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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.'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 Charles Baskerville

SHALES containing,"kerogen,," or bituminous matter, which on destructive distillation yield oily and tarry matters resembling petroleum are here designated as oil-shales. They differ from oil-bearing shales from which petroleum may be obtained by so-called mechanical means. The educts obtained by the destructive distillation resemble some or all the varieties of petroleum, depending on the character of the shale and the mode of treatment. Some shale oils have e a paraffin base, some an asphaltic base, or a combination; some run high in sulfur compounds, The methods of refining and cracking, therefore, are essentially the Sam as are used in refining petroleums. In 1860, in this country, over fifty companies were successfully distilling various bituminous natural materials for the production of "coal oil," used for illuminating purposes. The discovery of petroleum and the failure of these companies to save and utilize the valuable byproduct, ammonia, brought about their inevitable doom. Prior to that time, more or less successful efforts were made to produce from the shales of Scotland oils for illuminating and heating purposes. Competition of native petroleum from the United States early eliminated some of these companies and with the entrance of oil from the Russian and other fields into the world's markets, the Scottish oil-shale industry underwent serious and trying experiences until, in 1916, only four (Scottish) were paying concerns.. These survived only through energy and the application of skill in saving valuable byproducts. A few companies have successfully operated in France and New Zealand. The Canadian Government showed active interest in the New Brunswick shales, which exist in quantity and are more valuable than the Scottish shales. The retarded development of that very valuable asset of the Province of New Brunswick involves a pathetic history, which is lamentable. This was especially true when the product was so much needed in the prosecution of the war. The economic success of a shale-oil industry depends on the following factors:

Jan 6, 1919

By R. V. Horrigan

High purity ZrC14 (25 to 200 ppm of metallic impurities) can be readily prepared in simple apparatus by thermal decomposition of alkali chlorozirconate fused salts at 500° to 600°C and at atmospheric pressure. Suggested phase diagrams for the systems NaCI-ZrC14 and KCI-ZrCI, are presented. ALKALI chlorozirconate compositions — anhydrous fused mixtures of ZrCl4, NaC1, and KC1— are manufactured commercially and are used by the magnesium industry to introduce zirconium into magnesium alloys. Zirconium refines the grain size and improves the physical properties of many important magnesium alloys. In the course of working with chlorozirconate compositions of high ZrCl4 content, it was noticed that these salts decomposed progressively itwaswith increasing temperature to yield considerable amounts of a ZrCl4 sublimate of high purity together with a solid chlorozirconate residue. Further research led to: 1—improvements in the

Jan 1, 1956

By S. Stutz

COAL, like most other minerals, only exceptionally occurs in a sufficiently pure state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more percent in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but most frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypsum. In both cases the impurities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the, manufacture of iron. Coke will contain on an average at least ;fifty per cent, more ash and sulphur than the raw coal from which it is, made. To the manufacturer of iron every additional per cent. of ash which his coal or .coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight ; that is, a certain part of the coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the-iron-master that coke containing less ash makes the slag or cinder more liquid and less inclined to stick to- the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore and flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etc:, from the coal 'has as yet only been succesafully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By AIME AIME

IV. THE BOUNDARY BETWEEN STEEL AND IRON. It would be well to decide on a definite carbon-content to serve as a boundary line between ingot-iron and ingot-steel, between puddled-iron and puddled-steel, and between any other varieties of wrought-iron and weld-steel. Two plans have been considered. One is to draw this line at 0.32 per cent. of carbon or its equivalent in other elements, for the reason that this carbon-content appears to correspond to the critical point, 0, in the diagrams of Roberts-Austen and Rooze-boom.8 This has the merit of corresponding to a definite physical boundary. The other plan is to draw the boundary at 0.20 per cent. of carbon, because this is a convenient place to separate the important classes " soft steel " and " half-hard steel," so that if this point was adopted "ingot-iron " would be synonymous with "soft steel," and " ingot-steel " would be the equivalent of the two classes, " half-hard steel " and " hard steel."

Mar 1, 1908

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By Henry M. Howe

.... So, beyond and above the immediate and tangible ends of membership, ever-present and evident, selfish and generous alike; beyond and yet at the root of that genuine affection for our association which is so strong in many of us, there lies earnest sympathy with the ultimate and essential purpose of its being—that to which as a nucleus all other purposes are but contributory—which is, to

Jan 1, 1895

By Charles Baskerville

Shales containing "kerogen," or bituminous matter, which on destructive distillation yield oily and tarry matters resembling petroleum are here designated as oil-shales. They differ from oil-bearing shales from which petroleum may be obtained by so-called mechanical means. The educts obtained by the destructive distillation resemble some or all the varieties of petroleum, depending on the character of the shale and the mode of treatment. Some shale oils have a paraffin base, some an asphaltic base, or a combination; some run high in sulfur compounds. The methods of refining and cracking, therefore, are essentially the same as are used in refining petroleums. In 1860, in this country, over fifty companies were successfully distilling various natural bituminous materials for the production of " coal oil," used for illuminating purposes. The discovery of petroleum and the failure of these companies to save and utilize the valuable byproduct, ammonia, brought about their inevitable doom. Prior to that time, more or less successful efforts were made to produce from the shales of Scotland oils for illuminating and heating purposes. Competition of native petroleum from the United States early eliminated some of these companies and with the entrance of oil from the Russian and other fields into the world's markets, the Scottish oil-shale industry underwent serious and trying experiences until, in 1916, only four (Scottish) were paying concerns. These survived only through energy and the application of skill in saving valuable byproducts. A few companies have successfully operated in France and New Zealand. The Canadian Government showed active interest in the New Brunswick shales, which exist in quantity and are more valuable than the Scottish shales. The retarded development of that valuable asset of the Province of New Brunswick was most unfortunate, especially when the product was so much needed in the prosecution of the war. The economic success of a shale-oil industry depends on the following factors:

Jan 1, 1921

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By M. Lastra, A. Cruz, J. Menacho

The use of phosphates was studied as a way of purifying acidic copper leach solutions for direct electrowinning. The addition of 2.5 gpl phosphorus to plant solutions originally containing 6.25 gpl Fe (III) at pH 2 0 reduced the iron concentration by one half. Under identical conditions, but without phosphorous additions, the iron concentration was reduced by less than 1 gpl. Any residual phosphorous had no undesirable impact on electrowinning. The concentration ratio of Fe (III) to phosphorous which provides maximum iron elimination was determined. Higher ratios bring about a redissolution of the iron precipitate. Several ways of controlling iron with phosphates are discussed. These take advantages of more rapid and complete iron precipitation at lower pH levels.

Jan 1, 1980

By R. E. Head

UNDER existing economic conditions, the treatment of gold ores occupies an outstanding position in metallurgical activity. The increased price of gold has automatically brought about a reclassification of old dumps and low-grade orebodies, and many that formerly were considered valueless are now being vigorously investigated and worked. This situation has developed problems that have taxed the ingenuity and ability of metallurgists to the utmost. Some gold ores give a high extraction of gold by standardized methods of treatment; other ores of apparently similar character yield but a relatively small percentage of their gold when treated by the same processes.

Jan 1, 1936

By James C. Word, R. M. McLouski

This paper will describe the development and application of large-scale integration techniques employed in the fabrication of a germanium multielement array. The array consists of 100 by 228 PNP bipolar transistors fabricated on 5 mi1 centers. Back-biased p-n junction techniques are used for electrical isolation of the individual elements. The end use of the array is a high resolution, large area IR sensor. The monolithic array is fabricated in 1 ohm-cm p-type germanium epitaxially deposited on 6 ohm-cm n-type substrate. Epitaxy was accomplished through the hydrogen reduction of germanium te trachloride. Di-borane was used as the dopant. Base regions are achieved by the diffusion of arsenic from doped oxide or arsine sources. Oxide-masking of the arsenic im-pzlvity was achieved by the chemical deposition of a boron doped glass. The emitter is formed by an aluminum alloy diffusion technique. Vacuum deposited aluminum is used for the emitter, interconnections, and for the contact and bonding pads. ALTHOUGH a great volume of literature pertaining to the development of large scale integration techniques (LSI) has been published for silicon and in particular silicon imaging applications,' to date only a small number of similar devices have been constructed using germanium technology.' Since the physical and chemical properties of germanium are vastly different from those of silicon, the fabrication technology for integrated structures in germanium is also different from that of silicon. In particular germanium does not possess a stable oxide as can be grown on silicon by heating in an oxidizing ambient for masking of dopants and passivation. This paper describes the application of germanium LSI techniques employed in the fabrication of a multielement infrared sensor array. The array is used in a high resolution, large area infrared sensor for operation in the 0.8- to 1.5-u spectral range. Back biased p-n junction techniques are used for electrical isolation of individual elements. Discrete germanium devices have been fabricated routinely for some time. However, mainly due to the lack of a suitable mask for selective doping and the high current leakages inherent in germanium p-n isolation, few monolithic germanium structures have been constructed. THE INFRARED MOSAIC A cross-sectional view of the array is shown in Fig. 1. The monolithic structure consists of 12,800 PNP transistor elements in a 100 by 128 matrix fab- ricated on 5 mil centers. The emitters of each line of transistors are connected together using aluminum interconnects while the strip collectors are connected together in series at right angles to the emitter lines. The selection of this structure is dictated by the readout technique involved. Access to each element transistor is obtained by applying a bias voltage to a particular collector strip and separately interrogating each emitter row. A charge storage, i.e., an integration mode is used for reading out this particular array Construction techniques available for use with germanium do not include a selective p-type diffusion capability for surface concentrations greater than 10" per cu cm and junction depths greater than about 10 u. This fact limits the type of structure that may be used. Therefore, an array of PNP transistors that did not employ p-type diffusions was chosen. The structure was fabricated by growing a 1 ohm-cm p-type epitaxial layer on a carefully prepared 6 ohm-cm n-type substrate. N-type dopants were used for the isolation and base diffusions and alloyed aluminum was used to form the emitter junctions. The array was then completed by evaporation of aluminum interconnections and contact pads. SUBSTRATE AND SUBSTRATE PREPARATION Germanium substrates of (111) orientation grown by both Czochralski and zone leveling techniques were utilized for mosaic fabrication. Czochralski substrates were preferred because of the lower dislocation densities available in this type of material. Dislocation densities for the Czochralski material were typically less than 3000 per sq cm, while those for the zone leveled material were typically less than 5000 per sq cm. All substrates were uncompensated to minimize thermal conversion problems in subsequent epitaxial and diffusion processing. Both in-house and vendor polished wafers were used. The in-house polishing technique employed consisted of an initial gross chemical etch in CP4 to remove saw damage from both surfaces. This was followed by a chemical-mechanical polishing operation of one side of the wafer. The chemical-mechanical polishing solution used was Lustrox 1000 (Tizon Chemical Co.), and consists of zirconium dioxide, sodium hypochlorite, water and a surfactant. The wafer thickness before and after polishing was typically 0.020 and 0.010 in, respectively. THERMAL CONVERSION The problem of thermal conversion of both the substrate and epitaxial layer was particularly acute because of the relatively low carrier concentrations employed in both regions. This problem has been encountered by other workers in the past.3 Without special treatment before epitaxial growth substrate conversion (n-type to p-type) and changes in the re-

Jan 1, 1970

By Harlan N. Barton

A commercially available, portable X-ray spectrograph, lightweight and rugged for vehicle or field camp use, was used to determine Ba, Cu, Fe, Mn, Pb, Rb, Sr, and Zn in stream sediment geochemical samples. Investigations showed a relative standard deviation of 1-3%, detection limits of approximately 100 pg/g and significant matrix effects. Coefficients of correlation greater than 0.9 were obtained between portable X-ray and emission and atomic-absorption spectroscopy analyses. A geochemical map of a known mineralized area showed good agreement with maps prepared by other methods of analysis and sample media.

Jan 1, 1983

By H. N. Kalia, J. B. Gresham

Several attempts have been made in the past 60 years to commercialize the vast oil shale deposits of the US. However, the industry has yet to become economically viable. To date, it has not been possible to produce oil from oil shales at a competitive price compared with oil produced by conventional methods. The development work, nevertheless, has been fruitful in furthering the art of thick bed mining and technology of in situ retorting. The in situ method has the potential of recovering oil from thick beds, and the resource recovery potential is much greater than that from underground mining and surface retorting. In situ methods require that the shales/marlstones be fragmented in place to induce adequate porosity and permeability to allow in situ heating of the fragmented shales. This can be accomplished by using explosives. However, it has been found that the existing blasting systems, though very efficient, have some drawbacks. The explosives become insensitive when shot in multiplevertical decks. They can also become insensitive when spaced horizontally at close proximity to other charges. Also, since the blasting is done in a very limited free face, the delay time that can be allowed between charges is also quite limited. Consequently, it is not always possible to routinely predict the performance of the blasting system. Furthermore, since it is not possible to undertake secondary blasting, it is imperative that the blast design function properly. Recent successful retorting by Occidental Petroleum Co. Of Retorts 7 and 8 suggests that some of these problems may have been overcome. This paper addresses some aspects of in situ retorting and problems that have impeded the development of a viable oil shale industry in the US.

Jan 1, 1986

By T. Sterry Hunt

THE essential principle of this new process, now in operation in Chili and in North Carolina, for the extraction of copper from its ores, is the dissolving of the oxides of copper by a hot solution of protochloride of iron and common salt. In the action which takes place, the protochloride of iron is converted into peroxide, while the oxides of copper are changed into protochloride and dichloride, the latter of which, though insoluble in water, is readily soluble in a hot strong brine. From the solution thus obtained, metallic iron throws down the copper in a metallic state, regenerating the protochloride of iron; which is then ready for the treatment of a fresh portion of oxidized copper ore. In the case of slimy ores, the contact of the bath with the ore is effected by agitation in tubs; but when the ores are granular, lixiviation in large vats is equally efficient and simpler. The hot solutions, charged with chlorides of copper, are digested in tanks with scrap-iron, or better, are made to flow through covered channels containing the scrap-iron, and in their passage lose the whole of their copper; the reaction at the same time evolving so much heat as to keep up the temperature of the liquid. In order to prevent a certain loss of chlorine, which otherwise takes place from the production of some basic ferric chloride in the reaction between the ferrous chloride and the oxides of copper (both protoxide and dinoxide being generally present in calcined ores), a portion of sulphurous fumes from the roasting is made to pass through the regenerated bath before adding it to fresh ore. This has hitherto been effected by injection, with the aid of a jet of steam.

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By V. Koump, T. F. Perzak, R. G. Olsson

The rate of dissolution of recrystallized alumina in molten iron oxide in equilibrium with iron at 1450°C was studied by rotating alumina disks in the melt. The samples were rotated from 1 to 12 min at speeds from 54 to 3270 rpm. It is concluded from the experimental results that the process is limited by diffusion in the liquid boundary layer. The interdiffusion coefficient for the dissolution of alumina disks in pure molten iron oxide was estimated to be about 3 xl0-5= sq cm per sec. THE erosion of refractory materials is of considerable importance in iron- and steelmaking processes. Since many refractories contain alumina, this investigation was undertaken to develop a further understanding of the erosion mechanism. Shurygin et al.1-3 have investigated the rate of dissolution of alumina in molten silicates and molten fluorides by rotating alumina disks in various melts. The rates were reported to be limited by diffusion in the liquid boundary layer. In the present investigation the rate of dissolution of alumina in molten iron oxide in equilibrium with iron was studied in a similar manner; alumina disks were rotated at different speeds in molten iron oxide at 1450°C. The relationship between the rate of dissolution of the flat surface of the disk and the speed of rotation was used to determine whether the process is limited by diffusion in the liquid boundary layer or by some chemical reaction mechanism. APPARATUS AND EXPERIMENTAL PROCEDURE A schematic diagram of the experimental apparatus is shown in Fig. 1. The iron oxide melts were contained in 2-in.-diam high-purity iron crucibles that were centered in a cylindrical graphite susceptor. Prior to each sequence of experiments, sufficient reagent-grade ferric oxide was added to a crucible to form approximately 350 g of molten iron oxide; the depth of the melt was about 11/2 in. To prevent excessive erosion of the crucible, about 70 pct of the required iron was added to the crucible in the form of iron powder. The mixture was melted in an atmosphere of purified argon by induction heating with a 250-kc generator. After the oxide was molten, a Pt/Pt-10 pct Rh thermocouple at the exterior of the crucible was calibrated against an iron-sheathed thermocouple immersed in the melt and was thereafter used to regulate the melt temperature. All experiments were conducted at 1450°C with a probable error of 10°C. The alumina disks were constructed from pure re-crystallized alumina having a density of 3.7 g per cu cm (porosity approximately 6 pct). For each disk sample a 1-cm-diam alumina cylinder of known length (0.9 to 1.0 cm) was cemented into a ground seat at the end of a 1.27-cm-OD centerless ground alumina tube. The ends of the tube and cylinder were flush and served as the disk surface. When mounted in the apparatus the alumina tube was guided by tungsten carbide bearings and rotated by a variable-speed motor. The bearing and drive assembly could be raised and lowered in order to allow the sample to be quickly moved in and out of the melt. At the start of an experiment, a sample was preheated for several minutes directly above the melt, and then immersed in the middle of the melt to a depth of a in. and rotated for 1 to 12 min at speeds of 64 to 3270 rpm. The speed of rotation was measured by a hand tachometer. At the start and completion of each experiment, a melt sample was withdrawn with a cold copper rod and the alumina content was determined by chemical analysis. During individual experiments the alumina concentration of the melt changed by the order of 0.25 wt pct. Average melt compositions for individual experiments were used in the subsequent computations and were in the range between 0.12 and 4.3 wt pct alumina. The extent of dissolution was determined by sectioning the end of the sample and measuring the final length of the alumina cylinder with a microscope. Since the exposed end of the cylinder, i.e., the disk surface, was etched in a manner characteristic of this geometry, a number of measurements were made on

Jan 1, 1969