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By L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,' have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson' have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive

T. R. HARRISON, Washington, D. C. (written discussion). *-Mr. Kowalke shows that a high resistance millivoltmeter is subject to smaller errors, due to change in resistance of the thermocouple to which it is attached, than is a low-resistance instrument. He uses as examples instruments having resistances of 30 and 2 ohms, respectively. At the Bureau of Standards, resistances above 300 ohms would be considered high and 30 ohms rather low. In the tests on calorized-iron thermocouples, a difference between the first and third calibrations of the couples serves to show changes due to the intermediate heat treatment and only under certain conditions would changes in calibrations due to changes in the wire be detected by ,a recalibration after 1 1/2 in. had been cut from the hot-junction end of the couple and the ends rewelded. The calibration of a couple depends only on the thermoelectric prop-erties of that part of the couple which lies within the region of non-uniform temperature, i.e., the temperature gradient; hence, so long as the temperature gradient falls along wires of similar thermoelectric properties no change in the electromotive force is produced by altering the metals of those parts of the circuit that are at uniform temperature. Usually at the cold-junction end of the circuit, copper leads, brass binding posts, manganin resistance coils, and various other materials form part of the circuit, but so long as all are at a uniform temperature (or if for each junction between unlike metals there is a similar opposing junction at the same temperature) no resultant thermoelectromotive force will be produced thereby. Likewise, if a length of several inches at the hot-junction end of the couple is at uniform temperature, it matters not if this section is unlike other parts of the couple, so long as there is good metallic connection and no source of e.m.f. other than thermoelectric is present. Cutting off part of the hot end of the couple within such a region of uni-form temperature would not alter the e.m.f. of the couple.

Jan 12, 1919

By HUBERT O. De

IN December, 1936, several drilling tests were made at the Hubert O. De Beck feldspar mine at Green Mountain, N. C., to determine the most efficient type of hammier-drill bit and drilling method for use at this particular property. This mine is well recognized as having the hardest rock in the Burnsville - Spruce Pine feldspar district and drilling costs always have been high. Local structural deformation has greatly distorted and warped the normal crystalline structure of the feldspar so the rock is much tougher than usual. In studying drilling methods and bit types, available literature was re¬viewed but little specific data could be found on the direct comparison of four-point and six-point drill bits so the following results may be of some interest.

Jan 1, 1937

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,' and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-' Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967

By AIME AIME

MOTHER example of the broad field that is covered by the mining industry is the recent erection by the Phelps Dodge Corp. of a modern hospital building at Douglas, Ariz., and an identical one at the rejuvenated mining town of Morenci. Managers of even small mining properties are often called upon to build schools, houses, stores, maybe a jail, and provide sanitary arrangements, possibly the while acting as mayor of the town. Those who direct larger properties may have to build hospitals, as in the present instance, construct sewage disposal plants, and sometimes even build and manage railroads. A mining camp achieves its reputation among mining men not entirely by the grade or amount of its ore, or the skill of the operating staff in mining and milling it at a profit-the operation soon acquires a reputation as either a desirable or an undesirable place to live, regardless of its remoteness from what is euphemistically termed civilization. Such a community is indeed fortunate if it can boast of a good hospital.

Jan 1, 1940

By A. T. English

X-ray dif action techniques were used to investigate ordering and domain coalescence for the B2 (CsC1) superlattice in this alloy. Essentially complete disorder is obtainable by drastic quenching. isothertmal ordering occurs very rapidly at temperatures between 565° and 680°C, only a few seconds being required for development of substantial long-range order. A very fine antiphase dormain structure, found in samples annealed for short times, undergoes coalescence with further annealing. Domain "size" is found proportional to (t)1/2 . This Yate law can be derived by adapting the formalism of Hillert's analysis 01- metallurgical grain growth. For this Purpose the material is descvibed in terms of a "Swiss-cheese " structure, consisting of two multiply connected, mutually intertwined domain volumes. The observed activation enevgy for coalescence, 70 kcal per g-atom, agrees with an estit~lated value ,for volume diffusion in disordered rrzaterial. It is suggesled that the experimental value vejlects the substantially disordered environment of mobile vacancies located in the moving antiphase domain boundary. The alloy Fe-Co-2V is bcc below about 900'C and orders into a B2 (CsC1) superlattice below about 730c It has important applications in magnetic components, including many requiring extensive cold rolling.* example, Marcinkowski and Brown6 observed a re1atively small as-quenched domain size of about 250Å in B2 Fe3A1. Since there appear to be no published data on domain coalescence in B2 alloys, this process was studied in detail. MATERIALS AND EXPERIMENTAL TECHNIQUES A commercial high-purity alloy, nominally 49 Fe-49Co-2V, was obtained from the Arnold Engineering Co. in the form of cold-rolled sheet 0.004 in. thick. Samples were annealed for 1 hr at 800°C in dry H2 to produce disorder and quenched into iced brine. They were then annealed in a nitrate-nitrite salt bath for various times at temperatures between 525° and 625°C. Estimates of the LRO parameter S and the APD size D were made using established X-ray diffraction techniques. Superlattice peaks are best observed using CoKa radiation, for which the value of (fFe-fCo) is maximized. Peak-to-background intensity ratio was improved by filtering CoKß from the incident beam to eliminate sample fluorescence, and by using a pulse-height analyzer. The LRO parameter S was computed from the ratio of integrated intensities I 100/I 200- Owing presumably to systematic errors associated with the presence of crystallographic texture and X-ray extinction, only rough agreement was obtained between experimental and theoretical (absolute) intensity ratios. For this reason certain experimental refinements (e.g., use of balanced filters) were considered superfluous and were omitted. Emphasis was placed on maximizing intensity in order to reduce the time taken to accurately determine the contour of the very small (loo), peak. This was done by point counting 105 counts at appropriate intervals. Background intensity averaged about 1200 cps.

Jan 1, 1967

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,')' while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont's TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968

By Larry D. Patts

Section 317(e) of the Federal Coal Mine Health & Safety Act of 1969 directed the Secretary of the Interior to prepare standards under which all working places in a mine shall be illuminated by permissible lighting while persons are working in such places. Section 317(e) further provides that such working places shall be illuminated within 18 months after such standards are promulgated. In accordance with this section of the Act, there was published in the Federal Register for December 31, 1970, a notice of proposed rulemaking which prescribed the illumination to be provided in the working places of underground coal mines. In light of written comments, suggestions, and objections to this proposed rulemaking, the proposed standards were withdrawn and reproposed in the Federal Register for Wednesday, October 27, 1971. In light of further comments, suggestions, and objections, a public hearing was held on April 4, 1974, and standards were again reproposed and published in the Federal Register for April 1, 1976. Promulgation of the final lighting-standards &k place on October 1, 1976, which means that the underground coal mining, industry must comply with face illumination requirements by April 1, 1978.

Jan 3, 1978

By Fred C., Bond

DETERMINATIONS of circulating load in a classifier operating in closed circuit with a grinding mill are usually made from screen analyses of the mill feed and classifier products. The percentage remaining on someone selected screen size must be used in the calculation, and, because of the wide variation in average particle size between the mill feed and classifier overflow, an accurate and representative result at the selected mesh is often difficult to obtain. To overcome this difficulty and reduce the time required in making the determination, I have devised a method which uses the liquid-solid relationship in the circuit rather than screen analyses. The quantities required for the calculation include only the usual dilution and feed tonnage measurements, which should be made regularly in the course of ordinary mill operation and, in addition, the amount of new water added to the classifier, or to the head of the mill with the new feed. If measurements are obtained on both of these quantities it is possible to check the calculated circulating load, and to calculate the percentage of moisture in the new feed to the mill; or, if the latter is known, to check the feed tonnage.

Jan 1, 1937

By R. H. Tien

This paper presents an analytical solution of the problem of freezing of a semi-infinite slab with constant surface temperature; in this analysis accoz~nt is taken of the heat evolution during the solid-state transformations in the frozen skin. The regions where transformations occur are treated as plane isothermal heat sources; i.e., the rates of transformations are assumed to be infinite. In the model considered, three plane heat sources are assumed to be present in the frozen solid. The solution yields the temperature distribution in the solid, the rates of movement of the heat sources , and the rate of movement of the solidification front. It is shown that, although the sum of the heats of transformations in the solid is about 20 or 43 pct of the heat of fusion of iron or manganese, respectively, the effect of the heat evolution in solid-state transformations on the rate of solidification is insignzficant. IN several recent mathematical studies of solidification of liquid metals'-3 no account was taken of the heat evolution accompanying the solid-state transformations. In the case of, for example, steel, there are several phase transformations 6 -y, y -a, and the magnetic transformation. Whether or not a significant error is introduced into the mathematical simulation of solidification processes by the omission of the heat effects associated with these phase transformations is not known. The purpose of the present study is to investigate the effect of these phase transformations on the temperature distribution and the rate of solidification based solely on the heat transfer point of view. That is, for the sake of simplicity, freezing of a pure metal with solid-state transformations will be considered. The mathematical model which represents the present problem includes four moving heat sources representing freezing and phase transformations, 6— y — a — ferromagnetic. The thermal properties such as conductivity and specific heat, and so forth, are different from one phase to the other. But they are considered to be uniform over any particular phase. The usual Fourier heat flow law is employed. The concept of conservation of energy is applied at every heat source in order to estimate their rate of movement. The temperature distribution in the solid and the positions where transformations occur are expressed analytically in terms of error function solutions and four coefficients which are determined from four nonlinear algebraic equations. These coefficients can be calculated either by trial and error or by any numerical method. MATHEMATICAL ANALYSIS Fig. 1 is a schematic diagram showing the zones of different phases 1, 2, 3, and 4 in the solidified portion of a semi-infinite pure liquid metal. The heat is subtracted from the system at x = 0 which is maintained

Jan 1, 1968

By R. R. Webster, H. T. Clark

The side-blown converter has been investigated as a possible commercial process for the production of low nitrogen steel. During this work, two converters of 3-ton and 22-ton capacity were operated on a pilot plant basis for a total of 214 heats. The steel made in these converters was low in nitrogen and possessed good cold working properties. Some problems of converter operation remain to be solved. IN plants operating with a high iron capacity, sev-eral different refining methods are used in the conversion of the molten pig iron to steel. These include various ore practices in stationary and tilting open-hearths, the duplex process employing the Bessemer converter and open-hearth, and the Bessemer process. At J&L, a considerable part of the iron produced is handled by the Bessemer process, either alone or in conjunction with duplexing, and therefore an appreciable portion of the steelmaking research effort has centered about the method. This paper covers research work on the development of the side-blow converter for the commercial production of low nitrogen ingots and includes descriptions of the operation of a 3-ton and a 22-ton experimental converter at the Aliquippa Works. The refining of iron to produce steel requires the removal of a large portion of the carbon and silicon and the control of manganese, phosphorus and sulphur which are present in the iron in varying amounts. The first large-scale means of refining iron was the acid Bessemer process which was brought into use almost 100 yr ago. This method, using compressed air as the refining medium, accomplishes substantially complete removal of carbon, manganese and silicon. Phosphorus and sulphur are not affected but, by choice of an iron composition sufficiently low in these elements, a commercial product can be produced. Since the process will handle large tonnages rapidly, operates without external fuel and with a minimum of additional equipment, it quickly became the major tool in the early expansion of the steel industry. Later, the basic open-hearth process, by affording control of phosphorus and sulphur and by consuming the large quantities of steel scrap that were becoming available, forced the acid Bessemer process into a secondary position in the industry. During the past two decades the demand for steel to be used in cold forming and drawing operations has gradually increased. Bessemer steel, because of its work hardening and aging characteristics, is not as suitable for these applications as basic open-hearth steel, consequently the decline of the process was accelerated. More recently, because of changing economic conditions, this long range trend appears to have been arrested or perhaps reversed. Ingot production data for recent years furnishes only an incomplete picture of the importance of the converter in the American steel industry; open-hearth furnaces utilize large tonnages of blown metal for which no published statistics are available. Metallurgical Aspects The fundamental difference between Bessemer and open-hearth steels apparently lies not in the method of manufacture but, rather, in the differences in chemical composition of the two steels. It is further believed that the principal features distinguishing Bessemer from open-hearth steel are the higher nitrogen and phosphorus contents of the former. Evidence supporting this position is supplied by tests on laboratory induction furnace heats that were made to contain varying amounts of phosphorus and nitrogen but were otherwise similar to normal low carbon silicon-killed steels. Fig. 1, 2 and 3, summarizing the test results, are taken from G. H. Enzian's paper titled, "Some Effects of Phosphorus and Nitrogen on the Properties of Low Carbon Steels."' Fig. l indicates that phosphorus has a marked effect on the cold work embrittlement of steel as shown by the work brittleness test of Graham and Work.' In the low nitrogen steels, which as a group have the better cold working properties, the effect of phosphorus variations is the more pronounced.

Jan 1, 1951

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

US 4,135,913-Extraction of nickel values from iron-containing nickel sulfide ore, particularly pentlandite or nickeliferous pyrrhotite A mixture of raw ore, roasted ore, or iron powder, and coal as a reductant is heated to a temperature of 800- 1000° C in a nonoxidizing atmosphere to convert the bulk of the iron content to metallic iron while diffusing into the iron the bulk of the nickel, the mixture cooled, and the cool material separated into a magnetic fraction containing most of the nickel and a non-magnetic gangue fraction A Illis arid L S Renzoni, assigned to International Nickel Co, Inc Jan 23, 1979 7 pp (75-21) Filed 10-10-75 (621,343) Priority Canada, 10-27-72 (155,032) Same Canadian 981,910, dated Jan 20, 1976 Same British 1,389,145, dated Apr 3, 1975 US 4,135,917-In the recovery of gallium from a solution obtained by the digestion of bauxite or nepheline in an alkali solution for the production of alumina, the digestion solution is neutralized, the neutralized solution evaporated to an op¬timum caustic alkali concentration and adjusted to a ratio of alkali metal oxide to alumina of above 2, the corrected solu¬tion contacted with a gallium-aluminum alloy, arid high-purity gallium recovered from the solution by electrolysis or cemen¬tation K A Badaliants, et al Jan 23, 1979 6 pp (75-109) Filed 12-19-77 (862,201) Priority USSR, 12-22-76 (2,428,¬006) US 4,135,918-Extraction of copper from copper sulfide ore containing also one or more of the metals iron, nickel, arid cobalt Ore is roasted at a temperature of 750-800° C to expel sulfur, the sulfur-free calcine slurried in water containing a sufficient amount of sulfuric acid to supplement any sulfuric acid formed in situ, the slurry heated at 150-165° C in the presence of a reducing gas to form soluble sulfates of metals other than copper while reducing copper to elemental form, arid the slurry filtered to recover copper solids Any precious metals present in the ore will report with the copper solids V A Ettel, A P Devuyst, R Sridhar, arid C. E O'Neill, as¬signed to International Nickel Co, Inc Jan 23, 1979 5 pp (75-117) Filed 3-2-78 (882,610) Priority Canada, 5-13-77 (278,360)

Jan 1, 1980

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By F. W. Sperr

The byproduct coke oven is the most important artificial source of fuels for metals melting. Its products are solid, liquid, and gaseous in form. The amount of coke and primary byproducts obtained per ton of coal varies with the nature of the coal. The following represents the results obtained in many plants: Metallurgical coke (over 3/4 in.).............................. 69 per cent. of coal Domestic coke (1/2 to 3/4 in.)................................ 2 per cent. of coal Breeze (under 1/2 in.)...................................... 4 per cent. of coal Surplus gas, cubic feet per net ton........................... 6600 Gas for heating ovens, cubic feet per net tor i................. 4400 Tar, gallons per net ton.................................... 9 Ammonium sulfate, pounds per net ton....................... 25 Benzols, gallolls per net ton................................. 4 All of these products, except ammonium sulfate, have important fuel value. Part or all of the metallurgical coke may be crushed or screened to furnish additional domestic coke. If producer gas is used, there will be a surplus of 11,000 cu. ft. of coke-oven gas per net ton of coal. The use of coke in the metallurgical industries has been retarded by the mental attitude of writers who disregard the dependence of coke quality on the conditions of its manufacture. Terms like "byproduct coke," ('beehive coke," "48-hour coke," and "72-hour coke" are only generally descriptive and tell nothing of the coke quality. For example, one writeri stated that in brass-foundry practice, Connellsville coke is considered rnuch superior to byproduct coke on account of the high sulfur content of the latter. Another2 says, "At equal prices for hard Connellsville coke and for byproduct coke at the foundry door, the hard coke is unquestionably cheaper. It will melt more metal per ton than the byproduct coke and requires less labor, as the byproduct coke is less dense and burns faster, thus requiring more frequent firing." A little study of the conditions under which coke is manufactured will show the error in making general statements like these. The percentage of sulfur in coke depends largely on that in the original coal, and byproduct coke from a

Jan 1, 1921

By C. C. Koch, M. L. Picklesimer

PHYSICAL metallurgists interested in the alloying behavior and phase transformations in rare-earth metals and alloys require a strain-free polished and etched surface for both metallographic and X-ray examination. However, the rare earths have presented a problem in this respect since they are difficult to polish free from strain and are very reactive to the atmosphere. Their tendency to oxidize readily even at room temperature necessitates careful preparation and rather elaborate protection if their surface is to be examined for any length of time. The "light" lan-thanides (i .e., atomic numbers less than 63), especially lanthanum and cerium, are particularly bad in this regard; they oxidize very rapidly at room temperature. To eliminate the problem of plastic deformation remaining on the surface after mechanical polishing, electropolishingl and chemical polishing techniques2 have been developed. The electropolishing technique requires the specimen to be immersed in an electrolyte at -77°C and thus obviates a metallographic study of, for example, the fcc —double-hexagonal close-packed (dhcp) transformation in cerium which begins at -10°C. The chemical polishing solution has been used only on several of the "heavy" rare-earth metals. However, a convenient method for protecting the polished and etched surfaces from atmospheric corrosion has not been available. Our interest in the superconducting properties of lanthanum, and in the phase transformations in lanthanum and cerium, has led us to develop a technique for the metallographic preparation of lanthanum and cerium which clearly reveals the microstructure and preserves the etched surface for days. The specimens are chemically polished and anodized. The chemical polishing is performed at room temperature, the anodic oxide film provides the required protection from the atmosphere, and colors produced in the film provide a simple positive technique for phase identification. Lanthanum and cerium metal ingots obtained from Johnson Matthey and Co., Ltd., were remelted to suitable shapes and heat-treated to produce various microstructures. The samples were placed in epoxy mounts and, after a small hole was drilled in the back of the mount for electrical contact, were ground on silicon carbide

Jan 1, 1968

By James S. Baker

LARGER than continental United States but with only about one third the population, Brazil is a land of enormous potential wealth, waiting to be developed. During a recent visit to that country I saw Brazil at war and learned about some of the recent mineral developments. Many engineers and geologists have been sent to Brazil by various U. S. Government agencies to assist the Brazilian producers and co-operate with the Brazilian Government in producing needed war minerals. The Foreign Economic Administration staff of engineers has been active and through their assistance to the Brazilian producers, steadily increasing quantities of strategic minerals were provided to aid the United Nations' war effort. Mineral wealth has been found in almost every state of Brazil. Many mineral deposits have been discovered during the war period. Examples are: barite near Bahia; the tungsten and molybdenum deposits in Rio Grande do Norte; and corundum, beryl, and tungsten ores in Ceara.

Jan 1, 1945

"The pumping of the underground water of the Butte mines is largely done from two central plants of the Anaconda Copper Mining Co. The mines of one part of the mining district are served by a modern and mechanically efficient underground plant at the High Ore mine, and the remaining part by a similar one at the Leonard mine. Properties not affiliated with the A. C. M. Co. have separate pumping plants, although in several instances that company handles the water of outside companies, under which arrangement costly single plants are dispensed with. An extensive system of underground crosscuts and drifts connects these mines to both the main pumping plants, so that either may receive the water from all the mines in case there should be a failure in the other to perform its designed service.Quintuple) vertical electric pumps, 7 inches by 12 inches each, of a capacity of 600 gals. per minute under a head of 1,203 feet, are installed at both the plants. Each pump is direct connected to two 150 h-p. motors using 2,300 volts, the motors being on top of the pumps.At the High Ore plant the power cable of 400,000 c. m. is placed in a nearby shaft, the cable at present being hung from the surface to the 2,200 level. From this cable feeders of 300,000 c. m. are laid in connecting crosscuts to the pumping station at the High Ore shaft.The Leonard motors use 440 volts. The practice of building the pumps with the motors on top requires stations with high roofs, but permits the operation of the pumps if they should be submerged by an unusual flow of water."

Jan 1, 1913

By Russell A. Carter

Seven years of rising silver prices have effectively revived an historic Idaho mining district and given it a new lease on life. Initial production earlier last year from the DeLamar open-pit silver mine in southwestern Idaho ushered in a new era of mineral production in a region that has weathered boom-and-bust cycles reaching back the better part of a century.

Jan 1, 1978

By George C. Stone

AS most of you probably know, Australia has had many strikes. The two places that had the worst reputation were the Broken Hill mines and Port Pirie, where the smelter was located. About four or five years ago, the smelter changed hands. The new proprietors - immediately endeavored to get on better terms with the men and made such progress in that respect that, the men came to them and said, "There is no use giving us any more money. You have just raised our pay one- bob a day, but the store-keeper and the boarding-house keeper have raised their prices. The boarding housekeeper raised our board three bob a week and the storekeeper took the rest of it and we are no better off." Learning that what the men needed most was firewood wood the company bought the wood on a tract of ground across Spencer's Gulf and- sent men over to cut it. The wood was brought to the works and given to a man to cut up. He thought he had an easy job and loafed, but when the committee representing the men discovered that his loafing added to the cost of 'the wood, it promptly disciplined him and made -him work as he had never worked before. The next question that arose was the distribution of the wood. The committee got bids from several cartmen whose prices varied from about two to five shillings. It gave the work to the next to the lowest bidder. The fact that if delivering the wood cost more, the user would have to pay for it, was an entirely new idea to the men.

Jan 1, 1920