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By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

The first production on the Island of Trinidad was discovered 29 years ago; 13,275 acres were proved for oil and gas to the end of 1937, and 145,076,700 bbl. was produced from 2661 wells, or 10,928 bbl per acre. The production of oil in 1936 was 13,237,030 bbl. and in 1937 a new peak of 15,498,350 bbl. was reached. During November 1937, the daily average production was 43,350 bbl., or 35 bbl. per well, while the maximum gas production was 45 million cubic feet daily. Two hundred fifty wells were completed during 1937 and 15 abandoned. At the end of last year, 800 wells had been temporarily shut down, 1235 were producing oil and gas, and 2 were producing gas only. Six hundred seventy-nine dry wells had been drilled to the end of 1937. At the end of November 1937, the following oil-producing methods were in use: 395 wells flowing, 491 pumping, 97 on air-gas lift and 252 wells miscellaneous. There were no flooding operations. The oil is produced from the Miocene and Eocene and is of both asphalt and paraffin base. The gas produced averaged approximately 1050 B.t.u. per cu. ft. with 0.8 gal. of gasoline per 1000 cubic feet.

Jan 1, 1938

W. G. MATTESON, Houston, Tex.-I think that Mr. Powers has given us some very valuable information on the Healdton field, which is of material interest in view of the fact that the Healdton field has passed Cushing in the point of production, and if not leading, stands second only to the new El Dorado field in the point of production of the oil-in this country. Mr. Powers says that the deepest producing sand at Healdton is 1860 ft. Within the last 3 or. 4 months they have drilled to 2700 ft. there and found a sand which is producing very high-grade oil, if I remember correctly, about 42 gravity. Another very important point brought out by Mr. Powers is the fact that the Pennsylvanian beds and the Permian beds are conformable according to his interpretation. He seems to have based his interpretation upon the gathering of a number of well logs and a very careful study of them, but it seems to me the information furnished by the, well logs is really insufficient to justify such an important conclusion. In the first place, the difficulty of interpreting the line of demarcation between the Permian "Red Beds" of Oklahoma and the top of the Pennsylvanian is apparent, for the reason that sometimes the uppermost Pennsylvanian formation has a reddish phase and the line of demarcation is not very sharp.

Jan 4, 1918

Attention! Engineers! Geologists! Here is your Opportunity to be of Professional Service The war has interrupted the supply of many minerals, which were normally imported. In view of present transportation conditions, a serious shortage exists in certain materials and will soon develop in others. Some immediate action is imperative. The first thing is to take a careful inventory of American resources. We must know where the ore deposits are, what has hitherto hindered their utilization, what methods must be used, and what equipment will be needed if an emergency demands their rapid development. Many properties must be re-examined from a new point of view, that of present necessity rather than of normal profit. When the shortage is realized, the preliminary steps for relief should have been completed. It is a necessary and patriotic form of mineral insurance. Will you have a part in it? Do not forget that these are war times, and that what may have been valueless a year ago may be a "life-saver" now; an abandoned copper prospect of 1913 might make a successful pyrite mine in 1917. We are fighting an autocratic enemy who knows his resources to the last pound, and uses them with most efficient organization. We have no Kaiser, so each of us must do his share to put our Government in the same situation. The Government needs your facts.

Jan 8, 1917

By Robert Hunt

(New York Meeting, February, 1913.) I HAVE frequently stated that while the chemical composition of steel is important, yet even greater importance is connected with the mechanical and heat treatment of the metal. During the past year I encountered such a positive example of that fact that I deem it worth putting upon record. A prominent railway system divided an order for open-hearth steel rails between two steel works, both of which are under the control of the one corporation; giving to one about 18,000 tons, and to the other 7,500 tons of the same section and to be made under the same specifications. The rolling results obtained in the two mills varied so widely that a study of the figures is intensely interesting and serves to illustrate the advantages obtained by careful ingot casting, and, quite as pertinently, the possible benefits of careful subsequent heating and rolling with moderate reductions in the rolling process. The smaller order was rolled complete in four installments during the same months that the larger order was being made in six separate installments; but, to permit of exact comparisons, the totals of the four installments (completing the order with the mill which I will call A) are given with the totals of the first four installments of the larger order, made by the mill designated as B. These rolling results are:

Jan 5, 1913

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder's equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By Arthur Clark, Terrill

THE Tri-State field is now believed to be the largest zinc district in the world. It has a potential production sufficient to supply the entire zinc demands of the country. It is estimated that a train 70 miles long would be required to haul the district's 1919 output of 60 per cent. zinc concentrates. For many years,, including 1917, Missouri surpassed Oklahoma in zinc production. In 1918, however, Oklahoma led by a wide margin and, in 1919, Missouri produced less than one-sixth of the total for the three states, when Kansas replaced Missouri in second place in the production. The district is now producing one-third of the zinc of the world and twice as much as ever before at the present price.

Jan 1, 1920

By J. W. Stewart

ONE of the postwar problems posed for mineral engineering educators is the desire of some mature student veterans to finish their college education under the G. I. Bill of Rights as quickly as possible, a desire that is quite understandable. Not only have they lost several years of education, which they wish to make up as quickly as possible, but many are married and have families and want to become productive as soon as possible in order to support their families properly. The obvious solution to this problem, if it really is serious, would appear to be a continuation of the wartime Accelerated Program, as it was carried on in most colleges and universities. As a matter of fact some schools are known to have continued their wartime programs in one or another form. To ascertain just what our mineral engineering schools generally are doing to meet this postwar problem, last April a questionnaire was sent to administrative officers at colleges and universities

Jan 1, 1946

By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,'-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker's data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963

By W. M. Johns

The word "Flatland" should read "Flathead" in the title of the paper by Willis M. Johns on page 184 of the June 1962 issue. The correct title is "Belt Series in Lincoln and Southwest Flathead Counties, Montana." In the same paper, reference 12 on page 191, the publication is Bulletin 12, Montana Bureau of Mines and Geology, rather than Bulletin 17.

Jan 1, 1962

By D. H. Baldwin, R. E. Reed-Hill

WITH the polarized-light microscope, the basal-plane trace may be located on hcp crystal surfaces to an accuracy of approximately 1 deg. This determination can also be made on very small crystalline areas, approaching a micron in width. Measured basal-plane trace distributions on selected specimen surfaces can yield1,2 valuable texture information. However, the polarized-light microscope is probably best suited to orienting

Jan 1, 1965

By W. T. Nightingale

The three gas-producing "pools" discussed in this paper are in Sweet-water County, southwest Wyoming, and Moffat, County, northwest Colorado. Hiawatha, North Baxter Basin and South Baxter Basin gas fields became economically important in 1929 when a 330-mile gas line connected them with Salt Lake City, Ogden and towns en route. This development immediately focussed attention on the gas-producing fields and the efforts of the producing company to develop them in an orderly, economical manner. Several outstanding interests were acquired and working agreements made with others. Thus the interference of natural drainage areas was avoided, the pernicious practice of drilling direct

Jan 1, 1930

By J. C. METCALF

MORE than 80 per cent. of the iron produced in the United States and over 30 per cent. of the world's annual production is obtained in the Lake Superior district. Though iron ore was discovered on the Marquette range in 1844, the poor transportation facilities retarded the development of this region for many years. The structure of the Lake Superior basin is essentially an east-west synclinorium with steep dips on the south side of the lake and considerably flatter ones on the north and west. The Upper Huronian series, which -is the iron-bearing one of the formation, on the south side of the lake dips north from 55' to 80°, and on the north side dips south from 8" to 200. The series has been subjected to local folding and faulting, which have influenced the development of the mining systems used.

Jan 1, 1921

By Smith, George Otis

THE matter that I have on my mind this evening is engineering's need of an open forum. Our fathers of three centuries ago were pro-testanta for freedom of speech and thought in matters religious; later, our fathers were revolutionists for freedom of speech in matters political; until today freedom of speech has become so universal throughout the land that even in the sanctuary of our homes, at times, we have to turn off the loud-speaker. Talk is not always a condition of progress, but light is everywhere necessary to growth, whether the growing thing is a blade of grass, a baby chick, or a young idea, and we must regret anything that tends to shut out the light from the operations of business and industry. Of course, I realize there is little that is novel in what I am saying. Indeed, I have found that Dr. James Douglas-a name we love to honor in our Institute-as long ago as 1907, gave an address at the Toronto meeting that any of us would be proud to be author of twenty-one years after. Dr. Douglas at that time spoke on secrecy in the arts and the text then taken by this leader in metallurgical technique and in the constructive management of big business was "the dangerous temptation to adopt secretive methods by very large corporations." In both thought and language Dr. Douglas was direct and vigorous and he needs no internreter. He advocated the wide open door for ideas on two counts: advancement of technical knowledge and education of public opinion. A few sentences will serve not only to prove the vision of James Douglas, but also, I hope, tempt you to hunt up his address in the Institute's TRANSACTIONS, and thus get his whole thought first hand.

Jan 1, 1928

By AIME AIME

IT is unlikely that any oil field has ever threatened the future course of the oil industry as does Kettleman today. It seems that nature has striven to outdo herself in combining in this field every possible factor conducive to a tremendous production of the petroleum product in greatest demand-gasoline. This field already has 13,700 acres of proved land and an oil zone of known thickness of 1400 ft. It has wells yielding several thousand barrels of oil of virtually motor fuel grade, together with millions of cubic feet of gas at almost unheard of pressures. The field would have been the. answer to an oil man's prayer in times of under-supply, but now it is the oil man's nightmare, for drilled in -the manner of most other fields and without regard to available markets for oil and gas, the greatest physical and economic losses in the his¬tory of the oil industry will result.

Jan 1, 1930

By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,' a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By H. E. Cline, E. F. Koch, J. L. Walter

It has been postulated and, in a few instances shown, that some kind of dislocation structure will be present at semicoherent interfaces to accommodate small lattice mismatches. In the present study of the NiAl-Cr eutectic, regular arrays of interface dislocations are observed at the boundary between the chromium-rich rods and the NiAl-rich matrix. The networks were examined by transmission electron microscopy and selected area diffraction. The rods and the matrix have a crystallographic relationship in which all directions and planes of the two phases are parallel. The dislocation networks are cmposed of a<100> dislocations lying on the intersections of the cylinders with (100) planes. Dislocations forming hexagonal rather than square arrays are also observed at certain areas of the network. The morphology of the network is consistent with the interpretation of mismatch being accommodated by interface dislocations in the cylindrical geometry. The measured spacing between dislocations was used to calculate an apparent lattice mismatch between the phases (˜0.35 PCt)interface network energy (-140 ergs per sq cm), and network strengthening (-10,000 psi). It has been proposed by Frank and Van der Merwe1 that dislocations should be present at the boundary between two semicoherent crystallographically related phases. The role of the interface dislocations would be to reduce the internal stresses, caused by the mismatch in atomic spacing across the interface. Such dislocations have been observed at the interface between expitaxially grown films and Substrates.2-4 Interfacial dislocations have also been observed at precipitate-matrix interfaces.&apos;-&apos; Directionally solidified eutectics have been shown to have semicoherent phases1&apos; and would, therefore, be expected to have interfacial dislocations as found by Weatherly at a lamellar fault in A1-A12Cu.11 The NiAl-Cr eutectic appeared to be a promising system to examine because both phases are cubic, the lattice mismatch is small, and the phases are crys-tallographically related. Furthermore, the eutectic is easily thinned for transmission microscopy. Indeed, interfacial dislocations were observed and this report describes the nature of the dislocation networks in the boundary between the NiAl-rich ma-trix-phase and the fine chromium-rich rods.21 I) EXPERIMENTAL PROCEDURE Ingots, 3/4 in. in diam and 6 in. long were made by melting in vacuum and casting under argon using 99.9 pct pure material. The composition, in at. pct, was 33 pct Ni, 33 pct Al, and 34 pct Cr. The ingots were then placed in A1203 crucibles on a water-cooled base, melted by means of induction, and withdrawn from the hot zone at the rate of 1 in per hr under argon.* * T his material was first directionally solidified in this laboratory by E. R. Stover Slices were taken perpendicular to the growth direction of the directionally solidified ingot for metallography and for transmission electron microscopy. The electron transmission samples were thinned mechanically, then thinned electrolytically in A-2 electrolyte* *A-2 electrolyte: 62 ml perchloric acid, 700 ml ethanol, 100 ml butylcellosolve, 137 ml distilled H20. until a hole appeared in the foil. 11) EXPERIMENTAL RESULTS A) Optical Microscopy. The microstructure, viewed on a plane perpendicular to the growth direction, is shown in Fig. 1. The structure consists of cells or colonies of parallel chromium-rich rods in the NiAl matrix. The cells occur when there are impurities present12 or, in a ternary eutectic, if the composition is slightly off the eutectic composition. The axis of the chromium-rich rods is parallel to the growth direction except near the cell boundaries. Here the rods may assume angles to the growth direction; however, examination shows that the crystallographic relationship between the rod and the matrix remains the same. Fig. 1 includes cell boundaries where the rods formed at a large angle to the growth direction. The variation of rod position across the cells made it possible to Fig. 1-Structure on plane perpendicular to growth direction. Rods near cell walls are at large angle to growth direction. Magnification 315 times.

Jan 1, 1970

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.&apos;This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1&apos;2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.&apos;&apos;&apos; Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"&apos; have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970