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Testimony Re Contentions 2(e)(3),2(e)(4),2(j) & 2(k) Relating to Corrosion in General,Surveillance Program, Possible Boral Corrosion & Swelling & Possible Degeneration of Boral Density.W/Supporting Documents
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Issue date:	05/31/1979
From:	Draley J; ARGONNE NATIONAL LABORATORY
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	NUDOCS 7907110706
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IE 23IIC CCC.IITi RCOM UNITED STATES OF AMERICA NUCLEAR REGULATORY COMMISSION BEFORE THE' ATOMIC SAFETY AND LICENSING BOARD In the Matter of Commonwealth

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Docket Nos.

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Edison Company (Zion Station,

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Contentions 2 (e) (3) :

Corrosion 2 (e) (4 ) :

Surveillance Program Contention 2 (j )

Possible Boral Corrosion and Swelling Contention 2 (k)

Possible Degeneration of Boral Density May 31, 1979 308 043

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7907110706 br

Testimony relative to Commonwealth Edison Company proposed change to Operating License for Zion Nuclear Plant by J.

E.

Draley.

My testimony is in the form of general statements concerning corrosion and related reactions of the stainless steel /Boral storage rack tubes, followed by specific replies to the contentions of the State of Illinois, as identified as issues in this case by the NRC Licensing Board in the Board's " Order Following Prehearing Conference," January 19, 1979.

A statement of my professional qualifications is attached, as are the references which appear in this testimony.

GENERAL STATEMENTS CONCERNING CORROSION A.

Boric Acid Solution The solution used in the Zion spent fuel storage pool contains boric acid dissolved in high purity dionized water.

The solution is purified by passing a stream (approx.

100 gallons per minute) through a mixed bed ion exchanger that does not remove boric acid substantially.

This purifi-cation process has not been run at all times and the concentration of the boric acid has not been constant.

The average concentra-tion of boron has been a bit less than 2500 parts per million (ppm), ranging from 2000 to perhaps 2520 ppr and the typical pH has been 5.4, ranging from 4.7 to 5.6 in one period.

The

" normal" temperature of the pool water is 70 F, calculated 398 044

. to increase to 111 F when a 1/3 tore discharge of spent fuel is added (143 F if only one of the tw3 cooling heat exchangers is operating).

Boric acid is typically a benign che.T.ical in other-wise pure water from the point of view of corrosion, so long as the pH is not too low.

A significant adverse effect on the aluminum corrosion can be predicted if the pH is below about 4, depending on the temperature, the presence of other solutes, and the rate of flow of solution past the metal surface.

B.

Corrosion of Type 304 Stainless Steel In pure waner at storage pool temperatures, the uniform corrosion over the surface of austenitic stainless steels such as Type 304 is so slow as to challenge the ability of experimenters to measure it.

In fact, I know of no accu-rate measurement of this corrosion rate.

In my judgment the uniform penetration of 304 stainless steel is likely to be less than one ten thousandth of an inch in 40 years exposure to high purity water or to the 2500 ppm boric acid solution.

Under some circumstances, stainless steels, includ-ing Type 304, are susceptible to stress corrosion cracking.

However, there is considerable experience with stainless steel racks and pool liners.

No stress corrosion cracking of either has been found, even in weld-sensitized and residual stress regions,(1) and none is expected to occur in the Zion pool.

308 045

. In sufficiently aggressive solutions such as those containing a high concentration of chloride ion, and espe-cially in the presence of crevices, stainless steel has been known to suffer localized attack or pitting.

This type of attack has not been observed in storage pool water and is not expected to occur for the lifetime of the Zion pool.Il)

C.

Boral This product is manufactured by Brooks and Perkins, Inc., and, for Zion, consists of about 48% by weight of baron carbide (b C) particles embedded in a matrix of commercially 4

pure (1100) aluminum.

The size of the B C particles is given as60-200 mesh.

This boron carbide-aluminium material is formed into a plate, clad with 1100 aluminum on both sides.

The same aluminum alloy is inserted between the cladding plates at each end so that the resultant piece, after cutting for use in the racks, is covered on four of the six sides by 1100 aluminun; the side edges are left without cladding.

As in the case of stainless steel, the actual corrosion rates of aluminum alloys such as 1100 are so low after an initial period of exposure to pure water as to have challenged the skill of experimenters to determine it.

In fact our own observations for tests running nearly three years have shown that after an initial period lasting for several days the amount of corrosion increases only very slowly with further exposure times for temperatures of 50 C (122 F) and 70*C (158 F) in pure water.

At 70*C, after theO

. initial period, the amount of corrosion has been shown to vary with the logarithm of time for at leart two years. (2) The logarithmic intercepts and rate constants published in 1967 by Draley, Mori, and Loess (3) indicate that for storage pool temperatures the amount of uniform corrosion of 1100 aluminum should not exceed one ten-thousandth of an inch in 40 years of exposure in high purity water. Tests in boric acid have not, to my know1' edge, extended long enough to predict with precision the uniform corrosion rate to be expected. Short-term tests have shown that less corrosion occurs in the presence of a dilute boric acid solution than in water but it cannot confidently be stated that the corro-sion after 40 years will be as low as or less than that for pure. water. Consequently, I can only conservatively judge that the amount of corrosion in boric acid solution in the storage pool should be less than one thsusandth of an inch in 40 years of exposure. There has been enough testing of the bare edges of Boral in which the aluminum-boron carbide core material and the 1100 aluminum cladding is exposed to show that little or no accelerated corrosion occurs. For example, Weeks (4) reports no measurable deleterious attack in 19-1/2 years exposure in the Brookhaven Medical Research Reactor. In pure water or in boric acid concentrations not exceeding those in the storage pool no stress corrosion crack-ing or significant pitting is expected of Boral. 308 047

. D. Boral-Stainless Steel Couples When dissimilar metals are held in electrical con-tact, the corrosion of the metal that is electrochemically more active is sometimes accelerated and the corrosion of the metal that is electrocnemically more noble is sometimes retarded. The increased corrosion of the more active metal is known as galvanic attack. In the present instance, 1100 aluminum and the layered Boral product are anodic to or more active than the stainless steel jacket. In deionized water, essentially free of chloride ion, galvanic attack of aluminum coupled to stainless steel is very slight as long as the water purity remains high. In the presence of boric acid solution, at concentrations corresponding to the sto-rage pool water, one can expect some pitting of the edges of the Boral plates and perhaps the 1100 aluminum cladding when the electrical contact with the stainless steel jacket is good. The extent of pitting is not readily predictable because of lack of sufficient data in boric acid solution representatize of that expected within the Zion tubes and uncertaintier in the contact resistanct between the two metals that form insulating oxide films in air prior to fabri-cation and in the presence of water or boric acid solution when exposed to that environment. In any event, the resultant galvanic pitting is likely to slow down to such a low rate as to lead to little further pentration. The explanation for this nearly self-limiting process is probably related to the 048 Sgg

. very limited conductivity of the solution throtgh pores in the oxide that covers the growing pit. It is necessary for such ionic conductivity in the solution for the pit to-continue to propagate. The formation of pits of limited depth and the expected existenct of oxide on the surface make it unlikely that a significant amount of boron carbide will be lost from the edge of the Boral. Although there are no known careful examinations of surfaces after galvanic corrosion in boric acid solution containing 2500 ppm boron, Brooks and Perkins has measured the 3 electric current flowing betwaen Type 304 stainless steel and Boral during such exposure, both in aerated and deoxygenated (bubbling nitrogen gas) condition at 65 C (149 F). In addi-tion, a closed experiment has been run at 21 C (70 F), with no addition of gas (herein called stagnant). For the aerated and deoxygenated tests, the current varied irregu-larly with time, with an apparent trend downward after the first few weeks. The galvanic current deoxygenated was about one-fourth that in the aerated test. In the stagnant test, the current declined throughout, reaching negligible values after two or three months. Additional testing has also been done by Battelle Memorial Institute at a higher boric acid concentration, 32 g/1, containing about 5600 ppm boron. The pH was 3.8, the temperature 49 C (120 F). Galvanic currents between stainless steel and Boral or 1100 aluminum were higher than in the more dilute solution during the 54-day test. 00 Sgg Periodic inspection of the 1100 aluminum specimen during the course of the test showed severe pitting that appeared visually to have grown little deeper but covered an increasing area. This galvanic corrosion was clearly more severe than that which occurred in the more dilute boric acid solution. REPLIES TO CONTENTIONS Contention (2 ) (e) The ame,ndment request and supporting docu-mentation do not adequately discuss monitoring procedures. In the light of the proposed modification and long time storage of nuclear spent fuel the Applicant should clarify the following: (3) Method for detecting the loss of neutron absorber material and/or swelling of stainless steel tubes in storage racks. (4) Details of a corrosion test program to monitor performance of materials used in the construction of the racks. Reply Consideration of the corrosion behavior of the Boral leads to the judgment that significant amounts of boron vill not be lost from the Boral composite by corrosion. Similarly it is anticipated that no serious swelling of the vented steel tubes will occur in the storage racks, since the only known mechanisms that might produce substantial swelling involve the entrapment of gas inside the tubes or the production of 308 050 solid corrosion product with a volume greater than that of the metal from which it was prcduced. The former should not occur because the tubes will be vented and swelling by the latter mechanism should not reach serious proportions, as will be shown in the reply to Contention (2) (j ) (3). To assure that unexpected damage is not occuring, the surveillance program that will be put into effect when the new racks are installed (5) will provide an opportunity for inspection of specimens that are expected to behave in the same way as the actual tubes. Small vented specimens, very similar in character to the actual tubes, will be stored in the pool. These will be removed periodically, opened, and examined carefully for corrosion damage. In addition, two full-size storage tubes will be exposed in the pool near stored fuel so as to reproduce the radiation condition as well as exposure to the solucion. These tubes will be examined periodically for visual signs of swelling and will be opened and examined for loss of boron if examination of 10 boron content in those speci-the small specimens indicates mens below 0.02 gm/cm2, It is believed that with this program, indications of corrosion damage involving the possible loss of neutron absorber or swelling or other damage to the tubes will be detected in time to take any necessary remedial action for the storage tubes in the pool. It is believed that the corrosion reactions will be sufficiently slow that any Sgg 05i

. damage that occurs will not endanger the safe and effective operation of the storage pool. , Contention (2) (h) The amendment request and supporting docu-mentation have not analyzed the long term (including storage during the operating lifetime of the reactor) electrolytic corrosion effects of using dissimilar alloys for the pool liners, pipes, storage racks and storage rack bases, such as the galvanic corrosion'between unanodized aluminum as is used in Brooks and Perkins storage racks, and the stainless steel pool liner. Reply As has been indicated above in sections C and D it is not expected that there will be a significant electrolytic corrosion effect between boron carbide and 1100 aluminum, although it is likely that there will be a galvanic corro-sion effect between the Boral and the stainless steel tube. Whatever the magnitude of this effect, and it is not expected to pose a problem with respect to the integrity of the Boral, there will be no resic al effect of the galvanic interaction outside of the stainless steel tubes, so that the materials inside the tubes will have no interaction with fuel or with the tank liner. Contention (2) (j ) The amendment request and supporting docu-mentation do not give sufficient data to fully assess the durability and performance of the Boral-stainless steel tubes which form the spent fuel storage racks: Sgg 052

. (1) There is inadequate analysis of the corrosion rate of the tubes. Reply In Section B above I have provided information concerning the anticipated corrosion behavior of Type 304 stainless steel, the material of which the tubes are comprised. It is expected that the corrosion will be negligible as indi-cated in that section. (2) There is no calculation of tne effect of water chamistry on the Boral within the stainless steel. Reply This is discussed in Section C above. It is judged that the water chemistry will be favorable for the corrosion of Boral and that the total uniform corrosion of this material will not be in excess of 1/1,000 in. for the forty year lifetime of the racks. There could be a greater amount of local attack on the edges of the Boral and possibly at some loca-tions on the 1100 aluminum cladding on the Boral where it faces the stainless steel. In neither of these two loca-tions is the attack expected to be great enough to lead to serious loss of the neutron absorbing boron, or to cause swelling to an extent that would interfere with free move-ment of the stored fuel. (3) There is no mention of the possible swelling of Boral within the stainless steel tubes, a condition which could affect, among other things, removal of fuel asser.blies frcm the racks.

, Replv I am aware of two processes that could lead to swelling of the Boral within the stainless steel tubes. In the first, if the quality of the Boral is poor so that there is porosity, there could be a path for permeability of the core material by water. It wru'.d then be possible for reaction of this water with the aluminum at some internal place to produce hydrogen gas in quantities sufficient to expand the Boral, as by the formation of a:. internal blister. The location of such a blister might be some distance beyond that of the water that produced the gas, the hydrogen diffusing ahead of the water. This type of swelling should be self-limiting, since expansion of the blister should deform the piece enough to allow release of the hydrogen pressure. In the second mechanism scme local corrosion or pitting might be induced by galvanic interaction between the aluminum of the Boral and the stainless steel tubes (where the plates are pressed together). The solid corrosion product has a greater volume than that of the corroded metal, and local swelling could result. With respect to the first process, due to acci-dentally porous Boral, there has been n-experience of this kind of swelling at pool temperatures of conmercial grade good quality Boral either in the old formulation (see reference to the material in the Brookhaver. Research Reactor above in Section C) or in the new formulation, for which 308 054 there is less extensive experience. It did occur in some tests run by Exxon Nuclear Company (6), using snaciments of material, not used commercially, containing quantities of fine boron carbide, of the order of minus 300 to 350 mesh. It was at locations of such fine material that Exxon found the blisters to form. During mechanical testing of this type of material (not in contact with water or aqueous solution), Brooks and Perkins found areas of imperfect bonding between the core and cladding. Specifications for the boron carbide powder (size range) were then set at -60 + 200 mesh, and S no areas of poor bonding were discovered. This is the product that is used commercially. Because of universally good experience with the commercial product and the non-applicability of the Exxon results to such a product, no swellir.g of thi= type is expected in the Zion pool. Concerning the second swelling mechanism, the extent of ge.lvanic corrosion may be limited by solution depletion, depletion of available oxygen in the stagnant area, or poor electrical contact, as indicated above in Section D. If it is not so limited, it is conceivable that the entire thick-ness of the Boral might be converted to the aluminum corrosion product, a hydrated oxide, expected predominantly to consist of a crystalline form known as bayerite. Using the density of bayerite (2. 42 ), it can be calculated that the corrosion product will occupy a volume some 3.2 times that of the alumi-num from which it is formed. For a total Boral thickness of

. 0.073 inch, the maximum swelling would then be 0.234 inch, an amount that would not interfere with the movement of fuel within storage tubes. Another possible cwelling mechanism for unv+nted tubes, not involving the swelling of Boral, is the accumu-lation of entrapped gas between the Boral and the stainless steel tube. Assuming a leak near the bottom, access of solution to the aluminum and the production of some hydrogen as a corrosion product will be allowed. If the resultant gas (perhaps a mixture of the hydrogen and the air originally entrrpped during the manufac ure of the r.ube) nearly fills the free space between the Boral and the stainless steel tube, its pressure near the top wl.'l be in excess of that outside the tube by an amount that oculd bulge the stainless steel sheet. This is the mechanism believed to explain the swelling of some tubes in the speat fuel storage pool at the Monticello Plant last year. It should not occur at Zion due to the use of vented tubes. Contention (2) (x) The amendmer.t request and supporting documentation do not consider possible degeneration of the Boral densi'.y due either to generic defects or to mechanical failure which would diminish the effectiveness of Boral as neutron absorber, thus leading to criticality in the spent fuel pocl. Realv Generic effects in the form of porosity have been discussed Sgg 056

. in the preceeding reply. If there are mechanical defects, in which the Boral would fragment or break, the stainless steel tubing would keep it largely in position.

However, the fragmentation is considered highly unlikely in view of the good record of Boral products and in view of the excellent record for integrity of the Boral cladding alloy, 1100 alumi-num.

The risk of developing criticality in the pool on the basis cited is deemed negligible. 3Ob

.. REFERENCES L. BNL-NUREG-23021, J. R. Weeks, Corrosion of Materials in Spent Fuel Storage Pools, July 1977 (Brookhaven Nationa] Laboratory report); also Affidavit of John R. Weeks before the Atomic Safety and Licensing Board in the Matter of Public Service Electric and Gas Company, et al, (Salem Nuclear Generating Station Unit 1), Docket No. 50-272, 1979. 2. J. E. Draley, Shiro Mori, and R. E. Loess, The Corrosion of 1100 Aluminum in Oxygen-saturated Water at 70 C, J. Electrochemical Society, 110, pp. 622-627 (1963). 3. J. E. Draley, Shiro Mori, and R. E. Loess, The Corrosion of 1100 Aluminum in Water from 50 -90 C, J. Electrochemical Society, 114, pp. 353-354 (1967). 4. BNL-NUREG-25582, J. R. Weeks, Corrosion Considerations in the Use of Boral in Spent Fuel Storage Pool Racks, January 1979 (Brookhaven National Laboratory report). 5. Commonwealth Edison Co., " Neutron Absorber Sampling Plan - In Pool," May 25, 1979. 6. XN-NS-TP-009; Fuel Storage Racks Corrosion Program, Boral-Stainless Steel, November 9, 1978 (Exxon Nuclear Company non-proprietary version). }k)b

PROFESSIONAL RESUME FOR JOSEPH E. DRALEY Education Attended the Catholi.c University of America, 1935-9, awarded Bachelor of Applied Chemistry degree, 1939. Attended Catholic University, 1939-42 and 1945-46, awarded Ph.D. degree in Chemistry, 1947. Professional Career Metallurgical Laboratory, University of C.._cago, 1942-1945. Group Leader in Technical Division, then in Metallurgy Division, in charge of laboratory investigations in corrosion related to design and development of nuclear reactors. Aqueous corrosion of aluminum, uranium, thorium and their alloys; hydriding of uranium and thorium; formation and deposition of hydrous oxide films. Kellex Corp., New York City, 1945-46. Project engineer. Established plan for examination and evaluation of corrosion in gaseous diffusion plant; assisted in making company plans for the future. Kellex Corp., Applied Physics Lab., Silver Spring, Maryland, 1946-47. Project Engineer. Assisted in ram-jet development; research on heat transfer in supersonic airflow. Oak Ridge National Laboratory, Oak Ridge, Tenn., 1947-48. Metallurgy Division Section Chief in charge of corrosion research activities. Studied aqueous corrosion of beryllium and aluminum. Argonne National Laboratory, Argonne, Ill., Associate Chemist, 1948; promoted to Senior Chemist, 1955. Group Leader in Metallurgy Division, in charge of basic corrosion research, 194P-1968 (for applied research also during a part of this period). Corrosion of a number of metals and alloys in water, steam, and oxygen; application of materials to nuclear reactors. Coordinator for the Laboratory's program in sodium technology (Liquid Metal Fast Breeder Reactor Program), 1967-1969. Assistant Manager of the sodium technology program (Chemical Engineering Division), 1970-1971. Member Environmental State =ent Project, preparing National Environmental Policy Act i= pact state =ents for nuclear power plants, 1971-1974. Ass't. Laboratory Director for Program Planning 1974-1978. Manager, OTEC Biofouling, corrocion and Materials Project, Materials Science Division, 1978-present. Member, Argonne Senate Committee on Scientific programs, 1968-1972, Cha irman 1970-1971. Member, Argonne's CTR (Controlled Thermonuclear Research) Study Group, 1970-1973, Chairman 1972-1973. Awards: W. R. Whitney Award (National Association of Corrosion Engineers),1961, for outstanding contributions to the science of corrosion. Merit Award of the Chicago Technical Societies Council, 1970, for outstanding technical and social achieve =ents. Q

PROFESSIONAL RESUME FOR JOSEPH E. DRALEY (Contd) Technical Societies: Member of American Chemical Society Electrochemical Society American Nuclear Society (1969-1978) Amer. Inst. Min. Met. Pet. Engrs., The Metallurgical Society Amer. Assn. for the Advance =ent of Science Sigma Xi Chairman, Corrosion Division, Electrochemical Society, 1956-7 Editor, Corrosion Division, Electrochemical Society Journal,1957-8 Me=ber, Corrosion Resistant Metals Ceca., TMS AIME,1959 , Chairman,1967-9 Me=ber, Corrosion Research Council,1963-5 Chairman, Symposium on Corrosion by Liquid Metals, The Met. S oc., 1969 Other Professional Activities: Originator of periodic AEC Contractor Corrosion S,ymposia, 1951 Mc=ber, Shippingport Fuel Panel, 1953-6 Contributor to International Conferences on the Peaceful Uses of Atomic Energy, Geneva, 1955, 1958, 1964; participated in first and third Chairman, Gordon Research Conference on Corrosion, 1958 Member, Fluid Fuel Reactors Task Force, 1959 Organizer, International Symposium on Aqueous Corrosion of Reactor Materials, B russ els, 1959 Chief U. S. Delegate to International Atomic Energy Agency meeting on Corrosion of Reactor Materials, Salzburg, 1962 Exchange visitor to Russian Corrosion Che=istry Institutes,1962 Advisor ~to' Advances in Corrosion Science and Technology since 1965 Consultant to the Atomic Energy Commission on Minimization of River Pollution by Radioactive Ef fluents,1966-8 Member, ANL Study Group on Environmental Pollution, 1967 Participant, U. S. - U. K. Libby-Crocroft Exchanges on Corrosion, Harwell,1967 and Columbus, Ohio, 1968 Chairman, International Conference on Sodium Technology, Argonne, 1968 Invited lecturer at the Workshop on Biofouling at Thermal Power Plants, June 16-17, 1975, Johns Hopkins University Invited lecturer at the American Chemical Society, the Electrochemical Society, and the National Association of Corrosion Engineers series of lectures on Chemistry in Corrosion, Chicago, IL, March 30, 1976 o =

'l TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY and of Those under His Supervision (Publications are listed in the order: journal articles--contributions to books and symposia--Manhattan Project and A.E.C. reports) I. Dissertation for the Ph.D. decree: Joseph E. Draley, Complex of Cupric Ion with Acetate and Glycinate Ions in Aqueous Solution, the Catholic University of America, 1946. II. Publications in the Area of the Corrosion of Aluminum and its Alloys by Water: J. E. Draley and W. E. Ruther: Aqueous Corrosion of Aluminum: Part 1-Behavior of 1100 Alloy; Corrosion, 12, 441-448t, Sept. 1956. J. E. Draley and W. E. Ruther: Aqueous Corrosion of Aluminum: Part 2-Methods of Protection Above 200*C; Corrosion, 12,, 480t-490t, October 1956. J. E. Draley and W. E. Ruther: Corrosion of Aluminum in Reactor Service; Trans. Am. Nuc. Soc., 4, 197-8, Nov. 1961. J. E. Draley, W. E. Ruther and S. Greenberg: Aluminum Alloys with I= proved High Temperature Aqueous Corrosion Resistance; J. Nuc. Mat., 6, 732-740, July 1962. J. E. Draley, Shiro Mori, R. E. Loess: The Corrosion of 1100 Al in Oxygen-Saturated Water at 70*C; J. Electrochem. Soc., 110, 622-627, June 1963. S. Mori, R. E. Loess and J. E. Draley: An Eddy Current Gauge for Measuring Al Corrosion; Corrosion, 19, 269t-271t, Aug. 19 63. J. E. Draley, W. E. Ruther, and S. Greenberg: Corrosion Experience with Al Powder Products; J. of Powder Met., 1, 28-41, April 1965. S. Mori and J. E. Draley: Oxide Dissolution and Its Effect on the Corrosion of 1100 Aluminum in Water at 70*C; J. Electrochem. Soc., 114, 352-353, April 1967. J. E. Draley, S. Mori and R. E. Loess: The Corrosion of 1100 Aluminum in Water from 50 to 95'C; J. Electrocbem. Soc., 114, 353-354, April 1967. R. A. Legault and J. E. Draley: An Electrochemical Study of Aluminum Corrosion in Boiling High Purity Water; Corrosion, 23, 365-370, December 1967. J. E. Draley and W. E. Ruther: Corrosion of Aluminum and Its Alloys at Elevated Temperatures; Proc. Met. Info. Meeting, Oak Ridge April 11-13, 1955; TID-6502, pp. 669-680 (1960).

. TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) J. E. Draley and W. E. Ruther: Aqueous Corrosion of Aluminum Alloys at Elevated Temperatures; International Conference on the Peaceful Uses of Atomic Energy, June 1955, Vol. 9, pp. 391-396 and 441-444 (United Nations). J. E. Draley: Aluminum Corrosion at Elevated Temperatures; in TID-5606, Technical Briefing Session at Idaho Falls Nov. 1-2, 1955, pp. 5-17. J. E. Draley and W. E. Ruther: Aqueous Corrosion of Aluminum Alloys at Elevated Temperatures; Progress in Nuclear Energy, Series IV, pp. 333-351, 1956 (Pergamon Press). J. E. Draley: Contrib. to Conf. Corr. Aluminum in Water at High Temp., Chalk River, Dec. 18-19, 1956, Minutes by M. D. Ferrier, CRMet-700, June 1957. J. E. Draley, C. R. Breden, W. E. Ruther and N. R. Grant: High Temperature Aqueous Corrosion of Aluminum Alloys; Second United Nations International Conference on the Peaceful Uses of Atcmic Energy, September 1958, Vol. 5, p. 113. Also in Progress in Nuclear Energy Series, IV, Vol. 2, 1960, Pcrgamon Press pp. 284-300. J. E. Draley: Problems of Fuel Element Corrosion in Water; First International Symposium on Nuclear Fuel Elements, Jan. 1959, pp. 314-328 (Reinhold Publ. Co.). and J. E. Draley: Aqueous Corrosion of 1100 Alu=inum,of Aluminum-Nickel Alloys; International Conference on Aqueous Corrosion of Reactor Materials, Brussels, October 14-16, 1959, TID-7587, pp. 165-187. J. E. Draley and W. E. Ruther: The Corrosion of Aluminum Alloys in High Temperature Water; IAEA Conf. Corrosion of Reactor Materials, Salzburg, June 1962, Vol. I, pp. 477-498. W. E. Ruther and J. E. Draley: Aluminum Alloy Corrosion; Research Reactor Fuel Element Conf., Gatlinburg, Sept. 17-19, 1962; TID-7642, pp. 601-611. J. E. Draley and W. E. Ruther: Aluminum Alloys; Contribution to " Behavior of Cladding Materials in Water and Steam Environments", Edited by Sherman Greenberg; Reactor Technology, Selected Reviews - 1964, pp. 215-223 (USAEC). CT-3027 J. E. Draley, J. W. Arendt, G. C. English, E. F. Story, M. M. Wainscott and R. W. Berger: The Corrosion of Aluminum in Dilute Solutions; Laboratory Studies, June 19, 1945. CT-3057 J. E. Draley and G. C. English: Corrosion Researen--The Senling of Cracks in Aluminum Surfaces; October 19, 1944

. TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) AECU-2301; E. Draley and W. E. Ruther: Aqueous Corrosion of 2S UAC-659 Aluminum at Elevated Temperatures; Oct. 1952. ANL-4958 J. E. Draley, W. E. Ruther and Nancy Williams: Aqueous Corrosion of Aluminum-Lithium Alloys; December 29, 1952. (Classified) ANL-5001 J. E. Draley and W. E. Ruti.er: Aqueous Corrosion of 2S Aluminum at Elevated Temperatures; Feb. 1, 1953. ANL-5430 J. E. Draley and W..E. Ruther: Corrosion Resistant Aluminum Above 200*C; July 15, 1955. ANL-5658 J. E. Draley and W. E. Ruther: Experiments in Corrosion Mechanism: Aluminum at High Temperatures; April 1957. ANL-5889 Shiro Mori, J. E. Draley and R. B. Bernstein: Deuterium-(Adden.) Hydrogen Exchange in Boehmite Corrosion Product Formed On Pure Aluminum in Boiling Water; April 1961. ANL-5927 J. E. Draley and W. E. Ruther: Corrosion Resistance and Mechanical Properties of Aluminum Porder Products; March 1959. ANL-6015 J. E. Draley, S. Mori and R. E. Loess: Corrosion of 1100 Aluminum in Boiling H O and D 0; July 1959. 2 2 ANL-6053 W. E. Ruther and J. E. Draley: Corrosion of Aluminum-Uranium Alloys in High-Temperature Water; Nov. 1959. ANL-6207 J. E. Draley, W. E. Ruther and S. Greenberg: Corrosion of Aluminum and Its Alloys in Superheated Stea=; April 1961. ANL-6236 S. Mori, J. E. Draley and R. E. Loess: Crevice-Galvanic Corrosion of Aluminum; June 1966. ANL-6785 J. E. Draley, W. E. Ruther and S. Greenberg: Corrosion Experience with Aluminum Powder Products; Nov. 1963. ANL-7227 J. E. Draley and W. E. Ruther: Corrosicn of Aluminum Alloys by Floving High Temperature Water; January 1967. Publications _under his Supervision F. E. DeBoer: Discussion of Impedance Characteristics of Isolated Aluminum Oxide Films, by D. F. MacLennan; Letter to Editor, Corrosion, 15, 643t, Dec. 1959. R. K. Hart and W. E. Ruther: The Morphology of Surface Reaction Products on Aluminum; J. Nuc. Mat., 4, 272-280, Aug. 1961. R. K. Hart and J. K, Maurin: Morphology and Structure of Oxides Crown on Aluminum in Superheated Steam; Corrosion, 31,222-234, h) July 1965. ')@

_4_ TECICTICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) R. K. Hart: Morphology of Corundum Films on Aluminum; Fifth Int. Congress for Electron Microscopy, 1962. CT-3029 J. W. Arendt and W. W. Binger: Corrosion of Aluminum - Tuballoy Alloys; June 5, 1945. CT-3030 W. Binger: Galvanic Corrosion of 304 Stainless Steel, 25 Aluminum and 72S Aluminum; June 2, 1945. (Confidential) CT-3047 G. English: Corrosion of Unbonded Aluminum-Jacketed Slugs in Aqueous Medium; Jan. 30, 1945 (Confidential). CT-3095 John Mann: Improvements in Internally-Heated Slug Test; June 30, 1945. CT-3096 John Mann: Internally Heated Slug Test at 100% Power Level; June 15, 1945. CT-3040 J. Mann: Si=ulated Storage Basin Corrosion Tests, June 30, 1945. ANL-5500 W. E. Ruther: Corrosion Experiments with 2S Aluminum at 200*C; March 1956. ANL-5889 R. B. Bernstein: Hydrogen and Oxygen Isotopes Applied to the Study of Water-Metal Reactions. Exchange of D 018 with Alpha 3 Alumina Monohydrate; Aug. 1958. ANL-6144 Raymond K. Hart and M. J. Heyduk: Metallography of Aluminum and Some Aluminum-lw/o Nickel Alloys; March 1960. ANL-6230 Ray =ond K. Hart and Westly E. Ruther: Film Growth on Aluminum in High Temperature Water; April 1961. III. Publications in the Area of the Corrosion of Thori_um, Uranium, and their Allovs J. H. Kittel, S. Greenberg, S. H. Paine, and J. E. Draley: Effects of Irradiation on Some Corrosion-Resistant Fuel Alloys; Nuc. Sci. and Engin., 2_, 431-449, July 1957. Sherman Greenberg and Joseph E. Draley: Effects of Irradiation on Corrosion Resistance of Some High Uranium Alloys; Nuc. Sci. and Engin. ,3_, 19-28, Jan. 1958. J. E. Draley, S. Greenberg and W. E. Ruther: The High Temperature Aquecus Corrosion Resistance of the Uranium-5% Zirconium-1-1/2% Niobium Alloy; J. Electrochem. Soc., 107, 732-740, Sept. 1960. J. E. Draley and S. Greenberg: Aqueous Corrosion of Sw/oZr-1 1p/oSb-Uranium Alloy; Proc. Met. Info. Meet., Oak Ridge, April 11-13, 1955; TID-7502, pp. 640-652 (1960).

, TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) J. E. Draley: High Temperature Aqueous Corrosion of Uranium Alloys Containing Minor Amounts of Alloying Elements; International Conference on Aqueous Corresion of Reactor Materials, Brussels, October 14-16, 1959. TID-7537, pp. 390-404. J. E. Draley and S. Greenberg: Corrosion of Uranium Alloys; Reactor Handbook, Second Edition, Vol. I, pp. 183-191, Edited by C. R. Tipton, Jr.; 1960 (Interscience Pub.). CT-1943 J. E. Draley and G. C. English: Corrosion Research - Tuballoy and Alloys; July,1, 1944. CT-3043 N. Bensen, R. P. Straetz, and J. E. Draley: Autoclave Tests of Tuballoy Metal and Purified Hydrogen; June 20, 1945. CT-3044 R. P. Straetz and J. E. Draley: A Study of the Reaction Rate between Tuballoy Metal and Purified Hydrogen; June 20, 1945. CT-3045 R. P. Straet: and J. E. Draley: A Study of the Reaction Rate between Thorium and Purified Hydrogen; June 11, 1945. ANL-4862 J. W. McWhirter and J. E. Draley: Aqueous Corrosion of Uranium and Alloys: Survey of Project Literature; May 14, '952. ANL-4903 J. E. Draley: The Corrosion of Thorium; Oct. 3, 1952. ANL-5029 J. E. Draley and J. W. McWhirter: Effects of Metal Purity and Heat-Treatment on the Corrosion of Uranium in Boiling Water; April 14, 1953. ANL-5030 J. E. Draley, J. W. McWhirter, F. Field, and J. Guon: The Corrosion of Low-Zirconium / Uranium Alloys in Boiling Water; April 14, 1953. ANL-5078 J. E. Draley: Preliminary Report on Low-Columbium /Uraniu:f--- ~ - Corrosion Resistant Alloys; June 2/,1953. ANL-5530 J. E. Draley, S. Greenberg and W. E. Ruther: The High Temperature Aqueous Corrosion of Urcnirm Alloys Containing Minor Amounts of Niobium and Zirconium; April 1957. Publications under his Supervision Sherman Greenberg: Corrosion of Irradiated Uranium Alloys; Nuc. Sci. and Engin., Letter to Editor, 6, Aug. 1959. CT-2548 Rosner: Rate of Reaction Between Tuballoy and Water in a Hydrogen Atmosphere at Various Temperatures and Pressures; October 1944. CT-3023 R. B. Hoxeng: Corrosion of Construction Materials, Bonding Materials, and Uranium - An Electrochemical Investigation; May 2, 1945. (Confidential) TECHMICAL PUBLICATIONS OF JOSEPH E. DRALEY~ (Contd). CT-3031 Joyce M. Hopkins, Frederick Nelson and W. W. Binger: Corrosion of Tuballoy-Molybdenum Alloys by Water; May 31, 1945. CT-3035 Joyce M. Hopkins, W. W. Binger and Frederick Nelson: Aqueous Corrosion of Tuballoy-Silicon Alloys; June 14, 1945. CT-3036 J. W. Arendt, W. W. Binger, J. Hopkins and F. Nelson: Aqueous Corrosion of Thorium and Thorium Alloys; June 23, 1945. CT-3052 Frederick Nelson, W. W. Binger and Joyce M. Hopkins: Corrosion Testing of Tuballoy-Columbium Alloys; June 19, 1945. CT-3055 W. A. Mollison, G. C. English, and F. Nelson: Corrosion of Tuballoy in Distilled Water; June 23, 1945. ANL-5672 W. E. Ruther and W. B. Seefeldt: Aqueous Corrosion of Uranium and Uranium-6w/o Zirconium Alloy; Jan. 1957. ANL-7006 J. Y. N. Waag: Corrosion of Experimental Thorium-Base Alloys; Feb. 1965. IV. Publications in the Area of Corrosion of Zr, Hf, and their Allovs by Water or Oxveen J. Levitan, J. E. Draley, and C. J. Van Drunen: Low-Pressure Oxidation of Zirconium; J. Electrochem. Soc., 114,- 1086-89,(1967) D. H. Bradhurst, J. E. Draley, and C. J. Van Drunen: An Electrochemical Model for the Oxidation of Zirconium; J. Electrochem. Soc., 112, 1171-77 (1965) ANL-5165 W. E. Ruther and J. E. Draley: Solution Potentials of Zirconium Dec. 25, 1953 ANL-7252 J. Levitan, J. E. Draley, and C. J.-Van Drunen: S tudies- 'in Zirconium Oxida'; ion; December, 1966 Publications und'r his Supervision' e R. D. Misch and W. E. Ruther: The Anodicing of Zirconium and Other Transition Metals in Nitric Acid; I. Electrochem._ Soc., 100, 531-537, Dec. 1953;. ~ R. D. Misch and E. S. Fisher: Variation of Anodic Film Jrowth with Grain Orientation in Zirconium;-Letter to Editor, Acta Meta. 4,, 222, March 1956. s R. D. Misch and E. S. Fisher: Anodic Film Growth on Hafnium in Nitric Acid; J. Electrochem. Soc., 3, 153-156, March 1956. R. D. Misch: Dissolution of the oxide Film on Zirconium; Letter to Editor, Acta Metal. 5, 179-180, March 1957. R. D. Misch: Comments on Corrosion Behavior Zr-U Alloys in High Temper..;ure Water, by W.

c. Berry and R. S. Peoples; Corrosion, 14, 67, '

Qhb TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) R. D. Misch and F. H. Gunzel, Jr. : The Electrical Resistance of Oxide Films on Zirconium in Relation to Corrosion; J. Electrochem. Soc., 106, 15-20, Jan. 1959. S. Greenberg: Zirconium Alloys for Use in Superheated Steam; Letter to J. Nuc. Mat., 4_, 334-5, Aug., 1961. R. D. Misch and C. Van Drunen: The Oxidation of Zirconium Binary Alloys in 700*C 0xygen for Times up to 200 Days; Pub. in GEAP-4089, Proc. USAEC Symp. Zr Alloy Dev., Nov. 30, 1962, Vol. II, pp. 15-0 through 15-46. Sherman Greenberg and C. Arthur Youngdahl: Corrosion of Zirconium Alloys Containing Minor Additions of Iron and Copper or Nickel in Superheated Steam at 540*C and 650*C and 600 psig; Corrosion, 2_1,, 113-12 4, April, 19 65. 1 R. D. Misch: Electrode Reactions of Zirconium Metal; The Metallurgy of Zirconium, Edf. tors Lustman and Ker::e, pp. 663-677, 1955 (McGraw-Hill). ANL-5.'29 R. D. Misch: Anodi::ing as a Means of Evaluating the Corrosion Resistance of Zirconium and Zirconium Alloys; Dec. 1953. ANL-6149 R. D. Misch: Characteristics of Anodic and Corrosion Films on Zirconium; March 1960. ANL-6259 R. D. Misch: Electrical Resistance Studies of Anodic and Corrosion Oxide Films Formed on Zr; May 1961. ANL-6370 R. D. Misch, C. Van Drunen: Corrosion Studies o'. Ternary Zirconium Alloys in High Te=perature Water and Stea=; July 1961. ANL-6434 R. D. Misch and G. W. Iseler: Electrical Measurements on the Growing Scale on Zirconium-Titanium Alloys; Oct. 1961. V. Other Corrosion Studies and Reviews J. E. Draley: Fundamental Corrosion Studies; In Hea-ings Before Subcommittee on Res. and Dev. of the Joint Com. of At. En., Eighty-fifth Congress of U. S.; Second Session in Phys. Res. Prog. Rel. At. Energ., Feb. 3-14, 1958; pp. 304-313. J. E. Draley, J. A. Ayres, W. E. Berry, E. Hillner and S. P. Rideout: Corrosion in Aqueous Systems; 3rd Int. Conf. Peaceful Uses At. Energy, Oct. 1964, Vol. 9, pp. 470-481. J. E. Drale; Some Consequences of the Maintenance of Equilibrium of Alloying Constituents Between the Surface of Stai ' -.s Steel and Sodium in a Recirculating System; Proc. AIME Symp. Chemical Aspects of Corrosion and Mass Transfer in Liquid Sodium, Detroit, Oct. 1971, Ed. S. Jansson, AIME, 1973; pp'242-252. CT-1944 C. Wchlberg and J. E. Draley: Corrosion Res., Film Problems, 1944 b

. TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) Corrosion of Materials for ANL-4837 J. E. Draley and P. G. Drugas: Transparent Radiation Shields; October 28, 1949. J. E. Draley, S. Greenberg and W. E. Ruther: Corrosion of ANL-6206 Some Reactor Materials in Dilute Phosphoric Acid; April 1961. Publications under his Suoervision Influence of Oxygen on High Te~perature Aqueous W. E. Ruther and R. K. Eart: Corrosion of Iron; Corrosion, 19., 127t-133t, April 1963. R. D. Misch: (Discussion); Co'rrosion, 19, 420t, Dec. 1963. Titanium and Titanium Alloys in Mercury - Some Observations J ames Y. N. Wang: on Corrosion and Inhibition; Nuc. Sci. Engin. 18, 18-30, Jan. 1964. Corrosion of Steels and Nickel Alloys in W. E. Ruther and S. Greenberg: 111, 1216-1121, Superheated Steam; J. Electrochem. So:., Oct. 1964. of Metallic Additives on Mercury Corrosion of Ja=es Y. N. Wang: Effect Titanium; Corrosion, 21, 57-61, Feb. 1965. Growth of Ox$de Nuclei on Iron; Sixth Int. Cong. R. K. Hart and J. K. Maurin: Electron Microscopy, Kyoto, Japan, pp. 539-540, Maruzin Co. Ltd., 1966. Electrochemical Corrosicn CT-1703 Raymond B. Hoxeng, Interim.seport: Research; May 1, 1944. ANL-6070 S. Greenberg and W. E. Ruther: Aqueous Corrosion of Magnesium Alloys; July 1960. and Test Methods Publications Concerned with General Corrosion Theory VI. Some Unusual Effects of Hydrcgen in Corrosion J. E. Draley and W. E. Ruther: 104, 329-333, Jane 1957. Reactions, J. Electrochem. Soc., J. E. Draley: Discussica to paper by Carlsen; Corrosion, 14,, 55t-56t, Jan. 1958. A New Dynamic Test Facility S. Greenberg, J. E. Draley and W. E. Ruthe:- for Aqueous Corrosion Studies; Corrosion, 14, 191t-192t April 1958. Measuring J. E. Draley, W. E. "ither, F. E. DeBoer, and C. A. Youngdahl: for Polarization Studies in Distilled Water; Equipment J. Electroche=. Soc., 106, 490-494, June 1959. Y

_9_ TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) J. E. Draley, F. E. DeBoer and C. A. Youngdahl: The Polarization of Metals in Boiling Distilled Water; J. Electrochem. Soc., 108, 622-628, July 1961. J. E. Draley: Corrosion of Film Forming Metals - I; Chem. Engin., 69,, 256-259, Nov. 12, 1962. J. E. Draley: Corrosion of Film Forming Metals II; Chem. Engin., 69,, 152-156, Nov. 26, 1962. J. E. Draley: (Discussion); Corrosion, 19,, 407t, Dec. 1963. J. E. Draley: High Temperature Corrosion Tests; in Nuclear Reactor Experiments, pp. 329-335, Feb. 1958; (D. Van Nostrand). S. Mori, R. E. Loess and J. E. Draley: pH Microelectrodes for Use Near Corroding Metal Surf aces; Corrosion,19,,165t-168t, May 1963. J. E. Draley and J. R. Weeks (Ed's): Corrosion by Liquid Metals; Proc. TMS AIME Sy=p., Philadelphia, October,1969; Plenum Press, New York, 1970. .+ J. E. Draley: Corrosion by Valve Metals; pp 185-234 in Corrosion Chemistry, Ed's. George R. Brubaker and P. Beverly P. Phipps, American Chem. Soc., Washington, 1979. Publications under his Supervision j W. E. Ruther: An Eddy Current Gauge for Measuring Aluminum Corrosion; i Corrosion, _1_4_, 387t-388t, Dec. 1958._ C. A. Youngdahl and R. E. Loess: Instrumentation for Potentiostatic Corrosion Studies in Distilled Water; J. Electrochem. Soc., 114, 489-492, May 1967. i ANL-5227 W. B. Doe: Eddy Current Type Diameter G_auge for _ Corrosion Measurements. VII. Published Educational Lectures CL-606 Part 5 J. E. Draley: Corrosion; in Training Prog ram Lecture Notes, 1943. e J. E. Draley: Aqueous Corrosion of 25 Aluminum at Elevated Temperatures; A Short Course in Corrosion, U. of California, Feb. 1953; pp. 106-109 (U. of Calif. Press). J. E. Draley: Corrosion in the Atomic Energy Industry; Corrosion Short Course, Univ. of Oklahoma, April 1958, pp. 215-240. g VIII. Publications Concerned with Specific Reactor Systenq J. E. Draley: Fluid Fuel Power Reactors; Trans. Am. Nuc. Soc., 2, 46-47, Nov. 1959.

. TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd) TID-8507 Joseph E. Draley, with 14 Co-authors: Report of the Fluid Fuel Reactors Task Force; Feb. 1959. J. E. Draley and S. Greenberg: The Application of Materiais in Low Tc=perature Water and Organic Liquid Cooled Reactors; Sy=posium on Behavior of Materials in Reactor Environment, Feb. 20, 1956, (Institute of Metals Division of AIME) Special Report No. 2, pp. 33-53. ANL-6360 C. E. Stevenson, J. E. Draley, L. W. Frc==, Sheffield Gordon, H. P. Iskenderian, A. A. Jonke and R. R. Rhode: Organic Nuclear Reactors - An Evaluation of Current Development Progr ams; May 1961. IX. Publications Related to the Environ =ent and to Fusion Reactors Report of the Study Group on Environ = ental Pollution, Argonne National Laboratory, February,1967 J. E. Draley, B. R. T. Frost, D. M. Gruen, M. Kaminsky, and V. A. Maroni: An Assessment of Sc=e Materials Problems for Fusion Reactors; Proc.1971 Intersociety Energy Conversion Engineering Conference, Boston, 1971, pp 1065-75. Su==ary of Recent Technical Information Concerning Thermal Discharges into Lake Michigan, by Center for Environmental Studies and Environmental State =ent Project, ANL, for the Environmental Protection Agency, August 1972 (Section VI. Chemical Inputs, by J. E. Draley). J. E. Draley and S. Greenberg: Some Features of the Impact of a Fusion Reactor Pcwcr Plant on the Environment; Proc. Symp. Tech. Controlled Ther=onuclear Fusion Experiments and Engineering Aspects of Fusion Reactors, Aus tin. Texas, Nov. 1972; Tech. Information Service, 1974. ANL/ES-12 Joseph E. Draley: The Treatment of Cooling Waters with Chlorine, February 1972. ANL/ES-23 J. E. Draley: Chlorination Exp2riments at the John E. A=os Plant of the appalachian Power Co=pany, April 9-10, 1972; June, 1973. ANL-8019/LA-5336 T. A. Coultas, J. E. Draley, V. A. Maroni, R. A. Krakowski: An Environmental I= pact Study of a Reference Theta Pinch Reactor, February 1974. X. Other Publications CC-3019 R. A. Gustison, E. J. Frederick, E. F. Story, Jr. and J. E. Draley: The Determination of E=all A=ounts of I= purities in Water; April 30, 1945. i

TECHNICAL PUBLICATIONS OF JOSEPH E. DRALEY (Contd.) CM-436 Joseph E. Dralcy: Convective Cooling of Heated Surfaces by a Parallel Supersonic Air Stream. Applied Physics Laboratory, Silver Spring, Md., May 1947. TID-17940 J. E. Draley and F. W. Young, Jr.: Visit to Soviet Corrosion Chemistry Institutes; June 25 - July 4, 1962. Publications under his Suoervision F. E. DeBoer: Analysis for Magnesium in High Purity Aluminum; Letr.er to Editor, Nature, 184, 54-55, July 4, 1959. F. E. DeBoer: Purification cf Metals by Gas Chromatography; Letter to Editor, Nature, 185, 915, March 1960. Raymond K. Hart: Electron Diffraction Techniques and Their Applications to the Study of Surface Structure; Progress in Nuc. Energy Series IX, Analy tical Chemistry, Vol. 7, pp. 1-20, Pergamon Press, 1966. R. K. Hart and D. G. Pilney: A Cc= pact Vacuum Path 20 Scanner; The Electron Microprobe, Edited by McKinley, Heinrich and Wittry, pp. 472-479, John Wiley and Sons, Inc. 1966. R. K. Hart, T. F. Kassner and J. K. Maurin: Residual Gas Analysis in an Auxiliary Pu= ped Siemens Electron Microscope; Sixth Int. Cong. Electron Microscopy, Kyoto, Japan, pp. 161-162, Maruzin Co. Ltd., 1966. Raymond K. Hart: Composite Aluminum-Nickel Evaporated Films; J. Appl. Phys., 37, 2918-2919, June 1966. R. K. Hart; Electron Microscopy: The Righ Voltage Approach; Twenty-Fifth Annual Meet. Electron Micr. Soc. Am., Aug. 29-Sept. 1, 1967, Chicago, Illinois. R. K. Hart and D. G. Pilney: Effect of Spectral Line Shift on Microprobe Data, Sec. Nat. Conf. Electron Microprobe Analysis, June 14-16, 1967, Boston, Mass. CT-3049 C. Wohlberg, A. Schwebel, R. W. Berger and F. Nelson: Film Studies and Protection of Hydrous Oxides; June 18, 1945. II. Patents s J. E. Draley and W. E. Ruther: Nuclear Reactor Ccaponent Cladding Material; U. S. Patent 2,871,176; Jan. 27, 1959. Joseph E. Draley and Westly E. Ruther: Nuclear Reactors and Subassembly Therefor; Br. Patent 811,528; April 8, 1959. 308 071 ~

Professional Qualifications of Joseph E. Draley At Argonne National Laboratory I manage the OTEC (Ocean Thermal Energy Conversion) Biofouling, Corrosion, and Materials Project, carrying out a national program for the Department of Energy. In the present instance, testifying before the NRC Licensing Board, I speak on my own bel,alf and do not represent Argonne National Laboratory. At the Metallurgical Laboratory of the University of Chicago (3 years), Oak Ridge National Laboratory (1 l/2 years), and Argonne National Laboratory (20 years) I studied the corrosion and oxidation of metals, serving as group leader or Sectica Chief before going into =anagement. A considerable amount of the corrosion work done has been of direct interest for nuclear power plants. I have also studied the environmental impact of nuclear power plants in connection with construction permit or operating license applications. A professional resume is attached, giving these and other details. Over 150 technical publications have been authored by me or people working in groups I headed. Of these, I was author or coauthor of nearly 100 publications. The prepondcrant =ajority of all these publications were on the topic of corrosion or oxidation; many dealt with the aqueous corrosion of aluminum and a smaller number with the aqueous corrosion of stainless steel and circonium alloys. In a number of instances, publicaticns dealt with nuclear systems. A list of technical publications is attached. I have been active in corrosion affairs in the Electrochemical Society and the Metallurgical Society of the AIME, serving as Corrosion Division Chairman and corrosion editor of the official journal for the former, and chair:an of the Corrosion Resistant Metals Cocnittee of the latter. I helped to originate American Corrosion symposia related to nuclear energy and an international meeting (Brussels, 1959) on the sate topic. I participated in the Geneva Conferences on the Peaceful Uses of Atcmic Energy. I hold a bachelor's degree in chemical engineering (1939) and a PhD degree in chemistry (1947).

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BNL-NUREG-23021 INFORMAL REPORT CORROSION OF MATERIALS IN SPENT FUEL STORAGE POOLS J.R. Weeks July 1977 }{ Corresion Group Oepa_ ment of Applied Science Ereckhaven Na*_ienal Laboratory Cp On, New York 11973 308 07 4

TABLE OF CONTE!CS / L I S T O F TAB LE S -- --- ------ - --------- ----------------- -,,,, IN TRO D UCT I CN---- ---- --- ---~ ~------ -------------- 1 I MAT ER IALS -- -------- -- -------- -- ------------ 2 3 II WATER CHEMI STRY------------------ 3 1. SWR Fuel Pool Chamistry-------- 3 2. PWR Fuel Peel Chec:ist:f------ 3. B ic c i d e s -------------

4 5

III CORTSION OF MACRIALS IN FUEL STORAGE PCCLS-- 5 1. S tainles s Steels--------- .2. Al =in= Allo ys ----------------------- 5 3. Zircalcy Cladding----------

6

6 4.

Other Materials--------- 5. S tr e s s Co rr e s ien----------------------- 6 -- 7 6. Galvanic Co rre sion------- - - --- 9 27 S URyz :;;AN CI----------------- 10 V SCMMARY AND CINCLUSIONS-- ACZNCWLED GEMEIC S ----------------------------- 11 --- 1: RzzzRzN TA3 2 -- _ _----- _ _ ---- __ _ ----_ __ _ _ -- _ _ _ _-_ -- ___ --- _ 12, u, 13 e pyt%t .\\ 0l0 30B 1

LZS: or ygg TABLE 1 AND yxygg EMISTRIIs 73 g.q STogggg p -n a u - ~ ~ ~ - Ph \\ 07 6 308 u

INTRCDUCTICN The current delays in establishing a national fuel reprocess-ng center have required =any of the LWR licensees to expand their ue storage capahilities either by nodification of existing pccis or addition of new fuel storage pocis. This report reviews the potent a1 corrosien problens that night develop during the lcng-term (10 plus years) storage of nuclear fuels in these storage peois. A detailed review of the integrity of the fuel in storace pools is being prepared by Johnson fer ERra,(1) which has served sus-s repor*-. Zircalcy-clad fuels with as a basis *~ muc.u. oo urnups up to 33,000 mwd /M""J have been successfully stored in fuel storage peels for periods up to 13 years in U.S. pools and 14 vears ^ (at icwer burnups) in Canadian pocla. %N et b.v A I, 077 wa

MATzR:Ars Three g M Me:111,,re generall7 4n contact y1ty g e fuel agny,7e Pool wat**; the pocz zD e which i

1. - - C*17 stain ~

1*33 steel, gye storag eks which a

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**te:Lals Preseng in th* '*Uel element ynn which cc= n1y $ng3u
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~' wate: chem 5,t:7 used ~,, L Stora e at a at=be~ o,r,n

*S July 15 ' 19,' ~' '

nuclea

- - - cns' as available to the y~;g~

Exe,~.,ence v~t g

37 these mate:Lal3 ic~~ 1 "5 Periods c' I: (A

~ ~ time 1= reac~'~~~- cana13 y,,h* =eViewed b =#**' ,,~ ',['*'aloPcladgu,3 .um 'C3 residence < Pools og spent n - ~ A7ni!Lcant c-~~, Y'*3-None og the * =Atarials, gnu 3 g u ,, O Pe:Leds yet',

cuss og zo Y'A 3r as.

g. ~= this eny3,c, bee = bc::e eg. ? eXVe:Lence. 9 308 078 2

I WATER CHEMISTRY Because during the fuel unloading procedure the water in the fuel storage pool and the reactor pri=ar,( coolant =ix, an attempt is made to =aintain water purity in the fuel stcrage pool to ap-prox 1.cately the sa=e limits that are set for the primary reactor coolant. 1. SWR Fuel Pool Chemistrv In a 3WR this =eans that high purity de=ineralized water is typically =aintained with a filter-demineralizer to a total heavy ion centent of < 0.1 pp=, a pH range of 6.0 to 7.5, and a conductivity of < 1 u=ho/c=. The water is sa= pled daily to =eas-ure conductivity, and weekly for other i= purities, including chlorides. The de=ineralizers pri=arily re=ove silicates frc= the water, and are typically checked for their capacity to remove this species ence weekly. The primary source of the silicates =ay be dust frc= the air; the pools are nor= ally uncovered. On the aver- - age, fresh resin beds are installed nonthly, primarily because of increased pressure drops frc= silicate abscrption.I I The primary cent =ibution to the cenductivity is dissolved CO ; when the conduc-2 tivity exceeds 1 umhe/c= the de=ineralizers are changed. (2) During a visit in June, 1977, the water in the Ver=cnt Yankee fuel pool appeared extremely clear, with a distinct blue tinge to it, app ar-ently as a result of scatte=ing of the icnger light waves by the water and the use of mercury vapor lighting. 2. PWR Tuel Pecl Chemistry In a PWR, the fuel pool fregsently centains several thcu-sand pp= beric acid, which is added to other otherwise highly pure water. No neutrali:stien with LICE is used in the fuel stcrage ~ pocis; a typical pH( } value is 4.5. A pertien of the fuel pcci .c kkf h g(fk!b@$gA 3 s

coolant is continuously passed through a de=ineralizer resin and impurities, such as halides or sodir: ions, maintained below 0.15 ppm. Periodically the demineralizer resins are checked for their ability to re=cve halides and sodium icns; resins have been de;e.:.- cped by Rchm and Haas that are specific for removing halides.in the presence of beric acid. The manufacturer's claims in this =at-ter have been ecnfir=ed experimentally by one of the reacter ven-dors.(4I 3. Biocides: Biocides are not ec==cnly used in fuel storage pools at nuclear pcwer plants. Maintaining the water of the high purity needed for safe storage of fuel appears to inhibit biolcgical grcwth, and the use of stainless steel liners in the storage pcci also tends to centrol biclogical grcwth. The radiation levels frem the spent fuel stored in the peci also tend to sterilize the water, although radiation resistant bacteria are kncwn.

Finally, the continuous de=ineralization cf a pertien of the pecl water serves to filter cut any biological growth.

No biclegical fculing has been observed in 3 1/2 years cperation of the prairie Island spent fuel pcci, (3) in 3 1/2 years operation of the Verr:cnt Yankee, > 5 ymrs operation of the Maine Yankee, and > 10 years operation cf the Yankee-Rowe fuel storage peels,( } and no biccides have been added. The use of biccides can lead t= the presence of chieride icns in the peel which are potentially har=ful to the corrosien resistance of the =atorials stored in the pec1, and would be una:- ceptable during the mixing with the reacter primary ecciant that e occurs during refueling. They have been used in the ICPT fuel 7cci at Idaho Falls, which is a painted concrete pccl. ( - h ' 'i, .4 e v x) mi 'r n 4 Ob 30B

III CCRRCSICN OF MA'"ERIALS IN FUEL STORAGE PCOLS The corrosion rates of =irconiu=, stainless steels and Inconel in water of the quality ma btained in the fuel storage pools should General be negligible during periods upwards of twenty years. cerrosion 7: ate measurements for these materials in water of this quality ard temperature are not generally available, and any esti- =ates of corrosion rates =ust be extrapolated frc= =easurements at much higher temperatures. The primarf difference between the water cha=istrf in the fuel pocls and that in the reacter (other than the te=perature) is that the pools are exposed to the air and are presu=ed to contain dissolved oxygen up to the saturatien point. Since all the =aterials used are passivated by oxide films, the presence of oxygen in the water should net affect their cer-resien rates. 1. Stainless Steels Since the stai-less steels are used for the primarf pip-ing at substantially higher temperatees and in the presence of for oxygen in BWR's where stainless steels are deemed satisfacterf perieds up to 40 years, cerrosien in the fuel pcci shculd be =uch less than in the reacter, because of the icwer temperature. 2. ~Aluminu A11cys The anticipated corresion of the alu=inum alleys, 110C cr 6061, is negligible in water of this quality at te=peratures 0 up to the boiling point of water: at 125 C (257 F) a cc:"csien rate of 1.5 x 10 mils / day ( I has been =easured for alley 6061 ~4 alu=inu=, in water cf pE 7,,;hich correspcnds to a tocal cer esien of 1.1 =ils in twenty years. Since the exidation rate will cen-tinue te decrease slightly ever thic peried, this estimate should be censervative. At icwer temperatures, the rate will be even G~ t rm b .44 we

s i

lower. There is little difference in the co=osion rates of these two 111cys at temperatures below 150 C. The ancdization of the alu=inum co=ponents, which is occasionally used, should pro'act them even further frc= corrosion. 3. Zircaloy Claddinc ~ The rate of corrosien of zircalcy in fuel stcrage pocl waters is very Icw. serry (6) gives a cerrosien rate in 500 -2 =ils/ year, and shews it to be centinually de-water of 2 x 10 crea91ng up to times in excess of 10 or 15 years. At the lower te=peratures tha t prevail in fuel storage pocls, the ec=csion ( I rates shculd be even icwer. Morga. describes the corrosion rate of =ircalcy in pool water as being sufficiently low to pre-vide an adequate centain=ent ba=ler for at least 100 years. The oxygen cencentratian in the peal water should nec adversely affect corrosien of ircaloys. Zirconium and its alleys are protected frc= aquecus accesion by a strongly passivating oxide fi1=. The cxygen in the water shculd serve to prc=cte and III =aintain this passivation. Fur-her, Uhlig has stated that this passivity is naintained both in strong acids and in strong alkalis. 4. Other Materials The fuel bundle and stcrage rack materials =ay aisc include type 17-4 PE stainless steel and 2ncenel 718. Neither cf these alicys should undergo r.easurable general ec =csion in fuel stcrage pcci waters. t 5. Stress Corrosien Stress c=rresien of sainless steels and ircalcys in fuel stcrage pocis is h.ighly unlikely n occur provided the wacer eA(s?m% A nw m qw .Yr)h thQ(ff@ M 3@ 5

chemistry is maintained within the specified limits. Stress cer-rosien of sensitized stainless steels that are highly stressed has been observed in oxygenated water acididied to pE 5 nitric acid at temperatures up to 140 F.( 'his is, however, a slow process which tock 6 years to develop and occurred only in one highly, stressed, highly sensitized area. While it is i=pessible to rule cut ce=pletely that stress cerrosion of the stainless steel c: Incenel cc=ponents will occur in the fuel stcrage pcci, any snch occurrence would be highly localized and rare, and not lead a sericus proble=s with the stcrage racks or fuel bundle w=penents. No significant difficulties have been observed in fuel bundles exar.ined frc= a nu=ber of reacters. Stress cerrosien of 17-4 PE c is unlikely te occ= if the =aterial has received an 1100 i heat treatment. This heat treat =ent is cc=cnly specified for this =ararial when it will be exposed te reacter ecolants. Cc=penents of 17-4 PE given this heat treat =ent have been in service in the 3rcokhaven Eigh Flux Hea= Reacter (ETER), which centains high purity D 0 acidified with nitric acid to a pD of 5 end centaining 2 greater than S parts pe-d4cn of cxygen, for periods in excess of 12 years withcut any evidence of stress ccrresion er pitting.(~0), c This water chemistry and te=perature (145 ? =ax.) are similar to that prevelant in PWR fuel s crage pocls. 6. Galvanic correcien Galvanic couples between stainless steels, Incenei and zircalcy do not appear ec give rise te any 1ccalized cer esi:n in fuel pcci enviren=ents, since all of these naterials are prctected by highly passivating exide fitm, and are, therefore, at s' d'=- potentials in pure water. Alu=inu: alloys, which are also protected by passivating fi' nevertheless can be pitted in an acid enviren- =ent such as that presene in PWR fuel stcrage pccis, when ecupied te stainless steel. The ancdi:ation of alu=inum fuel storage racks A qs Y, ee'*, 1./I .A \\ , [ D \\ k 4/h1 h~ -.. 3 i ; N u v s' O

,(; y *..)p,e p.,

)\\ g'&,p.& oO

should minimice this occurrence. In BWR storage pools, the high electrical resistivity of the water should also serve to prevent galvanic attack. At the Oyster Creek Nuclear Pcwer Station, aluminum racks were originally placed directly in contact with the stain-less steel pool liner. Sc=e of these racks have been re=cved and examined after approxi=ately 7 years of service in typical BWR pool water.I11I No observable pitting of the alu=inu= was found at the point where it contacted the stainless steel. (11) At least ene nuclear utility (Ve=cnt Yankee) ha's also elected to provide additional protection against chis potential proble= by placing stainless steel feet en the racks, which, in turn, are electrically insulated from the alcninum with ABS plastic inserts. These have been dete=ined to be sufficiently far from the radia. tien scurce to prevent their decc= position by high energy s'-' flux. ( 2) These organic inserts are, in ny opinien, additional insurance that galvanic cerresion will net cccur. e O e n&s &y %;D. W'N A

8URWIIctygg A 8 Pent U*E*Piccessed yye~, (Scary prog g,, E**** bY the m Dtviggcn og y,,t ' E Cduction **d rep:ccess~ 1) 4 " ?? 197 Unde

gy3, 335* to be

** *^ 9e w:. 1

'Y'1Cated a acte:$3 tics .,g '**dAtten c

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Although h

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he pe:!c: eg

N05 a3 have not ye. ueen g,,ed cu 2e s

s

- tional sccpe o,. -y.s pre g,,=
i.~nLugg=9 Pc: Leg * **3=

a 'a*W se eez,,~.,ue~, yUndles 'a:c3 both ~

"# BWR s~c v't,, p:cy;a'~e add'< ;Ona a*==ance +

Of the ce. Bued in gg_ '~ ~~ ~~t? ct $;,3,,

1. 378 th:0ugheq' the ccun

.4 i s n., $ ~ p $b ' ll$g. f QtRgi'$a g rp u Dd p.s.o g) D R$$$ 'a g 085 ~ 9 308

Y s gyy,3,qy ASnt!! cant co -Wen of nuelcir fuel e' penents is 5,4 -hly un- "i likely to ace,,,, durinq ste age in fuel at P s at the reac '-- sites in,r,,cds of upwards of 20 Y' M o p:cvided thas' the Wate: e-gy Y,3 the duez, = age pccis La ma$n

~

tions, ang g " ", 4 levels in the Peel wate~-

E* to minn:g= 3,y,1s

{< _P3)- Stress coc:csta* Ca stainte4 steel cen-r ponents ',,,~,__alev clad ng canact be er'+'<' *,? ruled cu~~ uecaus e ~ of the lack *, Understande T c, the s~~ess states ang,5e degree sens' '-< -a -> on og g:,$,,"ess steel-ca S culd suc5-on the,*4-,alev c*'addinV it veuld be readily detec ed b utine 20^1tcring og 1 Water for '"adi -Y-Should $

e develop on
5-

'U*ss steel c: Inccnel comycnents os the fuel bundles' ;. Would be y;,,hlY localt e and C*1ikely

a 3'#"

U 817-

nifica, cverall dete.,cration.

pe *cd1c su veillance e, ,,e Mte:Lals.43 gg-,, ..ucher of nuclea-e,4 es is degn, l P anned unde-

'i,8 auspices of the U.s
E**:5? Besearch and ceye,,p-

=ent as <",,32:3ticn. 9o 4d. 4 9%' 9 so

10 se

ACECh*LEDGEM."CS 3 4 The assistance of Dr. A.B. Johnson, Jr., of Battelle Pacific Northwest Labcratory, in providing draft copies of his review (Leference 1) and in several useful discussions is gratefully ack-newledged. Representatives 5$ the Northern States Power Cc=pany, Yankee Atenic Electric Cc=pany, Duquesne Pcwer and Light Cc=pany, Jersey Central Pcwer and Light Cc=pany, and the Portland General Electric Cc=pany were very helpful in preparing this review. This work was perferned under the auspices of the United States Nuclear Regulatory C==ission a p& w$@ f (,,9:o:.: %

5. N.

g %{g. a s? 9 s hd ! 13

60 1. A.B. Jchnscn, Jr., " Behavior of Spent Nuclear Fuel in Water Pool Storage", BNWL-2256, Draft, May, 1977, also private com=unications, May, June and July,1977. 2. John R. Ecff=an, Yankee Atemic Electric Ccmpany, Private e ce=unications, June 6 and 7, and July 14, 1977. 3. Peter Jones, Northern States Pcwer Cc=pany, Private ce= uni-cations June 1 and July 15, 1977. 4. C. McCracken, Cc=bustion Engineering, Private ec=unication, June 3, 1977. 5. J.E. Draley and W.E. Ruther, Report No. ANL-5001, February, 1953. %d qgs 6. W.E. Berry, " Corrosion in Nuclear Applications", John Wiley m%$y- & Sons, N.Y., 1971, pages 107-116 Qg an bb. 7. W.W. Mcrgan, "he Manage =ent of Spent CANCU Fuel", Nuclear % 2a Technc cev 2 4,, 1074, pages 409-417. F@yy tern.3 8. H.H. Uh.lig, " Corrosion and Corresien Centrcl", Jchn Wiley & (Ih.

Sens, N.Y., Second Edition, 1971, pages 367-371.

a:q 9. R.R. Powell, J.G.Y. Chew, W.J. Brynda, M.E. Brecks, J.R. Weeks .. d% " Experience With Stress Cerrosien Cracking and Materials C.. t'm"" patibility at the Eigh Flux Bea: Reactor", CONF-730801, 166-N 180, 1973. 10. R.W. Pcwell & J.G.Y. Chcw, Brcckhaven National Labcratcry, Private cc==unications, 11. T.J. Madden, Jersey Central Pcwer & Light Cc=pany, Private cc=unication, May 19, 1977, 12. C.R. Ccoley, U.S.I.R.D. A., Private cc=unicatien, July 14, 1377 12

TABLE I MATERIALS AND WATER CHEMISTRIES IN LWR FUEL STORAGE PCCIS PLANT MATERIAL USE ENVIRC E :C ARIANSAS 304 SS A-276-71 or Rack 1800 pp:1 horen as (PWR) A-167-74 beric ac.4., 308 or 308' Electrode 304L ASTF.-A-167 I.J.ne.: 120 F fl 3EAVER V7' * "Y SS, 17-4 PH Racks, bolts 2000 pps beren as (PWR) beric acid, ~ ~ C1, F < 0.15 pps 3ROISWICK 304 SS Linar, racks 125 Y (max 150*F) (BWP) .E3C8 Electrodes g g, 17-4 PH - H1150, Bolts alC25 pH 6.0 - 7.5 ~ C1 < 0.2 ppm - ACT 1, Stafn.less steel Liner Deminerali:ed water 2 and 3 Al-6061-T5 Racks ,,3 ~~~ * (BWR) AS m-3-2C9 daep bed de=iner-alize FT. CAIEOOi 304 SS AS3-A-276-71 Racks 120 F or A 6h74 20C0 pp= beren as 3C8 er 3C8! Wald beric acid GO.T, R.E. 304 SS Racks Boric acid (PWR) !AC3CSSE Scrated SS and 304 SS Racks Ce=i.eralised water (3*a~d F" ' ~~0!:I 304 SS !iner, racks Ce=inerali:ed water PC2C I Filter and da-4ner-(3*a"4 alizar M": S"CNE 3C4 SS Linar, racks ce=ineralized water =U 2 + 2000 pp= beren as (PWR) ( beric acid ) e

TABLE I (continued) 2 PIXT"' MA"'IRIAL USE ENVIRChr. N-' NEE MII.E 304 SS Rack Declinaralized water PCrc 1 of BWR pri=ary cool-gg ant quality 125 P CYSTER CRIII Entire rack 304 SS Domineralized water (BWR) MIM-A-240 Plata, har Undisselved solids sheet AS21-A-193 Rivets, bolts < G.5 ppe ASO!-A-194 Nets 308 SS, AS!E SFA 5.9 Weld =atarial 0 PAI.*SACES 304 SS Racks 122 F - 157 F (PWR) 2000 pps berca as heric acid PI ~~o.IM Sa=a rack design as (3WR) vermont Yankee PODC BEAC3 304 SS Racks 2000 ppm boren as beric acid 130 F (PWR) PRAIRII IS.A E 304 SS Racks, liner De=ineralized water 1 and 2

7. ire al=y, 21-719 Fuel b " es (C1, F < 0.35 pps (PWR)

+ 2000 pp= beren as beric acid pH 4.5, 1 0 F QUAD CI-~. 4~ Sa=e rack design as 1 and 2 Cresden (3fa~/,) l TROJAN 304 SS Racks, linar 20C0 pp= beren as (PWR) Incenel Crid Mat'1. bor:..c ac.. 17-4 PH - H1100 Bolts and i Module threaded 140 F f*'t C1", F", 0.15 ppe d :n each s dth

TABLE I (continued) PLANT MATERIAL USE ENVIRONMI:iT

0RKEY PCI C Entire rack 304 SS Demineralized water 3 and 4 Free standing rack

,g.y ggg p 3 (PWR) ASOf-A-240 Sheet, plate i ASST-A-276 Bar as beric acid AWS-E-308-15 Weld wirn AWS-E-308-16 Weld wire 7EMCIC YAhes 356-T51 ASTM-B-26 Alus. Grid castings.

E 6 - 7.5 (BWR) 6061-0 er 5052-H32 Alum.

Cans (Cu, N.,, Fe, Eg, e tc. ) 6061-T651 Alum. Plates 2024-T4 Alum. Bolts, Pins < 0.1 ;In All aluminum alleys, 115 F anodized 4 304 SS Linar, feet Radionuclide < 10 ABS plastic insulaters between feet & alu=. cans YA!OCE ROWE 6061-T6 Alum. Racy. 130 F, scce tcren, S'i niass Staal Liner chloridas < 0.5 p;=

20N 304 SS Rack Beratad water (PWR) 105 F

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DISTRIBUTION LIST L.C. Shao (5) R.J. Stuart W.S. Ha::elton F.M. Al=eter H. Levin (5) W.Y. Kat D.H. Gurinsky corresien Group Files (10) 16 308 092 e

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ENL-N GEG-255 32 INF0FFMAL REPOIC LLMITED DIS'RIBUTION CCRRCSICN CCNSIDEPATICNS IN THE USE CF BORAL IN SPENT FUEL STCRAGE POOL RACKS J.R. Weeks Dece=ber 1978 Corrosion Science Grcup Cepartment of Nuclear Energy Brookhaven National Iaboratory Upton, New York 11973 NOTICT: This document contains preliminary information and was prepared primarily for interim use. Since it may be subject to revision or correction and does not represent a final report, it should not be cited as reference withcut the expresse consent of the author. )Ob FIN A31C6

TABLE CF CONTnITS Page LIST CF TABLES................................................. 11 LIST OF FIGURES................................................ iii INTRODUCTICN................................................... 1 CORROSICN CF BORAL............................................. 2 PITIING CF ALUMUiUM Of CCNTACT WITH STAR:LESS STEEL............ 3 CONCLUSICNS AND RECCMME iDATICNS................................ 5 A CKliCWLC GDENTS............................................... 6 i I N g 1

t LIST CP M LES TABLE I BMRR WA"'ER CHEMI STRY...................................... 7 M LE II HFB R S FP CHE4IS TRY........................................ s 308 096 u

LIST CF FIGURES Page FIGURE 1 Typical Corrosion Pattern for 1100 Al in Water ( Fr cxn ANL-5 0 01 )............................................ 9 FIGURE 2 BMRR Reactor Assembly. Hand drawn arrows indicates exposed Horal Sheets. Frczn BNL-600.............. 10-FIGURE 3 Schc=atic of 1/4" Boral Sheets in BMRR, Indicating Location of Punchings........................... 11 FIGURE 4 Microstructure of Sa=ple il as polished with 600 grit.............................................. 12 FIGURC 5 Microstructure of Sample #2 as polished with 600 grit............................................... 13 FIGURZ 6 Microstructure of Sample i'J as polished with 600 grit.............................................. 14 FIGURE 7 Microstructure of Sa=ple 44 as polished with 600 grit.............................................. 15 FIGURS 3 Microstructure of Sa=ple #5 as polished with 600 grit.............................................. 16 FIGURE 9 Microstructure of Sample #6 as polished with 600 grit......................................... FIGUPE 10 Neutron Attenuation Results on Samples 1-6 (?srfor=ed at U. of Michigan, Courtesy of Brooks G Perkins........................................... 15 FIGURE 11 I.lu=inu= Surfaces in Contact with 5tainless Steel Af ter 61/2 Months Exposure in the HFBR SFP, 2.5x............................. 19 wB 097 ui

INTRODUCTION Boral is a cermet of Boron Carbide "B C" in aluminum clad in 4 aluminum. It is manufactured in rolled sheets using techniques similar to those used in t'r' production of uranium aluminum fuel ele-meats. The core of the standard Boral contains 35: boron carbide by weight. Cladding material is typical 1100 aluminum. Where it is ex- 'ater in service, the edges of the Boral are recommended by a a the manufacturer to be clad with aluminum by welding. In Spent Fuel Fool (SFP) racks, the Boral is usually not a structural mecber but is inserted in cavities between the spent fuel storage positions in the racks. In these locations it is sealed by weiding to prevent access of water. Inherently, however, the cor-rosion of the Boral, both the boron carbide-aluminum cer=et and the aluminum cladding, should be minimal in a spent fuel storage pool. The cavities into which the Boral is sealed are typically fabricated of aluminum alloys, i.e. type 6061, or stainless steel. In either case, these are the structural = embers of the SFP racks. In an SFP, water chemistry tends to be strictly controlled be-cause the SFP water mixes with the reactor coolant during refueling procedures. In SFP's at BWR sites, water chemistry is typical of that of a BWR i.e. high resistivity neutral water. In SFP's at FWR sites water chemistry typically contains 2 to 3,000 parts per million pps boron as boric acid, which is there primarily to prevent dilution of the reactor primary coolant during ref: ling and is not relied on for criticality considerations. The water chemistries and anticipated 1

corrosion of SFP materials were reviewed in an earlier report. BNI.- NUREG IJG21, July, 1977. CORROSION OF BORAL Corrosion problems have developed in SFP's wh're water has inadvertentiv leaked into the cavities containing the Boral, In a 3'4R pool, swell

of the racks has been observed when water leaked into I

the cavities through a flaw in the seal weld at the bottom of the cav-ity. The swelling observed arises from the rapid initial corrosion of Al by water. Draley and Ruther (A%-5001, Feb. 1,1953) have shown that aqueous corrosion of 1100 A2 can be described in terms of a steady state slope and an intert.rp., as sketched in Fig. 1. This intercept was measured by them o be 21 + 5 mg/dm2 " metal corroded" over a range of temperatures (100 - 175'C) and pH (5 - 8.5). This " intercept" corrosion occurs within the first 5 days of i==ersion in water by a reaction of the type 2A1 + (3+x)R 0 Al 0.x H O + 3H - 2 23 2 2 Thus 21 mg Al can produce 21 X 3, or slightly more than 27 X 2 1 milli = ole H2 per dm2 of surface. The Brooks & Perkins Report 1577 says there are 3.4 x 102 dm2 Boral per tube in SPF racks such those at Monticello or 3rown's Ferry, so one could produce ap-as proximately 3.4 X 102 x 22.4 = approximately 7500cc H / tube, at 2 STP. This is more than enough to produce the necessary 6 psi to bulge the cladding in a void volume of 130cc. There is no reason to believe, however, that any 3 C will be 4 lost from the Boral by corrosion in the SFP water. In the Brookhaven 2

Medical Research Reactor, Boral has been exposed to the reactor cool-ant since January, 1959. Figure 2 shows a schematic of this reactor. The 1/4 inch Boral sheets are in the form of 2 half-cylinders. The upper edge of these sheets is unciad. The vertical edges appear by examination 3 situ with a periscope to be clad. In July of this year, samples were re=oved in the form of small punchings, three from each of the half-cylinders as shown on the attached sketch, figure 3. Each of these six speci= ens was cut in half, and one-half mounted for metallography. The resultant microstructures are shown in figures 4-9. Clearly there appears to be no systematic loss of the boron car-b id e. The other half of each of these specimens was analyzed by neu-tron attenuation at the University of Michigan under contract with Brooks and Perkins, the primary supplier. The neutron attenuation re-sults are shown in figure 10. All the results are within 20%, which with the small size of the specimens is probably within analytical er-One specimen, #5, was analyzed wet chemically by Brooks and ror. Perkins to contain 41.3% 3 C in the core, which is in the upper 4 range of boron concentrations for material produced in the 1950's. It, therefore, seems reasonable to conclude that no boron was lost frem the core of this Boral by exposure to the BMRR coolant over the 19 1/2 year period. In the location of the BMRR where it is used, there is little measureable neutron flux. Water chedstry in this re-actor is outlined in Table 1. PITTING OF ALUMINUM IN CONTACI WITH STAINLESS STEEL When aluminum is contacted with stainless steel in i:spure water, a potential exists for a galvanic attack of aluminum at the point of contact. In a STP environment, this attack is especially likely in a PWR pool containing boric acid at a pH around 4.5. Further, aluminum 3 h

borates can be produced which appear as a white fluffy dispersion in the water at a pH greater than about 4.5. Maintaining the pH below 4.2 causes the white fluffy material to disappear. Corrosion currents at a stainless steel to aluminum galvanic couple in boric acid were measured to average 2 mils per year although the presence of oxygen or hydrogen peroxide increased this value su,stantially. A nu=ber of references exist showing that pitting corrosion can occur in slightly acid waters at alwninum to stainless steel junctions. English and Griess (ORNL2TM-1030,1966) report pitting depths up to 45 mils in 12,500 hours (1 1/2 years) in pH 5 nitric acid solutions at 100*C. Lennox et al. (Materials Pet'formance, Vol.13,

2, page 31, 1974) measured pitting where type 5086 alwninum is coupled to type 304 stainless steel of the order of 30 mils in a year and one-half in Gatun Lake, Panama, and up to 40 mils in two years in the Pota=ac River at Washington. The general corrosion of this alloy was negligible in both environments.

In the HF3R SFP, water chemistry is similar to that in a 3WR STP except that conductivity may be slightly higher, and the pH slightly lower. Typical data are given in Table 2. Specimens of alu=inwn and stainless steel in contact with one another have been exposed in the RF3R pool for a period of six months at whien time they were examined and then reinserted for continued testing. There appears to be a general discoloration of the aluninum where it contacted the stainlesa steel and a small amount of pitting around the edges as shown in figure 11. It is highly unlikely, however, that pitting of this mag-nitude would result in significant loss of the boron should the Boral containing cavities be flooded over an extended period of time. 4 })Ob

Venting the upper end of the Boral chambers would probably al-leviate any concerns over swelling due to hydrogen generation. It might produce pitting corrosion and some of the whice alum'num borate deposits. I would recommend that a surveillance progrcm including aluminum to stainless steel couples be installed in SFP's in which the Boral cavities are vented. Any swelling due to hydrogen production should occur within a week or so of the tbse the water enters the an-nulus containing the Boral. However, should a leak develop in one of the seal welds at some future date after the racks are installed, the swelling could occur at that time. For this reason, venting or the capability for future venting, is probioly desirable. In general, I think the localized pitting corrosion that might result from venting the Boral cavities in SFP racks would be less of a safety concern than the swelling that might occur should they not be vented. In all SFP's the rack design should prevent contact between Al and the zircaloy fuel cladding, as this galvanic couple (especially in boric acid pools) can lead to hydriding of the zircaloy during storage, as de-scribed by A. 3. Johnson in BNWL 2256, September, 1977. CONCLUSIONS AND RECOMMENDATIONS 1. The swelling that has occurred in the Monticello SFP racks and might be anticipated to occur in other sisilar SFP racks results from initial corrosion of aluminum and not from corrosion of the boron carbide cermet. 2. Venting of these cavities in a BWR pool should not produce significant loss of the baron and should, therefore, be accepted by NRC provided the venting occurs at the upper edge so that any hydrogen prt sure from corrosion of the aluminum cladding will not build up to cause swelling of the racks. 5 300

3. Venting of the Boral cavities in a PWR rack might produce more pitting corrosion of the Boral. Again, however, it should not lead to major loss of the baron carbide. 4. Anodizing the Boral in these cavities would tend to reduce the hydrogen production in the cavities sliould SFP water leak in to them. Anodizing would probably not, however, prevent pitting of the aluminum. 5. In any fuel pool in which the 3 oral cavities are flooded intentionally or inadvertently, surveillance speci= ens should be pres-ent to determine on a periodic basis, i.e. once every few years, what is happening to the Boral in these cavities. 6. In any SFP, galvanic ccupling between Al in the racks and the zircaloy fuel cladding should be avoided, to prevent hydriding of the cladding during long term storage. ACKNOWLEDGEMENTS The assistance of the BNL Reactor Division staff, R.W. Powell, Head, in obtaining the 3 oral punchings from the BMRR spent fuel shielding is deeply appreciated. The metallography was perfor=ed by K. Sutter of SNL. 'Ihe neutron attenuation and wet chemistry results were obtained throug he courtesy of Mr. R. C. Kar: mar of 3 rooks and Pe rtcins, Inc. More detailed analyses of these specimens are underway at G.E., by A. Jacobs, and at Brooks and Perkins, and will be the sub-ject of a future report. 6 \\

T7.BI2 I BMRR HATER CHEMISTRY Tc=perature Inlet Cutlet T.S. P4 actor ON 100 F 115 F 136 F Reactor OFF 75-80 75-80 (Reactor CN less than 10% of time) Conductivity Normal Regenerate Alar 2 T.S. Demineralize (u=ho/c=t 325 C) <2 2 5 10 Alar:ned only once in 20 years, during RX leak. T.S. never exceeded. \\@ 7 gg

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DISTRIBUTICN LIST NRC Division of Cperating Feuctors V. Noonan W.S. Hazelten F.M. Alr.e te r (10) 'l Division of Syster.s Safety J.P. Knight S.S. Pawlicki H.F. Conrad B. Turovlin Brooks and Perkins R. Kar= tar Brcokhaven National Laboratory W.Y. Kato R.W. Pcwell Corrosion Science Group Files (25) 20
May 25, 1979 !GLTIN ABSCEBER SAMPLING PIAN - IN POOL A sampling plan to verify the integrity of the neutron absorber raterial employed in the high density fuel racks in the long-term envircrrent is described. The test conditions represent the vented conditions of the spent fuel tubes. The samles will be located adjacent to the fuel racks aM susperded frcra the spent fuel pool wall. Eighteen (18) test samples are to te fabricated in accordance with Figure 1 and installed in the pool when the racks are installed. 'Ihe procedure for fabrication and testing of samples shall be as follows: 1. Sa ples shall be cut to size and dried in an oven for five hours at 170 F, followed by a cycle at 600 F for three hDurs. 2. Samples shall be weighed irruliately follcwing renoval frtra the oven and weight in milligrams recorded for each sample. 3. Samples shall be fabricated in accordance with Figure 1 and installed in pDol. 4. Two sarples shall te rcreveri per schedule shown in Table 1. 5. Carefully cut samples apart at the weld without daraging the neutron abscrber, Wash with a soft brush in a mild abrasive and detergent solution, irrerse in nitric acid to rencve surface products, followed by a rinse of clean water and alechol. Dry in a 175 F oven for five hDurs, followed by a cycle at 600 F for three hours. 6. Weigh the samples and evaluate the weight chance in the neutron absorter raterial in milligrams per square centimeter par year. 7. Visually examine the clad surface for pitting. Take micrographs of the edge sur-face and any other s w areas. 8. If pitting is present, the depth of the four major pits are to be recorded and the average pit petraticn in mils of an inch per year determined.
. 9. Prepare report of sample test results and obser/ations. 10. Should any adverse conditions te detected, the samples may be subject to a 10 loading analysis. B
11. Mditionally, tw full length vented fuel storage tubes will be suspended in the I: col. They will be observed periodically for signs of swelling, and they will te opened and exruned should the stall specimens indicate any loss of abscrter material below.02gm/cn, Beron10, 2
12. Retain sa.ples. g
'~ ~ ' E ON g; UCLEAR PJEL STORAGE RACY.S CCRO.CSIC:1 PRCGRA'1, BORAL - STAI?;LESS STEEL (fiON-PRCPRIETARY VE.S!0li) MARCH 1979 O S@ CDMS
Xtf-NS-TP-009/NP E$ON g: NUCLEAR If tPOP. TANT NOTICE P.EGA: DING COMTENT5 AND USE OF THIS CCCU"ENT 1. Exxon Nuclear Ccmpany's warranties and representatives concerning the suDject matter of this document are those forth in the Agreement between Exxon Nuclear Company, set Inc. and the Cus tomer pursuant to which this document is issued. Accordingly, except as otherwise expressly provided in such Agreement, neither Exxon Nuclear Company, Inc. nor any person acting on its benalf makes any warranty or re-presentation, expressed or implied, with respect to the accuracy, ccmoleteness, or usefulness of the information contained in this document, cr that the use of any informatien, apparatus, method or process disclosed any liabilities with respect to the use of, or for damages resulting frca the use of any information, aoparatus, methcd or process disclosed in this document. 2. The information contained herein is for the sole use of Customer. 308 121
XN-f15-TP-009 I VALICATIT;G S!G::ATURES VALIDATING S:GNATURES: i Revision fio. and Date oo,, n n1_1n_7oi Rev. 0 (3/12/79) Revised Sections e.,, 4 o...., All Revised Pages Version Non-Proprietary Version Prepare'd Ey 4 Project Manager Date r o bo /7 3 3 k.: / 19 Centurred By tyr.Mecnanical /
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//[/M/ 7[ 3[/4/79 Date e 4 6r 1,w y, fig r. Licens_ing / Com::11ance Date u r/ i e _/79 I//4 /79 d / // / Approvec 5j . i ~ne w, e !1gr 5 crage'Encr. gr Services / Date n / /,y 3} iy/19
XII-IIS-I P-UU9/ fiP E C)hJ UCLEAR TABLE OF CONTENTS Pace ABSTRACT i 1.0 INTRODUCTIO:t 1-1 2.0 TEST FRCGPAM DESCRIPTIOt1 2-1 2.1 Specimen Cescription 2-1 2.2 Environment Cescription 2-2 2.3 Initial Measurements 2-3 3.0 SU" MARY 3-1 4.0 RESULTS 4-1 4.1 Internal Environment of Edge-Sealed and Storage Cell 5;ecimens 4-1 4.2 Visual Appearance 4-2 4.3 Weight Gain 4-3 4.4 Pitting 4-5 4.5 Metallography 4-6 4.5.1 Surface Corrosion Films -~ ~ 6-6 4.5.2 Edge Attack 4-7 4.5.3 Bulges 4-7 LIST OF REFERENCES }' O O ) G n4c5
X N-M S-T P-009/ ' P EQON NUCLEAR ABSTRACT Exxon Nuclear Company, Inc. has conducted a Boral*-Stainless Stcel Corrosion Program during the past 18 months to establish additional performance information for use of Eoral plates in spent fuel stor-age applications. The program consisted of a detailed review of ralated literature, an evaluation of test programs conducted by others, and additional corrosicn tests performed at Exxon Nuclear facilities. The objective cf the Exxon Nuclear test program was to obtain corrosion data for Boral-304 stainless steel test specimens in ' simulated PWR fuel pool environments so that reliable predictions could be made of wnat pnysical changes would occur in a defective, 1.e., unsealed spent fuel storage cell af ter a 40-year exposure. The Exxon Nuclear tests indicate that storage cells, containing a leak simula1.ing hole, will sustain aluminum corrosion at a rate which can be expected to c.onsume of the aluminum in the Scral core a f ter a 40-year exposure. Should Soral plates be exoosed to a tyoical PWR pool environment, the materiai is subjected to pitting, edge attack, and internal gas cressuri-
~~ation; but a effect on criticality safety is expected over the lifetine of storage cells cue to dislodgement of B;C particles.~~
The Soral test samoles discussed in this report are a neutron absorbing, shieicinq ma terial manufactured oy the Brooks and Perkins Company. The Boral specimens are a cc"nosite material consis ting of boron carbide evenly dispersed within a matrix of aluminum and clad wi th aluminum. 308 124 i cams
XN-US-TP-009/NP E' EQON NUCLEAR 1.0 INTRCCUCTION Prior to designing acks utilizing stainless steel clad Geral plates in PWR pool environments, Exxon Nuclear initiated, (during 1976 and early 1977), a review of applicable c:aterial corrosion literature and ;cr.duc:ed analyses of test results performed by others. Exxon Nuclear's reviaw of the related literature *, and performance of Boral in similar environments, indicated that there should be no adverse effect cr nuclear safety analyses of storage racks in a PWR pool environment. To provide further assurance of satisfactory material performance, Exxon Nuclear initiated a test program in February, 1977 to evaluate Scral clad in stainless steel 304 specimens in envircn-ments simulating utilization in Exxon Nuclear PWR storage rack applications. List of appropriate material contained in Reference section of this report. 308 125 1-G nac5
Xff-f15-I P-009/ fiP t'QON NUCLEAR 2.0 TEST PROCRAM DESCRIPTI0fl 2.1 SPECIMEN DESCRIPTION Exxon Nuclear's test program placed emahasis on investigation of Boral utilized in conditions typical of expected storage cells and PWR pool water environments. Consequently, storage cell component sections were fabricated wnich resembled the larger, full-size storage cells. Specifically, these reduced-size storage cell specimens consisted of inner and outer stainless steel 304 shrouds into wnich four (a) Boral p'ates were inserted. The con:plete assembly was sealed welded, resulting in 6" high x 6" wide test s;ecimens. Each c0mpleted cell specimen was made to simulate a leaking condition by drill-ing 1/16-inch holes as described in Appendix A. In order to separately observe and measure various corrcsion and material properties during the test, additional test specimens were utilized. These additional soecimens consisted of 2" x 2" coupons made as folicws: i 1) Open-edge Scral/ stainless steel composite; 2) Sealed-edge Boral/ stainless steel composites with a leak simulating hole; and, 3) Unencapsulated Eoral coucens. 2-1 308 126 cnas
Xi'-f;S-T P-C C9/ N P E ON UCLEAR 2.2 EN'/IRCI;MEtiT DESCRIPTICM Insulated nine (9) gallon polyethylene tanks, with fitted covers, were used for the plain Boral and open-edged Coral-stainless scecimens. Thirty (30) gallen tanks of the same construction were used for the closed-edge tests. Each tank was fitted with a stainless immersian heater and stirring mixer, which were affixed through openings in the tank covers. A stainless steel screen was used to hold the specimens off the bottom of the tanks and permit circulation of the environ-ment on all sides. In order to isolate the plain Boral speci-mens frcm the stainless steel screen, a pedestal was f3shicned from phenolic plastic. The open-edged composite samples, a 2" x 2" Scral piece sandwiched between two 2" x 2" stainless steel pieces, were held together with four (4) Met-clip springs, one along each edge. These were placed on the stain-less screens so that the clips held the specimens in a hori-zental position over the screen. The initial environment in each tank was deicnized water with a pH of 5.85 and a conductivity of 0.75 a mno/cm. Scric acid (H 80 ) and lithium nydroxide (LiCH H O) additicns were made 3 3 2 to produce the following: Envircnment A) Deicnized water plus 13.3 g/l Scric Acid (resulting in 2300 ppm Sc cn at 150*F). 2-2 30B 127 G A405
XN-fiS-TP-009/NP E ON UCLEAR Environment B) Deionized water,13.3 g/l Boric Acid, 0.0121 g/l lithium hydroxide Environment C) Deionized water plus 0.0121 g/l lithium hydroxide The specimens, were inmersed in each environment on July 1, 1977. The initial teqperature and pH of each environment were measured as follows: Environment pH Temoerature, F 1 5.20 146.4 2 5.53 147.2 3 9.15 153.4 T7e temperature and pH were measured daily. The temperature showed some fluctuations and variacs were installed in order to gain better temperature control. The pH in the borated solutions, I and 2, remained constant but in the alkaline tank, C, it dropped into the 7 range within days. In order to keep the solution pH in the alkaline range, addi-tional additions of lithium hydroxide were made. 2.3 INITIAL MEASUREMENTS Appendix A of this report contains descriptions of all Scral and stainless steel specimens utili:ed for the test crogram. The initial n:easurements and ning programs are also pro-vided in Apoendix A. 2-3 308 G8 cnas
XN-NS-TP-009/t:P E ON UCLEAR I 3.0 SUITARY No corrosion, pitting, nor stress-corrosion cracking was observed on any of the stainless steel coupons, or storage cell specimens used in this study. Tha austenitic stainless stee! can be expected to withstand exposure to borated fuel pool environments for the pro-jected forty-year life of spent fuel racks. Similarly, without a leak patn through the stainless steel liners, the interior Boral plates would not be subject to degradation as a result of aqueous corrosion. In the situation of a leak path through the stainless liners which permits the interior space to fill with the pool environ-ments, the results of the 2 month, 6 month, and 12 month exposure studies, show that Boral is subject '.c general corrosien, pitting and edge attack, and clad deformation due to internal gas pressurization. To varicus degrees, the severity of each of these corrosion effects depends on the particular environment chemistry and the specific geometry of the exposed materials. Based on comparisons between the four (J) specimen types and the three (3) environments used in this study, the following sumary can be drawn concerning the corrosien resistance of Boral and its suitability for use when exposed in stainless lined storage cells to barated environments. The general corrosion rate, as determined by weight gain measurements, When all the storage cell specimen data are examined on a se-n-leg olet, the amcunt of aluminum consumed in conversion to oxide after a 40-year exposure, is: percent for the icw cH and percent for the higher pH environments. 3-1 308 129 cnas
Xti-fl5-TP-009 E(ON NUCLEAR t'. The weight gains were lowest for the storage cell specimens in each of the three (3) environments, followed in general by the plain, open-edged, and edge-sealed specimens. The weight gains, measured for the plain and open-ecged s eci:rens, were nearly identical to each other in the three (3) environments. This similarly indicates that galvanic coupling between the stainless steel in the open-edged speciirens does not accelerate general corrosion in the Boral. In all three (3) environments, the edge-sealed specimens showed the greatest weight gain. 8 Similar considerations apoly to edge attack of the Soral. Hcwever, the depth of edge attack did not increase significantly br.*,cen the 3-2 308 130 Gn 005
Xil-IIS-TP-00ghiP E ON UCLEAR 6 and 12 month exposure. The deepest edge penetration, 0.023", was measured on the open-edged specimen in the low pli environment. No measurable edge attack was observed in the vicinity of the leak simulating hole in :ne Boral plates of the storage cell specimens. Gas generation, due to corrosicn of the aluminum in Boral, has been observed in the ecge-sealed specir: ens and the storage cell specimens. This gas has been observed to bubble from the upper hole in each of the storage cells. In several of the specimens removed af ter 12 months, bulges were observed between the aluminum cladding and the 3 C aluminum 3 core. The occasional unbonded layers of the Boral matrix occurred randomly and were observed in concentrated areas of very small B C particles 4 (i.e., >150 mesh). It has been determined that the Boral specimens provided by Brooks and Perkins for the UIC corrosion test progran con-tained a much higher concentration of small 3 C particles than utilized 4 for production Boral plates. Accordingly, it is possible that the small bulges observed on the sealed specimens may not occur in finished clates where improved B C and aluminum bonding result with larger 8 C particles. 4 4 The occasional lack of bonding between B C and aluminum particles also 4 allows a small amount of water to enter the inner cortions of the bulged specimens. Normally, water does not penetrate into well-bonded Boral plates and no internal corrosion can occur. The small bulges have not been reported or observed in prior related corrosion tes t programs. They appear to be a self-limiting pheno:renon, 33 e
hJUCLEAR where the gaseous corrosion product both causes the bulge and dis-places the water causing the corrosion.
~~inspection of both the aluminum cladding and inner Boral matrix demonstrates that no clad pitting cr deterioration of the inner face of cladding and Boral material occurred near the bulged areas.~~
Consequently shculd random small bulges occur, any dislodgement o; B C particles will be of no 3 significance on neutron shielding or attenuation properties. 6 e G ee ie -m-34 308 13 2
XN-IJS-TP.009/t;p E ON UCLEAR 4.0 RESULTS On June 30, 1978, after a ncminal 12-mcath exposure, the remaining three (3) plain Coral and three open-edged Boral-stainless composite specimens, were removed from the three (3) heated tanks. On August 10, 1978, the edge-sealed, and stcrage cell specimens, were r roved from their environments. These twelve (12) samples v.ere subjected to visual, metallographic, weight gain, and pit depth measurement analyses. This sactice of the report places emphasis en the de-tailed results obtained from the storage cell specimens. Appendix B presents additicnal test results for other specimens and contains most referenced tables and figures for infonnation presented in this section. Table 4.1 provides specimen identification num ers and exact lengths of excosure for each of the tv.elve (12) specimens eval-uated during the final period. 4.1 Jnternal Environment Of Edge-Sealed And Storage Cell Scecimens The pH of the solution, within the edge-sealed and storage cell specimens, was measured using indicater pacer for the former, and a Beckmann pH meter for the latter. Accroximately 2.5 grams of salution was contained in the edge-sealed speci-mens and 39 grams in the cell saecimens. In Table 4.2 is a sumuary of the interior pil of the edge-sealed and celi specimens for the 2, 3, and 12-ncnth exposures. 4-1 Q' 3@ cn.ms
XN-NS-TP-C09 /hP E ON g, UCLEAR For the high pH lithium environment, the interior pu consistently shows a decrease in pH toward a neutral value for all exposure times. A similar trend toward a more neutral pH is exhibited for the acidic envircnnents for exposures up to 6-months. After 12-months, the interior pH is the same as the bulk solution or, slightly more acidic. 4.2 Visual Accearance The storage cell specimens were disassembled and cut ccen to separate the Boral plates from the stainless 1.ners. A visual examination of each Boral piece was conducted using a Icw power steceo-microscope. The following observations were noted: Storace Cell Soecimen 33 (S.C.S.-3) Surfaces were generally metallic in coloration. Extra corrosion products, and some pitting, were seen en the faces and along the edges where the leak simulating holes were drilled through the stainless liners. Storage Cell Scecimen 46 (S.C.S.-61 Specimens are darker than SCS-3. Pitting is much less. Rust existed alcng edges where holes were drilled. Bulges were observed in the dimple area of plate S.C.S.-6(1), on both the outside and inside. 4-2 308 134 cn<os
XN-NS-TP-C09 /NP E ON UCLEAR Storage Cell Soecimen 19 (S.C.S.-9) Specimens were white in coloration with rust colored deposits along the edges where holes were drilled. BC 4 stringers were evident, but no pitting. Plate S.C.S.-9(4) had a 1-1/4" pure aluminum strip on one short edge. 4.3 Weight Gain Af ter the visual analysis, the appropriate Boral plate specimens were.veighed, oven-dried, and reweighed in order to determine the amount of. absorbed moisture in the core and the change in weight due to exterior and inte-rior corrosion. The specimens were dried in stages in an air-circulating oven for two (2) hours at 150, 200, 250 F, and for 24 hours at 200"F. The original weight, the weight prior to oven-drying, and the dried weight for each specimen, is listed in Table 4.3 A summary of the moisture absorbed weight percentages, for the 2-menth, 6-month, and 12-month exposures, is given in Table 4.4. The overall average for all soecimens, environments, and exposures, was This corresocnds to a minimum average porosity level in the Snral core of approximately The absorbed moisture decreased between 2-months and 6-months and increased between 6-renths and one year. This may be the result of an initial decrease in porosity as corrosion creducts were generated in tre core followed by a porosity increase as additional corrosion enlarged the pores. The greatest moisture absorotion occurred in the open-edged specimens in the A environment. This specimen also showed the greatest numcer of pits and would, therefore, contain the greatest amount of material capable 4-3 308 135 cn.ocs
XN-NS-TP-G09/NP EQON NUCLEAR of absorbing moisture. The least moistu,re, on the average, was in the storage cell Boral plates, which may be due to their larger size and lcwer edge to volume ratio. In Table 4.5, the corrosion weight gain percentaces are summarized for all the specimens tesced in the program The values, in brackets, have been corrected to account for the fact that certain of the 6" x 4" Boral plates in the cell specimens'contain,a strio of solid aluminum along one edge. Since this strip did not contain the normal porous core structure, it could contribute weignt gain only by external surface corrosion. To_make valid compariscns, using these specimens, their weight was re-duced by a factor corresponding to the reduced core volume. Under the assumption that the weight gain per ~ - centages are an indication of the extent of uniform corrosion in these specimens, the results presented in Table 4.5 show that the corrosion rates have decreased with increased exposure time. The results are plotted for each specimen type as a function of environment in Figures 4.4 througn 4.6. The weight gains are largest for the edge-sealed specimens in each environment. Similarly, they are the smallest for the storage cell specimens. In between, with very similar results, are the plain and open-edged specimens. The similar weignt gains, experienced by these two (2) specimen types, show that the general corrosicn is not accelerated due to coupling with stainless steel. 4-4 cnas
XII-fiS-T P- 009 /t;p E-ON UCLEAR When the weight gain values for the storage cell speci-mens are considered on a semi-logarithmic scale, the relationship appears to be amenable to extrapolation, as shown in Figures 4.7 through 4.9. From these figures, the extrapolated weight gain percentage and the calculated percent of aluminum consumed af ter 40 years exposure, are: 4.4 Pittina To evaluate the extent of pitting in the 12-month exacsure specimens, the corrosion products were cleaned frca the surfaces of a portion of one of the four (4) plates from each cell specimen. A surrary of the pitting frequency and pit depth, for the 6-month and 12-month exposures, is given in Table 4.6. The pit diameter for the 12-month specimens is also given in the table. Table 4.6 shows that the pitting characteristics af ter 12-months were very similar to those af ter 6-menths. Those specimens and environment combinations which did not pit or showed little pitting tendency af ter 6-months, showed no or few pits af ter 12-months, however, those with significant pits after 6-months had 3 large number of pi ts a f ter 12-months. Increased pitting was cbserved in the plain specimens in the A envircnment and in.ne edge-sealed specimens in the A and B environments. The other specimens shcwed nearly the same number of pits af ter 12-months as after 6-months. 4-6 g GR OCS
Ad -i,,)- 4 l'- L U'J/ lW E ON UCLEAR The pit depth, however, increased with the extended 12-month exposure. In scne cases where pits had not pene-trated the aluminum clad in 6-months, they had done so af ter 12 montns. 4.5 Metallocrachy Sections of Boral from each specimen were mounted ar.d metallographically polished in order to observe the thickness of surface oxidation films, the cepth of edge attack, the undercutting around drilled holes, and the nature of surface bulges. Sections were made along an edge for the plain and open-edged specimens, and through the drilled hole in the Soral for the edge-sealed and storage cell specimens. In addition, sections througn bulges in the specimens were made to characterize these structures. The specimens were back-filled with epoxy under vacuum conditicns to impregnate surface porosity, then rough polished on silicon carbide papers and final polished on diamond using automatic vibratory equioment. 4.5.1 Surface Corrosien Films The surface corrosion films on several of the scecimens were thick enougn to measure using a filar eye piece at a magnification of The film thicknen, as measured for these specimens, is listed in Table 4.7. The thickness for the C environment specimens was thickest, being a maximum of for the plain specimen. Uhere the bulge in this specimen caused the surfac9 layer to break apart, the corrosion films were much thicker. Appendix 3 contains photograpns showing the surface film in one area away from a Dulge and, for conoarisen, en a buige. 4-o 308 138 u,es s
Ai.-iia-i e-ov 1 Lir E/gON htJCLEAR C-4.5.2 Edge Attack Table 4.7 also shcws the depth of corrosive attack at the Boral coupon edges in the plain and open-edged specimens. The attack was greatest in the A envirencent and was somewnat greater in the open-edged specimen than in the plain specimen. Only one specimen of the six (6) edge-sealed and stcrage cell types showed accelerated corrosion around the partially. drilled leak simulating hole. This was the ecge-sealed specimen in the C environment. The similarity in edge attack between the plain and ocen-edged specimens again indicates a lack of corrosion acceleration due to galvanic coupling of the Bora' to stainless steel. 4.5.3 Bulges Several bulges were observed on the 12-month expcsure specimens. Similar bulges were not observed on scecimens exposed for 2-or 6-months. Table 4.8 lists the number of bulges observed on each specimen. Photograpns demcnstrating bulged areas are shcwn on Figures 4.2 and 4.3. The bulges are separations between the aluminum clad and the B C-aluminum matrix. They accear to result from gas 4 pressure caused by internal corrosion. The corrosicn of aluminum would generate hydrogen gas following the reaction 2A1 + 3H O - Al 02 3
~~3H '~~
2 2 4-7 308 139 Gn4C5
XN-NS-IP-On9 7,.p' E ON UCLEAR Such gas generation has been cbserved in the edge-sealed and storage cell specimens. To generate a bulge '..ould require sealing of the edges with corrosion products to enable the internal gas pressure to ircrease sufficiently to expand the ten mil aluminum c' adding. The edge-sealed specimens each had four (4) bulges. These specimens also showed the largest corrosion weight gains which ccule result in the sealing of edges in these specimens. 4-8 30b onacs
Xft-NS-TP-009/NP E ON UCLEAR REFEPE*!CES (1) Corrosion Cata Survey Fifth Edition,i: ACE 1974, P. 34. (2) A Guide to Corrosion Resis tance, J. P. Polar, Climax t'olybdenun Co., P. sa. (3) Corrosion and Corrosion Product Release in f:cutral Feedaater E. G. Brush and W. L. Pearl, Corr. V. 28, :o. 4, Aoril 1972, Pp.129-136. (4) Stress Corrosion Cracking Problens and Pesearch in Encrcy Systens Proccedings ERDA Meeting 2/24/75. ERDA 76-93, Edi ted by L. C. Janniello (5) Corrosion Resistance of Metals and Alloys, F. L. LaGue and H. R. Ccoson, Chapter 5, Cerrosion Testing, P. 136. (1963) Reinhold Publishina Caro. (6) Fundgrental Asnects of Stress-Corrosion Crackinq. ?! ACE 1969, Stress-Corrosion Cracking of I ron-tiickel-Carom 1un Al loys, R. 't. La tanision, R. W. S taehle, P. 214. (7) Corrosion and Corrosicn Control - Herbert H. Uhlig, John Wiley & Sens, flew York 1971, P. 309. (8) " Aquecus Cor. of Aluminum Part ! Behaviour of 1100 Alloy" J. E. Draley and W. E. Ruther, Corr. 12 4dit 1956. (9) Reactor Techno1;cv - Selected Reviews 1964 USAEC Aluminum Alloys, J. E. Draiey anc W. E. Rutner, P. 215. (10) "Resis tar.ce to Cerrosion and Urcss Corrosion," '.l. ii. Sincer, E. H. Hollings.! orth and D. O. Sprowls, in Aluminum Vol.1, ASM, Chic,1967. (11) Atlas of Electrnchemical E;uilibria in Aqueous Solutions, taarcel Pourbaix Pergamon Press,*:ew York (1966). (12) Acueous Corrosion of Aluminum Part I Behavior of 1100 Alloy, J. E. Draley and W. E. Ruther, Corr. 12 441t 1956. (13) '00servations on the >echanisms and Kinetics of Aquecus Aluminum Corrosic i, V. H. Troutner, Cerr. 13 595 (1957) (14) A Survey of Materials anc Corrosion in Dry C:ciing Applicaticns, 2 S. J: ns:n,P D. P. Pratt anc 3. E. Zima, 0r.:L-1953, UC-12 1976. (15) Priva te Conniunica tion between R. McGcey and B. C. Fryer. (16) Dynamic Corrosion Studies for the High Flux Isotone Reactnr J. L. Englis" and J. C. Griess, OR::L-TM-10301966, Oak Ridge ' ational Labora t:ry. (17) Calvanic Corrasion of Al Alloys I Effect of Dissimilar *':tal. F- " ins # eld, D. II. Hengstenbero and J. V. Kenkel Corr. Vol. 30, ?:n. 10, 0ct. l?70, P-343. ff- )hh 4-9 cnas
UNITED STATES OF AMERICA NUCLEAR REGULATORY COMMISSION BEFORE THE ATOMIC SAFETY AND LICENSING BOARD In the Matter of Commonwealth ) Docket Nos. Edison Ccmpany (Zion Station, ) 50-295 Units 1 and 2) ) 50-304 CERTIFICATE OF SERVICE I hereby certify that copies of " Testimony of J. E. Draley" dated May 31, 1979, have been served upon the following by deposit in the United States mail, first class, postage prepaid, this 31st day of May, 1979: Edward Luton, Chairman Dr. Forrest J. Remick Atomic Safety and Licensing 305 East Hamilton Avenue Board Panel State College, Pennsylvania 16801 U.S. Nuclear Regulatory Commission Atomic Safety and Licensing Washington, DC 20555 Board Panel U.S. Nuclear Regulatory Dr. Linda W. Little Commission Research Triangle Institute Washington, DC 20555 p. O. Box 12194 Research Triangle Park, Richard E. Webb, Ph.D North Carolina 27709 2858 111 Street Toledo, Ohio 43611 Docketing and Service U.S. Nuclear Regulatory Rick Konter Commission 617 Piper Lane Washington, DC 20555 Lake Villa, Illinois 60046 Richard Goddard Susan N. Sekuler Office of the Executive Assistant Attorney General Legal Director 188 West Randolph Street U.S. Nuclear Regulatory Suite 2315 Commission Chicago, Illinois 60601 Washington, DC 20555 Atomic Safety and Licensing Appeal Board U.S. Nuclear Regulatory Commission Washingic,n, DC 20555 i - /g[- Q( < h / { kYYA Philip P. Stgptoe g' }QO .}}

ML19241B120

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