Basic Research at HoneywellDr. Finn Larsen

Vice President for Research

I

The Nature of Oxidation: Studies In TheHigh-Temperature Oxidation of Alloys

Under high temperatures, oxidation is accelerated. Whilesome pure metals deteriorate rapidly, certain of theiralloys oxidize much more slowly. Accurate prediction ofalloy oxidation rates, however, awaits development of areliable mathematical model. At Honeywell Research, newtechniques have produced data that make la start towarda universally applicable theory.

With the single exception of gold, oxida-tion limits the use of all metals at hightemperatures. This is true because theproducts of corrosion do not have theproperties of the parent metal. In addition,corrosive products occupy more space

than the parent metal they replace, affect-ing dimensions and tolerances.

Corrosion is greatly accelerated by hightemperatures, putting serious limitationson progress in heat generating equipmentsuch as internal combustion engines,

rockets, nuclear reactors and electricalcontacts.

At the present time the accepted methodof inhibiting corrosion is to apply a pro-

tective coating to the metal to prevent themigration of oxygen atoms to the surfaceof the material. This, however, is expen-sive and in many cases not practical.We know that when an oxide free sur-

face is exposed to ordinary air at room

temperature the upper layers of the metalcombine with the oxygen atoms to forma thin film or scale (oxide). For furtheroxidation to occur the thin oxide filmmust be penetrated by either oxygenatoms migrating down to the fresh metalsurface or by metal atoms migrating out-.ward to the air. In most cases, one ofthese reactions predominates.- For Tabout 40-years metllurgists -haveworked with several classical equationsthat predict the rate of oxidation. How-ever, these equations apply rigorously onlyunder idealized conditions. They do notfully equate the mechanical and micro--structural features of a multi-layer oxide,.or the dislocations and stresses that affectthe oxidation process. For example: Isthe oxide film Xuctile or brittle? A changeof temperature puts thermal stress on theoxide and if it is brittle it will probablybreak off. These properties modify the

1976

classical theory. Al of these problemsmultiply and each influence is changedwhen an alloy is introduced.

Honeywell scientists hope to learn moreabout these alterinSInfluences in order toextend the classical equations. They are

analyzing multi-layer oxide scales with a

number of different laboratory methodsto build support for new, predictable be-havior.

Multi-layer scales are caused by theability of metals to have multiplevalences.The balan* between these layersis controlled by tmperature. When amulti-layer scale exists, oxides are oftenunable to relax the stresses that occur.These stresses are caused by the differ-ences in specific volume and the differencesin thermal coefficients of expansion be-tween the oxide and the metal. Whenthey cannot be relaxed, stresses may buildup and affect the rate of oxidation. Also,ifexternal stresses are applied to the mate-rial the rate of oxidation may be affected.The approach to this study quickly be-

comes a mixture of metallurgy and physicalchemistry. One technique in studying rateof growth of the scale has been to measurethe weight gain of a4oy during oxidation.Reliable data on 6id-tion has been Ab-tained in this manner.

To--determine the -directiola of.the mi-gration of ions and also measure thegrowth of individual layers, Honeywellscientists are welding thin platinum wiresto a specimen prior to heating. Thesemarker wires give a' point of reference tothe original surface. If oxvgen ions aremoving inward, the wire remains outsidethe surface. If cations- are moving out-ward, the marker wire will be under thesurface. This method has yielded valuablenew information on the formation ofoxides.

Microscopic examination also has beenhelpful in identifying layers, and X-raydiffraction has given positive identificationof the oxide phases.

Ideally we would like to completely in-hibit even the first monatomic oxide layer.At the present state of knowledge, thisseems unattainable. Our approach thenis to utilize the natural oxidation processbut control it. By doing this we permitthe formation of a thin film but seek tomake it impermeable to further ion mi-gration.

In our experiments Honeywell scien-tists have effected radical changes inoxidation rates by changing the oxidemicrostructure through heat treatment ofits alloy. For example, with an alloy of.87 Mg-.62 Cu, the oxidation rate canbe retarded and the resulting oxidationreduced by a factor of ten with properheat treatment.We now know that in a polycrystalline

structure, stress and mechanical proper-ties affect both the rate and the mechanismof oxidation. Also we know that the me-chanical properties of the oxide have adecisive effect on the tendency of theoxide to either spall or adhere.

This is a start toward the derivation of ageneral theory explaining the oxidation ofalloys. Though our research is basic atthis point in time, we expect it to yieldmany practical answers to assist the designengineers working on high temperatureproblems confronting today's nuclear andspace projects.

If you are engaged in scientific workrelating to oxidation of metals and wouldlike to know' more about Honeywell's re-search on this subject, you are invited tocorrespond with Dr. J. A. Sartell, Honey-well Research Center, Hopkins, Minnesota.

If you wish-a recent paper, "The Roleof Oxide Plasticity in the OxidationMechranism -of Pure Copper," by Dr.Sartell, write to Honeywell Research,Minneapolis 8, Minnesota.

Honey1we11t""SCEC VL133*A

SCIENCE, VOL. 133

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vised edition. The not infrequent wideseparation of text reference and colorplate could be avoided by a page refer-ence to assist the reader.

There is a brief glossary, a bibliog-raphy, and an index. The author, thephotographers, and the publisher are tobe congratulated for producing a workthat is well worth its purchase price.

ROBERT RUSH MILLERMuseum of Zoology,University of Michigan

Radiation Damage in Solids. DouglasS. Billington and James H. Craw-ford, Jr. Princeton University Press,Princeton, N.J., 1961. xi + 450 pp.

Illus. $12.50.

In recent years it has become in-creasingly apparent that many of themost useful and striking properties ofsolids depend directly or indirectlyupon the presence of imperfections inthe crystalline lattice, that is, upon

the defect structure of the solid. Dra-matic changes may occur in the physi-cal properties of materials subjected toenergetic irradiation, because of theproduction of defects. Unfortunatelyfor nuclear technology, such effectsare particularly pronounced in fissilematerials. In other engineering applica-tions, as well, new and stringent re-

quirements on defect structure havearisen for solids for use as structuralmaterials at very high or very lowtemperatures or for use as complexelectronic circuit components. Theavailability of very intense sources ofenergetic radiation which facilitatecontrolled investigation of the crystal-line defects thereby produced hastherefore encouraged the study of thesecrystal defects for their own sake.

Billington and Crawford, long asso-

ciated with fundamental studies, pri-marily in neutron damage, at OakRidge National Laboratory, have setdown a comprehensive yet compact ac-

count of the whole field of radiationeffects studied by physicists and metal-lurgists. Included in this volume are

accounts of the effects in metals, alloys,minerals and glasses, ionic crystals,semiconductors, and even in thoseparticularly perverse substances urani-um and graphite. Reference is made tothe work, through 1959, of nearly 600

scientists.Many useful criticisms and evalua-

tions of the work discussed are incorpo-23 JUNE 1961

rated. The authors have not hesitatedto include impartial accounts of con-flicting studies in which final judg-ments cannot yet be reached, but oc-casionally they have not been ruthlessenough to leave out some work whichis muddled or which defies comparisonwith other investigations.The treatment is well adapted to the

needs of one who is considering, doing,or interpreting experimental work onradiation damage or lattice imperfec-tions. Three introductory chapters pre-sent the essential results of existingcalculations of the inelastic interac-tions of radiation with solids as wellas of important secondary effects, anoutline of the influence of lattice im-perfections on the properties of solids,and a critical and practical discussionof radiation sources suitable for dam-age studies.As might be expected in a growing

field, progress in obtaining unambigu-ous experimental results and in under-standing them has been startlingly pre-cise in some cases and depressingly in-complete in others. Understanding ofa broad range of effects has now beenreached in a qualitative and phenom-enological manner.

R. 0. SIMMONSPhysics Department,University of Illinois

New Books

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der S. Wiener. Grune and Stratton, NewYork, 1961. 561 pp. Illus. $11.Annual Review of Medicine. vol. 12.

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terfere with other, independent effortsaimed at the same goal. While such in-dependent studies are unlikely to at-tain the national attention that wouldbe given to a more massive attack,they may well turn out to be more im-aginative and bolder in conception andmethod of attack. Such independentstudies should be encouraged, not dis-couraged, by the existence of a largeand coordinated effort.

An Observation

A most encouraging aspect of thethree conferences was the ease and sat-isfaction with which scientists, repre-senting all of the major scientific dis-ciplines, and educators, representingteacher education, administration, andthe classroom, were able to reachagreement about needs for improve-ment of early science education andways of bringing about that improve-ment. It was heartening to both scien-tists and educators to find such a highdegree of agreement upon the im-portance and the feasibility of thetask. The general spirit of the confer-ences was one of enthusiastic ac-ceptance of joint responsibility andconfidence that a large-scale, coordi-nated, and cooperative attack wouldproduce major improvements in sci-ence education at the elementary andjunior high school levels.

Reference

1. The background papers appear as articles bythe authors in Sc-hool Scienice acud Mathle-miiatics (Apr., Mfay, and June 1961).

Forthcoming Events

July16-21. International Conf. on Medical

Electronics, 4th, with Electrical Techniquesin Medicine and Biology, 14th annualconf., New York, N.Y. (L. E. Flory, RCALaboratories, Princeton. N.J.)

16-22. International Soc. for Clinicaland Experimental Hypnosis, Rio de Ja-neiro, Brazil. (ISCEH, 33 E. 65 St., NewYork 21)

17-22. Soil Mezhanics and FoundationEngineering, 5th intern. conf., Paris,France. (E. Caminade, Secretaire General,23 rue de Cronstadt, Paris 1 5)

18-20. Pulmonary StructuLre and Func-tion, Ciba Foundation Symp. (by invita-tion only), London, England. (CibaFoundation, 41 Portland P1., London, W.1)

18-21. Inorganic Polymers, intern.symp., Nottingh.m, England. (GeneralSecretary, Chemical Soc., BurlingtonHouse, London, WA, England)

21-22. World Power Conf. (membersonly), Moscow, U.S.S.R. (Central Office,

201-2 Grand Buildings, Trafalgar Sq.,London, W.C.2, England)

23-28. Otolaryngology, 7th intern.congr., Paris, France. (H. Guillon, Secre-tary General, 6 Avenue Mac-Mahon,Paris 17)

24-28. Nematology Symp., 6th intern.,Ghent, Belgium. (J. van den Brande, Soc.of European Nematologists, Rijksland-boushogeschool, Coupure links 23 5.Ghent)

24-29. Medical Electro-Radiological So-cieties, Latin Federation of, 5th congr.,Paris, France. (C. Proux, Secretary, 9 rueDaru, Paris 8)

24-30. Urology, 12th intern. congr.,Rio de Janeiro, Brazil. (J. Silva de Assis,Secretary, P.O. Box 1275, Belo-Horizonte,Brazil)

26. International Commission for thePrevention of Alcoholism, 7th annualmeeting, Washington, D.C. (InternationalHeadquarters, 6840 Eastern Ave., NW,Washington 12)

26-28. Detection and Assay of Hor-mones by Immuno-Clinical Means, CibaFoundation Colloqulium (by invitationonly), London, England. (Ciba Founda-tion, 41 Portland P1., London, W.1)

27-1. Macromolecular Chemistry, in-tern. symp., Montreal, Canada. (Organiz-ing Committee, P.O. Box 816, Sarnia, On-tario. Canada)

28-29. Linguistic Soc. of America,Austin, Tex. (A. A. Hill, Box 7790, Uni-versity Station. Austin 12)

30-2. Soil Conservation Soc. of Amer-ica, Lafayette, Ind. (H. W. Pritchard, 838Fifth Ave., Des Moines 14, Iowa)

30-3. International PsycholanalyticalCongr., 22nd, Edinburgh, Scotland. (MissC. de Monehaux, 53 York Terrace, Re-gents Park, London, N.W.1, England)

31-4. Biophysics, 1st intern. congr.,Stockholm, Sweden. (B. Lindstrom, Dept.of Medical Physics, Karolinska Institutet.Stockholm 60)

31-4. Differential Equations in Non-Linear Mechanics, Air Force Acad., Colo-rado Springs, Colo. (J. P. Lasalle, 7212Bellona Ave., Baltimore 12, Md.)

31-11. Physics of the Solar System andRe-entry Dynamics, conf., Blacksburg,Va. (Bureau of Public Relations, VirginiaPolytechnic Inst., Blacksburg)

31-12. Electric Power and Problems ofNuclear Power, seminar, U.N. EconomicCommission for Latin America, Mexico.D.F. (A. Dorfman, Chief, Energy andWater Resource Program, Avenue Provi-dencia 871. Santiago, Chile)

August

1-26. Functional Analysis, 8th Amer-ican Mathematical Soc. summer institute,Stanford, Calif. (P. D. Lax, AMS, 190Hope St., Providence 6, R.I.)

2-5. International Conf. of Pure andApplied Chemistry, 21st, Montreal, Can-ada. (R. Morf, Hoffmann-LaRoche, S.A.,Grenzachterstrasse 124, Basel, Switzerland)

3-5. Canadian Chemical Conf. and Ex-hibition, 44th, Montreal. (Chemical Inst.Of Canada, 48 Rideau St., Ottawa 2, Ont.)

5-9. International Rorschach Soc., 5thcongr., Fribourg-en-Brisgau, Germany. (A.Friedemann, Chemin des Pcheurs 6,Bienne, Switzerland)

SCIENCE, VOL. 133

6-10. Occupational Medicine and Tox-icology, 3rd Inter-American conf., Miami,Fla. (W. B. Deichmann, School of Medi-cine, Univ. of Miami, Coral Gables, Fla.)

6-12. Atmospheric Ozone and GeneralCirculation, symp., Arosa, Switzerland.(H. U. Duetsch, 20 Carl Spittelerstrasse,Zurich 53, Switzerland)

6-12. Chemical and ThermodynamicProperties at High Temperatures, symp.,Montreal, Canada. (N. F. H. Bright, Natl.Research Council, Ottawa, Canada)

6-12. International Congr. of Pure andApplied Chemistry, 18th, Montreal,Canada. (L. Marion, Natl. Research Coun-cil, Ottawa 2, Canada)

7-9. Guidance and Navigation Conf.,American Rocket Soc., Palo Alto, Calif.(J. J. Harford, ARS, 500 Fifth Ave., NewYork, N.Y.)

7-9. International Committee of Electro-Chemical Thermodynamics and Kinetics,13th meeting, Montreal, Canada. (N. Ibl,Eidg. Technische Hochschule, Laborato-rium fuir Physikalische tind Elektrochemie,Universitaitsstrasse 6, Zurich 6, Switzer-land)

7-9. Space Age Astronomy, intern.symp., Pasadena, Calif. (D. W. Douglas,Jr., Douglas Aircraft Co., Inc., SantaMonica, Calif.)

7-10. National Medical Assoc., NewYork, N.Y. (J. T. Givens, 1108 ChurchSt., Norfolk, Va.)

7-11. High Temperature Chemistry andThermodynamics, symp., Montreal, Can-ada. (L. Brewer, Dept. of Chemistry, Univ.of California, Berkeley)

7-11. Seminar on Fast and IntermediateReactors, International Atomic EnergyAgency, Vienna, Austria. (IAEA, 11 Kart-ner Ring, Vienna 1)

8-11. Poultry Science Assoc., State Col-lege, Pa. (C. B. Ryan, Texas A & M Col-lege, College Station)

8-16. Society of Protozoologists, Prague,Czechoslovakia. (N. D. Levine, Collegeof Veterinary Medicine, Univ. of Illinois,Urbana)

10-16. International Congr. of Bio-chemistry, 5th, Moscow, U.S.S.R. (N. M.Sissakian, Leninsky prospekt, 33, Moscow,B-71)

10-16. International Union of Bio-chemistry, 4th general assembly, Moscow,U.S.S.R. (R. H. S. Thompson, IUB, Dept.of Chemical Pathology, Guy's HospitalMedical School, London, S.E. 1, England)

12-19. Fast Reactions, summer school,Cambridge, England. (Secretary of theSummer School, Dept. of Physical Chem-istry, Lensfield Road, Cambridge)

13-18. Microchemical Techniques, in-tern. symp., University Park, Pa. (H. J.Francis, Jr., Pennsalt Chemical Corp.,P.O. Box 4388, Chestnut Hill Post Office,Philadelphia 18, Pa.)

13-18. Theoretical Aspects of Magneto-hydrodynamics, seminar, University Park,Pa. (Conference Center, PennsylvaniaState Univ., University Park)

13-19. International Assoc. of AppliedPsychology, 14th congr., Copenhagen,Denmark. (Congress Secretariat, 19 SanktPederstraede, Copenhagen K.)

13-19. Training for Research in theProcesses of Vision, 1st intern. conf.,Rochester, N.Y. (Office of Public Informa-tion, River Campus Station, Rochester)30 JUNE 1961

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14-17. Calorimetry Conf., intern., Ot-tawa, Canada. (J. E. Kunzler, Bell Tele-phone Laboratories, Murray Hill, N.J.)

14-19. International Medical Conf. onMental Retardation, 2nd, Vienna, Austria.(Miss E. Langer, Div. of Maternal andChild Health, State House, Augusta,Maine)

14-19. Symposium on Radiation, Vien-na, ALIstria. (World Meteorological Organ-ization, 1 Avenue de la Paix, Geneva,Switzerland)

14-25. Israel Medical Assoc., 5th worldassembly, Jerusalem, Israel. (Beth-Haro-feh, I Heffman St., Tel-Aviv, Israel)

14-26. Plant Pathology, conf., Lafa-yette, Ind. (J. F. Schafer, Dept. of Botany

and Plant Pathology, PurduLe Univ., La-fayette)

14-26. World Eucalyptus Conf., 2nd,Si-o Patulo, Brazil. (Intern. Agency LiaisonBranch, Office of the Director General,Food and Agriculture Organization, Vialedelle Terme di Caracalla, Rome, Italy)

15-17. International Assoc. of Milkand Food Sanitarians, Jekyll Island, Ga.(H. L. Thomasson, P.O. Box 437, Shelby-ville, Ind.)

15-18. Technical Assoc. of the Pulpand P.aper Industry, 12th testing conf.,Montreal, Canada. (TAPPI, 155 E. 44St., New York 16)15-24. International Astronomical Union,1th general assembly, Berkeley, Calif.

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(D. H. Sadler, Royal Greenwich Observ-atory, Herstmonceux Castle, Hailsham,Sussex, England)

16-18. Hypersonics Conf., intern., Cam-bridge, Mass. (J. J. Harford, AmericanRocket Soc., 500 Fifth Ave., New York.N.Y.)

18-2 1. Association of American Geogra-phers, East Lansing, Mich. (M. F. Burrill,1785 Massachusetts Ave., NW, Washing-ton 6)

19-30. Agricultural Economists, 11thintern. conf., Cuernavaca, Mexico. (J.Ackerman, Farm Foundation, 600 S.Michigan Ave., Chicago, 111.)

20-23. International Ergonomics Assoc..1st congr., Stockholm, Sweden. (T. Olson,Dept. of Industrial Physiology, G.C.I.Liding6vagen l, Stockholm)

20-24. American Veterinary MedicalAssoc.. Detroit, Mich. (H. E. Kingman.AVMA, 600 S. Michigan Ave., Chicago5, 111.)

21-23. International Hypersonics Conf.,Cambridge, Mass. (F. Ridell, Avco Re-search Laboratory, 301 Lowell St., Wil-mington, Mass.)

21-24. Biological Photographic Assoc.,Chicago, Ill. (Mrs. J. W. CrouLch, Box1668, Grand Central P.O., New York 17)

21 -24. International Conf. on Photo-conductivity, Ithaca, N.Y. (E. Burstein,Dept. of Physics, Univ. of Pennsylvania.Philadelphia)

21-26. International Congr. of Psycho-therapy, 5th, Vienna, Austria. (W. Spiel,Laza.rettg. 14. Vienna 9)

21-26. World Traffic Engineering Conf..Washington, D.C. (Intern. Road Federa-tion, 1023 Washington Bldg., Washing-ton 5)

21-27. International Assoc. of DentalStudents, congr., London, England. (D.H. Clark, Royal Dental Hospital, Leices-ter Sq., London, W.C.2)

21-31. United Nations Conf. on NewSoturces of Energy, Rome, Italy. (UnitedNations, New York, N.Y.)

2 1-2. International Congr. of PracticalMedicine, Merano, Italy. (BLmndesiirtzte-kammer, 1 Htidenkiampfstrasse, Cologne,Germany)

21-6. Pacific Science Congr., 10th,Honolulu, Hawaii. (Secretary General.10th Pacific Science Congr., Bishop Mu-seum, HonoluluLI)

22-25. International PharmacologicalMeeting. 1st, Stockholm, Sweden. (A.Wretlind. Karolinska Institutet, Stockholnm 60)|22-3(0. International Conf. on Proto-zoology, Praguie, Czechoslovakia. (N. D.Levine, College of Veterinary Medicine,Univ. of Illinois, Urbana)

23-25. Gas Dynamics, symp., biennial.Evanston, Ill. (J. J. Harford, AmericanRocket Soc., 500 Fifth Ave., New York.N.Y.)

23 -26. Electron Microscope Soc. ofAmerica, Pittsburgh, Pa. (Miss M. L.Rollins, AgricLultLural Research Service,U.S. Departnment of AgricultULre, P.O.Box 19,687, New Orleans 19, La.)

23-26. Institute of Management Sci-ences, 8th annLlal intern., Brussels, Bel-giLim. (W. Smith, Inst. of Science andTechnology, Univ. of Michigan, AnnArbor)

(See i ssue of 16 Juttie for comiprehensive list)

SCIENCE, VOL. 133