ML19029A828
| ML19029A828 | |
| Person / Time | |
|---|---|
| Site: | Salem  |
| Issue date: | 06/12/1979 |
| From: | Valore C Lower Alloways Creek Township, NJ |
| To: | Atomic Safety and Licensing Board Panel |
| References | |
| Download: ML19029A828 (38) | |
Text
l.W...A~ C9-RREsPoND~
e uNI'rED ::>TA'rES OF AMERlCA e
~UCLEA!<. REGULATORY COMMlSSiON
~efore the Atomic Safety and Licensing Board
- t/rij;J
. Docket No. S0-27Z In the Matter of ~.
PUBLIC SERVICE ELt:CTRIC Proposed issuance of Amendment b GAS CO. to Facility Operating License (Salem Nuclear Generating No. UPR-70 8tation, Unit Ul)
KES~ONSE TO THE ATOMIC SAFETY AND LICENSING BOARD uRDr.;R DATEu APRIL 18, .197Y Un Aprii 18, 1919, the Atomic ~afety and Licensing Board issued an Order presumably pursuant to Rule 2. 752.(c) or other applicable rule which provides for the submission of evidence addressed to the following questions:
"1. To what extent did the accident at Three Mile Island affect the spent fuel pool at that site?
- 4. It there had been an explosion or
'meltdown' at Three Mile Island, what affect would that have had upon the spent fuel pool? To what extent would it have mattered how much spent tuel was present at the pool?
- 3. If an accident such as the one at Three Mile.Island occurred at Salem, to what extent would the accident affect the spent fuel pool? If an explosion or 'meltdown' occurred at Salem, to what extent would it have mattered how much spent fuel was present at the pool at Salem?
The Intervenor, Township of Lower Alloways Creek, hereby submits the written testimony of Earl A. Gulbransen, Ph.D., P.E., wh1ch deals with questions Vl, U2 and #J. Dr. Culbransen's qualifications are
-1I attached to his testimony.
~1¥Jfu' G._~~:~.(, C!AL NUCLEAR COUNSEL FOR THE 'IDWNSHIP OF LOWER ALLOWAYS CREEK, mTERVENOR
RELAico~
~nIT.t:.I> STAT~S OF A1'-lliRI~A NuCL.t;AR REGULATORY COMMiSSION
- Before. the Atomic Safety and Licensing Board ln the Matter ot )
Docket No. ~0-272 PUHLI~ SERVICE ELECTRIC & )
GAS.COMPANY Proposed Issuance of Amedment to
)
Facility Operating License tSalem Nuciear Generating No. UPR-70 Station, Unit Bl) )
- 1*ES'l'IMONY OF EARL A. GULBRANSEN, Ph.D. , P. E *
.~N lRE!:iPECT TO BOARD. QUESTIONS 111, tt2, tt3,
. OF OKDeR DATED APRlL 18, 1Y79 My analysis of the accident of Three Mile lsland and the. potential involvement of the spent fuel pool and how that relates to Salem 1, necessarily involves some discussion of my opinions as to the use of Zirconiu:n Alloys as cladding -for the uranium dioxide fuel pellets *in nuclear reactors.
I believe the reactor at Three Mile lsland underwent a major temperature excursion during which, from available information, 1 would conclude that 10% - 15Z of the Zircaloy cladding reacted with steam to form Zirconium dioxide and hydrogen. This reaction furnished most of the hydrogen in the bubble at the reactor head.
Part ot the hydrogen probably penetrated the oxide film on the Zircaloy II cladding to dissolve in the metal and to torm zircon;t.um hydride, ZrH1
- 4
- This hydride has low hydrogen equilibrium pressures at the nor:nal operating temperature ot the reactor. Such reacted hydrogen obviously cannot be vented. I have prepared pa,pers 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 embrittlement of the cladding must have occurred with serious damage to the Zircaloy in the reactor. The spalled zirconium
hydride and zirconium oxide would fall to the bot.tom of the reactor together with the fuel pellets. The circulating cooling water continues to react with the treshly spalled zirconim hydride suf aces forming more zirconium dioxide and hydrogen. 1 predict that this reaction will continue until all of the Zircaloy II cladding is reacted.
As a result of the above analysis,.I suggest the following procedures:
- 1. Hydrogen in the cooling water should be ourned catalytically to prevent build up of another hydrogen buble in the reactor.
- i. 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 radioactive particulates. The only safe chemical and conditions after an accident like that at Three Mile island is to have all of the Zircaloy II reacted to the 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. Hydrogen gauges of high _sensitivity are now available or could be made in a short time.
- 4. I am much concerned about the e£fect of hydrogen on the reactor vessel and piping.
I strongly recommend that experiments be made on hydrogen embrittlement of the alloys used in the reactor and piping under conditions simulating those which occurred in the reactor.
- 5. I strongly recommend that experiments should
- be made on the effect ot hydrogen in the cooling water at high pressure on pre-oxidized Zircaloy II to evaluate the penetration and pick-up of hydrogen as a tunction of temperature and pressure *
- 6. 1 recommend 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.
- 7. ~en~it1ve hydrogen gauges should be instaLled on the primary and secondary loops and on the reactor itself to monitor the Zircaloy IJ. -
steam anct water reaction.*
I should like to repeat -that these suggestions are b'ased on extensive research in the field of gas-metal reactions. My own basic research on zirconium began 1Il 1~47 oefore the ronnation of tne lJl::!st.i.ngnout:1e Bettis Atomic Power Laboratories. Twenty years of nearly continuous research was conducted on the* reactions of zirconium, Zircaloy ll, Z1rcaloy IV and the other zirconium alloys with oxygen, air nitrogen and water vapor over a.
temperature range of :.!5°C to HOO"'C and at pressures. of a few torr to over luO atmospheres. This work was reported in 25 papeYS.and many research reports to the Westinghouse Electric Corporation.
Many important tehnical problems we.re solve& :including the solubility of hydrogen in zirconium, the crystal structure and range of homogeneity.
of zirconium hydride; ZrH1 . 4 , the rate of diffusion of hydrogen in zirconium, the role of oxide 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 comipounds, the rate of reaction of zirconiUI!l alloys in water at high pressure and the behaviour of Zircaloy II in fast flowing steam at temperatures above 1000°C.
After 25 years of research and development on !:he chemical and and metallurgical properties of metals and alloys used in nuclear power plants, I have come* to the conclusion that the current design and materials cannot give us a safe and well-~ngineered nuclear power plant.
The use of zirconium ailoys 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 nuclear power reactors zirconium cladding alloys react with oxygen in water for form an oxide layer which partially dissolves in the metal embr1ttling and weakening the metal tubing. Part ot the hydrogen formed 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 i,1U0° Celsius (198U° Fahrenheit) zirconium reacts rapidly with steam with a large evoiution of heat and the formation of free hydrogen~ with most metals to form intermetal.~ic compounds and with other metallic oxides to form its own oxide. Once zirconium is heated to 1,100° L:clsius, which could occur in loss of coolant accidents, its is difficuit to prevent further reaction, failure ot the tubing and of the reactor.
Tnere appears to be no way to overcome the inherent material problems associated with zirconium alloys and the current design of the reactor ureater wall thickness f ot cladding and lower operating termperatures of the fuel may help but the chemical and metallurgicai behaviour of -zir~dnl.um 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 mel.tdown or explosion as.posed in tne Board's question, 1t 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 fuel in spent fuel pools at reactor
sites in close proximity to operating nuclear reactors for long periods of time and in large quantities represents a significant involvement ot large amounts of radioactive material in the event a serious nucLear accident.
RECORD OF SCIENTIFIC AND ENGINEERING EXPERIENCE Earl A. Gulbransen CONTENTS o.o Abstract **.*. , ******. , *..****.....*.***********.*.** 1 Washington State University ************************ 3 2.0 Universitz of Pittsburgh ***************** .,......... . 3 2.1 'lbermodynamic Properties of Dilute Solutioas ******* 3 3.0 University of California ****.*** 0 ********* *>-- ...... . 3 3.l Thermodynamic Properties of Gases and Solu~ns ***c 4
- 4. 0 Tufts Universtty *.* , ....... 1: ******** * * ................ . 4 4.1 Geochemical* Research ***.***************** **-~ ******* 4 4.2 National Research Council Committee on the Determination of Geologic l'ime ............... - ******* 4 4.3 Closure ....... , . , ... , ............................... . 4 5.0 Westinghouse Electric Corporation Research l.a.boratories ....................................... . 6 5.l Dates, Position and Supervisor ..................... . 6 5;1. l *oxidation of Metals ..................... ****- ...... . 6 5.1.2 Consulting Activities ................................. 6 5.1. 3 World War II Work .*** ** .............................. . 6 5.1.4 Cl.oat.ire *** , , * , * , ............................ * * , ***** 7 5.2 Dates, Position and Supervisor ************* ........ 8 5.2.l Gas Reactions of Carbon 300-1500°C ................. . 8 5.2.2 Reactions of Zirconium and Zirconium Alloys .. etc. *** 8 i
CONTENTS 9.3 American Chemical Society, Pittsburgh Sec ti on Awar.d , , * * * * * . . * . * . . . . . . . . . . . . . * * * * * * . * . . . . 28 9.4 Electrochemical Society, Acheson.Award and Prize ...... , , . * . . . . . . ... . . . . . . . . . . . . . * * * * . . . . . . 28 10.0 Other Scientific Activities ....................... 29 10.l International Conference on Surface Reaction ****** 29 10.2 Gordon Research Conference on Metals ************** 29
- 10. 3 Gordon Research Conference on Corrosion ********** , 29
- 10. 4 Corrosion Research Council ' ...................... . 29 10.5 American Institute of Mining and Metallurgical Engineers Conference on Stress Corrosion Fracture
- 29 10.6 American Institute of Mining and Metallurgical Engineers Corrosion Resistant Metals Commitb!e **** 29
- 10. 7 American Chemical Society, Pittsburgh Section ***** 29
- 10. 8 Electrochemical Society, Pittsburgh Section ******* 29 10.9 Chemists Club of Pittsburgh ........................ 29 10.10 International Union of Pure and Applied Chem:Lstey ************ ~............................ 29
. 11.0 S~ey * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * *
- 30 iii
.. ----- -- ~:.* ** ... ,.._.~ ... *-** .
RECORD OF SCIENTIFIC AND ENGINEERING EXP*ERIENCE Earl A. Gulbransen ABSTRACT o.o Washington State College (now Washington St.ate University),
Pullman, Washington, graduated with honors, .June 11 1931, in Chemical Engineering and minors in Physics, Physical Chemistry and Mathematics. Teaching assistant and under-graduate research, 0.1 University of Pittsburgh, Pittsburgh, Pennsylvania, received Ph.D. degree in Physical Chemistry, August, 1934, with minors in Physics and Mathematics. Research work Cl'll. thermodynamics o! solucions. Teaching assistant in organic and physical chemistry.
0.2 University of California, Berkeley. National Research Council Past-Doctorate Fellowship in Physical Chemistry, September, 1934--
August, 1935. Research Associate in Physical Chemistry, September, 1935-August, 1936. Research work on thermod)'!lamics of gases and solutions.
0.3 Tufts College (now Tufts University), Medford~ Massachusetts, September, 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 Westinghouse Electric Corporation, Research and Development Center, Pittsburgh, Pennsylvania, July, 1940 to p-resent.
0.4.1 July, 1940 to July, 1947 - Research Enginee.r in Chemistry Depart-ment. Research on gas-metal and gas-solid reactions and energy sources for underwater propulsion.
0.4.2 July, 1947 to July, 1966 - Advisory Engineer. Research on gas-metal and gas-solid reactions w*ith special application to the nuclear power, lamp and electronic industries. Consulting work on chemical and metallurgical engineering processes.
1
0.4.1. 3 July, 1966 to Present - Consulting Scientist. Research on gas-mctal and gas-solid reactions with special emphasJs on applica-tions in flash lamps, incandescent lamps, nuclear power and high temperature technology, hot corrosion of gas turbines and coal gasification. Extensive consulting activities with Westinghouse Divisions on corrosion, high temperature sintering of tungsten.
getters for lamps, flash bulbs, hydrogen embrit tlement, stress corrosion cracking and structure of surfaces.
0.5 Other Activities. lbe complete record details my publications.
patents, scientific societies, awards and other scientiflc and engineering activities.
0.6 Summary. 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 work experience.
2
AMPLIFIED RECORD OP' SCIENTIFIC AND ENGINEERING EXPERIENCE Earl A. Gulbransen l.O Washingto~ State *university, Pullman, Washington. Bachelor of Science in Chemical Engineering with honors with minors in Physical Chemistry and Mathematics, June, 1931.
Between September, 1930 and Jilne, 1931, I worked as a laboratory assistant 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-matics and Physics , August, 19 34.
Between September, 1931 and August, 1934, I was a graduate assist-ant in organic chemistry under the Aupervision of Professor Lowy (deceased) and in physical chemistry under the supervision of Professor Stegeman (decenscd).
2.1 Thermodynamic Properties of Dilute Solutions My research supervisor was Professor A.L. Robinson (dec:Eased).
P.rofessors Robinson and Stegeman encouraged me to work in the field of Chemical Therm:>dynamics. I have followed ~heir suggestions and I have contributed extensively to the field. My thesis work was concerned with the thermodynamics of dilute solutions of aqueous electrolytes. To carry out this program I assembled the first precision adiabatic differential calorimeter in the United States.
My thesis work was published in the Joumal of the* American Chemi-cal Society, Vol. 56, 2637 (1934) and is referred to as paper num-ber 1 in Section 6.
3.0 University of California, Berkeley, California; Department of Chemistry.
In the sUlimier of 1934 I was awarded a National Research Council Post-Doctroate Fellowship in Physical Chemistry. I chose to work at the Chemistry Department of the University of California headed by Professor G.N. Lewie (deceased).
3
- . **':.""~~.,.--*~ . ._ -r.-*'"'*~u- -
3.1 lbermodynamic Properties of Solids, Liquide and Gases At the University of California I conducted research work in Professor Giaque's Low Temperature Laborntmry and with Professor Ran-dall. Together with Dr. E. Long, I detet::l~ned the data of state equation for phosphine. This work was publ1shed in the Journal of the American Chemical Society, Vol. 58,, 203 (1936). I worked also in the field of thermodynamics of sol~ions *and especially in non-aqueous solutions. I continued my ?,OS t-doctorate educa-tion by attending and participating in studiy seminars on radio-chemistry, theoretical physics, thermochemfstey and theory of solutions.
4.0 Tufts University, Medford, Massachusetts; Department of Chemistry
- and Chemical Engineering.
Between September 1, 1936 and July 1, 1940\, 1 was instructor in Chemical Engineering teaching Unit Processes, Chemical Engineering Thermodynamics, Gas Analysis and Analytical. Chemistry, I also supervised the research activities of 10 semior chemical engineer-ing students. Chairmen of the department, jf:n chronological order, were Professor Durkee ( deccnscd) nncl Professor Bak.er (deceased).
4.1 Geochemical Research At Tufts University I bcgnn a new field of research on geochemical and geophysical processes in nnture. This tbecamc possible by the rapid development. of mnss spectrometric measurement of abundance ratios of the elementnl. isotopes. ~ initia.t.ed, together with Dr. A.
O. Nier of Harvard University, .'.l coT11prchens'ive study of the abun-dance ratios of cl2 and cl3 of naturally oett:Urrln~ cnrbon compounds. This was a nioneering work and 1ed to the use of cl2/cl4 ratios for dating of matter. TI1e wcrk was '1Publ:ished in the Journal of the American Chemical Society, Vol. 61,
- 69 7 (1936).
4.2 N~tional Research Council Committee on the Determination of Geo-logic Time The head of this committee was Professor A.C. Lane. (deceased) of Tufts University. Professor Lane was later called the forgotten man of atomic energy. I worked with Professor Lane for 3 years*
developing research programs on the use of i.sotopes not only for geologic time evaluation but for developing. new methods for follow-ing geochemical reactions.
4.3 Closure In surnmnry, I spent 4 ycnrs nt Tufts University doing independent teaching and crea,ti ve research. nuring this period I maintai.ned 4
close comnnmication with the teaching and research staff at Harvard University and Massachusetts Institute of Technology by attending weekly seminars and by attending local scient~fic society meetings. None of trf'/ supervisors were Registered Pro-fessional Engineers.
5
s.o Westinghouse Electric Corporation, Research and Developr.:ent Cen-ter, Pittsburgh, Pennsylvnnfo. July 1, 1940 to Present.
Due to difficulties in financing research work at Tufts, I de-cided to leave Tufts University and join the Westinghouse Re-search Laboratories. Westinghouse, at that time, was attracting many good people with opportunities to work on basic research problems of interest 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: Messrs. A.A. Bates, Mana-ger, Chemistry and Metallurgy Department, and R.W. Auxier, Mana-ger, Chemistry Department. Neither were Registered Professional Engineers.
s.1.1 Oxidation of Metals My primary project was (1) to develop methods for the study of gas-metal reactions, (2) to use these methods for the study of the oxidation of a vnriety of the conunon metals and al.loys and (3) to develop theorcti cnl models to explain the experimental results. I developed for these studies a very sensitive micro-balnnce which was pl accll in the re;1ct lon system for dete.rmining the kinetics of .oxidation of metals. I developed a special electron diffraction cnmera for the study of the surface structure of the oxide films forml'<l *on m<.*ta l!I nt tcmpernturcs 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 metnlR during oxidation.
Twenty basic papers were pub! i8hcd <luring this period on (1) the kinetics of oxidation, (2) the crystal structure of- the oxide films
- and (3) the 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 used throughout the world for gas-metal studies. We have also contributed extensively to present understanding of the crystal structure and crystal habit of oxide fiims on metals.
s .1. 2 Consulting Activities During this period I acted as a consultant to the Westinghouse Lamp Division on metal problc.>ms. I afoo consulted with the electronics department, metallurgy department and chemical department at our Lnhoratories.
5 .1. 3 World War II Work During the period of 1942 - 1945, I worked on new methods of under-6
water 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 propulsion for torpedoes.
My suggestions on primary batteries led to a large contract with the govetnment for the production of a new type of battery powered torpedo. lbis work was terminated 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 vork of 1-4 professionals and technicians.
7
5.2 July l, 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 Chemistry Department. Neither were Registered P'rofessional Engi-neers.
On July l, 1947, I was promoted to the position of 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 administration, conduct and reporting of basic research activities in the area of surface reactions of gases with metals, alloys, non-..eta1s and oxides and the corrosion of metals and alloys, I reported directly to the manager of the Chemie try Department.
Our research activities were of three types: (1) programs developed in cooperation with Di visions of Westinghouse, (2) programs spon-sored by U.S. Government agencies and (3) basic research programs initiated to solve long-range research objectives of the company, The apparatus, 100thods and trcntment of the problem were essential-ly the same for the three types of research activ.lties.
5.2.l Gas Reactions of Carbon ~)0 - 1500°C This work was done for Bet tis Atomic Power Divisi.on and Astronuclear Di vision to provide basic inform.it ion on the react:ivity of carbon at high ter.:perature in the v:irious n1.1clcar power devices. Extensive studies were made on the reaction of pure graphite, pyrolytic car-bon and doped carbon lll.'.lterials with oxygen, a1r, hydrogen, carbon dioxide and helium at temperatures of 300° to 150{)°C, over a wide pressure range from a fraction of a torr to 76 torr and under a wide range of flow rates.
This \.'ork was done over the fifteen year period o-f 1950 to 1965.
The results were of immediate vnlue to the Oivisiuns. In addition, the "ork led us to a new Wlderstand ing of gas-solid reactions where the reaction product also was a gas. This work W'as reported in papers number 44, 45, 46, '~7, 113, 116, 117,' 122. 123, 124, 125~
126, 127, 135, 143, and 157 of the papers listed in Section 6.
Reaction of Zirconium and 7.irc~-!..~ Alloys t.rith Oxygen, Hydrogen, Nitrogen and Water Vapor This work was done for the Atomic Energy Commissi.on, Bettis Atomic Power Laboratories ancl our Commcrc i nl Atomic Power Di visions. The work was begun as a basic rcs~~rch program in 1947 before the for-mation of Bettis Atomic Power L.:lboratories. Twenty years of nearly continuous research ef furt. w:1~ carried out on the reactions of zir-coniu::i, Zircnloy II, Zjrcaloy lV :md numerous other zirconium alloys 8
with oxygen, air, hydrogen, nitrogen and water vapor over a*
temperature range of 25° to 800°C and pressures of a few torr to over 100 atmospheres. This work was reported in 25 papers which are referred to in Section 6 as papers number 35, 56, 56a, 59, 61, 62, 66, 68, 69, 70, 72, 73, 75, 77, 78, 79> 92, 132, 136, 137, 138, 142, 143, .146 and 151.
Many technical. problems were solved in these studies incl~ing 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 oxidation of zirconium in oxy-gen and in nitrogen, the types of hydrogen reaction with zi*r-conium intermetallic compounds and the reaction of zirconium al-loys in water at high pressure.
5.2.3 Oxidation of*the Refractory Metals, Tungsten, Molybdenum, Rhenium, Niobium and Tantalum
!bis work was done for Wright-Patterson Air Force Laboratories, U.S. ArrirJ Office of R~search,, Durham, Westinghouse Lamp Division and for Westingho~e Basic Research programs.
Twenty-six years of research effort was carried out on the reactions of ttmgsten, molybdenUI11, rhenium, niobium and tantalum with OX"j-gen, hydrogen and hydrogen-water vapor gas mixtures over a tempera-ture range of 25° to 2700°C, a w:f ck pre:*rnure range and in static and flow reaction environments. This work was reported in 20 papers which are referred to in Sec ti on 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 therioochemical stability of the oxide species.
Many technical problem 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-oxide gas species. Studies on the sintering of silicon, aluminum and potassium doped tungsten ingots showed the important role of the oxygen potential of the hydrogen-water vapor gas mixture in controlling the composition and properties of the tungsten ingots. Vapor pressure studies on molybdenum oxides demonstrated the high volatility of the trimer (Mo03) J9 5.2.4 Localized Oxidation and Stress Corrosion Cracking of Metals lnis work was ~tarted as n basic rcsenrch program and later sponsored 9
by the Office of Naval Research an<l 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 *hiskers and hladc;_shnpcd nnd. fan-ehap~d oxide platelets on iron and the mechanism of stress corrosion cracking of metals.
1bis work was reported in 20 papers which are referred to in
.section 6 as papers numbeT" 57, 58~ 65a, 83, 86, 88, 89, 90, 103, 104~ 105, 114, 121, 148, 149, 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 Oxidation of Alloys This work was started in 1945 as a basic research progra~ 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 carrie.d out on the kine tics of oxidation of type 304 stainless. steel, nickel-chromium-aluminum and iron-chromium-alumi-num alloys~ Crystal structure nncl crystal habit stud:i1!s on the oxide films ,.as correlated with the kinetic observations. This '*'
vork was reported in 16 papers which are referred to f,11 Section 6 as papers number 15, 16, 17, 19, 25, 26, 27, 29, 31. 52, 55, 63, 80, 84, 85 and 97.
These studies were vn l unblc in es tab 1 ishing the Wlique Tole of chrocium, aluminum, manganese, silicon and trace impurities in high temperature oxidation.
5.2.6 Thermochemical Analyses Thermochemical analysis was used as a discipline to gu:lde us in planning and interpret in~ all* of the research programs. In the early 1940's we searched the litcrHturc and assembled free energy and equilibria data on many oxi<l~ systems to evaluate t:he oxida-tion, reduction and sintering reactions of metals. This compila-tion of thermochemical informn ti on w.1s one of the first and was very important in our own work an<l as a help to others in our laboratory and in Wes tinghousc Di visions. Three special studies were made to develop thcrmochcmicnl qunntitics to help in our own studies: (1) vapor pressure of h~ryllium, paper number 38, (2) va-por pressure of chromium, papers number 50 nnd 67 and (3). vapor pressuT"c of molybdenum trioxide, pnpcr number 111. These papers helped us to develop models for the oxidation of beryllium, chromi-u::i and molybdenum.
Experimental thermochemical studies were also made for (1) zirconium-10
hydrogen system, papers number 59 and 62 and (2) columbium-hydrogen system, pa~er number 106. lbe results of this work were very valuable in using zirconiUID alloys as a cladding material in pressurized water nuclear power reactors.
5.2.7 Closure All of the work during this period was t.mder my direct supervision.
I participated in the planning, carrying out of the experiments, in the interpretation of the results and in the write-up of the results. During this period I supervised the work of 4-6 profes-sionals and 2-4 technicians, 11
- 5. 3. 2 Oxidation of Silicon and Silicon Carbide This work "1as begun by the Army Office of Resenrch, Durham, and .
later *continued as a basic research project *. Studies were made on the behavior of silicon, s 111 con oxide and silicon carbide in oxidizing and reducing gas atmospheres and in high vacuurn.
These studies confirmed thermochcmic.:i l predictions of two types of oxidation processes, active and passive. Very rapid oxidation (active) occurs in low pressure oxygen using high flow rates with loss of silicon monoxide and carbon monoxide. Very slow (passive) oxidation occurs in high pressure oxygen even in high flow rates with the formation of n protec~ive 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, 163 and 164 in Section 6. The re-sults of these studies have led to a new un~erstanding 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 oxida.tion has led to many new applications of thermochemical analysis in industry.
5.3.3 Hot Corrosion of Gas Turbine Alloys Tilis work developed from our interest in applying thermochemical analyses 'to high temperature cor roB ion processes in gns turbines, A lengthy paper entitled "Gcnernl Concepts of Oxidation and Sulfidation Reactions -- A Thermochemical Approach" was written.
This paper was published and is llstcd as pap.er number 160. This paper has led to further work with the Coal Gasification Project.
Here, cleaned low BTU coal gas will be used in n gas turbine at 1600°F. Thetmochemical analysis is being -used to guide us in planning and interpreting the extensive experimental program.
5.3.4 Sintering of Tungsten for Incnndesccnt Lamps Extensive thermochemical analysis has been used. to study the in-fluence of temperature and dew. point *of the hydrogen g~s 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 torr and in controlled hydrogen/water vapor gas mixtures at temperatures to 2700°C. This work demonstrated the important role of the dew point (oxygen potential) of the hy-drogen gas on the density and silicon, aluminum and potassium levels.
The experimental work con firmed the thermochemical predictions.
This work has not been pub l i she tl
- 13
6.0 PUBLICATIONS Dr. E. A. Gulbransen
- l. Integral Heats of Dilution, Relative Partial Molal Heat Contents and Heat Capacities of Dilute Sodium Chloride Solutions. E. A. Gtdbransen and
- A. L. Robinson. J. Am. Chem, Soc. 56, 2637 (1934).
- 2. Data of. State of Phosphine at Low Pressures and from 190 l:O 300 K. E. A. Long and E. A.* Gulbransen. J. Am. Chem. Soc. 58, 203 (1936).
J. \'ariations in the Relative Abundance of Carbon 1sotopes. .A. O. Nier and E. A. Gulbra.nsen. J. Am. Chem. Soc. 61, 697 (1936).
- 4. Thin Oxide Films on Iron. E. A. Gulbransen. Trans. Elec~rochemical Society
. Sl, 327-339 (1942).
). Some Observations on the Formation and Stability of Oxide Films. E. A. Gulbransen.
Trans. Electrochemical Society .§1, 375-389 (1942).
- 6. Transition State Theory of Formation of Thin Oxide Films en Metals. E. A.* Gulbransen.
Trans. Electrochemical Society .§1,*301-317 (1943).
- 7. Electron Diffraction AnalysiS of Surface Films. E. A. Gul.bransen. Electronics, January 1944 *
.*ti.* A Vacuum ~icrobalance 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 .§1, 463'-473 (1945).
_l), Electron*Diffraction Camera for the Study of High Temperamre Surface Reactions.
E. A. Gulbransen. J. Appl. Phys, l§., 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. 17, 646-52 (1945).
.., An Electron Diffraction and Electron Microscope Study of Oxide Films Formed on
- -* Xetals and Alloys at Moderate Temperatures I. Stripped Old.de Films of Metals.
R. T. Phelps, E. A. Gulbransen and J. W. Hickman. Ind. Eng. Chem. Anal. Ed.
1.§., 391-400 (1946).
. j.
New D~velopments in Surface Chemistry. E. A. Gulbransen. Metals Progress~
- !-!arch 1946.
. ~. A~ Electron Diffraction and Electron Microscope Study of Oxide Films Formed on
'Keals and Alloys at Moderate Temperatures II. Stripped Oxide Films Formed on
~i.::::als and Alloys. E. A. Gulbransen, R. T. Phelps .and J. lol. Hickman.
Ind. Eng. Chem. Anal. Ed. 1§., 640-652 (1946).
15
Dr. E. A. Gulbransen
- J, An Electron Diffraction Study of Oxide Films Formed on Metals and Alloys at
~igh Temperatures. 1. The Metals Fe, Co, Ni, Cr anu Cu. E. A. Gulbransen and J. \.l. Hickman. AIME Inst. Metals Div. Trans. 171, 306-331 (1947).
~ l>, An Electron Diffraction Study of Oxide Films Formed on Metals and Alloys at Eigh Temperatures. II. The Alloys Consisting Principally of Fe, Co, Ni*and Cr. J. W. Hickman and E. A. Gulbransen. AIME Inst. Metals Div. Trans. fil, 3.:..:.-370 ( 194 7).
- . An Electron Diffraction Study of the O~dde Films Formed on Molybdenum and Tungsten at High Temperatures. J. W. Hickman and E. A. Gulbransen. AIME Inst. Metals Div.
~rans. 171, 371-387 (1947),
_j, *7he*Kinetics of Oxidation Reactions. E. A. Gulbransen. Trans. Electrochemical Soc:. :ll, 573-602 (1947).
- ), An Electron Diffraction Study of the Oxide Films Formed on Oxidation Resistant
~lloys. J, W. Hickman and E. A. Gulbransen. Trans. Electrochemical Soc. i!.,
b05-620 (1947) *
. 0. The Kinetics of the Oxidation, Reduction and Vncuum Behavior of Molybdenum and its Oxides. E. A. Gulbransen and W. S. Wysong. AIME Metals Div. 175, 628-47 (1948).
. .l
- The Kinetics of Oxidation, Reduction and Vacuum Behavior of Tungsten and its C*xides. E. A. Gulbransen and W. S. Wysong. AIME Metals Div. 175, 611-27 (1948).
A High Temperature Electron Diffraction Furnace. E. A. Gulbranse*n. Rev. Sci.*
!m;cr. Hl, 546-550 (194.7).
J. ':"hin Oxic:ic Films on Aluminum. E. A. Gulbransen and W. S. Wysong. J. Phys.
Col lcid Chem. g, 1087.;.1103 (1947).
....
- ~nd Cobalt. *An Electron Diffraction Study. J, W. llic~an and E, A. Gulbransen.
J. Anal. Chem. 20, 158-165 (1948).
.) . Decarburi zation of Chrome Nickel Alloys by Their Surface Oxide in High Vacua
~t Elevated Temperatures. E. A. Gulbransen, W. S. Wysong and K. F. Andrew.
Trans. AIXE ~I 565-78 (1949).
A.n Electrun Diffraction Study of Oxidl.? Films Formed on Copper Nickel Alloys at Elevated Temperatures. J, W. Hickman and E. A. Gulbransen. Trans. AIME 180,
~3!.-46 (1949).
~ 7. An Electron Diffraction Study of Oxide Films Formed on Hastelloy Alloys A~ B, C and D. J. W. Hickman and E. A. Gulbransen. J. Phys. Colloid Chem. 52, 1186-1197 (l 948).
':::.6 ,* :~e Application*of Electron Diffraction Techniques to the Study of Corrosion Prvcesses. E. A. Gulbransen. Corrosion ii No. 9, 445-455 (1948).
16
Dr. E. A. Gulbransen
. ~. An Electron Diffraction Study of Oxide Films Formed on Ni chromes. J. W. Hickman-and E. A. Gulbransen. Trans. AIME 180, 519-33 (1949) *
.o. Kinetic and Structural Factors Involved in Oxidation of Metals. E. A. Gulbransen.
Ind. & Eng. Chem. 41, 1385-91 (1949).
- 11. Progress dans l'etude de l'oxydation supcrficielle des metaux et alliages a des temperatures elevees. E. A. Gulbransen. I - Revue de Metallurgie !2_, 181-204 (July 1948). II - Revue de Metallurgie 45, 287-300 (August 1948).
- _;2. The Reactions of Metals in High Vacuum. E. A. Gulbransen and It. F. Andrew.
Proc. of Pittsburgh International Conference on Surface Reactions *. Also published
'in J. Phys. & Colloid Chem. ~. 690-711 (1949).
- 13. Reactions of Zirconium, Titanium, Columbium and Tantalum vith the Gases, Oxygen, Nitrogen and Hydrogen at Elevated Temperatures. E. A. Gu1bransen and K. F. Andrew.
J. Electrochem. Soc * .2§., 364-376 (1949).
).:.. . Mullite and Zircon Furnace Tubes for High Temperature and High Vacuum Systems; A New Method for Measuring .Pressure. E. A. Gulbransen and K. F. Andrew.
Ind. & Eng. Chem. !, 2762-7 (1949).
is. Kinetics of the Reactions of Zirconium with 02 1 N2 and Hi. E. A. Gulbransen and K. F. Andrew. AIME Metals Trans. 185, 515-526 (1949).
1~. Kinetics of the Reactions of Titanium with 02. Nz ~nd H2. E. A. Gulbransen and K. F. Andrew. AIME Metals Trans. fil, 741-8 (1949).
- ,/. Reactions of Columbium and and Tantalum with 02 1 N2 and H2* E. A. Gulbransen and K. F. Andrew. J. of Metals, March 1950; Trans. AIME 188~ No. 3, 586-99.
~6. The Kinetics of the Reactions of Beryllium with Oxygen and Nitrogen and the Effect of Oxide and Nitrideon Its Vapor Pressure *. E. A. Gulbransen and K. F. Andrew. J. Electrochem. Soc. 21., 383-95 (1950).
- _1~. The Kinetics of the Reactions of Vanadium with Oxygen and Nitrogen. E. A. Gulbransen and K. F. Andrew. J. Electrochem. Soc. £, 396-404 (1950).
-~. Kinetics of Solid Phase Reactions in Oxide Films on Iron; The Reversible Transformation at or near 57o*c. E. A. Gulbransen and R. Ruka. J. of Metals, December 1950, 1500-1508, Trans. AIME, 188.
Kinetics and Mechanism of Solid Phase Reactions. E. A. Gulbransen and R. Ruka.
lnd. & Eng. Chem. il* 697-703 (1951).
Kinetics of the Oxidation of Cobalt. E. A. Gulbransen and K. F. Andrew.
- .1. Electrochem.* Soc. 98, 241-251 (1954).
17
Dr. E. A. Gulbrnnscn
!, Solid Phase Reactions in Oxide Films and Scales on Iron. E. A. Gulbransen.
Revue de Hetallurgie 48, 336-352 (1951).
.... Kinetics 0f Oxid.:ition of Artificial Graphite at Temperatu.yes of 425D to 575°C
.ind Pressures of 0.15 to 9.8 cm of Hg of 02. E. A. Gulbransen and K. F. Andrew.
Ind. & Eng. Chem. !Ji!., 1034-38 (1952).
- _1. Surf ace Oxide Fon:tation and Surface Roughness Studies in !!elation to Oxidat~on of Artificial Graphite at Temperatures of 25°C and between 425° and 575°C.
r:. A. Gulbransen and K* F. Andrew *. Ind. & Eng. Chem. 44,.. Jl.039-44 (1952).
- ')., ~!echanism of the Oxidation of Graphite at Temperatures of 425° to 575°C.
- E. A. Gulbransen. Ind *. & Eng. Chem. !!,i, 1045-4 7 (1952).
r~actinns of C~rbon Dioxide with Pure Artificinl Graphite at Temperatures of
- ,00° to 900°C. E. A. Gulbransen and K. F. Andrew. Ind. a. Eng. Chem. 44, 10.:.8-Sl (1952).
1:~11.' of Crysta.l Orientation in the Oxidation of Iron. E. &.. Gulbransen and R. Ruka. J, *Electrochem~ Soc. 99, 360 (1952).
El~dron Diffraction Studies on the Oxidation of Pure Cog..?Cr and Pure Zinc between 200° and S00°C. E. A. Gulbransen and W. R. McMillan. J. llectrochem. Soc. 99, :~*
J-)3 (1952).
A Preli:ninary Study of che Oxidation and Vnpor Pressure on 'Chromium.
E. A. Gulbransen and K. F. Andrew. J, Elt!ctrochcm. Soc. Sf9, 402-6 (1952).
~. S.irf ace S:-udies Using the Vacuum Microbalance. I I. High l'~mperature Reactions.
r:. A. Gulbransen. Advances in Catalysts, Vol. 5, *P* 120-li/.4 (1953), Academic Press, In('.*
_*..:. C:-ystal Structure Studies of the Oxide Film Formed ori a Sa.>ries of Nickel-Chromium
.*Alloys. E. A. Gulbransen and W. R~ McMillan. Ind. & Eng. Chem. _il, 1734-44 (1953).
J. T:1e M~chanism of Oxidation of Metals from the Viewpoint o.f the Transition State Ti1eory. E. A. Gulbransen. Pree. of International Symposi"1m on the Reacting of SoliJs (1952).
- The Kinetics of Oxidation of High Purity Nickel. E. A. GulbranRen and K. F. Andrew.
J. Electrochem. Soc. 101, 128-140 (1954).
T!1e Rat~ of OJ<;idat ion of Three Nickel-Chromium lleatcr Alloys between 500°C and Y.J0°C * . E. A. Gulbransen and K. F. Andrew. J. r:lectrochem. Soc. 101, 163-170 (1954),
...,. t*~echanism of the Reaction of Hydrogen with Zirconium. I. Role of Oxide Fil.ms, Pr~-TreJtments and Occluded Gases. E. A. Gulbransen and K. F. Andrew.
J. Electr.:ichem *. Soc. 101, 348-53 (1954).
18
Dr. E. A. Gulbrans~n
,..i. Role des pellicules superficielles sur la renction du zirconium avec l 'hydrogene.
E. A. Gulbransen and K. F. Andrew. Revue de Metallurgie. Ll, No. 2 (1954) *
. ]. Reaction de fer avec l'oxygene aux basses pres8ions et a des temperatures comprises entre 650°C et 850°C. E. A. Gulbransen. W. R. McMillan and K. F. Andrew.
Revue de Metallurgie Lll, No. 7 (1955).
)5. Electron Optical Study of Oxidation of High Purity Iron at Low Oxygen Pressures.
E. A. Gulbransen,. W. R. McMillan and K. F. Andrew. J. Metals §., AIME Transo 1.QQ,.
1027-34 (1954).
j9. Crystal Structure and Thermodynamics Studies on the Zircon*ium-Hydrogen Alloys.
E. A. Gulbransen. and K. F. Andrew. J. Electrochem. Soc. !Ql, 474-80 (1954).
- 0. *Classical Theory of Diffusion and the Oxidation of Metals. E. A. Gu1bransen.
Annals of the New York Academy of Sciences, Vol. 58, Art. 6, p. 830-42 (1954).
~ .
'J2~ The Solubility and Decomposition Pressures of Hydrogen in Zirconium. .E. A. Gulbransen and K. F. Andrew. J. of Metals L, 136-144 (1955).
,j3. Effect of Strain on the Oxtdation of Nickel.:.Chromium Heater Alloys. E. A. Gulbransen and K. F. Andrew. Spec. Tech. Pub. No. 171, ASTM, 35-46 (1955) *.
Role of Impurities in the .Oxidation of Metals. E. A. Gulbransen.
- Corrosion 12, 61-67 (1956).
- ,). A Ne..., Method for the Evaluation of High Vacuum* Furnaces and Heat Treating Atmospheres. E. A. Gulbranse_n and K*. F. Andrew. Presented at Vacuum. Metallurgy Symposium of. Electrothermics and Metallurgy Div. of Electrochem. Soc. (1954).
~a.
Formation de Germes des Atmospheres D' oxygene sous Des Press ions de 10
-s A 10
-7 mm de Hg A 850°C. E. A. Gulbransen and W. R. McMillan. J. de Chimie Physique 1956,
- p. 643-659.
ti6. Gas Metal Reactions of Zirconium.. E. A*. Gulbransen. Metallurgy of Zirconium,.
Lustman and Kerze. National Nuc.lear Energy Series, McGraw Hill (1955).
'. 7. Kinetics of th.e Oxidation of Chromium. E. A. Gulbransen and K. F. Andrew.
J. Electrochem._Soc. lQi, 334-38 (1957).
Oxidation of Zirconiu:n between 400°C and 800°C. E. A. Gulbransen and K. F. Andrew.
J. of Metals .2,, AIME Trans. 1.Q!, 394-400 (1957).
Oxidation of 50 Weight Percent Uranium-Zirconium Alloy. E. A. Gulbransen, R. G. Charles ands. Barnartt. J. Electrochem. Soc. 104, (1957).
19
Dr. E. A. Gulbransen
- .E,. Effect of Stress on Unusual Crystal Habits of Corrosion Product.s on Iron. Nickel, Chromium and Stainless Steels. E. A. Gulbransen arid T. P. Copan. General Motors S)'UlpOsium on Stress and Fatigue in Metals, Edited by G. M. Rasswc11er and
- w. L. Grube.
HL Effect of Stress and Environment on the Micro topology of the Corrosion Product.
E. A. Gulbransen and T. P. Copan. Book - Metallurgical Society Conferences Vol. 4, "Physical Metallurgy of Stress Corrosion Fracture", lnterscience Publishers, 1959.
- 19. Elect.ran Microscopy and Electron Diffraction Studies of Oxide Fi.lms Formed on Iron in Water and Oxygen Atmospheres. E. A. Gulbransen and T. P. Copan. ASTM
_Special Tech. Pub. No. 256, Symposium on Identification of Water-Formed Deposits.
- 10. ?1icrotopology of the Surface lteactionsof Oxygen and Water Vapor with Metals *
. E. A. Gulbransen and*T. P. Copan. Faraday Society Discussions 1959, No. 28.
- H. Kinetics of the Oxidation of Pure Tungsten from 500° to l300°C. E. A. Gulbransen and K.. F. Andrew. J
- Electrochem. Soc. 107, (1960). *
- !2. Hydrogen in Zirconium - A Simple Experiment in Chemical Equi.libria. O. M. Katz and E. A. Gulbransen. J. Chemical Education lZ_, 533 (1960).
- U. The lnv.isible* Armor - Surface Films on Hetals. E. A. Gulbransen. Chapter in Book "Saturday Science", E. P. Dutton & Co., Publbhers.
.... Aluoinum *Reactions with Water Vapor, Dry Oxygen, Moist Oxygen and Moist Hydrogen bct...,een 500°C and 625°C. P. E. Blackburn and E. A. Gulbransen. J. Electrochem.
- Soc. 107, No. 12 (1960) *
-*0. Thermochecical Analysis of the Reactions of HCl, NaCl, M.gClz, Water Vapor and Oxygen ._.ith Fe, Ni and Cr and Their Implications in Stress Corrosion Fracture.
E. A. Gulbransen. Metallurgical Society Conferences, Vol. 4, "Physical Metallurgy of Scress Corrosion Fracture", Interscience Publishers, 1959,, p. 364-370.
Trans. AI!-1.E 221, 1247-1252 (1961).
- -; . Perrneabil ity and Diffusivity of Hydrogen Through a Pnllndium Tube. 0. M. Katz and E. A. Gulbransen. Rev. Sci. Instr. ].1, 615-7 (1960).
- 1. Electron Diffraction. Adapter for the EMU-30 Electron Microscope. E. A. Gulbransen*
and T. P. Copan. Reprinted by RCA for overseas distribution.
21
Dr. E. A. Gulbransen JO. The Eff cct of Pressure on Microgravirnetric Studies in Hydrogen. O. M. Katz and E. A. Gulbransen. Vacuum Microbalance Techniques, Vol. 1, Plenum Press, 1961, P* 111.
- 12. An Enclosed Physical Chemistry Laboratory - The Vacuum .Microbalance. E. A. Gulbransen and l{. F. Andre~. Vacuum Microbalance Techniques, Vol. l~ Plenum Press, 1961, P* 1.
- 13. Crystal Habit and the Corrosion of Iron. E. A. Gulbransen and T. P. Copan.
Nature 1869 959 (1960).
_!-'.+. CrystJll Habit and the *corrosion of Iron. E. A. Gulbransen and T. P. Copan.
European Regional Conf. on Electron Microscopy, Delft, Holland, (1960).
- JS. Oxidation of Copper between 250° and 450° and the Growth of CuO Whiskers".
E. A. Gulbransen, T. P. Copan and IC F. Andrew. J. Electrochem. Soc. !Q!!, 119 (1961).
)b.. Thermodynamic FunctiOns for the Columbium~Hydrogen System,, o. M. Katz and F.. A. Gulbransen. "Columblum Metallurgy", AIME and Interscience, N.Y., p. 523 (1961) *
.; . Some Observations on the Uranium + Niobium - Hydrogen System. o. M. Katz and F.. A. Gulbransen. J. Nuclear Matls. 2_, 269 (1962).
- ,. C0rrosion by Gases. E. A. Gulbransen. Encyclopedia of Science and Technology.
'!.::Graw-liill Book Co., 1960.
'l, lnvar Beam Balan~e* for.tne Study of Fast Chemicnl Reactions. E. A. Gulbransen and K. F. Andrew. Vacuum Microbalance Techniques, Vol. 2, p. 129, Pl.enum Press, Inc.
~.Y. (1962). .
. Ii. Kinetics of Oxidation of Pure Tungsten, 1150°C-1615°C. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. J. Electrochem. Soc. 111, 103 (1964).
'.1. \'apor Pressure of Molybdenum Trioxide. E. A. G~1lbransen, IL F. Andrew and F. A. Brassart. J, Electrochem. Soc. 110, 242 (1963).
- 12. Four Types of Oxidation Processes in the Oxidn.tion of Tungsten. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. Proc. AIME Symposium, N. Y, , 1962. p. 81..
E. A. Gulbransen, T. P. Copan and W. M. Hickam. Proc. of 5th Inter. Cong. for Electron Microscopy, Philadelphia, 1962.
- j, Oxidation of Moiybdenum sso* to 1700°C. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. J. Electrochem. Soc. 110, 952 (1963).
22
1--
- Dr *. E. A. Gulbransen
- J. 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. Gulbrnnsen, K. F. Andrew and F. A. Brassart* J. Electrochem. Soc. 110, 476 (1963).
-I* High Tecperature Oxidation of Tungsten, Molybdenum and Carbon. E. A. Gulbransen.
- Na tu re fil, 82 (1963) ~
High Temperature Furnace and Reaction System for Temperatures up to 1600°C.
E. A. Gulbransen, K. F. Andrew and F. A. Brnssart. Vacuum Microbalance T.:chniques, Vol. 3, p. 1799 Plenum Press, 1963.
... A't>lation of Graphite in Oxygen and Air at 1000° to 1400°C Under Flow Conditions
- E. A. Gulbransen, K. F. Andrew and F. A. Brassart. Carbon, l, 413 (1964).
Occluded Gases in Transition Metals. -o. M. Katz und E. A. Gulbransen.
Chapter 4, "Non-Stoichiometric Compounds." Academic Press, 1964.
.:. . ~1odels of Oxidation Processes Occurring in Oxide Whiskers and Platelets on Iron .
at 400° to 500°C. E. A. Gulbransen. Colloque International sur les Processus*de
~:ucleation dans les Reactions des Gaz Sur les Metaux et Problemes Connexes, June 1963. Centre ?;at ional de la Rech ere he Sci en tif ic. Rev. Met:allur-g. g,
.:SJ (1965).
Ahlation of High Purity and Nuclear R~nctor Core l.raphite in O:icy~cn and Air.
E. A. Gulbr~nsen, K. F. Andrew, F. A. ilrassart an<l A. L. Feild, Jr. J. Nuclear
~~ts.* 11, (1964).
Oxidation of Graphite,- ~lolybdenu:m and Tungsten nt 1000°C to 1600°C. E: .. A. Gulbransen~--
K. F. Andre'-* and F. A. -Brassart .. Progress in Astronautics & AeronautiC$, Vol. 15, ***
Heterogeneous Combustion, p. 227, Academic Press, New York, 1964.
-'.'xication of Pyrolytic Carbon 1000°C to 1500°C and Oxygen P.ressures of 2 t.o 38 Torr.
E. A. Gulbransen, K. F. Andrew and F. A. Bra.ss*Ht. J. Electrochem. Soc. 111, 6~6 (1964). --
- . Reaction of Graphite with Carbon Dioxide at 1000°C to 1600°C Under Flow Conditions.
E. A. Gulbransen, K. F. Andrew and F. A. Brassart. Carbon£, 421 (1965).
- . Study of Fast Reactions in Flow Environments. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. Vacuum Microbalancc Techniques !!_, p. 127,. Plenum Press, Inc.,
- ~e*J York (1965).
7!.~ Reattion of Hydroien with Graphite at 1200° to 1650°C. E. A. Gulbransen,
- . F. Andrew and F. A. Brassart, J. Elcctrochcm. Soc. 112, 49 (1965).
! ::-.: roduc tory Remarks: Fourth Informal Vacuum Mic rohalance Conference~
~-A. Gulhrans~n. Vacuum MicrobalancL! Techniques i* p. xi, Plenum Press, N.Y. (1965).
23
Dr. E. A~ Gulbransen
- 1. General Concepts of Gas:-Metal Reactions. E. A, Gulbransen. Corrosion 21, 76 (1965).
- 3. Oxidation of Silicon at High Temperature and Low Pressures under Flow Conditions and the Vapor Pressures of Silicon.* E. A. Gulbransen, K. F. Andrew and F. A. Brassart *. J. Electrochem. Soc. 11?, 834 (1966).
.... Oxidation of Silicon Carbide at llso* to 1400°C and at 9 x 10-J to 5 x io*l Torr Oxygen Pressures. E. A. Gulbransen, K. F. Andrew and F. A. Brassart.
J. Electrochem. Soc. fil, 12 (1966).
.). Nature of the Reaction Products Formed in the Graphite Hydrogen Reaction at 130o*-1soo 0 c at 19 Torr. E. A. Gulbransen and w. M. Hickam. Electrochemical Technology 1* No. 5-6 (1967).
ti. Thermochemical and Structural Aspects of the Reaction of Hydrogen with Alloys
~nd Intermetallic Compounds of Zirconium. A. R. Pcbler and E. A. Gulbransen.
Electrochemical Technology i, No. 5-6 (1966).
~
.. A Hot Extraction Method for Hydrogen Analyses of Zirconium and Zirconium Alloys Using Cryogenic Pumping. E. A. Gulbransen and K. F. Andrew. Electrochemical Technology 1, 471 (1967).
'-i
' . Iii gl1 Temperature Oxidation in Flow -Reaction Systems. E. A. Gulbransen, K. F. Andrew and F. A. Brassart. Proc. of 3rd International Congress on Metallic Corrosion.* Moscow, USSR (1966).
- '* Gas-Solid Reactions in Flow Environments at High Temperatures. E. A. Gulbransen.
~at. Acad. Sci. Nat. Res. Council Publication No. 1970 (1967) *
. J. Oxidation of Zirconium and Zirconium Alloys in Water Vapor Atmospheres Containing Trace Amounts of Oxygen at 375* and 575°C *. E. A. Gulbransen and K. F. Andrew.
Electrochemical Tech~ology i* No. 3-4 (1966) *
. J. The Graphite Hydrogen Reactions and Their Implication in Geochemistry.
E. A. Gulbransen. Nature 111, 1420 (1966) .
., . Crystal Morphology and Mechanisms of Growth of a-Fez03 Whiskers on Iron.
R. L. Tallman and E. A. Gulbransen. J. Electrochem. Soc. 114, No. 12 (1967) *
.). The Oxidation of a Series of Dilute Zirconium Alloys at 500°C in a Water Vapor At~osphere Containing Trace Amounts of Oxygen. E. A. Gulbransen and K. F. Andrew.
Co:-rosicn Q, 231 (1967).
24
Dr. E. A. Gulbransen
., 6. Equilibrium Studies on the Systems ZrCr2-H2, ZrV2-H2 and ZrM02-H2 Between 0° a:id 900°C *. A. Pebler and E. A. Gulbransen. Trans. Met. Soc. of AIME 239, 1593 (1967).
- .' ~
. Oxida*tion of Rhenium and a Rh.enium-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 Common Metals 14, 217 (1968).
Localized Oxidation Processes on Iron. E. A. Gulbransen. Proc. of Conf. on "Interfac~ Conversion", Oct. 1967, Ford Motor Co.,
Dearborn,
Mich.
.:. 9. Selected Area Electron Diffraction Study of Twinned a-Fei03 Blade-Like Platelet Growths on Iron. R. L. Tallman and E. A. Gulbransen.
J. Electrochem. Soc. ]J2_, 770 (1968).
'.Q. Dislocation and Grain Boundary Diffusion in the Growth of a-Fe203 Whiskers on Iron. R. L. Tallman and E. A. Gulbransen. Nature 218, No. 5146, 1046 (1968).
I Oxidation Studies on Zirconium Alloys in High Pressure Liquid Water at 360°C.
E. A. Gulbrar.sen and K_. F. Andrew. J. Electrochem. Soc. 116, 659 (1969).
'l
~.* Hign Te:npcrature Reaction Studies with the Microba lance. E. A. Gulbransen and F. A. Brassart. Chapter in Book on "Vacuum Micr-obalances" by S~ Wolsky.
I nterscience Publishers, New York, 1969.
.:... Localized Diffusion Processes in the Growth of. fl-Fei03 Whiskers and Platelets o:-i Iron. E. A. Gulbransen, T. P. topan and K. F. Andrew. Chimiaa, Dec. 1969, Feitknech t Nu:nber ..
-. r~e:-moche~istry E. A. Gulbransen.
and the Oxidation of Refractory Metals at High Temperatures.
Corrosion l§_, No. 1, 19-28 (1970).
.c ) . T~e lnter-pretation of Vacuum Microbalance Studies of High Temperacure Oxidation c: ~aterials. E. A. Gulbransen. P.roc. Sch Informal Vacuum Microbalance Conf.
\' acuu::1 ~Ucrobalance Techniques, Vol. 8, Evaluation of Gas-~etal Reactions by Means of Thermochemical Diagrams.
S. A. Jansson a~d E. A. Gulbransen. Proc. Fourth International Congress on Metallic Corrosion, Amsterdam, 1969.
JI *
~
\'aporiza tion Chemistry in the Oxidation of Carbon, Silicon, Chromiwn, Molybdenum a:i.d Niobiur.. E. A. Gulbransen and S. A. Jansson. Published in book "Heterogeneous Kinetics at Elevated Temperatures", Ed. G. R. Belton and W. L. Worrell, Plenum Press. *~ew York, 1970;
- .it:. Selec:ed Area Electron Diffraction Study of a-Fe203 Platelet Growths Twinned on I~ist Grain Boundaries. R. L. Tallman and E. A. Gulbransen. J. Electrochem.
Soc.; 117, 250 (1970).
25
7.0 PATENTS 7.1
- Photoflash Lamp with Yttrium Combustible Filling, June 27, 1972. U.S.
3,672,814.
7 .2 Photoflash Lamp and Multiple Flash Lamp System, July 4 9 1972. U.S. 3,675,004, Earl A. Gulbransen, R. L. Tallman, K. F. Andrew, and B. T. Buzalski 7.3 Yttrium-Hydrogen Isotope Compositions for Radiochemical. Reaceions, February 13a 1973, U.S. 3, 716,491, L. N. Yannopoulos, s. A. Janssoa, and E. A. Gulbransen.
7.4 Yttrium Alloy Getter, September 29, 1971, Great Britain 1,248,184, S. A. Jansson, E. Ao Gulbransen, and L. N. Yannopoulos.
27
- .
8.0 SCIENTIFIC SOCIETIES 8.1 American Chemical Society 1936 - Present 8.2 tlectrochemical Society 1941 - Present
- 8. 3 A::lerican Institute of Mining and Metallurgical Engineers - Institute of Metals Division 1946 - Present 8.4 Chemists Club of Pittsburgh 8.5 Former Member Electron Microscope Society, American Society of X-Ray and Electron Diffraction, American Association for the Advancement of Science.
9.0 AWARDS 9.1 America11 Institute of Mining and Metallurgical. Engineers Award for Out-standing Research - 1949.
'j * .. National Association of Corrosion Engineers, Willis Rodney Whitney Awa~d - 1952 *.
9.) A:::ierican Checical Society, Pittsburgh Section Awurd - 1961.
'j. 4 Electrochemical Society, Acheson A\o.7nrd and Prize - 1964.
28
... _ _ .,....,. *. _ r
10.0 OTHER SCIENTIFIC ACTIVITIES 10.1 International Conference on Surface Reactions - 1948 - Cha~rman and Organizer.
10.2 Gordon Research Conference,Metals Conference - 1952 -Chairman and Organizer.
10.3 Gordon Research Conference, Corrosion Conference - 1955 - Chairman.
10.4 Corrosion Research Council, Member 1958-1964 - Chairman 1963-1964.
10.5 AIME Conference on Physical Metallurgy of Stress Corrosion Fracture - 1959 -
Program Chairman.
- 10.6 AIME Corrosion Resistant Metals Committee, Member 1957 - 1965.
10.7 American Chemical Society, Pittsburgh Section - Chairman 1959-1960.
10.8 Electrochemical Society, Pittsburgh Section - Chairman 1947.
J0.9 Chemist Club of Pittsburgh, Chairman - 1956.
10.10 International Union of Pure and Applied Chemistry, Membeir Committee on Pure Metals.
29
11.0 Summary Thirty-three of m'f thirty-nine years of scientific and engineer-ing experience have been in the field of gas-metal and gas-solid reactions including research, development, ~onsul ting and super-vis ory activities.* lbe time span of 1940 - 1973 includes the period in which gas-metal reactions were juet beginning to be studies in our unlversities to the present period where the study of gas-solid reactions is essential iD the preparation and use of materials.
- My first activities at Westinghouse were to develop new and im-
- proved instruments for the study of gas-metal. reactions. We de-veloped the vacuum microbalance method for die study of the kinetics of oxidation, medium and high vol~aige electron diffraction methods for the study of the crystal structmre of thick and thin oxide films and electron microscope methods f'or the study of the crystal habit of oxide films. A combinatioa of these methods was used to experimentally characterize a wide variety of oxi-dation, volatilization, hydrogen rcductioa amd hydr1ding reactions.
A second phase of this work was to interpret. the results of the experimental studies. We made important theoretical contributions
- to gas-solid reactions us!ng thermochemical analyses* kinetic theory, transition state theory of chemical reactions, diffusion theory and classical di ff us ion rn te theory *.
. We have studied over a thirty-three year period a broad spectrum of gas-metal and gas-solid reactions. lbe oxidation reaction of the following elements and alloys have been studied: iron, nickel, cobalt, copper, aluminum, magnesium, chrondmm, berylliunt, titani-um, vanadium, zirconium, rhenium, silicon, niobium, tantalum, molybdenum, tungsten, uranium, stainless steels, nickel-chromium, iron-nickel-chromium, iron-chromium-aluminum, zirconium-tin, Zirc-aloy and a large number of zirconium-intermecallics. The hydro-gen and nitrogen reactions of zirconium, titanium, niobium, tanta-lum, Zircaloy and the zirconium-intermetallics '"'ere studied. We have worked extensively on the oxidation, reduction and volatili-zation reactions of SiC, Si02, A1 2o3 , W-0, Mo~ and U-0 systems.
Over the years the gas environmeT"ltS have changed from simple oxi-dation and reduction gas environments to complex environments of mixed gases such as hydrogen-water vapor gas mi.xtures, inert gases containing traces of water vapor, nitrogen, oxygen, etc. and air containing water vapor and traces of sulfur gases. Also, temperatures have risen from temperatures below 1000°C to temperatures up to 280C°C. *These t:rends in more complex 30
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, transformers, fur-naces, ovens, electrical heaters, incandescent lamps, flourescent lamps, automotive lamps, cameras, . flash lamps, high temperature materials, ceramics, electrical heater alloys, magnetic alloys, protective coatings,. electroplated coatings and corrosion resistant alloys.
From the beginning I have been affiliated with individuals and groups dedicated to solving technical problem using the best
- of modern theoretical and experimental methods. My scientific
- work has taken me to meetings and discussions all over the United States. and in many foreign countries including Canada, England, France, U.S.S.R., Japan, Norway, Sweden, Switzerland and Italy. As a result I am familiar with scientific and engi-neering work in TJt;/ area of competence in many cotmtries and know most of the workers.
Signed .
31
e UNITED STATES OF J\,MERIC. ~ C91lREspoNDENCE NUCLEAR REGULl\TORY 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 j l)
CERTIFICATE OF SERVICE
- I I
. I hereby certify that copies of Earl A. Gulbransen' s testimony i I
on behalf of the intervenor, Township of Lower Alloways.Creek, in response I to the Board Order dated April 18, 1979 I in the above captioned matter have been served upon the attached* list by deposit* in the United States mail at the
~ost office in Northfield, N.J., thereon, this 12th day day Of June *, 1979 .
A , JR.~ Specia Nuclear Counsel for the Intervenor, the Township of Lower Alloways Creek Dated: June 12, 1979 *
~--~~~--~~
' (
~
Gary L. Milhollin, Esq. Richard Fryling, Jr., Esquire Chairman, Atomic Safety Assistant General Solicitor
& Licensing Board *Public Service Electric &
1815 Jefferson Street Gas Company Madison, Wisconsin 53711 80 Park Place Newark, No J. 07101 Glen o. Bright Member, Atomic Safety Keith Ansdorff, Esquire
& Licensing Board Assistant Deputy Public Advocate U. S. Nuclear Regulatory Commission Department 0£ the Public Advqcat Washington, D. C. 20555 Division of Public Interest Advo P. O. Box 141 D~. James C. Lamb, III Trenton, New Jersey 08601 Member, Atomic Safety &
Licensing Board .Panel Sandr~ T. Ayres, Esquire 313 Woodhaven Road Department of the Public.Advocat Chapel Hill, N. C. 27514 520 East State Street Trenton, N. J. 08625 Chairman, Atomic Safety and Licensing Appeal Board Panel Mr. Alfred C. Coleman, Jr.
u~ S. ~uclear Regulatory Commission Mrs. Eleanor G. Coleman Washington, D. c. 20555 35 "K" Drive Pennsville 7 N. J. 08070 Cho.irman, Aton:ii'c Safety &
Licensing Board Panel Office of the Secretary .
L'. S .- r~uclear Regulatory Commission Docketing and Service Section t.J;is hi ngton, D. C. 2055 5 U. s~ Nuclcn~ Regulatory Commiss Washington, D. C. 20555
- Barry Smith, Esquire Off ice of the Executive Legal Director June D. MacArtor, Esquire
- u. S. Nuclear Regulatory Commission Deputy Attorney General
- Washington, D. c. 20555 Tatnall Building, P. 0. Box 1401 Dover, Delaware 19901 Mark L. First, Esquire
- neputy Attorney General Mr. Lester Kornblith, Jr.
Department of Law & Public Safety Atomic. Safety and Licensing Boar' Environmental Protection Section U. S. Nuclear Regulatory Commiss 36 West State Street Washington, D. C. 20555 Trenton, N. J. 08625
~ark J. Wetterhahn, Esquire for Troy B. Conner, Jr., Esq.
1747 Pennsylvania Avenue, N. W.
Suite 1050
- Washington, D. C. 20006