Search Documents

By G. E. Johnson

LEAD SMELTERS AND REFINERS in 1932 were confronted with the problem of adjusting operations and costs to curtailed production and consumption at reduced prices, a problem which has been partially solved at least by improvements in operating technique and increased efficiency. At the Mount Isa properties in Australia, a third blast furnace and additional Dwight-Lloyd sintering machines were installed during the year, designed to increase the production to 6,000 tons of bullion per month. The large proportion of lead carbonate in the ores to be treated has presented metallurgical problems. Of the total lead contained in the concentrates to be smelted, two-thirds is Dresent as carbonates and one-third as sulfides. In the iiitial operations, the resulting Dwight-Lloyd sinter was soft, contained an excessive amount of fines, and was easily fusible. When charged to the blast furnaces it developed accretions in the upper part of the furnace owing to the easily fusible lead carbonates softening and fusing at the top of the charge column. This was remedied by the addition to the sinter feed of diluents of higher melting point, granulated slag and crushed limestone. The sinter feed consists of concentrates, Cottrell dust and wind-box cleanings, totalling 57 per cent of the charge; return sinter fines 15 per cent; granulated slag 23 per cent; and crushed limestone 5 per cent. The sinter produced contains 34 per cent lead and 0.5 per cent sulfur. Experiments indicated that double sintering under these conditions was of no advantage, so the original plan of single sinter treatment was retained.

Jan 1, 1933

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By Knut Conradsen

In the study 208 heavy mineral concentrates (pan samples) from Jameson Land, East Greenland, are considered. Each concentrate has been analysed (by spectroscopy) for the content of (approx.) 25 elements. Furthermore the exact sampling position and the geological characteristics of the environment have been registered. In the study is shown how different multivariate methods combined with geological knowledge of the area can be used in the interpretation and classification of the data. Special emphasis is put on the problem of finding reliable expressions for the background level of the element concentrations in the area. This is done by means of severel discrimination procedures. The other main subject is a demonstration of the applicability of isoscore maps - originating from factor analyses - in the evaluation of the co-variability of the data, and thus give another way of classifying the individual samples according to the content of different elements.

Jan 1, 1977

By Oswald J. Heinrich

THE origin of spontaneous combustion in collieries is, of course, chiefly due to bad system in laying out the pits, unclean workings, insufficient ventilation, and neglect in damming off works after they are exhausted of the main coal. This is particularly indispensable in the Richmond field, because it is difficult and dangerous here, on account of the inferior roof, to remove the last vestiges of coal ; and we are compelled also to retain all the slates and bands, as far as possible, in the pit, to help fill up, although such material is liable to fire. This, however, can be prevented to a great extent, as mentioned below. I am satisfied that the only system of working this thick coal is by cross-cutting (Querbau, ouvrage & travers) or working in benches, as practiced in France (Creusot, Rive de Gier, St. Etienne), in Silesia (Kiinigsgrube), which I have used as far as it is practicable in an old pit, almost torn to pieces by former workings. Modifications may, of course, be needed, even in the same pit, on account of irregularities in the seam. I am also satisfied for economical reasons (on account of the heavy cost for timbering) that pits here ought to be worked upwards, even if it requires a longer period of time to win the coal, and a greater outlay of capital to commence with. The various saddle-shaped " troubles " making natural minor basins in the main basin aid in the execution of this plan. A pit worked once ought to be worked out clean, given up, and dammed off forever. If sections of proper height are assumed, according to the required amount of production for a certain period of time, they ought to be worked out and filled in as much as possible, dammed off, and ultimately allowed to fill up with water, in order to protect the upper works in future from fire in the gob below. This I consider indispensable, because we may not be able profitably to fill in all the ground. To do so we have to use the waste of the mine, although it is liable to fire in time. In using this stuff, it ought to be surrounded by walls of rock not liable to take fire, laid firmly in clay, the gob being in the middle, and firmly covered and packed with clay on top. In

By Victor Homerberg

A STUDY of the correlation of the mechanical properties, and of the microstructure with the heat treatment of 60-40 brass has been confined, heretofore, to the rolled or extruded material as received from the manufacturer. The results obtained by Babson and Buhler,1 Bengough and Hudson,2 Stead and Stedman,3 and Brayton4 have been confined to the treatment of the material as received. No attempt was made to get the material into a given condition and then to work from this basis. To start with a given structure would have the decided advantage of making the work independent of the original condition, hence, to make the results reproduceable. In a previous paper, it was shown, in connection with the study of the transformation that occurs at about 470° C., that if specimens were quenched to produce the beta structure and then reheated, the beta would begin to break down, at approximately 200° C., into a very finely divided alpha. It was predicted that important results might be obtained if test pieces were to be given a similar double heat treatment and then tested for the mechanical properties as well as a study of the microstructure. The material used in the present investigation was a ¾ -in. round bar of extruded muntz metal of the following composition: Copper, 61.05 per cent.; zinc (by difference), 38.90 per cent.; lead, 0.05 per cent.; iron, trace; tin, nil.

Jan 3, 1924

By Robert S. Archer, Zay Jeffries

It is about fifteen years since the development in Germany, largely by Alfred Wilm, of the aluminum alloy called duralumin. In this alloy, combining as it does the tensile strength of mild steel with the lightness and corrosion resistance of aluminum, a distinctly new material was presented to the engineering world. Despite the evident usefulness of this material, however, its commercial development has been slow, due in part to the difficulties involved in its fabrication. In view of the potentially great utility of strong aluminum alloys, it seemed desirable to find means of producing such alloys with better fabricating properties, and work was undertaken with this object in the laboratories of the Aluminum Company of America several years ago. This work has resulted in the production of two new types of aluminum alloy of the "strong alloy" class, having distinctly improved fabricating qualities. The knowledge gained has also made it possible to produce alloys of the duralumin type with greater strength and hardness than previously obtained. There have thus been made available some new engineering materials which it is the object of this paper to describe. These alloys, induding duralumin, are fundamentally wrought alloys. Castings of the same compositions heat treated in the same manner give inferior physical properties, particularly as to ductility. The statements made subsequently concerning properties and heat treatment apply to material that has received sufficient working to thoroughly break down the cast structure. The material referred to has, in general, undergone a reduction in section of at least 80 per cent, by mechanical working. It may be mentioned in passing that other compositions have been found that are suitable for the production of the maximum physical properties in heat-treated castings.

Jan 1, 1925

By H. P. Moore, R. W. Fenn, Harold Margolin, W. R. Hibbard

DEFORMATION lines, also called etch markings or strain markings, are noneffaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries.1 Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrette to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation required for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted deformation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson' observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brick9 noted that deformation lines in 70-30 brass apparently associated with {111} planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards11 reported that in copper cold rolled less than about 50 pct few strain markings were apparent but for higher. reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass

Jan 1, 1948

By W. F. Boericke

WORLD production of silver in 1929 totaled 256 million ounces. In 1928 production was 258 million ounces, and in 1927, 254 million ounces. With an actual decrease in the amount of silver produced last year, as compared with 1928, and an increase over 1927 of less than one per cent, obviously there has been no overproduction of the metal in the popular sense. But the price of silver tells a different story. For 1927, the average quotation was 56.37 cents; it was 58.17 in 1928, and 53.0 in 1929. During the last year it reached a high point of 57 cents in January, and fell steadily, without interruption to the downward trend, to a low of 47 cents in December. Since then it has dropped to an all time low of 43 cents on February 6.

Jan 1, 1930

By Adrian Brown

Over the last decade, a number of large slopes have been excavated in rock which contains families of joints or faults which dip steeply into the cut slope. Despite the absence of "adverse" structures, these slopes have exhibited alarming movement rates at very modest heights (as little as 100 meters) and slope angles (as little as 20º). Classical stability analysis suggests that such slopes should be unconditionally stable. This paper describes the toppling mechanism which has been found to be the cause of the observed movements and develops a general method for analysis of it. Simple cases are analyzed in order to provide charts which allow quick evaluation of the likelihood of this phenomenon occurring. The safety implications of such movements in slopes are also examined.

Jan 1, 1982

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By H. C. Theuerer

EVEN the highest purity silicon available for semiconductor use contains significant amounts of donors and acceptors, usually aluminum, phosphorus, and boron. Aluminum and phosphorus can be removed from silicon by adaptations of the zone refining techniques' widely used with germanium. Removal of boron, however, has been a difficult problem. The approximate distribution coefficient for boron in silicon is 0.8, so that while zone refining is possible, it is not very effective in any reasonable number of passes. It has been found, however, that boron can be effectively removed from silicon by treatment of a liquid zone with hydrogen and water vapor. Starting with 40 ohm-cm, n-type silicon, use of zone refining coupled with hydrogen

Jan 1, 1957

By J. C. Smock

The primitive mode of mining clay by open workings, in which the overlying beds of earth (commonly termed the " bearing ") were removed, and the clay then dug out by sinking shallow pits, is still the prevalent and almost universal mode of extraction. This is particularly true of our cretaceous and tertiary clays, which are generally earthy in character, and but slightly covered by drift and alluvium. The most accessible beds in many of our clay districts have been worked out, and clay miners are compelled to search for new outcrops, or to remove thicker beds of top dirt or bearing. Under this stimulus subterranean working, or mining proper, has been suggested. A brief notice of this new mode, as employed by Mr. Otto Ernst, near the head of Chesquake's Creek, three miles south of South Amboy, New Jersey, is here presented for your consideration. Previous to mining, the old mode of extraction, digging pits, was found to be too expensive, in' consequence of the heavy amount of top dirt and the excessively large amount of water in these overly

By J. C. Smock

THE primitive mode of mining clay by open workings, in which the overlying beds of earth (commonly termed the "bearing") were removed, and the clay then dug out by sinking shallow pits, is still the prevalent and almost universal mode of extraction. This is particularly true of our cretaceous and tertiary clays, which are generally earthy in character, and but slightly covered by drift and alluvium. The most accessible beds in many of our clay districts have been worked out, and clay miners are compelled to search for new outcrops, or to remove thicker beds of top dirt or bearing. Under this stimulus subterranean working, or mining proper, has been suggested. A brief notice of this new mode, as employed by Mr. Otto Ernst, near the head of Chesquake's Creek, three miles south of South Amboy, New Jersey, is here presented for your consideration. Previous to mining, the old mode of extraction, digging pits, was found to be too expensive, in' consequence of the heavy amount of top dirt and the excessively large amount of water in these overly-

Jan 1, 1875

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the re crystallization temperature of nickel has been investigated. All additions raised the re crystallization temperature. Both the rate of change of re crystallization temperature with at. pet solute and the limit of initial linearity are found to correlate with the free atom ground state outer electron configuration of the solute element. A comparison of all of the correlations for the transition elements studied has yielded a set of empirical relations, which allows the prediction of the effect of dilute binary transition elements on the recrystallization temperature of other transition elements. The work of Abrahamson, et al.1-7 on dilute binary solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and re-crystallization temperature. Further, it has been shown3,4 that the limit of initial linearity may also be correlated with the solute electron configuration. Since previous studies have dealt with bee and hexagonal base elements, this study is made to note what effect, if any, the fee base structure might have. Nickel also serves to give a solvent configuration which will allow the comparison of all of the transition element solvents. Olsen8 has studied the effect of some trace elements upon the recrystallization of nickel. He included only Ti, Zr, W, Mn, and Co of the transition elements. The differences in change of recrystallization temperature were attributed to the solute atom size and to the solubility of the solute in nickel. PROCEDURE All alloys were made using 99.9 + pet Ni with 0.003 C, 0.015 Fe, 0.007 0, and 0.0007 H. The solute elements were 99.9 + pet pure. According to the published binary phase diagrams9 and metallo-graphic examinations at X750, all solute elements were in solid solution. The alloys were arc melted and remelted four times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot forged at 800oC to 0.750 in. diam, machined to 0.60 in., vacuum annealed for 1 hr at 700°c, swaged to 0.40 in. and annealed at 700oC for 1 hr in vacuum. The grain size was checked and found to be 77 * 20 grains per sq mm. The specimens were then swaged to 0.187 in., yielding 76 ± 1 pet cold work. All alloys were then chemically analyzed for the solute addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The swaged rod was cut into 8.25 in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was maintained at 250" to 850°C over an eight inch length, recorded by twelve thermocouples. Control was ± 3oC, accomplished at the hot end. The recrystallization was determined metallo-graphically over the entire specimen. The criterion chosen was that point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be generally ± 3oC.

Jan 1, 1962

By L. L. Wyman

IN order to clarify and amplify the existing data concerning the action of the cementing material in cemented tungsten carbide alloys, the authors have initiated this investigation of the entire range of cobalt-tungsten carbide alloys. Inasmuch as the ultimate objective is relative to what actually goes on during the sintering of cemented tungsten carbide materials, this work was necessarily restricted to heat treatments similar to those used in actual production of these materials. In the course of numerous experiments, the authors have noted several conditions that indicated that there was a solubility to be considered. Among these factors are the following: 1. Many of the alloys showed a much larger amount of binding constituent to be present than could possibly be accounted for by the cobalt content. 2. In many areas, grains of the carbide constituent are much larger than the particles of carbide originally added. In addition, these grains are of very regular contour. 2a. In samples of cemented tungsten carbide which had been fused in the atomic hydrogen torch in the presence of excess hinder constituent, immense grains are formed, and their shapes are very regular. This is also true when the cemented tungsten carbide of 13 per cent. Co content is fused alone in the atomic hydrogen torch. Contrary to general expectation, chemical analysis of this material, after fusion in the atomic hydrogen torch, checks the analysis of unfused material. 3. In making the cemented tungsten carbide materials by the process of exerting the pressure at the time of heating a certain portion of the contents squeezed out of the mold. Chemical analysis has shown that this material contains approximately 12 to 20 per cent. of tungsten. The microstructure shows a cored dendritic structure interlaced with eutectic network, and some graphite, as shown in Fig. 1. 4. Thermal analysis of these materials has consistently indicated an arrest point close to 1350° C.

Jan 1, 1930

By AIME AIME

MINERALS and mineral resources are recognized as one of the things that nations are prone to quarrel about. The territory that was arbitrarily incorporated into the Polish Republic after the World War produces a variety of essential minerals on a substantial scale. The accompanying table has been compiled to give some idea of the relative importance of this production. Poland, before the recent war started, had an area of 150,000 sq.mi., just a little larger than the State of Montana. Its population was 32,000,000, equal to that of New York, New Jersey, Pennsylvania, Connecticut, and Massachusetts. Though not a highly industrialized country it nevertheless has important mines, steel plants, petroleum refineries, and sundry metal-fabricating manufactories. Coal, petroleum, iron and steel, zinc, lead, pyrite, potash, and salt are produced in excess of the country's domestic consumption. It has no appreciable production of copper, chromium, tungsten, nickel, tin, mercury, manganese, aluminum, magnesite, fluorspar, or graphite.

Jan 1, 1939

By A. J. Conelius, D. P. Sobocinski

This paper presents a correlation for predicting the behavior of a water cone as it builds from the static water-oil contact to breakthrough conditions. The correlation is partly empirical and involves dimensionless groups of reservoir and fluid properties and of production and well characteristics. The groups were deduced from the scaling criteria for the immiscible displacement of oil by water. The correlation is based on a limited amount of experimenfal data from a laboratory sand-packed model and on results from a computer program for a two-dimensional, incompressible system. Because the correlating groups are dimensionless, they can be used to estimate the performance of water coning cases not specifically considered in the correlation. However, despite its dimensionless nature, the correlation is not completely general and will not provide meaningful estimates of cone behavior in many situations. INTRODUCTION AND BACKGROUND The production of water from oil wells is a common occurrence which increases the cost of producing operations and may reduce the efficiency of the depletion mechanism and the recovery of reserves. We will deal with one cause of this water production, namely, coning. The coning of water into a producing well is caused by pressure gradients established around the wellbore by the production of fluids from the well. These pressure gradients can raise the water-oil contact near the well where gradients are most severe. Gravity forces that arise from fluid density differences counterbalance the flowing pressure gradients and tend to keep the water out of the oil zone. Therefore, at any given time, there is a balance between gravitational and viscous forces at points on and away from the completion interval. When the dynamic forces at the wellbore exceed gravitational forces, a cone of water will ultimately break into the well to produce water along with the oil. We can expand on this basic visualization of coning by introducing the concepts of stable cone, unstable cone and critical production rate. For instance, if a well is produced at a constant rate and the pressure gradients in the drainage system have become constant, a steady-state condition is reached. If, at this condition, the dynamic forces at the well are less than the gravity forces, then the water or gas cone that has formed will not extend to the well. Moreover, the cone will neither advance nor recede, thus establishing what is known as a stable cone. Conversely, if the pressure in the system is in an unsteady-state condition, then an unstable cone will continue to advance until steady-state conditions prevail. If the flowing pressure drop at the well is suffcient to overcome the gravity forces, the unstable cone will grow and ultimately break into the well. It is important to note that in a realistic sense, stable cones may only be "pseudostable" because the drainage system and pressure distribution generally change. For example, with reservoir depletion, the water-oil contact may advance toward the completion interval, thereby increasing chances for coning. As another example, reduced productivity due to well damage requires a corresponding increase in the flowing pressure drop LO maintain a given production rate. This increase in pressure drop may force an otherwise stable cone into a well. The critical production rate, well known in the literature, is the rate above which the flowing pressure gradient at the well causes water (or gas) to cone into the well. It is, therefore, the maximum rate of oil production without concurrent production of the displacing phase by coning. At the critical rate, a built-up cone is stable but is at a position of incipient breakthrough. Numerous papers have been published on critical rates. Some of the better known of these include the work of (1) Muskat and Wyckoff,' who first dealt with the coning problem; (2) Chaney, et al,' who developed expressions similar to those of Muskat but who presented results in a conven ient-to-use graphical form (the "Sun" method); and (3) Meyer and Garder,b hose analysis is based on radial-flow formulas. One assumption in critical production rate analyses is that the cone has built-up to just before its breakthrough into the well. But, these analyses reveal nothing directly about the time it takes for the cone to build up to this incipient breakthrough position. Thus, water-free oil can be produced from a well for prolonged periods at rates above the critical rate before the well reaches the condition to which the critical rate applies. The published literature contains little on the rate of growth of a cone. Experimentally, Meyer and Searcy studied the rate of rise of a cone in a Hele-Shaw model.' Additional related work on water breakthrough and produced water-oil ratios in water driven reservoirs was reported by Muskat," Hutchinson and Kemp," Henley, et al,' and Stevens, et a1.B Theoretically, the basic coning equations for a water-oil system can be developed by applying the conservation of mass to each of the phases, relating flow velocities with pressure by Darcy's law, and relating pressures across water-oil interfaces by capillary pressure. With the usual boundaries at the well and reservoir limits, the solution of the resulting equations for the time behavior of a water-oil interface constitutes a free-surface, boundary-value problem. The shape of the boundary depends on the internal potential distribution, while this

Jan 1, 1966

By C. S. Finney, John Mitchell

On December 31, 1959, there existed in the United States 15,993 slot-type coke ovens capable of producing 81,447,700 net tons of coke. These ovens were concentrated in 74 coke plants in 21 different states. As of the same date, there were 7448 beehive ovens in existence at 45 plants in the states of Pennsylvania, Virginia, West Virginia, and Kentucky. Total annual capacity of the existing beehive ovens was 4,368,800 net tons, but only 5148 ovens with a capacity of 3,131,600 tons were in operating condition. It is interesting to compare the average dimensions of slot-type ovens built during recent years with the 30 ft x 5 ½ ft x 16 ½ in. ovens erected at Syracuse, N. Y. in 1892. A composite oven built according to the average dimensions of all those erected between 1954 and 1958, for instance, would be 39 ft long. 12 ft high, and 18 in. in width. The coal capacity would be 16 tons as against the 4.4 tons which could be charged to the Syracuse ovens. Of the 15.993 slot- type ovens in existence at the end of 1959, by far the greater number were built by the Koppers Co. whose total of 11,280 ovens included 7891 Koppers- Becker and 3389 Koppers ovens. Of the remainder, there were 3260 Wilputte, 1350 Semet-Solvay, 63 Otto, and 40 Simon Carves ovens. By-product coke oven plants are usually classified either as furnace or merchant plants. According to the definitions used by the US Bureau of Mines, the former are "those that are owned by or financially affiliated with iron and steel companies whose main business is producing coke for use in their own blast furnaces. All other coke plants are classified as merchant. They include those that manufacture metallurgical, industrial, and residential heating grades of coke for sale on the open market; coke plants associated with chemical companies or gas utilities; and those affiliated with local iron works, where only a small part (less than 50 pct of their output) is used in affiliated blast furnaces." The annual coke capacity of the merchant plants during 1959 was 10,393,000 tons. However, the by-product oven of today is essentially an appurtenance of the iron and steel industry, rather more than 87 pct of total by- product coking capacity being concentrated at furnace plants. This was not always so. There was a time when the merchant plants played a much greater part in meeting the US demand for coke and gas. High noon for the merchant plants was reached during the early 1930's. By 1932 there were as many by- product oven installations being operated by the merchant sector of the industry as by the coke divisions of the iron and steel industry (44 of each), and in the same year the merchant plants produced 46.5 pct of all by-product coke made in the country. Since that time their contribution has drastically declined. In 1940 merchant plants were responsible for only 23.2 pct of total US production, and by 1950 their number had decreased to 30 plants which turned out 18.5 pct of the total by-product coke made. At the end of 1959 only 20 of the 74 existing by-product oven installations were merchant plants. They ac- counted for 12.5 pct of the year's production, or 6,849,786 net tons. This percentage has remained fairly constant since 1954. There are several reasons for the decline of the merchant coking industry. For example. On the grounds of economy, quality control, continuity of supply, and so on, the iron and steel industry usually prefers to control its own mines and carbonize its own coal at or near to the blast furnace rather than rely on independent operators for metallurgical coke. As the steel companies have enlarged their own coking facilities, so has the need for coke obtained from other sources declined. Furthermore, not only has the steel industry increased in self-sufficiency by building mare coke ovens during recent years, but it has also progressively improved the fuel efficiency of its blast furnaces. During the years 1947-49 the average coke consumption per ton of pig iron was 1892.8 lb. During 1958 the corresponding figure was 1613.4 lb. There are many individual furnaces where still better results are being obtained, and further reductions in the average may be expected. Perhaps the greatest threat to the merchant coking plant has been the fantastic increase in the use of natural gas and petroleum products for purposes which manufactured gas once served. So deadly has the com- petition from natural gas and oil been that it has almost eliminated by-product oven installations owned by public utilities. In the peak years of the early 1930's there were 23 such public utility plants. In 1960 only two were left. One of these, owned by the Citizens Gas and Coke Utility, was at Indianapolis, Ind.; the other was the plant operated by the Philadelphia Electric Co. at Chester, Pa. The non-utility merchant plants have also been sorely hit. With gas sales revenues reduced, domestic

Jan 1, 1961

By B. J. Yamada, D. W. Fuerstenau

Long-chained neutral molecules (decyl alcohol) increase the flotation of corundum with sodium dodecylsulfate and trimethyldodecylammonium chloride as collectors. This phenomenon is postulated to result from coadsorption of the neutral molecules with the collector ions. Flotation and streaming potential experiments have shown that sodium laurate is an effective collector for corundum at more dilute concentrations than sodium dodecylsulfate or sulfonate.1>2 It has been postulated that this phenomenon results from the adsorption of both laurate ions and lauric acid molecules, whereas sodium dodecylsulfate can be adsorbed only as dodecylsulfate ions, since this collector does not hydrolyze under flotation conditions. Similar effects have been observed in alkaline solutions with dodecylammonium chloride and trimethyldodecylammonium chloride as collectors.' If in- creased flotation occurs with the collectors which hydrolyze because of adsorption of the neutral molecules, purposeful addition of long-chained molecules should increase the flotation rate of minerals with such collectors as sodium dodecylsulfate or trimethyldodecylammonium chloride because these long-chained molecules should coadsorb with the collector ions. The effect of neutral molecules on flotation in these cases must depend on an adsorption mechanism which differs from that proposed by Cook for the adsorption of xanthic acid molecules by galena. For neutral molecules to function as collectors in the flotation of insoluble oxide minerals, adsorption of organic ions must first occur to provide a means of anchoring the fatty acid or amine molecules. Without adsorption of collector ions, flotation does not occur even in the presence of large quantities of neutral molecules, as is indicated by the cessation of flotation at low pH values with soaps as collectors or at high pH values with primary amine salts as collectors.' Neutral molecules, such as fatty acids, must be adsorbed through van der Waals attraction between the hydrocarbon chains of the adsorbed soap ions and the hydrocarbon chains of the fatty acid molecules. The mutual association of hydrocarbon chains results

Jan 1, 1962

By L. G. Schulz, P. Spiegler

The electrical resistivity and the temperature coefficient of resistivity were measured with a potentiometric method using pure mercury as a reference material. Measurements were made nea,v roorn temperature. A detailed study was made of Hg,TI, near its melting temperature. THE work to be described was originally undertaken to provide the necessary data for interpreting the results of some optical experiments,' but because of the growing importance of liquid metals,273 it appeared that the results of the resistivity measurements should be published separately. For convenience the alloys selected were those which are liquid at room temperature. Special consideration was given to the Hg-T1 alloy closely corresponding to Hg,Tl, because recent X-ray diffraction results of Smallman and Frost seemed to show that the solid structure may persist to some extent into the 1iquid. EXPERIMENTAL PROCEDURE A potentiometric method was employed in which the resistivity of mercury was used as a reference. The essential features of the samples are shown in Fig. 1. A capillary tube CT with a bore of approximately 1.5 mm was fitted into two end cups, T, which were made of Teflon. A pair of current electrodes CE were immersed into the excess liquid metal which partly filled the end cups. The potential electrodes PE were inserted into CT through short pieces N of a no. 18 hypodermic needle held in place with Saureisen cement SC. As shown, the lower ends of the PE7s were reduced in diameter to 0.25 mm to minimize the distortion of the liquid metal cross section. Several methods were used to insert an alloy into the sample, but the usual one with mercury alloys was to fill the sample container with a weighed quantity of pure mercury* and then add weighed the sample tube in a vacuum. Because of rapid corrosion, samples containing gallium were of necessity prepared in a vacuum. To obtain the specific resistivity of an alloy the resistance of the sample containing the alloy was measured and compared with the resistance when the container was filled with mercury. Resistances were measured in the temperature range of 20" to 60°C to obtain the temperature coefficient of resistance. The electrical measurements were made by connecting the sample in series with the standard one-ohm resistance, and the potential drop measured alternately over the sample and the standard resistance. To correct for stray thermoelectric effects provision was made for reversing the direction of the current, and the true potential drop was taken to be the average of that obtained for the two directions of current flow. Various materials were used for the electrodes, the most uniform results being obtained with nickel. EXPERIMENTAL RESULTS The numerical results are presented graphically in Figs. 2 and 3 and in tabular form in Tables I and 11. Following are remarks on results of individual alloys. 1) Hg-In—This was the first alloy studied, and

Jan 1, 1960