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By S. Korman, S. B. Tuwiner

Chalcocite flotation is affected by agitation intensity during conditioning. Sodium sulphide in minute quantity may activate or depress, depending on conditions. Oxygen is a depressant while oxygen and sulphide neutralize each other by re-action at the mineral surface. Diffusion across a stagnant film at the surface governs reaction rates, while film thickness is reduced upon increase of agitation intensity.

Jan 2, 1950

By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By G. O. Hiers

THE object of the experiments reported in this paper is to determine the eutectic composition of copper and tin and to determine the location of the part of the liquidus line immediately above the eutectic composition in copper. Three methods were used in the investigation: (1) the method of dissolving copper in a bath of molten tin at constant temperature, with the idea that when the bath was saturated with copper its copper content, by analysis, together with the temperature at which the saturation took place would locate a point on the liquidus line (2) the method of the differential cooling curves, and (3) the method of microscopic examination. This paper is principally concerned with the results of the last two methods mentioned. The results of the first method, that of dissolving copper in molten tin, did not agree with the .results of Miller,1 by the same method, nor with the results of other investigators by other methods, nor yet with the results of the cooling-¬curve experiments and microscopic examination reported here.

Jan 1, 1929

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

As is known to representatives on Engineering Council, the Patents Committee of Council has collaborated with the similar committee of National Research Council in developing a scheme for the improvement of the method of dealing with patents in this country. The staff of the Patent Office is itself actively engaged in this effort. Out of the report prepared by the National Research Council, and approved and adopted by Engineering Council as the report also of its Patents Committee, remedial legislation has taken form. Three hills have been introduced, known as H.R. 5011, a bill to make the Patent Office independent of the Department of the Interior or any other department, and to simplify the procedure of the Courts with reference to assessment of damages or profits for infringement of patents; H.R. 5012, a bill to establish a single Court of Patent Appeals; and H.R. 7010, a bill to increase the force and salaries in the Patent Office. Chairman Charles A. Terry, of the Patents Committee, requests that representatives of Engineering Council write to their congressmen, urging the passage of these hills and so far as convenient, request their friends to do likewise.

Jan 9, 1919

By D. J. McAdam, R. W. Mebs

The technical cohesive strength of a metal means, not the interatomic forces, but the technically estimated resistance to fracture. An example of such resistance to fracture is the so-called "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. According to the prevalent view,8 the technical cohesive strength of a metal. in any particular state as regards prior mecharlical treatment and heat-treatment, is determined by a limiting value of the algebraically greatest principal stress. In two previous papers by one of the authors, evidence was presented to indicate that the technical cohesive strength of a metal cannot be represented by a single stress value, but that it comprises an infinite number of values corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength thus comprises an infinite number of technical cohesion Limits, each representing a specific stress combination at fracture. In the same papers, evidence was presented that plastic extension causes a continuous increase in the technical cohesive strength. Such a variation is not in accordance with the prevalent view that plastic extension first increases, then decreases, the technical cohesive strength.' In this paper, as in the previous papers,14.15 the algebraically greatest principal stress will be designated S1, the least principal stress will be designated 33, and the intermediate principal stress will be designated S². The technical cohesion limit under polarsymmetric tension (S1 = S2 = S3) will be termed the "disruptive stress," and the cohesion limit under unidirectional tension (S2 and S3 = o) will be termed the "severing stress."l4, .l5 The yield strength of a metal, according to the generally accepted theory, may be represented by a constant value of the shearing-strain energy, and hence by a constant value of the sum of the squares of the three principal stress differences. In the second of the previous papers,15 however, evidence was presented that the limiting yield stress decreases with increase in the volume stress, the algebraic average Of the three principal stresses.* This in fluence of the volume stress becomes prominent only in the field of triaxial tension. In the two previous papers,".'5 diagrams were presented to show the variation of the technical cohesion limit, yield stress, and ultimate stress with the combination of principal stresses and with plastic extension. Those diagrams and the resultant • Any stress system ma? be resolved into a polarsymmetric stress causing pure volume strain and a combination of pure shearing stresses. which cause no change of volum

Jan 1, 1945

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The effect of machine stiffness on discontinuous flow and fracture of the 2024 aluminum alloy was studied in tension at 4.2OK. An increase of machine stiffness was found to decrease the amount of elongation and drop in load during discontinuous flow, thereby postponing fracture to larger strains and higher stresses. The possibility of utilizing stiffened tools in deformation processing to suppress shear fracture originating from unstable flow was indicated. The problem of nucleating discontinuous flow and the role of the effective mass of the system in discontinuous flow were also considered. AT low temperatures the plastic flow of metals is often discontinuous, with sudden load drops and elongations.1,3 Basinski1,4 has presented strong evidence that discontinuous flow, at least in aluminum alloys, occurs under nearly adiabatic conditions. During testing the load may drop suddenly and flow become localized when the thermal softening, due to heat generated in plastic straining, is greater than the strain and strain-rate hardening. This instability criterion is more easily satisfied at low temperatures because 1) the volume specific heat is reduced so that relatively large temperature increases are possible in straining, and 2) the flow stress is relatively temperature-dependent. The important role of adiabatic shear in ductile fracture processes has been emphasized,5-1 and consideration has already been given to the influences of thermal and mechanical properties on the tendency of a material to undergo adiabatic shear.17677 By focusing attention on how the mechanical loading system influences low-temperature discontinuous flow, additional insight into adiabatic shear and its effect on fracture may be gained. EXPERIMENTAL PROCEDURE Because of its low thermal conductivity, the 2024 aluminum alloy exhibits a highly consistent discon- tinuous-flow behavior at 4.2°K and was therefore chosen as the material for study. Machined specimens of 0.113 in. diam and 1.125 in. gage length were solution heat-treated at 490°C for 3 hr, quenched into cold water, and immediately immersed in liquid nitrogen until just before testing. Testing was done at 4.2°K by immersion in liquid helium at a crosshead drive rate of 0.03 in. per min. As normally used (hard-machine basis), the spring constant of the testing machine was k = 25,000 lb per in. By inserting beam springs in series with the specimen, this value could be lowered by a factor of about 100. Details can be found elsewhere.? As a result of variable machine stiffness, the actual strain rate ranged from about 3 x 10 5 to 3 x 10-4 per sec from one test to another, as well as within any one test. However, preliminary tests had established that the tensile curves were not altered significantly by this strain-rate variation. Fig. 1 shows a typical load vs plastic-elongation curve for a solution heat-treated 2024 aluminum alloy specimen pulled in the standard hard machine (k = 25,000 lb per in.) at 4.2"K. The elastic extension has been subtracted. Plastic flow proceeded smoothly from yielding at approximately 22,000 psi (load = 220 lb) to a strain of about 4 pct at which point the flow became discontinuous. The magnitude of the load drops as well as the plastic elongation per drop increased with increasing strain until the specimen finally broke abruptly. The load-elongation behavior of a sample tested with a relatively soft machine under otherwise identical conditions is given in Fig. 2. In general, there

Jan 1, 1964

By F. N. Koepel, L. A. Callaway

The property of the Andes Copper Mining Co. is in the central part of the Republic of Chile, Province of Atacama, about 75 miles to the eastward from the port of Chafñaral. At this point the Andean system is made up of two principal ranges, and the mine and metallurgical plant are both on the westerly slope of the outer or western range. Mean elevation of the mine is 10,500 ft., while at the plant the elevation ranges from 9445 to 9700 ft. A meter gage railroad extends from the company's port at Barquito, near Chañaral, to the reduction plant at Potrerillos. This road has a total length of 94 miles, of which 57.79 miles are owned by the Andes Copper Mining Co. and the remainder of the road is controlled by the State. Development of the Potrerillos mine and installation of the metallurgical equipment presented unusual difficulties due to the arid nature of the country, high altitude and remoteness of the location from any considerable center of population. As a primary step it was necessary that railroad transportation be provided in order that mine development and plant construction could go forward on an economical basis. Provision of an adequate supply of water for domestic and metallurgical uses involved the construction of approximately 178 miles of pipe lines, all of which have their sources at altitudes ranging from 12,000 to 14,000 ft. above sea level and traverse rough and difficult terrane. Water for metallurgical use is brought to Potrerillos from the Ola River, a stream originating in the high cordillera to the eastward from the property. It is delivered by means of a steel pipe line, 32 miles long, having diameters ranging from 22 to 36 in. Domestic water is supplied to the various camps through a system of pipe lines aggregating 146 miles in length, the Ola water being unfit for this purpose. These conductors gather water from numerous springs in the high mountains to the eastward from Potrerillos and deliver it to the mine, the reduction works and the port at Barquito. Extensive permanent housing facilities had to be provided as it was necessary to care for more than 3000 workmen and employees at the

Jan 1, 1934

By AIME AIME

General Local Committee.-John Fritz, Chairman; A. B. de Saulles, Vice-Chairman.; R. M. Bird, Treasurer; Henry S. Drinker, Secretary; Robert H. Sayre, E. P. Wilbur, Charles M. Dodson, Abraham S. Schropp, E. M. McIlvain Archibald Johnston, A. B. Fichter, C. G. Convers, W. A. Wilbur, Garrett B. Linderman, Frederick Conlin, George Pettiuos, Albert Brodhead, Garrett L. Hoppes, M.B. Cutter, H. J. Seaman, C. A. Matcham, B. F. Fackenthal, Jr., A. L. J. Queneau, Geo. R. Elder, Eldridge Wilbur, William H. Chandler, Mansfield Merriman, Joseph F. Klein, William S. Franklin, William Esty, Joseph AN'. Richards, Howard Eckfeldt, John D. Irving. Transportation Committee.-H. J. Seaman, C. A. Matcham, B. F. Fackenthal, Jr., A. B. Fichter, A. L. J. Queneau, Henry S. Drinker. Hotel Committee. -Garrett B. Linderman, Charles M. Dodson, W. A. Wilbur, Garrett L. Hoppes, Albert Brodhead. Steering Committee.-William S. Franklin, William Esty, John D. Irving, R. M. Bird, the members of the Tau Beta Pi Society of Lehigh University. Committee on Meetings - William S. Drinker, Joseph W. Richards, Howard Eckfeldt. Entertainmment Committee.-W. A. Wilbur, E. M. McIlvain, Archibald Johnston, A. B. de Saulles, G. G. Convers,.A. L. J. Queneau, Garrett B. Linderman, Frederick Conlin, George Pettinos, Garrett L. Hoppes, Henry S. Drinker, William S. Franklin, Eldridge Wilbur, Robert M. Bird, Secretary. The opening session was held at 8.30 p.m., Wednesday, February 21, 1906, in Gymnasium Hall of Lehigh University, which had been tastefully decorated with flags and bunting. Dr. Henry S. Drinker, President of Lehigh University, and Secretary of the General Local Committee, called the meeting to order, and welcomed the Institute to the Bethlehems, where its first meeting, after its organization in May, 1871, at Wilkes-Barre, was held in August, 1871.*

May 1, 1906

By Harold Margolin

The Ti-Al system certainly merits the investigative attention it has been receiving and this latest contribution by Blackburn is therefore to be welcomed. The titanium-rich end of the phase diagram shown here, as well as the diagram by crossley,17 Clark et a1.,18 and Tsujimoto and Adachi,29 reveal no other intermediate phase than Ti3A1, although a previous work by Ence and Margolin20 had reported an additional intermediate phase. Since then, Buerger Precession pictures of single crystals of 10.5, 11.5, and 12.5 wt pct A1 were made at New York university21 and the extinctions were found to be typical of a D6h a Ti structure. Some superlat-tice spots and/or streaks suggesting the presence of an Mg3Cd structure, i.e., Ti3Al, were also found. Since these specimens had been quenched from the y region20 and had revealed a Ti, it was concludedz1 that y does not exist and the structures interpreted as m + y could not be so considered. The absence of normal two-phase behavior in these structures had been indicated in the paper. Accordingly, the two-phase region y + 6 becomes a + Ti3Al and there is some agreement between the results of Blackburn and of Ence and Margolin20 as to both shape and existence above 900°C of an a + Ti3Al field. Crossley 17 proposed that Ti3Al is a line compound which decomposes congruently at 900°C. It is difficult to discount entirely the fact that clear two-phase structures, varying in amount with position in the two-phase field, could be detected above 900°C by Ence and Margolin.20 Precipitation during quenching could not have been so regular and the twin-phase syndrome17 does not apply. The heat treatment and quenching technique was essentially the same as was used by Crossley, whereas Blackburn, who used a rapid quenching procedure, also showed a two-phase a + Ti3A1 field above 900°C. If the two-phase field exists above 900° C, it is easy to picture a two-phase field which could account for the data of Crossley below 900°C without invoking a line compound existence of Ti3A1. All that would be necessary would be an 0 + Ti3Al/Ti3Al boundary which curved sharply to higher aluminum contents below 900° C. It is clear that the controversy must be solved by techniques which obtain data at elevated temperatures without quenching. It is conceivable that the difference in width of the a + Ti3N fields reported by Blackburn and by Ence and Margolin is due to the longer annealing times used by the latter investigators. The criterion for establishment of equilibrium in our work20 was the

Jan 1, 1969

By S. W. Miller

DURING the examination of welds made in steel by the oxy-acetylene and electric-arc processes, the writer has met with some unusual structures, which he has not encountered elsewhere. They seem to be quite closely associated with the welding methods used, and characteristic of them, and would seem to be worth noting, especially as the references to them in the literature are few, and their explanation not clear or complete. An introductory word or two about fusion welding may not he out of place. The oxy-acetylene process is based on the great and very local heat generated by the burning of acetylene in the presence of commercially pure oxygen, the two gases being thoroughly mixed before combustion. The theoretical temperature is somewhat under 4000° C., but on account of various losses, the actual maximum temperature is probably about 3000° C. 1 The electric-arc process, using a metal electrode, which is also the filling rod, generates a still higher and more local temperature. The actual temperature of the positive crater of the carbon arc is given as 3500° C.2 No figures have been found for the temperature of the arc using a metal electrode, but it would probably not be very different from that of the carbon arc, and probably higher than that of the oxy-acetylene flame. The greater localization of the electric arc is due to the fact that it is not surrounded by a large envelope flame as well as to its higher temperature; while the oxy-acetylene white cone, or welding flame, in which the carbon of the acetylene is burned to CO, is surrounded and preceded by -a long envelope flame, itself of quite high temperature, in which the CO is burned to C02, and the hydrogen of the acetylene to

Jan 2, 1918

By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By L. L. Handy

The most common method of identifying hydrocarbon-bearing strata in a well that penetrates many different formations involves measurement and interpretation of the electrical properties of the formations as determined by electrical logs. Even though this method is used extensively, and even though in a great many instances it is capable of indicating presence of oil or gas, situations arise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1. A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the actual resistivity of the uninvaded zone with existing logging devices. 2. A formation in which invasion has been so extensive that a value for the uninvaded zone resistivity cannot be obtained. 3. A very shaly formation in which the resistivity index, I, is lower than that usually associated with productive formations. 4. Laminated formations comprised of thin productive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to permit measurement of uninvaded-zone resistivity with existing logging devices. 5. Productive formations in which the water saturation is high. To extend the utility of electric log interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations. Some time ago, in connection with research on the wettability of reservoir rock, an investigation was conducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.' The resistivities after extraction were generally lower. Other tests made on the cores indicated that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments'," have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting properties of the surfaces of core material affect electrical resistivity, a series of experiments was conducted. Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a low water saturation, then flooded with brine to a final residual oil saturation. Resistivity measurements were made on each group. Both groups were then flooded with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent. These experiments showed that the resistivity of a core containing oil could be altered by changing wet-tability of the core. Moreover, the possibility was introduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock containing gas and water might be expected to be similar to that of a rock containing oil and water, such a method should also be applicable to identification of gas-bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon saturation therein. Those strata showing significantly increased invaded-zone resistivities would, therefore, contain hydrocarbons; those with no significant change would be filled only with water. Addition of a reverse-wetting agent to a hydro carbon -bearing zone which is, by nature, already preferentially oil wet would not result in an enhancement of its resistivity. It is generally believed, however, that most hydrocarbon-bearing strata are preferentially water wet.

By W. W. Schmittroth, A. Y. Bethune

The commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "super-purity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,' it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon were not desirable. The use of special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1949

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.' All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan' and of Bogdandy and

Jan 1, 1967

By George A. Morrison

A deposit Of limestone Was known to exist at a depth of 2000 ft under the property of the Columbia Chemical Division of the Pittsburgh Plate Glass Co. at Barber-ton, Ohio. A 662-acre site was selected for the projected mine, some two miles northwest of the plant and near the main line of the Erie Railway. An electric railway 8800 ft in length connects the mine and the plant. The deposit is overlain by 18 ft of un-consolidated (sand and gravel), 100 ft of water-bearing sandstone, and finally 2080 ft of shale into which thin layers of sandstone are embedded. The limestone bed itself is 345 ft thick and overlies 200 ft of gypsum. A 300-ton-per-hour capacity mine was decided upon. Two shafts were deemed advisable, one for production and the second for service; and these were sunk 550 ft apart, one to a depth of 2323 ft and the other to 2258 ft. Each is 16 X , ft in the clear and timbered with 6-in. steel H-sets on 8-ft centers, using 3/8 X 4 X 4-in. angles as studdles. Twelve inch I-beams were used at 160 ft intervals as bearers set in deep hitches and concreted to a vertical depth of 8 ft. Wooden sheathing was first employed but sloughing of the shale created a pressure on this lining and finally concrete was deemed necessary. Water was encountered only within the first 315 ft, flowing at 60 gpm and by grouting this was reduced to 15 gpm. Temporary wooden sinking headframes were installed with 300 cu ft capacity storage pockets and with doors automatically controlled by air cylinders by hoistmen. Each shaft was operated on four 6-hr shifts. The usual V-cut was drilled at the center of the shaft and the round consisted of 34 holes- A 40 pet gelatin dynamite was employed with some 60 pet in the cut holes. Drilling crews consisted of four to six men. Shale drilled easily but became more bed in depth and sandstone wore away the gauge Of the bits rapidly. A room-and-pillar mining system was adopted whereby rooms turned off on 80-ft centers, each room 40-ft wide and 50-ft high. Rib pillars between rooms were cut into 100 ft lengths by frequent holes. Ventilation is achieved through the two shafts, the down-draft through the service shaft, and the return through the pr0duction shaft. The hoist has a a Of 300 tons per hour and is equipped with 10-ton balanced skips requiring. a 2-min cycle Or 30 trips Per hour- Hoisting is designed to Operate by automatic loading and no hoistman is required for normal Operation. The 48 X 60 in. jaw primary crusher is underground. It is fed through chute and chain feeders and is flood-oil lubricated and cooled. An inclined belt conveyor returns oversized material to the crusher. Tramming is by Diesel-powered trucks.

Jan 1, 1948

By George A. Morrison

A deposit Of limestone Was known to exist at a depth of 2000 ft under the property of the Columbia Chemical Division of the Pittsburgh Plate Glass Co. at Barber-ton, Ohio. A 662-acre site was selected for the projected mine, some two miles northwest of the plant and near the main line of the Erie Railway. An electric railway 8800 ft in length connects the mine and the plant. The deposit is overlain by 18 ft of un-consolidated (sand and gravel), 100 ft of water-bearing sandstone, and finally 2080 ft of shale into which thin layers of sandstone are embedded. The limestone bed itself is 345 ft thick and overlies 200 ft of gypsum. A 300-ton-per-hour capacity mine was decided upon. Two shafts were deemed advisable, one for production and the second for service; and these were sunk 550 ft apart, one to a depth of 2323 ft and the other to 2258 ft. Each is 16 X , ft in the clear and timbered with 6-in. steel H-sets on 8-ft centers, using 3/8 X 4 X 4-in. angles as studdles. Twelve inch I-beams were used at 160 ft intervals as bearers set in deep hitches and concreted to a vertical depth of 8 ft. Wooden sheathing was first employed but sloughing of the shale created a pressure on this lining and finally concrete was deemed necessary. Water was encountered only within the first 315 ft, flowing at 60 gpm and by grouting this was reduced to 15 gpm. Temporary wooden sinking headframes were installed with 300 cu ft capacity storage pockets and with doors automatically controlled by air cylinders by hoistmen. Each shaft was operated on four 6-hr shifts. The usual V-cut was drilled at the center of the shaft and the round consisted of 34 holes- A 40 pet gelatin dynamite was employed with some 60 pet in the cut holes. Drilling crews consisted of four to six men. Shale drilled easily but became more bed in depth and sandstone wore away the gauge Of the bits rapidly. A room-and-pillar mining system was adopted whereby rooms turned off on 80-ft centers, each room 40-ft wide and 50-ft high. Rib pillars between rooms were cut into 100 ft lengths by frequent holes. Ventilation is achieved through the two shafts, the down-draft through the service shaft, and the return through the pr0duction shaft. The hoist has a a Of 300 tons per hour and is equipped with 10-ton balanced skips requiring. a 2-min cycle Or 30 trips Per hour- Hoisting is designed to Operate by automatic loading and no hoistman is required for normal Operation. The 48 X 60 in. jaw primary crusher is underground. It is fed through chute and chain feeders and is flood-oil lubricated and cooled. An inclined belt conveyor returns oversized material to the crusher. Tramming is by Diesel-powered trucks.

Jan 1, 1948

By S. A. Montague

Mica can claim a considerably greater importance than would be assumed from its comparatively small dollar volume, which came to about $37,000,000 for the United States industry as a whole in 1957. Mica is one of the strategic minerals. We must depend on imports from distant sources for virtually all of our requirements of high grade block and all of our mica splittings. Mica is essential and indispensable for vacuum tubes and high-performance condensers, two electronic components which are vital military necessities besides being nearly indispensable to civilization today. Composition and Properties Mica is the general name for a group of some nine different minerals, two of which, muscovite and phlogopite, are the minerals used by the mica industry as its raw material. Several of the other varieties are commercially useful-vermiculite, * used for heat insulation in expanded form, and lepidolite, used as an ore of lithium while the others-biotite, roscoelite lepidomelane, paragonite and zinnwaldite have little or no commercial importance. Biotite frequently occurs as an undesirable impurity in muscovite. Table 1 lists various properties and other data concerning muscovite and phlogopite. Chemically, mica is a complex silicate of sodium, potassium and aluminum. Most varieties of muscovite are higher in sodium, and of phlogopite in magnesium. There are no important uses of mica where the chemical analysis is important, except that in some uses of ground mica, the content of iron oxide present as an impurity must be kept to a very low limit. Muscovite occurs in a range of color from the so-called India "ruby" which is more closely a pinkish brown, to light and dark green, with numerous other intermediate shades. Ruby color is usually preferred by industry, especially in the better qualities. When split very thin the color in most [ ] micas disappears. Muscovite mica is frequently found containing black and red "stain" as a homogeneous part of the books or sheets. In most cases this stain or impurity is magnetite

Jan 1, 1960

By J. H. L. Vogt

TABLE OF COKTENTS. [ ]

Jan 1, 1902

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966