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By C. K. Dumbauld, B. E. Morgan

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By C. S. Smith, Chih-Chung Wang

D. Turnbull—In the opinion of the writer the most interesting result described in this paper is that the distribution of tin with respect to solidification temperature has several fairly well-defined maxima. It appears that each peak may be associated with a catalytic impurity of some rather specific composition. Recently we have obtained some additional evidence in favor of this viewpoint in experiments on the supercooling of lead droplets coated with different surface films. The distribution of lead droplets, ostensibly coated with lead sulphate, with respect to solidification temperature exhibited two distinct and reproducible maxima, one at 20" supercooling and the other at 47". On the other hand, when the droplets were ostensibly coated with halide films, no solidification was perceptible until the aggregate was supercooled more than 55". Upon further cooling a single well-defined peak centering at 60" supercooling was observed. Since the particle size distribution was the same in these two sets of experiments it appears that the most reasonable interpretation of the results is that the sulphate surface film or its reaction products with lead are much more effective in catalyzing the nucleation of lead crystals than are lead halide films. C. S. Smith (authors' reply)—Dr. Turnbull's experiments with lead drops coated with various surface films are most interesting. However, before drawing conclusions from the cooling curves described in the paper as to the existence of a few nucleus types effective at a few different temperatures, one must consider the state of subdivision of the liquid metal. In the A1-Sn alloy used, the tin was not in uniform droplets but tended to collect in three distinct shapes—in long interconnecting prisms along grain edges, in somewhat elongated interdendritic branching pools. and in isolated droplets. A single nucleus will solidify only the metal in contact with it, and the heat evolved will be proportional to the connected volume. A uniform distribution of nuclei of random effectiveness in such an alloy will cause peaks on the specific heat curve on cooling, which correspond to the volume distribution of tin and tell nothing about the nucleus type. In any real alloy both effects will be combined, and it seems impossible at present to distinguish between them. M. B. Bever—The thesis of this interesting paper is supported by a combination of positive and negative evidence. The authors have shown that under certain conditions a liquid phase may undercool, if it is dispersed in a thoroughly discontinuous manner throughout a solid matrix. They also found that undercooling

Jan 1, 1951

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1951

The United States has not begun commercial operations to tap its largest poten-tial sources of oil supply - oil shale and coal. The reason is that domestic petrol-eum has been plentiful in the past and liquid products probably could be produced from it at the lowest cost. In view of the ever-increasing need for petroleum in the United States, the critical international situation threatening foreign supplies, the growing demands for steel, and the heavy costs to industry of constantly discovering and developing new oil fields, it is believed that the prompt development of a synthetic fuel industry based on oil shale and coal is not only requisite to safeguard our oil supply but is an economically sound course for the foreseeable future. To neglect its development is to close our eyes and minds to our own resources at a time when they are needed critically. It also is apparent now that neither the Government nor industry would be taking any considerable economic risk in starting the initial plants, especially as measured against their potential value in meeting critical oil and chemical demands and in building a new industry in the West.

Jan 1, 1951

Jan 1, 1951

By John Griffen

This paper records over twenty years' experience with the use of the Rheolaveur system in the United States, showing its ability to meet changing conditions caused by the dirtier mine output of present-day mechanical mining methods. Data are given on size ranges handled, number and capacity of units installed, maintenance experience, and operating results on two-product and three-product separations. IT is not the purpose of this paper to discuss the principles employed in the Rheolaveur system of fine-coal cleaning as these have been fully covered in the technical literature of the Institute."2 Rather, our purpose will be to record the highlights of over 20 years' experience in the United States with Rheolaveur fine-coal launders, which will indicate their capabilities and costs of cleaning and their adaptability to meet the changing conditions caused by present-day mechanical mining methods. Rheolaveur fine-coal launders are used in the United States to treat a wide variety of size ranges of fine coal, the coarsest being 1/2 in. to 0 and the finest about 1/8 in. to 0. In Europe feeds as coarse as 5/8 in. and as small as 1/2 mm (28-mesh) to 0 are being cleaned. The size ranges usually handled in this country are 3/8 to 1/4-in. round to 0. Thirty five units with a combined hourly feed capacity of 3200 tph have been installed in the United States. Individual units are cleaning as little as 25 tph, while others are cleaning as much as 200 tph. Rheolaveur fine-coal launders offer cleaning units of high capacity and are outstanding in requiring a minimum of building space per ton of input. Experience has shown that maintenance costs are low. Several installations were made in the Pittsburgh district from 1928 to 1930, and since that time operation has been largely two shifts per day. Minor repairs to liner plates and Rheo boxes have been required during the intervening years, but no major replacement of launders was required until 1947 and 1948. At one of these plants, launders operated for 17 years before they were replaced and during that period over 26,000,000 tons of —5/16-in. coal were cleaned. The effect of the much dirtier raw coal produced by mechanical loading of the Pittsburgh seam is shown by the following tests. The data in table I summarize the performance of a Rheo fine-coal unit when cleaning hand-loaded raw coal. The —4-in. raw coal fed to the cleaning plant analyzed only 8.16 pct ash and 1.31 pct sulphur and contained 4.6 pct sink, 1.55 sp gr. Two years later, in 1945, mechanically-loaded coal from the same mine was cleaned in the same plant. The feed, —4 in., then analyzed 20.10 pct ash and 1.53 pct sulphur and contained 20.2 pct sink, 1.55 sp gr. The performance of the Rheo fine-coal unit when cleaning this coal is given in table 11. It will be noted that the +48-mesh coal is cleaned almost as thoroughly as in table I. The large amount of high-ash slimes produced from the dirtier feed are responsible for the higher ash of —--48-mesh washed coal in table 11. In this plant the Rheo fine-coal unit did not get the full load of refuse resulting from mechanical

Jan 1, 1951

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By D. C. Hilty, W. Crafts

Determination of the solubility of oxygen in iron containing silicon, or manganese, or both, has confirmed the earlier work on silicon, shown that manganese is more effective than expected, and has demonstrated that the combination of silicon and manganese is a much stronger deoxidizer than might have been inferred from their individual effects. SILICON and manganese are of primary impor-tance in the deoxidation of steel, and a study has been made at the Union Carbide and Carbon Research Laboratories, Inc. of the solubility of oxygen in iron in the presence of silicon and manganese, singly and in combination, as a basis for more effective control of inclusion formation. The investigation was carried out with the same equipment and experimental procedure that were used in the determination of the oxygen solubility of iron containing aluminum'. The heats were melted in a rotating crucible furnace under an argon atmosphere. Bath temperatures were controlled by platinum/platinum +10 pct rhodium thermocouples to attain equilibrium at 1550°, 1600°, and 1650°C, so that oxygen solubility isotherms were determined directly without requiring calculation from a temperature coefficient. A detailed description of the furnace and procedure is given in the paper on aluminum deoxidation1. Oxygen solubility in the presence of more than 0.10 pct silicon was found to approximate earlier determinations closely, but some deviation was observed at lower silicon contents. Manganese appeared to be more effective than had been anticipated. The combination of silicon and manganese lowered the solubility for oxygen markedy as compared with either silicon or manganese alone. Although the solubility for oxygen in the presence of both silicon and manganese represents only a part of the information needed to control inclusion formation, it suggests a partial explanation of the benefits of this combination that have been observed in practice. Manganese and Oxygen in Liquid Iron: The study of oxygen in iron in the presence of manganese was carried out in magnesia crucibles of the type furnished commercially for laboratory induction furnaces. Alumina crucibles were unsatisfactory, because the work on the aluminum-oxygen equilibria in iron' had shown that merely melting iron in an alumina crucible limited the solubility of oxygen to a level considerably below that anticipated for moderate concentrations of manganese. Silica crucibles appeared unsuitable because of the dangers of excessive fluxing by the melt. Moreover, as will be shown later, melting iron in a silica crucible also limits the oxygen content below that in equilibrium with

Jan 1, 1951

By R. E. Kennedy

The presence of combustible gases and vapors in air can constitute n extremely serious explosion hazard. This hazard is even greater when explosive mixtures are confined under high pressures, as the pressure can become tremendous immediately before the container is ruptured. Because of its interest in safety in mining and. allied industries, the U. S. Bureau of Mines has investigated the explosive properties of a number of gaseous and liquid compounds; the results of these investigations have been published in various government papers and journal articles. The increased use of liquefied, petroleum gases has intensified interest in the effect of high pressures on the explosibility of propane-air mixtures. The limits of flammability of natural gas-air mixtures have been determined at pressures ranging from 50 min. Hg to 3,000 p.s.i. As it is known that a combustible. gas or vapor cannot burn or explode when the oxygen content of the atmosphere is less than a certain value, critical values were determined for the oxygen content of atmospheres to which nitrogen had been added as a diluent. In this connection limits of flammability were determined for ethane in atmospheres containing added. nitrogen or carbon dioxide at pressures up to 900 p.s.i.g.

Jan 1, 1951

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

H. Schwartzbart and W. F. Brown, Jr.—The authors have divided the effects of recovery on the true stress-true strain curve into two types; metarecovery, which effects only the first part of the curve or the yield strength, and orthorecovery, which effects the flow stress at any strain. Both of these are said to be true recovery effects, involve no recrystallization, and are explained by the removal of two different types of imperfections caused by work hardening. However, there seems to be some question as to whether the data are sufficiently conclusive to exclude, as an explanation of the authors' results, a mechanism based on the relief of residual stresses between the grains or slip bands and recrystallization. It appears that metarecovery could be interpreted in the same fashion as a customary interpretation of the Bausch-inger effect. The balanced system of internal stresses which exists between grains in a strained specimen due to varying orientation and, hence, yield strengths, of the different grains is responsible for a reduced yield strength in compression following pre-tension, and, similarly, for an elevated yield strength in tension following pre-tension. If the specimen is now heated so that the internal stresses are relieved by creep, then the yield strength in tension following tension will have been reduced and in compression following tension will have been raised. There seems to be a very strong case for the lack of recrystallization in the aluminum investigated by the authors, if one defines recrystallization as the presence of visually detectable new grains or accepts the X-ray evidence as conclusive. One must remember, however, that the appearance of spots on the back-reflection X-ray patterns cannot be taken as the time when recrystallization first started. The areas of recrystallized strain-free material must first have grown to a size large enough to give distinct spots on the patterns and this may take some time. Averbachl7 in an investigation of brass has shown that recrystallization can be detected by extinction measurements at temperatures lower than those based on hardness or X-ray line width determinations. It can be seen from fig. 10 that the rate of recrystallization is extremely low over a considerable time period at the onset of the process. Observations on the rate at which small amounts of recrystallization effect the flow stress would have given further insight as to whether undetectably small amounts of recrystallization might have been responsible for orthorecovery. Also, the question arises as to whether the effects observed in fig. 6 for various times and temperatures could not have been obtained if the time at 212°F were sufficiently long. In addition, the argument that the curve in fig. 10 is not sigmoidal seems weak in view of the scattering of the points. It is conceivable that an accurate determination of the curve for the first 100 hr would exhibit a relationship other than the one drawn. There is one point we would like to raise about the condition of the starting material. The authors annealed their material at 750°F for 15 min to remove the effects of any previous work hardening or machining strains. Reference to the work by Anderson and Mehl shows that this treatment may not have completely recrystallized the aluminum, so that the starting material may have had some strained areas. Higher temperatures or longer times may have been required to remove the effects of any small strains. We would like to mention some results of tests being conducted at the Lewis laboratory of the National Advisory Committee for Aeronautics in an investigation of the Bauschinger effect in relation to fatigue. Tests were performed on annealed electrolytic copper and several annealed brasses. Specimens were pre-strained 1 pct in tension and then tested in compression or tension with and without intermediate stress-relieving annealing treatments at 500°F for various times. Specimens heated at 500°F for 10 1/2 hr showed an elevation of the flow curve in compression and an approximately equal lowering of the flow curve in tension when compared with the curves for the un-heat treated specimens. After approximately 0.8 pct strain, all flow stresses coincided and were equal to the flow stress of the virgin material at this strain. This behavior is consistent with the metarecovery observed for aluminum by the authors and for which a residual stress model can be used. On the other hand, increas-

Jan 1, 1951

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

The Writer's knowledge of this region began in 1912, while he was with the Geological Survey of South Australia, and, investigated the principles governing the occurrence of fresh and saline ground waters in the area then being opened for closer settlement by the railways under construction from Port Lincoln.These field investigatons for water were extensive rather than intensive, but other examinations covered certain mineral aspects. The Writer also has' had the benefit in the preparation of this paper, of later work done by others, as well as of the monumental earlier work in South Australia by the late H. Y. L. Brown.AREAThe area dealt with, approximately 21,000 square miles, lies to the south of the latitude of Port Augusta.TOPOGRAPHYAs a whole the region is one of low relief, but the Olinthus Range, west of Cowell and north of Cleve, reaches an elevation of 2,000ft., while there is als0 a high area west of Port Lincoln and Tumby Bay. At the north end of the region the Gawler Ranges are formed by the dissection of a thick sheet of felspar porphyry extending over two degrees of longitude, by a width of 20 to 70 miles, with fairly uniform maximum elevations of the undissected portions of the order of 1,000 ft. above sea level. South of the Gawler Ranges are many isolated ridges up to 1,000ft. in height, generally sedimentary and trend...

Jan 1, 1951

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By R. Ruka, E. A. Gulbransen

ONE of the interesting questions in the understanding of the reaction of iron with oxygen is the kinetics and the mechanism of the crystal structure changes occurring in the formation and breakdown of the oxide film. In a recent work' the electron diffraction method was applied to the study of the solid phase reactions occurring internally in the oxide film on iron above 570°C and under vacuum conditions. The higher oxides which form under oxidizing conditions are reduced internally by the diffusion of iron into the oxide leaving the bulk of the oxide FeO (wüstite). This paper will ask and consider three questions. These are: (1) What is the nature of the depressed transformation temperature for the Fe3O4 + Fe ? 4Fe0 reaction in very thin oxide films?; (2) What is the mechanism of the forward transformation of Fe3O4 to FeO at or near 570°C?; and (3) What is the nature and mechanism of the slow reverse transformation of FeO to Fe3O4 and Fe below 570°C?. The composition of the oxide as well as its electrical, magnetic, mechanical, and chemical properties depends upon the kinetics of these reactions. Literature Survey The composition of the oxide film on pure iron at temperatures up to 570°C has been studied extensively by the electron diffraction method. Nelson,' Jackson and Quarrell,3 and Gulbransen and Hick-man4 have shown that Fe3O4 and a-Fe2O8 are formed in the temperature range of 225" to 570°C, while y-Fe,O, is most likely formed below 225°C for long oxidation times. In very thin films FeO (wüstite) is found to form at temperatures as low as 400°C, and its existence depends essentially upon the extent of initial oxidation. FeO is not found in the formation of thick films below 570°C. On the other hand X-ray5 and micrographic8 studies show that Fe3O4 may exist as the main com-ponent in thick films up to 650°C, well above the equilibrium temperature for the reaction Fe3O4 + Fe ? 4FeO. The kinetics of the forward and reverse trans-formations of the reaction Fe3O4 + Fe ? 4FeO have not been studied in oxide films. However, analysis of the data of Gulbransen and Hickman4 on the heat-ing and cooling of iron oxide films of known thick-nesses in high vacua shows that the forward reac-tion proceeds rapidly even for a 4000 A film at temperatures of 575" to 600°C. The reverse reaction or decomposition of wüstite (FeO) occurs at tem-peratures below 450°C. Thus, there appears to be a slow process in the decomposition which is in marked contrast to the rapid forward reaction. The decomposition of a bulk sample of FeO free from the metal has been studied extensively by Chaudron, Benard and coworkers using the micro-graphic, X-ray diffraction, and thermomagnetic methods. Chaudron7,8 first observed that the de-composition of FeO (wüstite) below 570°C occurs by the reaction 4FeO ? Fe3O4 + Fe. Later work by Chaudron and Forestier5 showed that the rate of de-

Jan 1, 1951

By Paul M. Tyler

Higher freight rates and better methods of beneficiation now may make it more economical to open inferior deposits closer to a glass factory than to work higher-grade deposits farther away. Nature of impurities and special treatments as well as common practice of sulphuric acid leaching are described. HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for substandard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade silica sand are abundant, but most of the best deposits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.O.b. cost of mining and treatment may be much higher than at a higher grade deposit farther away. Particle-size distribution is a feature of glass-sand specifications. As long as glassmakers insisted upon having their sand principally coarser than 100-mesh, any material was automatically excluded from consideration that could not be purified without fine grinding or other drastic treatment which greatly reduces the size of the quartz grains. However, re- cent large-scale tests in Norway' showed that finely-crushed quartz used in a soda-lime-silica glass batch caused it to melt and become refined appreciably faster than when ordinary coarse (Belgian) sand was employed. Dust losses were negligible. Since the pre-war cost of sand was only 3 pct of the manufacturing cost of the glass, it was deemed economical to pay twice as much for crushed quartz because of the saving in wear and tear on the furnace walls. In the author's unverified opinion, sand ranging in size between 150 and 400-mesh would probably be superior to that in the more usual range of 20 to 100-mesh. Former objections to fine sand (other than dust) were doubtless fostered by the natural concentration of impurities in the finer sizes. Ordinarily the most objectionable, as well as the commonest, impurity from the standpoint of the manufacturer of any but the cheaper qualities of colored glass is iron. No natural sands are really pure silica. Even water-clear quartz crystals are likely to contain impurities in the form of solid solution as well as inclusions which cannot be eliminated except by chemical treatment that will break down the silica lattice. Pure white pegmatite quartz will usually analyze 0.01 pct or more of iron oxide, and ordinary vein quartz and the quartz grains in most

Jan 1, 1951

By Harlowe Hardinge, R. C. Ferguson

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,' believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months' test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors' reply)—For one, I heartily agree with Mr. Johnson's opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one's figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer's analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By System By John E. Owen, Walton J. Greer

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By H. Rush Spedden, Arvid Thunaes

Pilot plant test work in 1942 and 1943 showed that by a combination of deslim-ing, fine-size classification, and Sullivan deck concentration it is possible to recover heavy minerals such as cassiterite at least as fine as 10 microns in size. This appreciable improvement in gravity concentration practice has been substantiated by several full-sized plants. IN the past, mills treating ores of tin and tungsten by gravity concentration have recovered very little mineral finer than 325 mesh, although some form of slime concentration has been generally attempted by the use of buddies or round tables. This paper describes a series of pilot plant tests made in 1942 and 1943 in which the use of the Sullivan deck was investigated for the recovery of an appreciable amount of the fine values formerly lost. The investigation was initiated by the U. S. Government in an effort to increase the wartime production of tin. Bolivian milling practice at that time included jigging of the coarse sizes, tabling of the intermediate sizes on conventional shaking tables, and the use of buddies or round tables on the finest sizes. Flotation of the pyrite was employed at different stages of the treatment, depending upon the quantity present and the preference of the operator. Usually good recoveries and the bulk of the production were made in the jigging and tabling operations provided that these sections were not overloaded. Buddies and round tables were used for a small additional recovery if it could be shown that they could pay for their high cost of operation. Extensive test work established that by a combination of desliming, classification, and Sullivan deck treatment, cassiterite as fine as 10 microns (1500 mesh) could be recovered when proper conditions were maintained. This test work has been verified by several full-scale installations. The method is generally applicable to the preconcentra-tion of large tonnages of low-grade ores or tailings for the recovery of a small amount of a valuable heavy mineral. The Sullivan deck (or now the Denver Buckman tilting concentrator), which is the essential part of the method, was devised originally for the recovery of tin from tailings of the Sullivan concentrator, Kimberly, B. C. Since the material treated contained only 0.05 pct Sn, it was impractical to attempt to recover cassiterite finer than 500 mesh.*

Jan 1, 1951

By R. W. Jenkins, O. J. Neslage

MINE operators today are paying increased attention to the mechanization of drilling operations as an important factor in increasing efficiency and decreasing costs. Recent progress in the design of drill jibs for mounting on drill carriages, or jumbos, has done much to advance the mechanization of mining methods. This progress has introduced new opportunities in the application of "jib jumbos" that are worth serious consideration. An attempt will be made here to classify the various types of jumbos and drill mountings available for level development and flat stope work, t6 indicate applications, and to measure their effectiveness in relation to their cost. The data here are based on a wide variety of field usage, and are offered only to point up, in a general way, the relative efficiency in proportion to cost. It should be remembered that any contemplated jumbo installation must be studied to determine what type of installation is most suitable, considering ground conditions, loading, timbering and haulage equipment, service available, and attitude of manpower. Early Drill Carriages: The advantages of some sort of a drill carriage were recognized at the time rock drills were introduced. In drift or heading operations where a fairly standard drill round and cross section were anticipated, as well as in flat bedded deposits where standard slabbing rounds were used, track and crawler-mounted drills found an early application. These first drill jumbos were little more than drill carriers, designed locally and manufactured with materials at hand. Of comparatively simple construction, function, and low capital cost, they usually consisted of a hinged column which supported one or more drills on arms or universal bars. When the column was pivoted vertically, the drills were moved into position. Screw jack extensions reached from the column to the roof and floor to hold the drill rigid. In some cases, particularly in tunnel jumbos, enough weight was carried that rail clamps or roof jacks were sufficient. Many of these column and arm-type jumbos, usually equipped with air and water manifolds, steel racks, and staging for drillers, are still in use today. Some have employed air or hydraulic extensions for securing the columns. They offer the equip-saving advantage of having all the necessary out, ment together, and they un be moved i and t. set up and torn down as a unit. Boom-type Jumbos: When the advantages of to column-type jumbo were seen, operators could to realize the further gains possible. More time could be saved with mechanical assistance to position api drill vertically. A rack on the column and a pinion on the arm for raising and lowering the drill in the manner of a quarry bar were tried with some success. The most outstanding solution to the vertical handling problem was reached with the boom-type of jumbo. Here two or more machines were mounted on a cross arm at the end of a boom that was pivoted at the rear of the track. This was raised and lowered by various mechanical aids. Occasionally air or hydraulic power was used. Nearly all of today's wagon drills use this boom-type principle. Boom jumbos represent a savings in time and physical effort expended in raising and lowering the drills. The boom must be balanced by the roof of the truck which is secured by rail clamps or type jacks. The most successful application of areawhere this of jumbo has been in the Tri-State area where multiple long-feed machines are used on caterpillar-mounted, boom-type jumbos for slabbing

Jan 1, 1951

By Irving Fatt, Herman Dykstra

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.' Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George' showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille's Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell's equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille's Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy's Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy's Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI' By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951