of H/Cl 1 , no beryllium chloride is formed as the more stable HCl may be preferred to be formation. Results of changes of beryllium chloride with the H/Cl ratio shown in Figures 3 and 4.

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20

NP(Moles of Phase)

15

10

0 0 0.5 1 1.5 2 2.5

N(C2Cl3H3)/N(H2O)
Gas H2O(L) BeO(S)

Figure 1: Property Diagram of BeO in TCA

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20 NP(moles of Phase)

15

10

0 0 0.5
Gas

1 1.5 N(C2Cl3H)/N(H2O)
H2O(L) BeO(S)

2
BeCl2(Beta)

2.5

Figure 2: Property Diagram of BeO in TCE

Table 1: The Product of BeCl2 in Different Solvents H/Cl C BeCl2 Name Formula in in Product the Solvent the Solvent Carbon tetrachloride CCl4 Yes 0/4 1 Chloroform CCl3H Yes 1/3 1 Dichloromethane CCl2H2 No 2/2 1 methyl chloride CClH3 No 3/1 1 Tetrachloroethylene C2Cl4 Yes 0/4 2 trichloroethylene C2Cl3H Yes 1/3 2 dichloroethylene C2Cl2H2 No 2/2 2 vinyl chloride C2ClH3 No 3/1 2 hexachloroethane C2Cl6 Yes 0/6 2 pentachloroethane C2Cl5H Yes 1/5 2 tetrachloroethane C2Cl4H2 Yes 2/4 2 trichloroethane C2Cl3H3 No 3/3 2 ethylene dichloride C2Cl2H4 No 4/2 2 ethylene chloride C2ClH5 No 5/1 2 hexachlorobenznene C6Cl6 Yes 0/6 6 Yes 1/5 6 pentachlorobeznene C6Cl5H1 tetrachlorobenznene C6Cl4H2 Yes 2/4 6 trichlorobenznene C6Cl3H3 No 3/3 6 dichlorobenznene C6Cl2H4 No 4/2 6 monochlorobenznene C6ClH5 No 5/1 6 Figure 3 shows that BeCl2 increases as the ratio of solvent to water increases and as the H/Cl ratio decreases, while Figure 4 shows the same pattern even with a H/Cl ratio of zero. Considering these results, it suggested to use the solvents with less carbon containing a higher ratio of H/Cl in the cleaning process. However, these predictions, based on theoretical calculations, need to be verified experimentally. In addition, the effect of the solvents with a ratio 1 needs to be experimentally assessed. In order to find the influence of Cl- in Celotex on beryllium metal, CCl4 is chosen to simulate the reaction between BeO and Cl-. The property diagram is shown in Figure 5. From Figure 5, it can be deduced that Cl- in CCl4 causes corrosion of BeO to form the product of BeCl2. Therefore, Cl- in Celotex can potentially lead to beryllium corrosion.

7 6 5 4 N(BeCl2) 3 2 1 0 0 0.5 1 1.5 2 2.5 N(Solvent)/N(H2O )

H/Cl=0.2

H/Cl=0.33

H/Cl=0.5

CCl3H (H/Cl=0.33) C2Cl5H(H/Cl=0.2)

C2Cl3H(H/Cl=0.33) C2Cl4H2(H/Cl=0.5)

C6Cl5H(H/Cl=0.2) C6Cl4H2(H/Cl=0.5)

Figure 3: BeCl2 in Solvents with Different Ratios of H/Cl

12 10 8

N(BeCl2)

6 4 2 0 0 0.5 1 1.5 2 2.5

N(Solvent)/N(H2O)
CCl4 C2Cl4 C6Cl6 C2Cl6

Figure 4: BeCl2 in Solvents with H/Cl of Zero

25 20 NP(moles of Phases) 15 10 5 0 0 0.5 Gas 1 1.5 N(CCl4)/N(H2O ) H2O(L) BeO(S) 2 BeCl2(Beta) 2.5

Figure 5: The Property Diagram of BeO in CCl4

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4. POURBAIX DIAGRAM OF BERYLLIUM AT 50C Many investigations of beryllium passivity as a function of solution pH have been published. The Pourbaix diagram (or potential-pH diagram) of beryllium at room temperature, available in the literature, indicates a passivity region from a pH 4 to pH 11 (Figure 6). However, the actual temperature for the beryllium metal cladding is around 50C. In order to understand the passivity of beryllium to changes with the temperature, the Pourbaix diagram of beryllium at 50C was done by calculating Nerst equations. The general reaction for a half-cell can be written:
aA + bB = cC + dD

electrons exchanged in the reaction; F is Faraday's constant, and a is the activity of reactants or products in the reaction. Reactions of beryllium involved in the Pourbaix diagram are as follows: Be = Be + + + 2e Be + + + H 2 O = BeO + 2 H + Be + H 2 O = BeO + 2 H + + 2e 2 BeO + H 2 O = Be2 O32 + 2 H + (a) (b) (c) (d)

2 Be + 3H 2 O = Be2 O32 + 6 H + + 4e (e) The Pourbaix diagram of beryllium at room temperature was done according to Nerst equations for above reactions of beryllium in Figure 6. The Pourbaix diagram of beryllium at room temperature agrees with the published literature in which a passivity region is located from a pH 3.4 to pH 11.6. A Pourbaix diagram of beryllium at a room temperature of 50C was also done (Figure 7). Figure 7 also shows that a passivity region is located from a pH 3.5 to pH 10.5. Comparing to the passivity region at room temperature, there is almost no change at 50C. Therefore, the actual temperature (50C) does not affect the passivity of beryllium in aqueous solutions significantly, and the data associated with beryllium corrosion at room temperature are applicable to an actual situation.

(1)

where a is the mole of reactant A ; b is the mole of reactant B ; c is the mole of product C , and d is the mole of product D. Nerst equation for the general reaction (1) is as follows:
E = E0 acad RT a c a d 2.3RT ln a b = E 0 log a b nF nF a a a a

(2)

where E is the half-cell electrode potential; E 0 is the half-cell electrode potential at standard state; R is the gas constant; T is absolute temperature; n is the number of

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-1.0 -1.1 -1.2 -1.3

(b)

-1.4 -1.5 -1.6 -1.7

(d)

Corrosion Be
++

Passivition BeO

Corrosion B e 2O 3
2-

-1.8 -1.9

Potential (V)

-2.0 -2.1 -2.2 -2.3 -2.4 -2.5

(a)

(c)

Immunity
-2.6 -2.7 -2.8 -2.9 -3.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

(e)

Be

pH

Figure 6: Pourbaix Diagram of Beryllium at Room Temperature

-1.0 -1.1 -1.2 -1.3

(b)

-1.4 -1.5 -1.6 -1.7 -1.8 -1.9

Corrosion Be
++

Passivition BeO

(d)

Corrosion O3 Be 2
2-

Potential (V)

-2.0 -2.1 -2.2 -2.3 -2.4 -2.5

(a)

(c

Immunity
-2.6 -2.7 -2.8 -2.9 -3.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

(e )

Be

pH

Figure 7: Pourbaix Diagram of Beryllium at 50C

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5. CONCLUSIONS It is essential for the study of beryllium corrosion to identify it during different periods. The chlorinated solvents can cause the beryllium corrosion because they have the ratio of H/Cl <1 with the existence of carbon. Beryllium dichloride increases as the ratio of H/Cl decreases.

Thus, it is suggested that the solvents used in the cleaning process have low carbon and a high ratio of H/Cl. In addition, there is no effect of temperature on the passivity of beryllium at 50C compared to room temperature. Thus, experiments about beryllium corrosion can be done at room temperature, and the data can be applicable.

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REFERENCES 1. Birkbeck, J. C., Kuehler, N. L., and Moddeman, W. E. (1997). X-ray photoelectron spectroscopic (XPS) examinations of beryllium metal surfaces exposed to chlorinated solvents. The Journal of Surface and Interface Analysis (to be published). 2. Henshall, G. A. (1996). A phenomenological approach to simulating the evolution of radioactivewaste container damage due to pitting corrosion. Materials Research Society Symp. Proc. 412, 613-619. 3. Hill, M. A., Butt, D. P., and Lillard, R. S. (1997). The passivity and breakdown of beryllium in aqueous solutions. The Journal of the Electrochemical Society, 145(8), 2799-2806. 4. Hill, M. A., Butt, D. P., and Lillard, R. S. (1996). The corrosion/ electrochemistry of beryllium and beryllium weldment in aqueous chloride environment. Internal Los Alamos National Laboratory Report to be distributed to Pantex and Lawrence Livermore National Laboratory Personnel. 5. Jones, D. A. (1996). Principles and prevention of corrosion (2nd ed.). Upper Saddel River, NJ: Prentice-Hall, Inc. 6. Korb, L. J., Olson, D. L. et al. (1987). Metals handbook (9th Ed.) V. 13. Metals Park, OH: American Society for Metals. 7. Lee, J. H., Atkins, J. E., and Andrews, R. W. (1996). Humid-air and aqueous corrosion models for corrosionallowance barrier material. Materials

Research Society Symp. Proc., 412, 571580. 8. Lillard, R. S., Hill, M. A., and Butt, D. P. (1997). Preliminary investigation into the corrosion of beryllium exposed to Celotex and water. Internal Los Alamos National Laboratory Report to be distributed to Pantex and Lawrence Livermore National Laboratory Personnel. 9. Marsh, G. P., Bland, I. D., and Taylor, K. J. (1988). Statistical study of pit propagation in carbon steel under nuclear waste disposal conditions. British Journal of Corrosion, 23(3), 157-164. 10. Mellan, I. (1977). Industrial Solvents Handbook. Park Ridge, NJ: Noyes Data Corporation. 11. Pourbaix, M. (1974). Atlas of Electrochemical Equilibria in Aqueous Solutions (2nd). Houston, TX: National Association of Corrosion Engineering. 12. Shoesmith, D. W., King, F., and Ikeda, B. M. (1996). The indefinite containment of nuclear fuel wastes. Materials Research Society Symp. Proc., 412, 563-570. 13. Shoesmith, D. W., Ikeda, B. M., and King, F. (1992). Effect of radiation on the corrosion of candidate materials for nuclear waste containers. Materials Research Society Symp. Proc., 412, 563-570. 14. Stonehouse, A. J., and Beaver, W. W. (1965). Beryllium corrosion and how to prevent it. Materials Protection, January, 24-28.

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