Search Documents

By Rudolph G. Wuerker

THE Krupp-Renn Process,[1] has been successfully used to treat low-grade iron ores, laterites, titaniferous sands, and other minerals, and before World War I1 25 units were built by the Krupp-Grusonwerk, Magdeburg, Germany. J. J. Howard[2] has shown theoretical advantages of the pyro-metallurgical treatment over conventional approaches; and the process was described by R. Durrer[3].

Jan 1, 1951

Jan 1, 1968

By C. D. Thurmond

Jan 1, 1968

Jan 1, 1968

Jan 1, 1959

By Howard Martens, Pol Duwez

XPERIMENTS were performed on a Cr-Fc alloy Econtaining 44.7 pet Cr in order to determine the heat evolved during the transformation of the a solid solution into the s phase, and the change in volume accompanying the transformation. Since previous measurements on the rate of formation of a from s indicated that the reaction was quite fast as soon as the equilibrium temperature of 820°C was exceeded by some 50°, standard thermal analysis experiments were performed on heating specimens of s at the rate of approximately 40°C per sec. A definite thermal arrest was observed at 870"C, Fig. 1. This result indicates that the reverse seaction of into a is exothermic. From the heating curve of Fig. 1, taking 15°C per sec as the heating rate in the neighborhood of the transformation, 2.4 sec as the time for transformation, and assuming that the specific heat of the alloy at 850°C is an average between iron and chromium, namely 9.5 cal per mol per "C, the latent heat of transformation is approximately 342 cal per mol. The order of magnitude of this latent heat was also obtained by comparing the heating curve of Fig. 1 with a similar curve obtained with pure iron under identical experimental conditions. It was found that the length of the thermal arrest for s was about 1.8 times as long as that for iron. Since the latent heat of the a to 7 iron transformation is 203 cal per mol1, 2 the latent heat of it to a would be 365 cal per mol, which is in relatively good agreement with the value determined from the heating curve. For the determination of volume change, thermal expansion curves were recorded using a specimen containing 44.7 pet Cr and completely transformed to cr by previous treatment. The curves were recorded at a rate of heating of about 4°C per min and at approximately 840°C a sharr, increase in length of about 0.08 pet took place. Fig. 2. It is therefore established that the specific volume of a near the transformation temperature is about 0.24 pet smaller than that of a, and consequently, when the s phase forms in an a matrix, it would tend to shrink away from the matrix. Since the s phase is known to be extremely brittle, these results offer an explanation for the microscopic cracks often observed in the a phase under the microscope. The results of this study are in qualitative agreement with previously published data on stainless steel 19-9DLa and on a Cr-Fe alloy containing 45 pet Cr.' The increase in density due to the transformation from n to s given in ref. 4 is 0.90 pet. These measurements, however, were made at room temperature. whereas the presently reported 0.24 pet is the change at the temperature at which the transformation takes place during heating. In the graph of Fig. 2, the percentage change in length that would be observed at room temperature is given by the length X, which is about 0.27 pet. This would correspond to 0.81 pet in volume change. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. DA-04-495-ORD-18 with the Army Ordnance Corps, Washington, D. C. The authors wish to thank this agency for permission to publish the results of this investigation. References I H. Klinkhardt: Measurements of True Specific Heats at High Temperatures. Annalen der Physik (1927) 84, pp. 167-200. - H. Esser and W. Runghardt: Influence of the Method, of Dctcrmination on the Measured Heat Content of Iron. Archtvo ffur Dct Eisenhiittenwesen 11934) 8, pp. 37-38. J. J. Gilman, P. K. Koh, and 0. Zmeskal. Delta Ferrite Formation and its influence on the Formation of Sigma in a Wrought Heat Resisting Steel. Trans. ASM 1 1949) 11, pp. 1371-1388. 1 J. M. Thomas: Discussion of ref. 3. Trans. ASM (1949) 41, pp. 3 390-1392.

Jan 1, 1957

By J. B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method' was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about 1/2-in. water pressure. No loss of air was evident. Fig. 2 presents typical data for a standard Denver sub-A 24x24-in. unit cell operated at impeller speeds from 0 to 710 rpm. Each plotted point represents the average for five readings distributed over the entire cell surface. Readings were taken with only water passing through the cell. Results of this type have been used in a study of the influence of operating variables on cell performance and in detecting inherent differences in the operating characteristics of cells of various kinds. Although the information presented in Fig. 2 resulted only with water passing through the cell, the apparatus is suitable for use during flotation of coal when various reagents are present. Possible modi- fications that might prove convenient under special circumstances include varying the size and shape of the receiver and substituting a calibrated, inverted, water-filled carboy or other gas-measuring device for the wet-test meter. If such modifications result in excessive back pressures, some form of draft should be applied at the discharge end of the measuring system.

Jan 1, 1959

By K. S. Seljesater

SINCE the development of dispersion-hardenable lead-antimony alloys1 in the laboratories of the Western Electric Co., Inc., studies have been made of the effect of various third constituents on these alloys.2 This paper covers a study of the effect of small amounts of arsenic. This element is important since it occurs as an impurity in many commercial antimonial leads and the results obtained are particularly interesting as indicating a class of addition agents which exert a stabilizing effect on dispersion-hardened alloys. EXPERIMENTAL In order to-study the effect ,of increasing amounts of arsenic, a series of alloys were made up containing 1 per cent. antimony, and arsenic varying from 0. to 0.10 per cent., the balance Doe Run lead (99.997 per FIG. 1..-CHANGE OF MICRO-BRINELL HARDNESS WITH TIME OF 1 PER CENT. LEAD-ANTIMONY ALLOY. cent. lead). The alloys were cast into bars 1 ½ in. wide by ¾ in. thick and cold-rolled to about 1/8 in. thickness. Three samples of each composition were annealed 1 hr. at 225° C. and quenched in water. One set was aged at room temperature, one at 50° C., and the third at 100° C., the

Jan 1, 1929

Jan 1, 1967

By R. W. Raymond

THE sudden death of Dr. Drown, on Nov. 17, 1904, brought to multitudes the pang of personal loss. Of all those who, as students at Lafayette College, the Massachusetts Institute of Technology and Lehigh University, were brought under his influence, not one can have forgotten him, and all will now acknowledge, with an unfading gratitude, what they owe in professional equipment to his wise, clear, skillful guidance, and in character to his sympathetic, stimulating personality. Outside of this wide circle, the experts of both hemispheres will lament the departure of one who, in his department of scientific inves¬tigation, both knew what work was needed, and how to do it so that it needed not to be done again. The older members of the American Institute of Mining Engineers will remember with gratitude the part he took, as Secretary from 1873 to 1884, in promoting the interest of that organization, and in shaping the plan and policy which it has followed with such noteworthy success. And, in addition to all these (though partly included among them), there are a host of friends; who can scarcely think of the public loss by reason of their own. Thomas Messenger Drown was born March 19, 1842, at Phil¬adelphia, Pa. His parents were natives of New England; and. he was the youngest of their three sons. He received his preliminary education in the public schools and the High School of Philadelphia, from which he was graduated in 1859. Be-

Jul 1, 1905

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By AIME AIME

[SECRETARY&apos;S NOTE.-Since the Committee on Publication of United Engineering Society, will issue a memorial volume re¬porting these proceedings in full, an outline only will be here given. The sessions were held in the Main Auditorium.¬R. W. R.] COMMITTEES. EXECUTIVE.-J. W. Lieb, Jr., Chairman; C. W. Rice, Secretary; John Hays Hammond, Chas. Wallace Hunt, F. R. Hutton, Charles Kirchhoff, T. C. Martin, E. E. Olcott, Chas. F. Scott, Samuel Sheldon, Ambrose Swasey. INVITATIONS.-R. W. Raymond, Chairman; Charles Kirchhoff, Secretary; A; C. Humphreys, Robert W. Hunt, L. B. Stillwell. PROGRAM.-A. R. Ledoux, Chairman; C. W. Rice, Secretary; Theodore Dwight, Chas. Wallace Hunt, T. C. Martin, Ralph W. Pope, Joseph Struthers. WAYS AND MEANS.-James Douglas, Chairman A. R. Ledoux, Secretary; H. R. Brown, J.-M. Dodge, C. L. Edgar, John Hays Hammond, W. M. McFarland, E. E. Olcott, Samuel Sheldon, J. G. White. HISTORICAL AND PUBLICATION PRESS.-T. C. Martin, Chairman; Albert Spies, H. H. Suplee.

May 1, 1907

Jan 1, 1970

By P. Niessen, W. C. Winegard, C. J. Beingessner

DURING the last 10 years, several grain-growth studies have been made using zone-refined metals with controlled amounts of solute to elucidate the interaction of solute with moving boundaries. In all these studies, it was more or less implicitly assumed that the alloys used were, after recrystallization and grain growth, homogeneous within the grains with respect to solute and lattice defects. This note deals with observations made on microstructures originating from solidification of dilute alloys and from grain growth. Briefly, the experimental procedure used in these studies was the following: zone-refined cadmium and master alloys were melted and cast in Pyrex under vacuum to produce bars 14 mm in diam and about 150 mm long. These bars were cut into 8-mm-thick slices which were mechanically and chemically polished. The specimens were then deformed 30 pct in compression and given a 1-week anneal at 260°C in argon. After this anneal, a second deformation produced completely recrystallized samples 4 mm thick. The time-temperature controlled anneals were carried out in a bath of silicone oil. After the grain-growth anneal, the specimens were polished in Gil-man&apos;s&apos; solution (33 g CrOs, 6 g NazSO, in 100 ml of water). Several etches were used depending on the alloy investigated, but mostly a mixture of concentrated HC1 and HNOj (98:2 vol) was employed. In all the alloys examined, the ease with which substructures could be revealed depended strongly on the crystallographic orientation of the surfaces of the grains. However, very frequently the microstructures to be discussed here etched up over broad areas comprising several grains. Fig. 1 is a micrograph of a Cd-0.05 at. pct Mg alloy annealed for 100 sec at 270°C. Different substructures are seen in this photograph. A denotes the now existing grain boundaries. The well-defined lines and points marked B are the remains of a solidification substructure. The lines are boundaries between cell colonies, and the points are nodes located on regular two-dimensional cells. This cellular structure has the same appearance as that found by weinberg2 for rapidly quenched Zn-Au alloys. The "ghost boundaries", marked C, are very similar in appearance to a grain boundary array in a polycrystalline sample. Repeated polishing and etching showed that all the substructures observed were three-dimensional. To date, the ghost boundaries have been clearly observed in all samples containing 0.005, 0.01, 0.05, and 1 at. pct Mg, and in samples containing 0.01 at. pct Zn. Attempts to outline these ghost boundaries in cadmium alloys containing 0.01 at. pct Ag and Au were only partially successful. In these alloys, parallel lines, having a resemblance to the ghost boundaries in the Cd-Mg and Cd-Zn alloys, were observed, but it was not possible to obtain complete arrays of ghost boundaries which extended over several grains. It is possible that a different etch than that presently employed would reveal the ghost boundaries in the Cd-Au and Cd-Ag alloys as clearly as in the Cd-Zn and Cd-Mg alloys. A close examination of the ghost structure showed that it consisted of linear etch-pit arrays, Fig. 2. The ghost boundaries were resolvable even in grains which showed over-all faceting due to the etching, as seen in the corner of Fig. 2. The general appearance of the ghost structure suggests that it originated during grain growth. This is supported by the observation that the mesh width in the ghost-boundary array generally increased with increasing final grain size. To test whether the ghost structure was formed during the long homogenizing anneal or during the grain-growth anneal, some as-cast samples were deformed and given a grain-growth anneal. This anneal was terminated by air cooling or

Jan 1, 1967

University of Alabama University, Alabama Mining and Metallurgical Society WILLIAM R. HIGGS, President ROBERT E. MEAD, Secretary J. R. CUDWORTH, Faculty Sponsor MILTON H. FIBS, Counselor University of Arizona Tucson, Arizona Miners&apos; Society LEE BLESSING, President R. W. CORY, Secretary E. P. MATHEWSON, Faculty Sponsor B. R. HATCHER, Counselor University of California at Los Angeles Los Angeles, California Student Chapter, A.I.M.E. ARCHER WARNE, President ROBERT JOHNSTON, Secretary E. K. SOPER, Faculty Sponsor EMILE HUGUENIN, Counselor Colorado School of Mines Golden, Colorado Student Chapter, A.I.M.E. J. Ross REED, President ANDREW PERRY, JR., Secretary J. BURNS READ, Faculty Sponsor A. W. NEWBERRY, Counselor

Jan 1, 1936

By Willard P. Ward

The numerous direct processes which have been patented and brought before the iron-masters of the world, differ materially from that now introduced by Mr. Wilson. After a careful examination of his process, I am convinced that Mr. Wilson has succeeded in producing good blooms from iron-ore, and I think that I am able to point out theoretically the chief reasons of the success of his method. Without going deeply into the history of the metal, I may mention the well-known fact, that wrought-iron was extensively used in almost all quarters of the globe, before pig or cast-iron was ever produced. Without entering into the details of the processes by which this wrought-iron was made, it suffices for my present purpose to say that they were crude, wasteful, and expensive, so that they can IE employed to-day only in a very few localities favored with good and cheap ore, fuel, and labor. The constructiou of larger furnaces and the employment of higher temperatures led to the production of a highly carbonized, fusible metal, without any special design on the part of the manufacturers in producing it. This pig-iron, however, could be used only for a few purposes for which metallie iron was needed; but it was produced cheaply and with little loss of metal, and the attempt to decarbonize this product and bring it into a state in which it could be hammered and welded was soon successfully made. This process of decarbonizatioa, or some modification of it, has successfully held the field against all, so-called, direct processes up to the present time. Why ? Because the old-fashioned bloomeries and Catalan forges could produce blooms only at a high cost, and because the new processes introduced failed to turn out good blooms. Those produced were invariably "red-short," that is, they contained unreduced oxide of iron, which prevented the contact of the metallic particles, and rendered the welding together of these particles to form a solid bloom impossible. The process of puddling cast-iron, and transforming it by decarhonization into wrought-iron has, as everybody knows, been in successful practical operation for many years, and the direct process referred to so closely resembles this, that a short description of the theory of puddling is not out of place here.

Jan 1, 1884

By AIME AIME

WITH the example of the steel open-hearth men and their round table conference before the copper men, the query naturally arose "Why cannot we do likewise?" The advantage of pooling and comparing knowledge on smelting in the copper reverberatory furnace seems particularly pertinent at this time when all metallurgical economies possible must be rigorously enforced. A great deal of data had also been obtained and filed during the period of litigation over the Carson patent, and it would naturally be available with the cessation of further suits. With these ideas in mind, H. Foster Bain took up the advisability of holding such a conference directly with the heads of all the companies in the United States operating copper reverberatories, and found a nearly unanimous response. The mining companies appointed representatives directly, or indicated to the heads of various metallurgical operations what members of their staffs should be sent to such a conference.

Jan 1, 1930

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

By G. R. Mansfield

THE geologic structure of the Idaho phosphate field has an important bearing on the classifica-tion and the exploitation of the lands that contain phosphate. Maps and structure sections1 recently made available show that the phosphate is mainly preserved in downfolded or downfaulted areas. Since the phos- phate beds are generally rather soft and lie between harder and thicker formations they have been forced to adjust themselves to these formations during epochs of disturbance of the earth&apos;s crust, so that they are frequently affected by minor folds and by faults which may help exploitation by producing undue thickness at certain places or may hinder it by cutting out the phosphate at other places where according to expecta-tion it should be present. A particularly important structural feature which affects both the distribution and the exploitation of the phosphate beds is the great Bannock overthrust by which one or more slices or blocks of the earth&apos;s crust have been pushed over other blocks like ice cakes on a pond. Thus in this region a great flap of folded rocks lies across other rock structures for a distance of approximately 35 miles. Most of the commercially accessible phosphate deposits, shown in the maps that accompany the report cited, are in this flap, which con-stitutes the upper block of the overthrust. In some places, however, the phosphate in the lower block is also accessible. In both blocks post-phosphate rocks exposed at the surface here and there indicate that phos-phate beds may lie at greater or less depth below. The presence of the Bannock overthrust beneath much of the area reported is known by the occurrence of windows in the upper block both within the quadrangles mapped and in areas farther west. The portions of the lower block exposed in these windows show stratigraphic dis-cordance with the surrounding formations. The depth of the fault plane at most places, however, can be told only by drilling or actual mining. Some of the folds in the upper block are relatively deep and it seems fairly certain that the phosphate that may originally have been present in their deeper parts has been removed by thrust faulting. The estimates of phosphate reserves in folds liable to be affected by the Bannock overthrust may therefore need ultimate revision depending on the depth of this fault plane, as it may subsequently be ascertained.

Jan 1, 1928

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-&apos; to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6&apos;9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3&apos;5&apos;7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5&apos;7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f &apos;([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1&apos; Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962