ML19225A246

Testimony of EA Gulbransen Re Questions 1-3 of ASLB 790418 Order.Storage of Spent Fuel Pools at Reactor Sites Involves Large Amounts of Radioactive Matl in Event of Serious Nuclear Accident.Certificate of Svc Encl

ML19225A246
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Site:	Salem
Issue date:	06/15/1979
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NuCLtAR REGULATORY COMMISSION gg Before the Atomic Safety and Licensine Board .

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PUBLIC SERVICE ELECTRIC & J GAS COMPANY Proposed Issuance of Amedment to

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(Salem Nuclear Generating Facility Operating License Station, Unit #1) ""

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IESTIMONY OF EAFl. A. GULBRANSEN, Ph.D. , P.E.

INiREbPECT TO BOARD QUESTIONS F1,#2, #3, OF ')KDER DATED APRIL 18, 1979 My analysfs of the accident of Three Mile island and tht. potential involvenent of .he spent fuel pool and how that relates to Salem 1, necessarily involves some discussion of my opinions as to the use of Zirconium Alloys as cladding for the uranium dioxide fuel pellets in nuclear reacrors.

I believe the reactor at Three Mile island underwent a major te=perature excursion luring which, f rom available information, i would conclude that 10% - 15.: of the Zircaloy cladding reacted with steam to form Zirconium dioxide and hydrogen. This reaction furnished most or the hydrogen in the bubble at the ream - head.

Part or the hydrogen probably penetraced the oxide film on the Zircaloy II cladding to dissolve in the metal and to torm zirconium hydride, ZrH This hydride has low hydrogen equilibrium pressures at the normal operating temperature or the reactor. Such reacted hydrogen obviously cannot be vented. I have prepared papers reported in the literature which described my work on this reaction. This work showed that hydrogen gas rapidly penetrates the oxide. At defects and edges spalling of the hydride and oxide could occur. I suggest that this reaction may have occurred in the reactor absorbing the hydrogen bubble. With or without spalling embrittle=ent of the cladding must have occurred with serious da= age to the Zircaloy in the reactor. The spalled zirconium no 03 7907180wl

hydride and zirconiua oxide would fall to the bottom of the reactor together with the fuel pellets. The circulating cooling water continues to react with the treshly spalled zirconim hydride sufaces forming more zirconium dioxide and hycrogen. 1 predict that this reaction will continue until all of the Zircaloy 11 cladding is reacted.

As a resuit of the abovc analysis, I suggest the following procedures:

1. Hydrogen in the cooli y; water should be ourned catalytically to prevent build up of another hydrogen buble in the reactor.

Z. The low temperature Zircaloy II - water reaction will continue as noted above. All released gases must be filtered and trapped before burning to remove radioactive gases and 'cetoactive particulates. The only safe caemical and conditions after an accident like that at Three Mile island is to have all of the Zircaloy Il reacted to 2e oxide.

3. hydrogen in the circulating cooling water must be monitored and removed until a near zero value is attained to insure that no metal and hydride remains. A temperature excursion with unreacted metal and hydride in the reactor could lead to reformation of the hydrogen bubble. Ilydrogen gauges of nigh . sensitivity are now available or could be made in a short time.

4. I am much concerned about the effect of hydrogen on the reactor vessel and piping.

1 strongly recommend that experiments be made on hydrogen e=brittlement of the alloys used in the reactor and piping under conditions si=ulating those which occurred in the reactor.

5. I strongly recommend that experiments should be made en the ef fect or hydrogen in the cooling water at high pressure on pre-oxidized Zircaloy II to evaluate the penetration and pick-up or hydrogen as a tunction of te=perature and pressure.

6. i reco= mend calculations on how much of a rapid Zircaloy II - steam or water reaction could occur before the hydrogen formed embrittles the cladding and ruins the reactor.

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sensitive hydrogen gauges should be installed on the primary and secondary loops and on the reactor itself to monitor the Zircaloy 11 -

steam anc water reaction.

I should like to repeat that these suggestions are based on extensive research in the field of gas-metal reactions. My own basic research on zirconium began in 1947 oefore the tormation of toe Westingnouse Bettis Atomic Power Laboratories.

Twenty years of nearly continuous research was conducted on the reactions of zirconium, Zircaloy II, Zircaloy IV and the other zirconium alloys with oxygen, air nitrogen and water vapor over a te=perature rant,e of 25*C to 800 C and at pressures of a few corr t o over lu0 atmospheres.

This work uas reported in 25 papers and many research reports to the Westinghouse Electric Corporation.

Many important tehnical problems were solved including the solubility of hydrogen in zirconitm, the crystal structure and range of homogenei of circonium hydride, ZrH y,4, the rate of diffusion of hydrogen in circonium, the role of cxide films on hydrogen adsorption, the rate of oxidation of zirconium in oxygen, the rate of nitride formation in nitrogen , the types of hydrogen reaction with zirconium intermetallic compounds ,

the rate of reaction of zircenium alloys in water at high pressure and rne behaviour of Zircaloy II in fast flowing steam at temperatures above 1000*C, Af ter 25 years of research and development on the chemical and and =etallurgical properties of =etals and alloys used in nuclear power plan ts , I have come to the conclusion that the current design and materials cannot give us a safe and well.enginacred nuclear power plant.

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The use of zirconium alloys as cladding material for the hot uranium oxide fuel pellets if a very hazardous design concept since zirconium is one of our most reactive metals chemically.

At tne operating temperature of nitclear power reactors zirconium cladding alloys react with oxygen in water for form an oxide layer which partially dissolves in the metal embrittiing and weakening the metal tubing. Part or the hydrogen tormed in the zirconium metal reaction dissolves in the metal and may precipitate as a hydride phase also embrittling and weakening the metal tubing.

At temperatures above 1,100* celsius (198u* Fahrenheit) zirconium reacts rapidly with steam with a large evolution of heat and the tormation of free hydrogen, with most metals to form intermatallic compounds and with other metallic oxides to form its own oxide. Once zirconium is heated to 1,100* celsius, which could occur in loss of coolant accidents, its is difficult to prevent further reaction, failure et the tubing and of the reactor.

There appears to be no way to overcome the inherent material problems associated wit h zirconium alloys and the current design of tne reactor Greater wall thickness for cladding and lawer operating termperatures of the fuel may help but the chemical and metallurgicaI behaviour of zifcodlum alloys cannot be overcome. No backup or alternative design is available if the present design and materials prove unreliable.

Considering the potential and consequences of a meltdown or explosien as posed in :ne Board's question, it would be more consistent with the safety and health of the public to store spent fuel away from operating nuclear reactors. The storage of spent tuel in spent fuel pools at reactor 3 21 O f.iG

sites in close proximity to operating nuclear reactors for long periods of time and in large quantities represents a significant involvement or large amounts of radioactive material in the event a ser:ous nuclear accident.

RECORD OF SCIENTIFIC AND ENGINEERING EXPERIENCE Earl A. Gulbransen CONTENTS Page 0.0 Abstract ........................................... 1 1.0 Was hin n t en S ta t e Unive rs i ty . . . . . . . . . . . . . . . . . . . . . . . . 3 2.0 Unive rsity o f P i t ts b u r g h . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.1 Thermodynamic Properties of Dilute Soluticas . . ... . . 3 3.0 Unive rsity o f Ca li f o rn ia . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 3.1 Thermodynamic Properties of Cases and Solutions .. . . 4 4.0 Tu f ts Un i ve rs i t y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4.1 Geo che =1 cal ' Res ea rch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4.2 National Research Council Conmittee on die De te rmina tion o f Geolo gic Time . . . . . . . . . . . . . . . . . . . . . 4 4.3 Closure ............................................ 4 5.0 Westinshouse Electric Corporation Research Laboratories ....................................... 6 5.' Dat e s , Posi tion and S upe rvis o r . . . . . . . . . . . . . . . . . . . . . 6 5.'l .1 0 xi d a t i on o f Me t a ls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 5.1.2 Cons ultin g Ac ti vities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 5.1.3 Wo r ld W a r I I Wo rk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 5.1.4 Closure ............................................ 7 5.2 Dates, Position and Supervisor ..................... 8 5.2.1 Gas Reactions of Carben 300-1500*C ................. 8 5.2.2 Reactions of Zirconium and Zirconium Alloys,etc. ... 8 1

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. CONTENTS Page 9.3 A:serican Checdcal Society, Pittsburgh Section Award ..................................... 28 9.4 Electrochemical Society, Acheson Award a n d P ri z e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 10.0 Othe r Scien tific Activities . . . . . . . . . . . . . . . .. . . . . . . 29 10.1 International Conference on Surface Reactica ...... 29 10.2 Gordon Research Conference on Me tals . . . . . ... . . . . . . 29 10.3 Gordon Research Conference on Corrosion ........... 29 10.4 Co rro si on Res earch Co un cil . . . . . . . . . . . . . . . . . . . . . . . . 29 10.5 American Institute of Mining and Metallurgical Engineers Conference on Stress Corrosion Fracture . 29 10.6 American Institute of Mining and Metallurg; Leal Engineers Corrosion Resistant Metals Commitece ... . 29 10.7 American Chemical Society , Pittsburgh Sectica . . . . . 29 10.8 Electrochemical Society, Pit *sburgh Section .. . . . . . 29 10.9 Chemists Club of Pit tsburgh . . . . . . ................ 29 10.10 International Union of Pure and Applied Chemistry ......................................... 29 n.0 S

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RECORD OF SCIENTIFIC AND ENGINEERISC EXPERIENCE Earl A. Culbransen ABSTRACT 0.0 Washington State Collene (now Washington State University),

Pullman, Washington, graduated with honors, June,1931, in Chemical Engineering ar d minors in Physics, Physical Chemistry and Mathecar .:s. Teaching assistant and under-graduate research.

0.1 University of Pittsburch, Pittsburgh, Pennsylvania, received Ph.D. degree in Physical Chemis try, August, 1934, with minors in Physics and Mathematics. Research work on thermodynamics of solutions. Teaching assistant in organic and physical chemistry.

0.2 University of California, Berkeley. National Research Council Post-Doc torate Fellowship in Physical Chemistry, September,1934-August, 1935. Research Associate in Physical Chemistry, September, 19 35-Augus t , 1936. Research work en ther=odynanics of Bases and solutions.

0.3 Tufts College (now Tufts University), Medford, Massachusetts, Se p tembc. , 19 36-June, 1940. Instructor in Chemical Engineering, Physical Chemistry and Analytical Chemistry. Research work on mass spectrometrically determined abundance ratios of carbon isotopes in nature.

0.4 Westin2 house Electric Corporation, Research and Development Center, Pittsburgh, Pennsylvania, July,1940 to present.

0.4.1 July,1940 to July,1947 - Research Engineer in Chemistry Depart-ment. Research on gas-metal and gas-solid reactions wid energy sources for underwater propulsion.

0.4.2 July,1947 to July,1966 - Advisory Engineer. Research en gas-metal and gas-solid reactions with special application to the nuclear power, la=p and electronic industries. Consulting work on chc=1 cal and m tallurgical engineering processes.

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0. 4.1. 3 July,1966 to Present - Consulting Scientist. Research rn gas-metal and gas-solid reactions with special emphasis on applica-tions in flash lamps, incandescent lamps, nuclear power and high temperature technology, hot corrosion of gas turbines and coal gasification. Extenedve consulting activities with Westinghouse Divisions on corrosion, high temperature sintering of tungsten, getters for lamps, flash bulbs, hydrogen embrittlement, stress corrosion cracking and structure of surfaces.

0.5 other Activities. The complete record details my publications, patents, scientific societies, awards and other scientific and engineering activities.

0. 6 Summarv. For the 26 years between July,1947 to the present I have been responsible for scientific and engineering work on a wide variety of chemical and metallurgical problems. I have had a total of 39 years of independent and supervisory scientific and engineering vork experience.

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AMPLIFIED RECORD OF SCIENTIFIC AND ENGINEERING ET ERIENCE Earl A. Culbransen 1.0 Washinstton State University, Pullman, Washington. Bachelor of Science in Chemical Engineering with honors with minors in Physical Che=istry and Mathematics, June,1931.

Between September, 1930 and June, 1931, I worked as a laboratory assis tant in analytical chemistry. My supervisor was Dr. Lyle Gilbertson.

2.0 University of Pittsburgh, Pittsburgh, Pennsylvania; Department of Chemistry. Ph.D. in Physical Chemistry with minors in Mathe-catics and Physics, August, 19 34.

Between Septe:ber,1931 and August, 1934, I was a gradrate assist-ant in organic chemistry under the supervision of Profe2.sor Lowy (deceased) and in physical chemis try under the supervisic.4 of Professor Stege=an (deceased).

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Thermodynamic Properties of Dilute Solutions My research supervisor was Professor A.L. Robinson (deceased).

Professors Robinson and Stegeman encouraged me to work in the field of Chemical Ther.:cdynamics. I have followed their suggestions and I have contributed extensively to the field. My thesia work was concerned with the thermodynamics of dilute solutions of aqueous electrolytes. To carr,/ out this program I asse= bled the first precision adiabatic dif ferential calorimeter in the United States.

My thesis work was published in the Journal of the American Chemi-cal Society, Vol. 56, 2637 (1934) and is referred to ao paper num-ber 1 in Section 6.

3. 0 University of California, Berkeley, California; Department of Che=1s try.

In the su=mer of 1934 I was awarded a National Research Council Post-Dectroate Fellowship in Physical Chemistry. I chose to work at the Chemistry Department of the University of California headed by Professor G.N. Lewis (deceased).

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3.1 Thermodynamic Properties of Solids , Liqu!.ds and Gases At the University of California I conducted research work in Professor Claque's Low Temperature Laboratory and with Professor Ran-dall. Together with Dr. E. Long, I determined the data of state equation for phosphine. This work was published in the Journal of the American Chemical Society, Vol. 58, 203 (1936). I worked also in the field of thermodynamics of solutions and especially in non-aqueous solutions. I coctinued my pos t-doctorate educa-tion by attending and participating in study seminars on radio-chemistry, thoretical physics, thermochemistry and theory of solutions.

4.0 Tuf ts University, Medford, Massachusetts; Department of Chemis try and Chemical Engineering.

Between September 1,1936 and July 1, 1940, I was ins tructor in Chemical Engineering teaching 'Init Processes, Chemical Engineering Thermodyna=ics, Cas Analysis n .J Analytical Chemistry. I also supervised the research activities of 10 senior chemical engineer-ing setdents. Chairmen of the department, in chronological order, were Professor Durkee (deceased) and Professor Baker (deceased).

4.1 Geochemical Research At Tufts University I began a new field of research on geochemical and geophysical processes in nature. Thir became possible by the rapid development of mass spectrometric measurement of abundance ratios of the elemental isotopes. I initiated, together with Dr. A.

O. Nier of Harvard University , a comprehensive study of the abun-dance ratios of Cl2 and Cl3 of naturally occurring. carbon co= pounds. This was a nioneering work and led to the use of C12/C14 ratios for dating of matter. The werk was published in the Journal of the American Chemical Society, Vcl. 61, 697 (1936).

4.2 National Research Council Committee on the Determination of Geo-logic Time The head of this committee was Professor A.C. Lane (deceased) of Tuf ts University. Professor Lane was later called the forgotten man of atomic energy. I worked with Profesace Lane for 3 years developing research programs on the use of isotopes not only for geologic tine evaluation but for developing new methods for follow-ing geochcedcal reactions.

4.3 Closure In summary , I spent 4 years at Tuf ts University doing independent teaching and creative research. During this period I maintained 4 ._

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close cot:::runication with the teaching and research staff at Harvard University and Massachusetts Institute of Technology by attending weekly seminars and by attending local scientific society meetings. None of cry supervisors were Registered Pro-fessional Engineers.

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5.0 Westinchouse Electric Corporation, Research and Developeent Center, Pittsburgh, Pennsylvania. July 1,1940 to Present.

Due to difficulties in financing research work at Tuf ts, I de-cided to leave Tuf ts University and join the Westinghouse Re-search Laboratories. Wee;.inghouse, at that time, was attracting many good people vii opportunitics to work on basic research p rob b.--a of ine:. rest to the electrical manufacturing industry.

5.1 Between July 1,1940 and about July 1,1947, I was employed as a Research Engineer in the Chemistry and Metallurgy Department.

My supervisors were, chronologically: Mess rs. A. A. Bates , Mana-Ser, Chemistry and Metallurgy Department, and R.W. Auxier, Mana-ger, Chemis try Department. Neither were Registered Professional Enginee rs.

5.1.1 0xidation of Metals My primary project was (1) to develop mcchods for the study of gas-metal reactions, (2) to use these methods for the study of the oxidation of a variety of the common metals and alloys and (3) to develop theoretical models to explain the experimental results. I developed for thcse studies a very sensitive micro-balance which was placed in the react ion system for determining the kinetics of oxidation of metala. I developed a special cle: tron dif fraction camera for the study of the curface structure of the oxide films formed on metain at temperatures up to 1000*C.

I also developed with my co-workers methods for using the newly developed electron microscope for the study of the crystal habit of oxide films formed on metals durinp, oxidation.

T* enty basic papers were published during this period on (1) the kinetics of oxidation, (2) the crys tal s tructure of the oxide fil'ts and (3) che crystal habit of the oxide films. These papers are listed as papers number 4-23 in Section 6. The vacuum microbalance method has been duplicated and tmed throughout the world for gas-me tal s tudies. We have also centributed extensively to present understanding of the crystal structure and crystal habit of oxide file:s on me tals.

5.1.2 Consultine Activities During this period I acted as a censultant to the Wes tinghouse Lamp Division on metal problems. I ah.o consulted with the electronica department, metallurgy department .ind chemical department at our Laboratories.

5.1.3 World War II Work During the period of 1942 - 1945, I worked on new methods of under-6 . , 1 O

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vater propulsion, including rocket and jet propulsion, primary batteries, chemical power plants and gas turbines. I also car-ried out, with the help of technicians, experimental work on duct prepulsion for torpedoes.

My suggestions on primary battaries led to a large contract with the government for the production of a new type of battery powered torpedo. This work was termir.ated in 1945 at the end of the war.

5.1. 4 Closure During this seven year period I worked as an independent research engineer. For part of the time I supervised the work of 1-4 professionals and technicians.

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5.2 July 1,1947 to July 1,1966, Advisory Engineer My supervisors were, in chronological order: R. Auxier, Manager, Chemistry Department, and W.T. Lindsay, Jr., Manager, Physical Chemis t ry Department. Neither were Registered Professional Engi-neers.

On July 1,1947, I was promoted to the position oi Advisory Engi-neer. In this position, I conducted basic research projects di-rectly and with the help of other professionals and technicians.

I was primarily responsible for the adminiatration, conduct and reporting a ' asic research activities in the area of surface reactions of gases with metals, alloys , non-metals and oxides and the corrosion of metals and alloys. I reported directly to the manager of the Chemis try Department.

Our research activitics were of three types: (1) programs develeped in cooperation with Divisions of Westinghouse, (2) pro cams spon-sored by U.S. Covernment agencies and '1) basic research programs initiated to solve long-range research objectives of the company.

The apparatus, methods and treatment of the problem were essential-ly the same for the three types of research activities.

5.2.1 Cas Reactions of Carbon 300 - 1500

• C This work was done for Bettis Atomic l'ower Division and Astronuclear Division to provide basic information on the reactivity of carbon at high t =cperature in the various nucicar power devices. Extensive studies were made on the reaction of pure graphite, pyrolytic car-bon and doped carbon materials with oxygen, f r, hydrogen, carbon dioxide and helium at temperatures of 300* so 1500*C, over a wide pressure range from a fraction of a torr to 76 torr and under a wide range of flow rates.

This work was done over the fif teen year period of 1950 to 1965.

The results were of immediate value to the Divisions. In addition, the work led us to a new understanding of gas-salid reactions where the reaction product also was a gas. This work was reported in papers number 44, 45, 46, 47, 113, 116, 117, 122, 123, 124, 125, 126,127,135,143, and 15 7 of the papers lin ted in Section 6.

5.2.2 Reaction of Zirconium and Zirconium Allovs with Oxvgen, Hy d ro gen ,

Nitrocen and Water Vapor This work was done for the Atomic Energy Comadssion, Bettis Atomic Power Laboratories and our Commercial Atomic Power Divisions. The work was begun as a basic research pro,, ram in 1947 before the for-mation of Beteis Atomic Power Laboratories. Twenty years of nearly continuous research ef fort was carried out on the reactions of zir-conium, Zircaloy II, Zircaloy IV and numerous other :irconium alloys 8

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with oxygen, air, hydrogen, nitrogen and water vapor over a-temperature range of 25' to '0*C and pressures of a few torr to over 100 atmospheres. Thio work was reported in 25 papers which are referred to in Section 6 as papers number 35, 56, 56e, 59, 61, 62, 66, 68, 69, 70, 72, 73, 75, 77, 78, 79, 92, 132, 136, 137,138,142,143,146 and 151 hany technical proble=s were solved in these studies including the solubility of hydrogen in zirconium, the crystal structure and range of homogeneity of zirconium hydrides, the rate of dif-fusion of hydrogen in zirconium, the role of oxide films in hydrogen adsorption, the rate of o::idation of zirconium in oxy-gen and in nitrogen, the types of hydrogen reaction with zir-conium intermetallic compounds and tb reaction of zirconium al-loys in water at high pressure.

5.2.3 0xidation of the Refractory Metals , T tngs ten, Molybdenum, Rhenium, Niobium and Tantalum This work was done for Wright-Patterson Air Force Laboratories, U.S. Ar=y Of fice of Research, Durham, Wes tinghouse Lamp Division and for Westinghouse Basic Resca"-h programs.

Twenty-six years of research ef fort was carried out on the reactions of tungsten, molybdenum, rhenium, niobium and tantalum with oxy-gen, hydrogen and hydrogen-water vapor gas mixtures over a temrera-ture range of 25' to 2700*C, a wide pressure rang,e and in static and flow reaction environments. This work was reported in 20 papers which arr referred tc in Section 6 as papers number 17, 20, 21, 33, 37, 91, 106, 110, 111, 112, 113, 115, 117, 123, 129, 147, 156,157,159,164 and 166.

The studies included kinetic studies on the oxidation reaction and the role of volatile oxide species on the rate of oxidation, the crystal structures of the oxide films , the mechanisms of oxidation and the thermochemical stability of the oxide species.

Many technical proble=s were solved in these studies. The work pointed out the difficulties inherent in using these materials in high temperature oxidizing gas environments due to the formation of volatile metal-cxide gas species. Studies on the sintering of silicon, aluminum and potassium deped tungsten ingots showed the i=portant role of the oxygen potential of the hydrogen-water vapor gas =ixture in controlling the composition and properties of the tungs ten ingots. Vapor pressure studies en molybdenum oxides demonstrated the high volatility of the crimer (Mc0 3) 3 5.2.4 Localized Oxidation and Stress Corrosica Cracking of Metals This work was started as a basic research program and later sponsored

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by the Of fice of Naval Research and the Westinghouse Stress Cor-rosion Cracking Committee. Eighteen years of research work was carried out on the nucleation of oxides on iron, the formation of oxide whiskers and blade-shaped and fan-ehaped oxide platelets on iron and the mechanism of stress corrosion cracking of metals.

This work was reported in 20 papers which are referred to in Section 6 as papers number 57, 58, 65a, 83, 86, 88, 89, 90, 103, 104, 105, 114, 121, 148, 349, 150, 153, 155, 158 and 165.

The results of this work has suggested new models for the oxidation of metals , new mechanisms for the rapid transport of metal in oxide structures and a new model for the stress corrosion cracking of metals.

5.2.5 0xidation of Alloys This work was started in 1945 as a basic research program since Westinghouse was interested in developing better heat resistant alloys for electric stoves, steam and gas turbines and for use in a wide variety of electrical apparatus. Twenty years of re-search was carried out on the kinetics of oxidation of type 304 stainless steel, nickel-chromium-aluminum and iron-chronium-alumi-num alloys. Crystal s tructure and crys tal habit studies on the oxide films was correlated with the kinetic observations. This work was reported in 16 papers which arc referred to in Section 6 as papers number 15, 16, 17, 19, 25, 26, 27, 29, 31, 92, 55, 63, 80, 84, 85 and 97.

These studies were valuabic in establishing the unique role of

' h romi um, aluminum, manganese, silicon and trace impurities in high temputature oxidation.

5.2.6 The rmocher.ical Analyses Thermochemical analysis was used as a discipline to guide us in planning and interpreting all of the research programs. In the early 1940's we scarched the literature and assembled f ree energy and equilibria data on many oxide systems to evaluate the oxida-tion, reduction and sintering react ions of metals. This cenpila-tion of ther=ochemical information was one of the firs t and was ve ry important in our own work and as a help to others in sur laboratory and in Westinghouse Divisions. Three special studies were made to develop thermochemical quantitics to hcip in our own studies: (1) vapor pressure of beryllium, paper number 38, (2) va-por pressure of chremium, papers number 50 and 67 and (3). vapor pressure of =olybdenum trioxide, paper number 111. These papers helped us to develop =odels for the oxidation of beryllium, chromi-um and molybdenum.

Experimental thermotherd cal studies were also made for (1) zirconium-10

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hydrogen system, papers number 59 and 62 and (2) columbium-hydrogen system, paper number 106. The results of this work were very valuable in using zirconium alloys as a cladding material in pressurized water .suelear power reactors.

5.2.7 closure All of the work during this perf od was under my direct supervision.

I participated in the planning, carrying out of the experiments, in the interpretation of tha results and in the write-up of the results. During this period I supervised the work of 4- -- fes-sionals and 2-4 technicians.

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5. 3. 2 Oxidation of Silicon and Silicon carbide This work was begun by the Arny Of fice of Research, Durham, and later continued as a basic research project. Studies were made on the behavior of silicon, silicon oxide and silicon carbide in oxidizing and reducing gas atmospheres and in high vacuum.

These studies confirmed thermochemical predicticus of two types of oxidation processes, active and passive. Very rapid oxidation (active, occurs in low pressure oxygen using high flow rates with lose of silicon monoxide and carbon monoxide. Very slow (pcssive) oxidation occurs in high pressure oxygen even in high flow rates with the formation of a protective oxide. Thermo-chemical analysis shows the equilibrium pressure of silicon monoxide at the silicon / silicon dioxide or silicon carbide /sili-con dioxide interface determines the type of oxidation reaction.

The results of these studies were reported in papers number 133, 134, 156, 157, 158, 160, 161, 16 3 and 164 in Sec tion 6. The re-suits of these studies have led to a new understanding of high temperature oxidation of materials where volatile gases are formed at internal interfaces. Also, the success of the use of thermo-chemical analysis in the interpretation of oxidation has led to many new applicatiens of thermochemical analysis in industry.

5. 3. 3 Hot Corrosion of Cas Turbine Alloys This work developed from our interest in applying thermochemical analyses to high teeperature corrosion procesocs in gas turbines.

A lengthy paper entitled " General Cor.cepts of Oxidation and Sulfidation Reactions -- A Thermochemical Approach" was written.

This paper was published and is listed as paper number 160. This paper has led to further work w.ith the Coal Casification Project.

Here, cleaned low BTU coal gas w;11 be used in a gas turbine at 1600*F. Thermochemical analysis is being .used to guide us in planning and interpreting the extensive experimental program.

5. 3. 6 Sintering of Tunas ten for Incandes cent Lamp s Extensive thermochemical analysis has been used to study the in-fluence of temperature and dew point of the hydrogen gas used in the sintering process on the density and silicon, aluminum and potassium analysis of the tungsten. A special high temperature, high vacuum furnace was installed to carry out sintering reactions in high vacuum of 10-7 tore and in controlled hydrogen / water vapor gas mixtures at te=perat ures to 2 700* C. This work demons trated the important role of the dew poin t (oxygen ratential) of the hy-drogen gas on the density and silicon, aluminum and potassium levels.

' The experimental work confi rmed the thermochemical predictions.

This work has not been published.

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6.0 PUBLICATIONS Dr. E. A. Culb ransen 1, Integral Heats of Dilution, Relative Partial Molal Heat Contents and Heat Capacities of Dilute Sodium Chloride Solutions. E. A. Gulbransen and A. L. Robinson. J. Am. Chem. Soc. Sj,, 2637 (1934).

2, Data of State of Phosphine at Low Pressures and f rom 190 to 300 K. E. A. Long and E. A. Gulbransen. J. Am. Chem. Soc. 58, 203 (1936).

3. Variations in the Relative Abundance of Carbon Tsotopes. A. O. Nier and E. A. Culbransen. J. Am. Chem. Soc. 61,, 697 (1936).

4 Thin Oxide Films on Iron. E. A. Gulbransen. Trans. Electrochemical Society S1,, 327-339 (1942).

3, Some Observations on the Formation and Stability of Oxide Films. E. A. Gulbransen.

Trans. Electrochemical Society 82, 375-389 (1942).

o, Transition State Theory of Formation of Thin oxid: Films on Metals. E. A. Gulbrare in.

Trans. Electrochemical Society 81, 301-317 (1943).

, Electron Diffraction Analysis of Surface Films. E. A. Gulbransen. Electronics, January 1944 g, A Vacuum Microbalance for the Study of Chemical Reactions on Metals. E. A. Gulbransen.

Rev. Sci. Instr. 15, 201-204 (1944).

9, The Oxidation and Evaporation of Magnesium at Temperatures from 400 to 500*C.

E. A. Gulbransen. Trans. Electrochemical Society 87, 463-473 (1945).

,u, Electron Diff raction Camera for the Study of High Temperature Surface Reactions.

E. A. Gulbransen. J. Appl. Phys. 16, 718-24 (1945).

,1, A Use of the Electron Microscope in Chemical Microscopy. E. A. Gulbransen.

R. T. Phelps and Alois Langer. Ind. Eng. Chem. Anal. Ed. 11, 646-52 (1945).

,,, An Electren Dif fraction and Electron Microscope Study of Oxide Films Formed on Metals and Alloys at Moderate Temperatures I. Stripped Oxide Films of Metals.

R. T. Phelps, E. A. Gulbransen and J. W. Hickman. Ind. Eng. Chem. Anal. Ed.

11, 391-400 (1946).

3, New Developments in Surface Chemistry. E. A. Culbransen. Metals Progress, March 1946.

,,, An Electron Diffraction and Electron Microscope Study of Oxide Films Formed on M.etals and Alloys at Moderate Temperatures II. St ripped Oxide Films Formed on v.etals and Alloys. E. A. Gulbransen, R. T. Phelps and J. '4. Hickman.

Ind. Eng. Chem. Anal. Ed.18, 640-652 (1946) .

15

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Dt. E. A. Culbransen

'). An Elcetron Diffraction Study of Oxide Films Formed on Metals and Alloya at High Temperatures. I. The Metals Fe, Co, Ni, Cr and Cu. E. A. Gulbransen and J . W. Hi c k=an. AIME Inst. Metals Div. Trans. 171, 306-331 (1947).

10. An Electron Diffraction Study of iside Films Formed on Metals and Alloys at Hign Temperatures. II. The Alloys Consisting Principally of Fe, Co, Ni and Cr. J . W. Rickman and E. A. Gulbransen. AIME Inst. Metals Div. Trans. 171, 344-370 (1947).

1. An Electron Diffraction Study of the Oxide Films Formed on Molybdenum and Tungsten at High Temperatures. J. W. Hickman and E. A. Gulbransen. ALME Inst. Metals Div.

Trans. 171, 371-387 (1947).

3. The Kinetics of Oxidation Reactions. E. A. Culbransen. Trans. Electrochemical Soc. 91, 573-602 (1947).

j. An Electron Diffraction Stud *

• the Oxide Films Formed on Oxidation Resistant Alloys. J. W. Hickman and E. A. Culbransen. Trans. Electrochemical Soc. 91, 0u5-620 (1947).

,0. The Kinetics of the Oxidation, Reduction and Vacuum Behavior of Molybdenum and its Oxides. E. A. Gulbransen and W. S. Wysong. AIME Metals Div. 175, 628-47 (1948).

1. The Kinet ics of Oxidation, Reduction and Vacuum Behavior of Tungsten and its Oxides. E. A. Culbransen and W. S. Wysong. AIME Metals Div. 175, 611-27 (1948).

_. A High Temperature Electron Diffraction Furnace. E. A. Culbransen. Rev. Sci.

I nst r. 16, 546-550 (1947).

. Thin Oxide Films on Aluminum. E. A. Cuibransen and W. S. Wysong. J. Phys.

Colleid Chem. 51, 1087-1103 (1947).

.. exide Films Formed on Titanium, Zirconium and Their Alloys with Nickel, Copper

.ind Cobalt. An Electron Diffraction Study. J. W. Hickman and E. A. Culbransen.

J. Anal. Chem. 20, 153-165 (1948).

,. Decarburization of Chreme Nickel Alloys by Their Surf ace Oxide in High vacus at Elevated Temperatures. E. A. Gulbransen, W. S. Wysong and K. F. Andrew.

Trans. AIME 180, 565-78 (1949).

o, An Electron Diff raction Study of 0xide Films Formed or Copper Nickel Alloys at Eleva t ed Temperatures. J. W. Hickman and E. A. Culbransen. Trans. AIME 180, 534-46 (1949).

, An Electron Dif f raction Study of Oxide Films Formed on Hastelloy Alloys A, B, C and D. J. W. Hick =an and E. A. Gulbransen. J. Phys. Colloid Chem. 52, 1186-1197 (1948).

. ;3, The Application of Electron Diffraction Techniques to the Study of Corrosion Processes. E. A. Culbransen. Corrosiim 4, No. 9, 445-455 (1948).

16

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Dr. E. A. Culbr.msen

9. an Electron Dif f raction Study of Oxide Films Formed on Nichromes. J. W. Hickman and E. A. Culbransen. Trans. AIME 180, 519-33 (1949).

o. Kinetic and Structural Factors Involved in Oxidation of Metals. E. A. Culbransen.

Ind. & Eng. Chem. 41, 1385-91 (1949).

q. Progress dans l' etude de l'oxydation superficielle des metsux et alliages a des temperatures elevees. E. A. Culbransen. 1 - Revue de Metallurgie 45,, 181-204 (July 1948). II - Revue de Metallurgie 4j,, 287-300 (August 1948).

i;. The Reactions of Metals in High Vacuum. E. A. Culbransen and K. F. Andrew.

Proc. of Pittsburgh International Conference on Surface Reactions. Also published in . Phys. & Colloid Chem. 53,, 690-711 (1949).

+3. Reactions of Zirconium, Titanium, Columbium and Tantalum with the Cases, Oxygen, Nitrogen and Hydrogen at Elevated Temperatures. E. A. Gulbransen and K. F. Andrew.

J. Electrochem. Soc. 96, 364-376 (1949).

m, Mullite and Zircon Furnace Tubes for High Temperature and High Vacuum Systems; A New Method for Measuring Pressure. E. A. Culbransen and K. F. Andrew.

Ind. & Eng. Chem. 4, 2762-7 (1949).

5.

Kinetics of the Reactions of Zirconium with 0 2. N2 and H2 . E. A. Culbransen and K. F. Andrew. AIMZ Metals Trans. 185, 515-526 (1949).

Kinetics of the Reactions of Titanium with 02, N; and H 2. E. Julbransen and K. 7. Andrew. AIME Metals Trans. 185, 741-P (1949) .

7 Reactions of Calu=bium and and Tantalum with 02 , N2 and H2 . E. A. Culbransen and K. F. Andrew. J. of Metals, March 1950; Trans. AIME 188, No. 3, 586-99.

.. The Kinetics of the Reactions of Beryllium with Oxygen and Nitrogen and the Ef fect of 0xide and Nitride on Its Vapor Pressure. E. A. Culbransen and K. F. Andrew. J. Electrochem. Soc. 97, 383-95 (1950).

>. The Kinetics of the Reactions of Vanadium with Oxygen and Nitrogen. E. A. Culbransen and K. F. Andrew. J. E' ec trochem. Soc. 97, 396-404 (1950).

J. Kinetics of Solid Phase Reactions in Oxide Films on Iron; The Reversible Transformstion at or near 570*C. E. A. Gulbransen and R. Ruka. J. of Metals, December 1950, 1500-1508 Trans. AlMZ, 188.

Kinetics and Mechanism of Solid Phase Reactions. E. A. Culbransen and R. Ruka.

'ad. & Eng. Chem. 43,, 697-703 (1951).

,, Kinetics of the Oxidation of Cobalt. E. A. Gulbransen and K. F. Andrew.

1 Electroches. Soc. 98, 241-251 (1954).

=

Dr. E. A. Gulbransen 3 Solid Phase Reactions in Oxide 141ms and Scales on Iron. E. A. Gulbransen.

Revue de Metallurgie 48, 336-352 (1951).

., Kinetics of Oxidation of Artificial Graphite at Temperatures of 425* to 5? S*C and Pressures of 0.15 to 9.8 cm of Hg of 02 E. A. Culbransen and K. F. Ar. drew.

Ind. & Eng. Chem. 44, 1034-38 (1952).

.,, surf ace Oxide For=ation and Surf ace Roughncsc Studies in Relation to Oxidation of Artificial Grapbe at Temperatures of 25*C and between 425* and 575'l.

E. A. Culbransen and K. F. Andrew. Ind. & Eng. Chem. 44,1039-44 (ms52) .

.,, Mechanism of the oxidation of Graphite at Temperatures of 425* to 575*C.

E. A. Culbransen. Ind. & Eng. Chem. 44,, 1045-47 (1952).

reactions of Carbon Dioxide with Pure Artificial Graphite at Temperatures of

.00* to 900*C. E. A. Gulbransen and K. F. Andrew. Ind. & Eng. Chem. 44, 1048-51 (1952).

., P..,le of Crystal Orientation in the Oxidation of Iron. E. A. Gulbransen and k, Ruka. J. Electrochem. Soc. 99,, 360 (1952).

, Ele..ron Dif f raction Studies on the Oxidation of Pure Copper and Pure Zine between 2C0* and 500*C. E. A. Gulbransen and W. R. McMillan. J. Electrochem. Soc. 9 9,,

393 (1952).

Freliminary Study of the Oxidation and Vapor Pressure of Chromium.

E. A. Culbransen and K. F. Andrew. J. Electrochem. Soc. 99, 402-6 (1952).

^~

surf ace S:udies Using the Vacuum Microbalance. II . High Temperature Reactions.

E. A. Gulbransen. Advances in Catalysts, Vol. 5, p. L20-174 (1953), Acad emic Press. Inc.

Crystal St ructure Studies of the Oxide Film Formed on a Series of Nickel-Chromium Alloys. E. A. Gulbransen and W. R. McMillan. Ind. 6 Eng. Chem. 45, 1734-44 (1953).

3, T,e Mechanism of Oxidation of Metals f rom the Viewpoint of the Transition State Tneory. E. A. Gulbransen. Proc. of International Symposium on the Reacting of Solids (1952).

The Kinetics of Oxidation of High Purity Nickel. E. A. Colbransen and K. F. Andrew.

J. Electrochem. Soc. 101, 128-140 (1954).

The Rate of Oxidation of Three Nickel-Chromium Heater Alloys between 500*C and 9;0*C. E. A. Culbransen and K. F. Andrew. J. Electrochem. Soc. 101, 163-170 (1954).

u. ':ec han i s of tae Reaction of Hydrogen with Zirconium. I. Role of Oxide Films,

'r e-Trea tments and Oc cluded Cases. E. A. Gularansen and K. F. Andrew.

- J. Electracnen. Soc. 101 348-53 (1954).

18

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Dr. E. A. Culbransen

... Role des pellicules superficielles sur la reaction du zirconium avec l'hydrogene.

E. A. Culbransen and K. F. Andrew. Revue de Metallurgie, L1, No. 2 (1954).

7. Reaction de fer avec l'oxygene aux basses pressions et a des temperatureu comprises entre 650*C et 850*C, E. A. Culbransen, W. R. McMillan and K. F. Andrew.

Revue de Metallurgie Lll, No. 7 (1955) .

,s. Electron Optical Study of Oxidation of High Purity Iron at Low Oxygen Pressures.

E. A. Culbransen, W. R. McMillan and K. F. Andrew. J. Metals 6, AIME Trans. 200, 1027-34 (1954).

39. Cr,stal Structure and Ther=odynamics Studies on the Zirconium-Hydrogen Alloys.

E. A. Culbransen and K. F. Andrew. J. Electrochrm. Soc. 101,, 474-80 (1954).

.0. Classical Theory of Dif fusion and the oxidation of Metals. E. A. Culbransen.

Annals of the New tork Acade=y of Sciences, Vol. 58, Art. 6, p. 830-42 (1954) .

,1 . Diffusion of Hydrogen and Deuterium in High Purity Zirconium. E. A. Gulbransen and K. F. Andrew. J. Electrochem. Soc. 101, 560-66 (1954).

J. The Solubility and Decomposition Pressures of Hydrogen in Zirconium. E. A. Culbransen and K. F. Andrew. J. of Metals 1,136-144 (1955).

.3, Effect of Strain on the Oxidation of Nickel-Chromium Heater Alloys. E. A. Culbransen and K. F. Andrew. Spec. Tech. Pub. No. 171, ASTM, 3 5-46 (1955) .

,. Role of Impurities in the Oxidation of Metals. E. A. Gulbransen. Corrosion 11, 61-67 (1956).

5, A New Method for the Evaluation of High Vacuum Furnaces and Heat Treating Atmospheres. E. A. Culbransen and K. F. Andrew. Presented at Vacuum Metallargy Sy=posium of Electrothermics and Metallurgy Div. of Electrochem. Soc. (1954).

,. Formation de Germes des Atmospheres D'oxygene sous Des Pressions de 10 -5 A 10 -7 =m de Hg A 850*0. E. A. Culbransen and W. R. McMillan. J. de Chimie Physique 1956,

p. 543-659.

to. Cas Metal Reactions of Zircoriuc. E. A. Gulbransen. Metallurgy of Zirconium, Lustman and Ker:e. National Nuclear Energy Series, McGraw Hill (1955).

Kinetics of the Oxidation of Chromium. E. A. Culbrarsen and K. F. Andrew.

J. Electrochem. Sec. 10', 334-38 (1957).

, , Cxidation of Zirconiu= between 400*C and 800*C. E. A. Culbransen and K. F. A .d rew.

J. cf Metals 9. AIME Trans. 209, 394-400 (1957).

, 0xidatien of 50 Weight Percent Uranium-Zirconium Alloy. E. A. Culbransen.

R. C. Charles and S. Barnartt. J. Electrachem. Soc. 104, (1957).

19

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Dr. E. A. Culbransen

6. Effect of Stress on Unusual Crystal Habits of Corrosion Products on Iron, Nickel, Chromiu and Stainless Steels. E. A. Gulbransen and T. P. Copar.. C2neral Motors Symposium on Stress ar.d Fatigue in Metals, Edited by G. M. Rassweiler and W. L. Crube.

4. Ef fect of Stress and Environment on the MicrotoPelogy of the Corrosion Product.

E. A. Gulbransen and T. P. Copan. Book - Metallurgical Society Conferences Vol. 4, " Physical Metallurgy of Stress Corrosion Fracture", Interscience Publishers, 1959.

19. Electron Microscopy and Electron Dif f raction Studies of Oxide Films Formed on Iron in Water and Oxygen Atmospheres. E. A. Gulbransen and T. P. Copan. ASTM Special Tech Pub. No. 256, Sy:posium on Identification of Water-Formed Deposits.

Q. Microtopology of the Surface Reactions of Oxygen and Water Vapor with Metals.

E. A. Culbransen and T. P. Copan. Faraday Society Discussions 1959, No. 28.

fl. Kinetics of the Oxidation of Pure Tungsten from 500* to 1300*C, E. A. Gulbransen and K. F. Andrew. J. Electrochem. Soc. 107, /1960).

.: . Hydrogen in Zirconium - A Simpie Experiment in Chemical Equilibria. O. M. Puntz and E. A. Culbransen. J. Chemical Education . 533 (1260).

o. The Invisible Ar=or - Surface Films on Metals. E. A. Culbransen. Chapter in Book " Saturday Science", E. P. Dutton & Co., Publishers.

.. Alu=inum Reactions with Water Vapor, Dry Oxygen. Moist Oxygen and Moist Hydrogen between 500*C and e25*C. P. E. Blackburn and E. A. Gulbras.aen. J. Electrochem.

Soc. 107, No. 12 (1960).

-9. Thermochemical Analysis of the Reactions of HC1, Nacl, MgCl2, Water Vapor and Oxygen with Fe, Ni and Cr and Their Implications in Stress Corrosion Fracture.

E. A. Culbransen. Metallurgical Society Conf erences, Vol. 4, " Physical Metallurgy of Stress Corrosion Fracture", Interscience Publishers, 1959, p. 364-370.

. Vaper Pressure Studies of Iron and Chromium and the Alloys 5.41 Al - 94.6 Fe.

21. 9 Cr - 7 o.1 Fe , and 4. 8 Al - 21. 5 Cr - 7 3. 7 Fe . E. A. Gulbransen.

Trans. AIMI 221, 1247-1252 (1961).

. Per.eability and Diffusivity of Hydrogen Throunh a Palladium Tube. O . M. Ka tz and E. A. Culbransen. Rev. Sci. Instr. 31, 615-7 (1960).

Electron Diffraction Adapter for the EMU-3D Electron Microscope. E. A. Gulbransen and T. P. Copan. Reprinted by RCA for overseas distribution.

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Me & m,m m em, sw . > m m m e memeam M w **^

Dr. E. A. Culbransen O. The Effect of Pressure on Microgravimetric Stud: es in Hydrogen. O. M. Karz and E. A. Gulbransen. Vacuum Microbalance Techniques, Vol. 1, Plenum Press, 1961, p. 111.

d. An Enclosed Physical Chemistry Laboratory - The Vacuum Microbalance. E. A. Culbransen and K. F. Andrew. Vacuum Microbalance Techniques, Vol.1, Plenum Press,1961, p. 1.

23. Crystal Habit and the Corrosion of Iron. E. A. Gulbransen and T. P. Copan.

Nature 186, 959 (1960).

4 Crystal Habit and the Corrosion of Irnn. E. A. Gulbransen and T. P. Copan.

European Regional Conf. on Electron Microscopy, Delft, Holland, (1960).

.5. Oxidation of Copper batween 250' and 450* and the Growth of Cu0 " Whiskers".

E. A. Gulbransen, T. P. Copan and K. F. Andrew. J. Electrochem. Soc. 108, 119 (1961).

m. Thermodynamic Functions for the Columbium-Hydrogen System. O. M. Katz and E. A. Gulbransen. " Columbium Metallurgy", AIME and Interscience, N.Y., p. 523 (1961).

Some Observations on the Uranium + Niobium - Hydrogen System.

. O. M. Kat: and E. A. Culbransen. J. Nuclear Matls. 5,, 269 (1962).

Cerrosion by Gases. E. A. Gulb; ansen. Encyclopedia of Science and Technology.

'::Graw-Hill Book Co., 1960-4 Invar Beam Balance fc c the Study of Fast Chemical Reactions. E. A. Gulbransen and K. F. Andrew. Vacuus Microbalance Techniques, Vol. 2, p. 129, Plenum Press, Inc.

': . Y . (1962).

Yinetics of Oxidation of Pure Tungsten, ll50*C-1615'C. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. J. Electrochem. Soc. 111, 103 (1964).

.t. Vapor Pressure of Molybdenum Trioxide. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. J. Electroches. Soc. 110, 242 (1963).

.2. Four Types of Oxidation Precesses in the Oxidation of Tungsten. E. A. Gulbransen, K. F. Andrew and F. A. Brassact, Pre _. AIh Symposium, N.Y. , 1962, p. 81.

Oxide Growths on Pure Iron in Oxygen, Water Vapor and Carbon Dioxide Atmospheres.

E. A. Gulcransen, T. P. Copan and W. M. Hickam. Proc. of 5th !nter. Cong. for Electrcn Microscopy, Philadelphia, 1962.

,. Jxidation of Molybdenum 550' to 1700*C. E. A. Culbransen, K. F. Andrew and

c. A. Brassart. J. Electroc hem. Soc. 110, 952 (1963).

99

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. Dr. E. A. Culbransen 6 Studies on the Oxidation of Graphite at Temperatures of 600* to 1500*C and at Pressures of 2 to 76 Torr of Oxygen. E. A. Culbransen, K. F. Andrew and F. A. Brassart. J. Electroches. Soc. 110, 476 (1963).

. High Te:perature Oxidation of Tungsten, Molybdenum and Carbon. E. A. Culbransen.

Sature 198, 82 (1963).

. High Te=perature Furnace and Reaction System for Temperatures up to 1600*C.

E. A. Culbransen, K. F. Andrew and F. .'.. Brassart. Vacuum Microbalance Techniques, Vol. 3 p. 179, Plenum Press, 1963.

. Ablation of Graphite f.n Oxygen and Air at 1000* to 1400*C Under Flow Conditions.

E. A. Culbransen, K. F. Andrew and F. A. Brassart. Carbon, 1, 413 (1964),

,. Occluded Cases in Transition Metals. O. M. Katz and E. A. Gulbransen.

Chapter 4 "Non-Stoichiometric Compounds." Academic Press, 1964.

. Models of Oxidation Processes Occurring in Oxide Whiskers and Platelets on Iron at 400* to 500*C. E. A. Culbransen. Colloque International sur les Processus de Nuc1 cation dans les Reactions des Caz Sur les Metaux et Problemes Connexes, June 1963. Centre National de la Recherche Scientific. Rev. Metallurg. 62,

_53 (1965).

Ahlation of High Purity and Nuclear Reactor Core Graphite in Oxygen and Air.

C. A. Culbransen, K. F. Andrew, F. A. Brassart and A. L. Feild , J r. J. Nuclear "ats. 13, 40 (1964).

Oxidation of Graphite, Molybdenum and Tungsten at 1000 *C to 1600*C. E. A. Culbransen, K. F. Andrew and F. A. Brassart. Progress in Astronautics & Aeronautics, Vol. 15 Heterogeneous Combustion, p. 227, Academic Press, New York, 1964.

, ?xida' ion of Pyrolytic Carbon 1000*C to 1500*C and Oxygen Pressures of 2 to 38 Torr.

E. A. Culbransen, K. F. Andrew and F. A. Brassart. J. Electrochem. Soc. 111, c26 (1964).

Reaction of Graphite with Carbon Dioxide at 1000*C to 1600*C Under Flow Conditions.

E. A. Culbransen, K. F. Andrew and F. A. Brassart. Carbon 2, 421 (1965).

Study of Fast Reactions in Flow Environments. E. A. Culbransen, K. F. Andrew and F. A. Erassart. Vacuum Microbalance Techniques i, p. 127, Plenum Press, Inc.,

New York (1905).

~.m Reaction of Hydrogen with Graphite at 12 00

• t o 16 50

• C. E. A. Culbransen,

. F. Andrew and F. A. Brassart, J. Electrochen. 30c. 112, 49 (1965).

.troduc:ary Re= arks: Fourth Informal Vacuum Mic robalance Conf erence.

. A. Cu15:ansen. Vacuum Microbalance Techniques i. p. x1, Plenum Press, N.Y. (1965).

23

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- - - - . .. .. _ s. , --

Dr. E. A. Culbransen

1. General Concepts of Cas-Hetal Reactions. E. \. Culbransen. Corrosion 21, 76 (1965).

3. Oxidation of Silicon at High Te=perature and Low Pressures under Flow Conditions and the Vapor Pressures of Silicon. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. J. Electrochem. Sec. 113, 834 (1966). '

Oxidation of Silicon Carbide at 1150' to 1400*C and at 9 x 10

~

~I Torr to 5 x 10 Oxygen Pressures. E. A. Culbransen, K. F. Andrew and F. A. Brassart.

J. Electroches. Soc. 113, 12 (1966).

$. Nature of the Reaction Products Formed in the Graphite Hydrogen Resetion at 1300*-1500*C at 19 Torr. E. A. Culbransen and W. M. Hickamu Electrochemical Technology 5 No. 5-6 (1967).

9. Thermochemical and Structural Aspects of the Reaction of Rydrogen with Alloys ar.d Inter =etallic Compounds of Zirconium. A. R. Pcbler and E. A. Culbransen.

Electrochemical Technology 4, No. 5-6 (1966).

'. A Met Extraction Method for FJdrogen Analyses of Zirconium and Zirconium Alloys using Cryogenic Pu= ping. E. A. Culbransen and K. F. Andrew. Electrochemical Technology 1, 471 (1967).

.. Hi gl. Tc=perature Oxidation in Flow Reaction Systems. E. A. Gulbransen, K. F. And r ew a nd F. A. Brassart. Proc. of 3rd International Congress on Metallic Ce rrosion. Moscow, USSR (1966) .

Cas-Solid Reactions in Flow Envircr;ments at High Temperatures. E. A. Culbransen.

Nat. Acad. Sci. Nat. Res. Council Publication No. 1970 (I567).

, 0xidation of Zirconium and Zirconium Alloys in Water Vapor Atmospheres Containing Trace A=ounts of Oxygen at 375' and 575'C. E. A. Culbransen and K. F. Andrew.

Electrochemical Technology 4, No. 3-4 (1966).

3. The Graphite Hydrogen Reactions and Their Implication in Cecchemistry.

E. A. Culb rans en. Nature 212, 1*20 (1966).

.. Crystal Morphology and Mechanis=s of Crowth of a-Fe2 0 3 '"hiskers on Iron.

R. L. Tall =an and E. A. Culbransen. J. Electrochem. Soc . 114, No . 12 (19 6 7) .

..e Oxidatio.: of a Series of Dilute Zirconium Alloys at 500*C in a Water Vapor Atmospha

• Containing Trace A=ounts of Oxygen. E. A. Culbransen and K. F. Andrew.

cerrosica 23, 231 (1967).

32? O,0

= .

Dr. E. A. Culbransen

.o. Equilibrium Studies on the Systems ZrCr2-H2, ZrV -H2 2 and ZrMo2-H2 Between 0*

and 900*C. A. Pebler and E. A. Gulbransen. Trans. Met. Soc. of AIME 239, 1593 (1967).

.. Oxidation of Rhenium and e Rhenium-8% Titanium Alloy at Oxygen Pressures of 1 to 10 Torr and at 800* to 1400*C in Flow Environments. E. A. Gulbransen and F. A. Brassart. J. Less Oc= mon Metals 14, 217 (1968).

.6. Localized Oxidation Precesses on Iron. E. A. Culbransen. Proc. of Conf. on "inte rf ace Conversien", Oct. 1967, Ford Motor Co. ,

Dearborn,

Mich.

,9. Selected Area Electron Diffraction Study of Twinned a-Fe20 3 Blade-Like Pla t ele t Growths on Iron. R. L. Tallman and E. A. Gulbransen.

J. Electrochem. Soc. 115, 770 (1966).

50. Dislocation and Grain Bour.dary Diffusion in the Growth of c-Fe2O3 Whiskers on I ran. R. L. Tallman and E. A. Gulbransen. Nature 218, No. 5146, 1046 (1968).

!, 0xidation Studies on Zircenium Alloys in High Pressure Liquid Water at 360*C.

E. A. Culbransen and K. F. Andrew. J. Electrochem. Soc. 116, 659 (1969).

2. Hign Temperature Reaction Studies with the Microbalance. E. A. Gulbransen and F. A. Brassart. Chapter in Book on " Vacuum Microbalances" by S. Wolsky.

Interscience Publishers, New York,1969.

2 Locali:ed Dif fusion Processes in the Grewth of n-Fe20 3 Whiskers and Platelets on Iren. E. A. Gulb ransen, T. P. Copan and K. F. Andrew. Chimica, Dec. 1969, Feitknecht Number.

.. Thermochemist ry and the Oxidation of Ref ractory .Mctals at High Temperatures.

E. A. Culbransen. Corrosica 26. No. 1, 19-28 (1970).

3 Tne Interpretation of Vacuum Microbalance Studies of High Temperature Oxidation c; Materials. E. A. Gulb ransen. Proc. 8th Informal Vacuum Microbalance Conf.

Vacuum Microbalance Techniques, Vol. 8.

,6. Evaluation of Cas-Metal Reactions by Means of Thermochemical Diagrams.

S.A. Jansson and E. A. Gulbransen. Proc. Fourth International Congress on Metallic Corrosion, A=sterdam, 1969.

7. Vaporization Chemistry in the Oxidation of Carbon, Silicon, Chromium, Molybdenum and Niobium. E. A. Gulbransen and S. A. Jansson. Published in book " Heterogeneous Kinetics at Eleva ted Temteratures", Ed. G. R. Belton and W. L. Worrell, Plenum Press, New York, 1970.

d. Selected Area Electran Diffraction Study of a-Fe20 3 Platt. ,wths Twinned on

, Twist Crain Ecundaries . R. L. Tallman and E. A. Gulbransen. J. Electrochem.

Soc., 117, 250 (1970).

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7.0 PATENTS 7.1 Photoflash La=p with Yttrium Combustible Filling, June 27, 1972, U.S.

3,672,814.

7.2 Photoflash La=p and Multiple Flach La=p System, July 4,1972, U.S. 3,675,004, Earl A. Gulbransen, R. L. Tallman, K. F. Andrew, and B. T. Buzalski 7.3 Yttrium-Hydrogen Isotcpe Compositions for Radiochemical Reactions, February 13, 1973, U.S. 3,716,491, L. N. Yannopoulos, S. A. Jansson, and E. A. Gulbrausen.

7.4 Yttriu= Alloy Getter, Septe=ber 29, 1971, Great Britain 1,248,184, S. A. Jensson, E. A. Gulbrausen, and L. N. Yannopoulos.

8.0 SCIENTIFIC SOCIETIES 8.1 American Chemical Society 1936 - Present 8.2 Electrochemical Society 1941 - Present 8.3 American Institute of Mining and Metallurgical Engineers - Institute of Metals Division 1946 - Present 8.4 Chemists Club of Pittsburgh 8.5 Force - Member Electron Microscope Society, American Society of X-Ray and Electron Diffraction, American Association for the Advancement of Science.

9.0 AWARDS 9.1 A=crican Institute of Mining end Metallurgical. Engineers Award for Out-scanding desearch - 1949.

v.2 National Association of Corrosion Engineers, Willic Rodney Whitney Award - 1952.

v.3 American Che=ical Society, Pittsburgh Section Award - 1961.

v.4 Electroche ical Society, Acheson Award and Prize - 1964.

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10.0 OTHER SCIENTIFIC ACTIVITIES 10.1 International Conference on Surf ace Reactions - 1948 - Chair =an and organizer.

10.2 Cordon Research Conference,Hetals Conference - 1952 - Chairr.an and Organizer.

10.3 Gordon Research Conference, Corrosion Conf erence - 1955 - Chairman.

10.4 Corrosion Research Council, Member 1958-1964 - Chairman 1963-1964.

10.5 AlhI Conference on Physical Metallurgy of Stress Corrosion Fracture - 1959 -

Program Chair =an.

10.6 AIME Corrosion Resistant Metals Committee, Me=ber 1957 - 1965.

10.7 A=erican Chemical Society, Pittsburgh Section - Chairman 1959-1960.

10.8 Electrochemical Society, Pittsburgh Cection - Chairman 1947.

20.9 Chemist Club of Pittsburgh, Chairman - 1956.

10.10 International Union of Pure and Applied Chemistry, Member Coc:sittee on Pure Metals.

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e 11.0 S u==a ry Thirty-three of my thirty-nine years of scientific and engineer-ing exp< 'suce have been in the field of gas-metal and gas-solid reactions including research, development, consulting and super-visory activities. The ti=c span of 1940 - 1973 includes the period in which gas-metal reactions were just beginning to be studies in our universities to the present period where the study of gas-solid reactions is essential in the preparction and use of materials.

My first activitics at Westinghouse were to develop aev and in-proved instruments for the study of gas-cetal reactions. We de-veloped the vacuum microbalance method for the study of tae kinetics of oxidation, medium and high voltage electron diffraction methods for the study of the crystal structure of thick and thin oxide films and electron microscope methods for the study of the crys tal habit of oxide films.

A co=bination of these methods was used to experimentally :haracterize a wide variety of oxi-dation, volatilization, hydrogen reduction and hydriding reactions.

A second phase of this work was to interpret the results of the experimental s tudies. We made importan t theoretical contributions to gas-solid rea tions using thermochemical analyses, kinetic tS+ory, transition state theory of chemical reactions, diffusion theory and classical dif fusion rate theory.

We have studied over a thirty-three year period a broad spectrum of gas-metal and gas-solid reactions. The oxidatica reaction of the following elements and alloys have been studied: iron, nickel, cobalt, copper, aluminum, ma gnes ium, chromium, beryllium, titani-t:m, vanadium, zirconium, rhenium, silicon, niobium, tantalum, molybdenum, tungsten, uranium, stainless steels, nickel-chromium, iron-nicke l-ch romi um, iron-chromium-aluminum, zirconium-tin , Zirc-aloy and a large number of zirconium-intermetallics. The hydro-gen and nitrogen reactions of zirconium, titanium, niobitan, tanta-lum, Zircaloy and the zirconium-intermetallics were studied. We have voried extensively on the oxidation, reduction and volatili-

atien reactions of Sic, SiO . ^102 2 3, W-0, Mo-o and U-O sys te=s .

Over the years the gas environce,ts have changed from simple oxi-datien and reduction gas environments to co= plex environawusts of mixed gases such as hydrogen-water vapor gas mixtures, inert gases containing traces of water vapor, nitrogen, oxygen, etc. and air containing water vapor and traces of sulfur gases. Also, tempe ra t urs have risen f rom temperatures below 1000*C to temperatures up to 2800*C. These trends in more complex 30 ,oG O j l. /

reaction environments and higher temperatures has required a great deal of care in the planning and interpreting of the data.

My professional activities have brought me into contact with a wide spectrum of products: nuclear reactors, steam generators, electrical generators, gas turbines, motors, trans formers , fur-naces, evens, electrical heaters, incandescent lamps, flourescent la=ps , automotive lamps , cameras , flash lae:ps, high cen:perature materials, ceramics, electrical heater alloys, magnetic alloys, protective coatings, electroplated coatings and corrosion resistant alloys.

From the beginning I have been af filiated with individuals and groups dedicated to solving technical problems using the best of modern theoretical and experimental methods. My scientific work has taken me to meetings and discussions all uwer the United States and in many foreign countries including Canada, England, France, U.S.3.R. , Japan, Norway, Sweden , Switzerland and Italy. As a result I am f amiliar with scientific and engi-neering work in my area of co=petence in many countrice and know cost of the workers.

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Signed L Ox-w s i

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ilh Av UNITED STATES OF AMERICA D CORRESPONDD*CE NUCLEAR REGULATORY COMMISSION Before the Atomic Safety and Licensing Board In the Matter of  :

PUBLIC SERVI E ELECTRIC  : DOCKET NO. 50-272

& GAS CO.

(Salem Generating Station  :

Unit #1)

CERTIFICATE OF SERVICE I hereby certify that copies of Earl A. Culbransen's testimony on beha.f or the intervenor, Township of Lower Alloways Creek, in response to the Board Order dated April 18, 1979 in the above captioned matter have been served upon the attached list by deposit'in the United States mail at the post office in Northfield, N.J., with proper ,,ostage thereon, this 12th day day of June ,

1979,

/

CeWAMRG( J A , Special Nuclear j Counsel for the Intervenor, the Township of Ecwer Alloways Creek Dated: June 12, 1979

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({ WJi' JUN 151973 >

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Gary L. Milhollin, Es . Richard Fryling, Jr. , Esquire Chairman, Atomic Sa<cty Assistant General Solicitor

& Lice. sing Boar Public Service Electric &

1815 Je :ferson Stre, Gas Company Madison, .is'unsin 33711 80 Park Place Newark, N. J. 07101 Glen O. Bright Member, Atomic Safety Kei*h Aasdorff, Esquire

& Licensing Board Assistant Deputy Public Advocate U. S. Nuclear Regulatory Commission Department of the Public Advocate Wa s hirigton , D . C. 20555 Division of Public Interest Advoc P. O. Box 141 Dr. Ja.ies C. Lamb, III Trenton, New Jersey 08601 Memb'.r, Atomic Safety &

Licensing Board Panel Sand ra T. Ayres, Esquire 313 Woodhaven Road Department of the Public Advo'cate Chapel Hill, N. C. 27514 520 East State Street Trenton, N. J. 08625 Cna i rma n , Atomic Safety and Licensing Appeal Board Panel Mr. Alfred C. Coleman , Jr.

C. 3. Nuclear Regulatory Commission Mrs. Eleanor G. Coleman Washington, D. C. 20555 35 "K" Drive Pennsville, N. J. 08070 Chairman, Atomic Safety &

Licensing Board Panel Of fice of the Secretary F. 5. t,uelear Regulatory Commission Docketing and Service Section Washington, D. C. 20555 U. S. Nuclear Regulatory Commissi Washington, D. C. 20555 Ba rry Smith, Esquire Office of the Executive Legal Director June D. MacArtor, Esquire U. S. Nuclear Regulatory Commission Deputy Attorney General Washington, D. C. 20555 Tatnall Building, P. O. Box 1401 Dover, Delaware 19901 Mark L. First, Esquire Deputy Attorney General Mr. Lester Kornblith, Jr.

Department of Law & Public Safety Atomic Safety and Licensing Boarc Environmental Protection Section U. S. Nuclear Regulatory Commissi 36 West State Street Washingtnn s D. C. 20555 frenton, N.J. 08625

.' ark J. Wetterhahn, Esquire for Troy B. Conner, Jr. , Esq.

1747 Pennsylvania Avenue, N. W.

Suite 1050 Washington, D. C. 20006

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