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By Robert I. Jaffee, Bruce W. Gonser

Recent work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. Materials and Alloying -4s in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni. and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about I050 C, and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. Thermal Analysis In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,' a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By Walter R. Crane

Operators of diamond drills have long been familiar with threadlike markings or riflings on cores but apparently have given but little serious thought to the conditions that are responsible for their production. The opinion generally held by those who have observed the phenomena is that the riflings are produced directly or indirectly by vibration, but so far as the writer is aware no systematic attempt has been made to demonstrate the fact. A careful search through the literature on diamond-drilling practice has been rewarded by only one reference to such markings of cores. J. N. Justice1 writes, "Of the peculiarities met with in the core, I will mention only one. The core from the "H" drill, at about 360 ft. came out rifled and pentagonal. The change from the circular to the pentagonal was sudden, and for 9 ft. this structure was maintained, when suddenly it returned to the circular. I have not been able to find any one who can explain the cause of this change of form. The drill men marveled at it and suggested vibration, six-stone bits, and several other hypotheses which need not be mentioned." The writer became interested in the matter of core riflings some 10 years ago while in the Flat River lead region of Missouri, where many remarkable examples of "rifled" cores were observed and collected. Since that time similar phenomena have been observed in various localities throughout the United States and Canada, and samples have been gotten together illustrating a large number of variations in form. After a careful study had been made of the material at hand it seemed desirable that certain data should be obtained from the experience of others regarding the normal action of diamond drills in forming cores, portions of which are occasionally rifled, before an attempt was made to draw any conclusions as to their cause. About 20 letters were addressed to diamond-drill companies, operators, and engineers actively engaged in drilling operations, with a

Jan 1, 1917

By F. A. Crossley

The additions: o, Sn, Zr, Cb, Mo, and V were studied for their effects on the a/a + Ti3A1 boundary of Ti-A1 base ternary alloys. These additions were chosen because of their importance to commercial titanium alloy practice—oxygen as the major impurity (in terms of influence on mechanical properties) and the others as major alloying additions. The composition and temperature ranges of investigation varied according to the system as shown in Table I. The principal means of investigation was light-microscopy. The basis of the ternary studies was the recently determined titanium-rich end of the Ti-A1 system.' MATERIALS, METHODS, AND PROCEDURES Ingots were prepared in 15 g size for all alloys except those of the Ti-Al-Mo and Ti-A1-V systems which were prepared in 20 g size. These alloys were prepared from high-purity, electrolytically refined titanium obtained from the Bureau of Mines, Boulder City Metallurgical Laboratory, Boulder City, Col., and Chicago Development Corp., Riverdale, Md., for the 15 g and 20 g ingots, respectively. The alloying additions were obtained from commercial sources, and were at least of 99.9 pct purity, except the V-15 wt pct A1 master alloy for vanadium additions. This alloy was of 98.2 pct purity; the major impurities were 0.37 wt pct Fe and 0.38 wt pct Si. The ingots were prepared by multiple melting in a nonconsum-able-electrode arc furnace. The ingots were covered with Markal coating "CR-T22" (Markal Co., Chicago) to protect them from scaling. Markal coating is applied as a slurry of solids in a volatile carrier liquid. The coated article is air dried. Upon heating to the hot working temperature the coating fuses to form a glassy, protective film. The ingots were heated to 1000°C and rolled to 0.16 in. thickness, reheating after each pass. The glassy film was removed by sand blasting. Ten mils were removed from all surfaces by grinding and/or pickling (3 pct HF, 30 pct HN03, balance water). Grinding was always followed by pickling to remove traces of the grindmg medium. Hydrogen removal was accomplished by vacuum annealing at 1000°C for 2 hr to a final pressure of about 0.02 µ Hg. This was followed by annealing in evacuated Vycor bulbs (800°C, 2 hr, ice brine quenched (IBQ)) in order to maximize ductility. The materials were then lightly pickled and cold rolled to 0.12 in. thickness or cracking, whichever occurred first. After rolling, 1/2 by 1/4 in. specimens were cut for the equilibration anneals given in Table 11 and carried out as previously described.1 Final polishing of the specimens for metallographic examination was done by electrolytic means. Specimens were first examined without etching under bright field and polarized light illumination, for this is the only means of detecting the "two-phase" phenomenon.1,2 The term "two-phase syndrome" refers to Ti-A1 al-loys which appear on the bases of their chemical, phys-ical, and mechanical properties, to be two-phase, but are actually single phase and inhomogeneous in composition. Since processing and heat treatment of the alloys of the first group were completed before the two-phase syndrome was discovered, a number of the specimens were found to exhibit this phenomenon—80 pct of those of the Ti-Al-Zr system, 5 pct of those of the Ti-Al-Sn system, 30 pct of those of the Ti-Al-Zr system. The affected specimens were homogenized by heating above the ß transus temperature and quenching. The heat treatment and working schedules to accomplish this are given in Table 111. After rolling, specimens were pickled (3 pctHF, 30 pct HNO3 in water) to remove 1 to 2 mils from the

Jan 1, 1970

By W. D. Haselton, J. B. Newsom

SAFER, cheaper, and faster sinking of mine openings seems to have been realized with the completion of a borehole 5 ½ ft. in diameter and 1208 ft. deep, in Minnesota, during 1938. Moreover, as the opening is to be used solely for ventilation, its circular cross section, smooth walls and freedom from fire hazard recommend it in comparison with the usual timbered shafts of rectilinear cross section. It should be pointed out that a drill hole sunk without the use of explosives frequently will stand open without support, whereas a shaft sunk by standard procedure using dynamite usually must be timbered because of the wall-shattering effect of explosives. The saving in maintenance resulting from the elimination of timber is obvious. The work was done by Pickands Mather & Co. at its Zenith mine, Ely, Minn. This company wanted a ventilation opening capable of delivering 50,000 cu. ft. of air per minute to the fourteenth level, 1200 ft. below the surface. While several general articles1-3 have described the method used, detailed time and performance records have not been presented before. Moreover, with a method as new as this, it is important to compare the results attained under widely varying conditions. Among the new conditions faced at Ely were some extremely hard rock, a series of vertical fractures, seepage water, and some long stretches of sound rock which, combined with excellent equipment, gave a chance to operate without unusual delays. Developments in boring large holes have generally taken the obvious course of increasing the size of the equipment, a line of attack that has resulted in putting down 3-ft. diameter holes at damsites for studying the foundations4 and in drilling ventilation openings between levels at Butte.5 Such drills operate from the collar of the hole, and the power from the drill is transmitted to the cutting tool through drill rods or pipes. In order to keep down the volume of rock that must be ground to sludge, the cores in large-diameter drilling are made as large in diameter as possible. Their large diameter increases their weight per foot of length, which

Jan 1, 1939

By AIME AIME

ALFRED WILLIAM GAUGER ??Al" or '?Doc" to his many friends in the coal and chemical industries- is known for his research talents and organizing ability. Appropriately the first public recognition of his technical ability was by the A.I.M.E. in the publishing of a paper by George A. Burrell and Alfred W. Gauger in the "Transactions" for the year 1916. "Al" Gauger was born at St. Paul, July 31, 1892. He graduated in chemistry at the University of Minnesota in 1914. A year later he began his initiation into the mysteries of coal mining when he joined the safety division of the U. S. Bureau of Mines at Pitts- burgh, serving from 1915 to 1917.

Jan 1, 1944

Said Plutarch a long time ago, ?To appreciate a man's work at the full, it is well to know the man himself, his circumstances and the incidents of his career." He might as truly have said "gift" instead of "work." Ambrose Swasey, engineer, collaborater with scientists, promoter of engineering research, patron of Engineering Foundation, advancer of the good of mankind, modest gentleman and generous giver, is, happily, well known to a great many engineers, who will therefore more fully appreciate his recent additional gift, for the use of the Engineering Foundation, which; purpose is "the furtherance of research in science and engineering, and the advancement of the profession of engineering and the good of mankind." But full appreciation of a gift of money necessitates more than acquaintance with -the giver and knowledge of the amount. Its timeliness; its inspiration; the character and continuity of its benefits, all must be comprehended. But whose imagination, though far-visioned as the great telescopes Mr. Swasey has built, can see the limits of benefit of such gifts as he has made to the Engineering Foundation, attracting-as they will-other gifts and evidences of, devotion to a great cause-? Every such gift lays responsibilities upon the recipients. Will American engineers grasp not merely, their pecuniary value but also emulate the spirit of fraternity and desire for harmony which have accompanied them? Shall we not work together and with Ambrose Swasey to advance still further the good of mankind, thus to demonstrate an acceptance of our obligations to humanity which is a counterpart in a democracy of the noblesse oblige of aristocratic tradition?

Jan 12, 1918

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

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

Jan 1, 1967

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

By C.A. Zapfee, C. E. Sims

An investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. Apparatus The apparatus is shown in Fig. r and the system is shown by diagram in Fig. 2. Furnace, A lmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In this furnace fres oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1943

By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

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

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 Ian Campbell, G. Austin Schroter

Although there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological features of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable foundation upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when .subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the literature heretofore. The nomencelature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation.'" The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefor? is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines8' classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treatment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomenclaturc: of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respecbively, for the two types indicated.

Jan 1, 1942

By T. B. Counselman

PRobably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of beillg high in phosphorus hecause of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetitc area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mincs, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these Ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium. and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that contitue- our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers and tables, which later were replaced by classificrs. Ore particles finer than I00 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes., The latest and most important process that has been 38

Jan 1, 1944

By R. N. Dokken, J. F. Elliott

A high-temperature solution calorimeter was used to measure directly the partial molar heat of mixing of nickel in the Cu-Ni system, 0 to 15 at. pct Ni and 1200°C; of silver in the Cu-Ag system, 0 to 50 at. pct Ag and 1100°C; and of cobalt in the Cu-Co system, 0 to 6 at. pct Co and 1200°C. The heats of fusion of copper and silver were also detervnined directly. The results of these investigations are as follows: Cu-Ni: HM = [2.64 + 0.25Xm JXNiXCy kcal/g-U~OI Cu-Ag: HM =[4.00 + 0.31XAglXAgXCu kcal/g-atom Cu-Co: HF~ = [8- 5X~,]X& kcal/g-atotn Cu, AH, = 3290 * 275 cal/g-atom Ag, AH, = 2890 * 250 cal/g-atom The performance of the calorimeter was enhanced by improving the operational and control procedures, particularly the temperature-wieasuren~ent method and the solute-addition practice. The interpretation of the experimental data was improved by developing machine computational techniques that increased the speed, flexibility, and accuracy of the treatment of the data. THIS paper reports further measurements of the heats of solution of liquid metals with the high-tem- perature solution ca1orimeter.l Measurements were made of the partial molar heats of mixing in the following liquid alloys: Cu-Ni, Cu-Ag, and Cu-Co. In addition the heats of fusion of copper and silver were also determined. The apparatus and the experimental procedure were essentially those of Benz and Elliott.2 Several modifications in the experimental method and the means for interpreting the data were incorporated in this study to improve the results. The operation of the calorimeter and its characteristics will be described only briefly here. The

Jan 1, 1965

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation's model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,' which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson' showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation's model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By M. H. Gaskell, D. M. Kehn, G. T. Pyndus

A correlation of the bubble point pressure for black oil systems is developed using the standard physical-chemical equations of soiutions. The correlation is based on 158 experimentally measured bubble point pressures of 137 independent systems and is expressed in terins of the usually measured field pnrameters— flash separation gm-oil ratio, rank oil gravity, total gas gravity, and reservoir temperature. The data were obtained on systems produced in Canada, Western and Mid-Continent01 United States, and South America. The average error (algebraic) in the representation is 3.8 per cent, and the maximum error encountered is 14.7 per cent. INTRODUCTION In the absence of experimentally measured properties of reservoir fluids, it is often necessary for the field engineer to make estimates regarding the fluid properties based on the usually measured producing parameters. To aid in these estimations, various correlations have appeared in the literature in recent years. Among the pertinent properties of interest is the bubble point pressure. A correlation for this parameter has been reported by Standing'. However, this correlation was based essentially on California produced crudes and this limitation was pointed out with its presentation. The correlation presented in this paper utilized data on crude oil systems from Canada, Wes- tern and Mid-Continental United States, and South America. CORRELATION DEVELOPMENT The basic assumption used in this development is the same as employed by Standing', There is a wide variety of ways to combine these parameters; however, in this instance the combination was made on the basis of Henry's law2. Accordingly, the relationship proposed is Although Eq. 2 defines an individual system, it is of limited value since H' is a function of gas-phase composition and the system temperature. It was observed that for the systems where the bubble point was measured at several temperatures that the ratio of the bubble point pressures and the ratio of the corresponding absolute temperatures (R) were practically identical. Thus, for correlation purposes the bubble point pressure may be taken as a direct function of the absolute temperature. This relation is valid only for those systems that are not near the critical point. Accordingly, this correlation will be inadequate for systems in the region of the critical point. The solubility of the various hydrocarbons found in the gas phase increases with the molecular weight. Thus, the saturation pressure should be inversely related to the gas gravity. Applying these principles to Eq. 2 and rearranging terms gives: The variables 02 the left side of Eq. 3 were designated as the "hubble point pressure factor". The number of mols of tank oil per barrel is a function of the "mclecular weight" of the tank oil. Although the tank oil is a complex mixture, it was assumed for the purposes of this correlation that a unique molecular weight could be assigned to a given oil. This was designated as the "effective molecular weight", and was related to the oil gravity, This empirical relationship was developed simultaneously with the correlation by assuming values of M,. and working to obtain a smooth curve for both the correlation and the effective molecular weight. The relationship between the oil gravity and the effective molecular weight used in this correlation is shown in Fig. 1. The effective molecular weight is somewhat higher than the molecular weight of the C fraction. The difference between these values is largest for the low-gravity systems. It is noted that this effective molecular

By H. J. Morel-Seytoux

The influence of patten, geometry on assisted oil recovery for a particular dispIacement mechanism is the object of investigation in this paper. The displacement is assumed to be of unit mobility ratio and piston-like. Fluids are assumed incompressible and gravity and capillary effects are neglected. With these assumptions it is possible to calculate by analytical methods the quantities of interest to the reservoir engineer for a great variety of patterns. Specifically, this paper presents (1) very brieily, the methods and mathematical derivations required to obtain the results of engineering concern, and (2) typical results in the dorm of graphs or formulae that can be used readily without prior study of the methods. Results of this work provide checks for solutions obtained from programmed numerical techniques. They also reveal the effect of pattern geometry and, even though the assumptions of piston- like displacement and of unit mobility ratio are restrictive, they can nevertheless be used for rather crude but quick, cheap estimates. ,These estimates can be refined to account for non-unit mobility ratio and two-phase flow by correlating analytical results in the case M = 1 and the numerical results for non-piston, non-unit mobility ratio displacements. In an earlier paper1 it was also shown that from the knowledge of closed form solutions for unit mobility ratio, quantities called "scale factors" could be readily calculated, increasing considerably the flexibility of the numerical techniques. Many new closed farm solutions are given in this paper. INTRODUCTION BACKGROUND Pattern geometry is a major factor in making water-fIood recovery predictions. For this reason many numerical schemes have been devised to predict oil recovery in either regular patterns or arbitrary configurations. The numerical solutions, based on the method of finite difference approximation, are subject to errors often difficult to evaluate. An estimate of the error is possible by comparison with exact solutions. To provide a variety of checks on numerical solutions, a thorough study of the unit mobility ratio displacement process was undertaken. To calculate quantities of interest to the reservoir engineer (oil recovery, sweep efficiency, etc.), it is necessary to first know the pressure distribution in the pattern. Then analytical procedures are used to calculate, in order of increasing difficulty: injectivity, breakthrough areal sweep efficiency, normalized oil recovery and water-oil ratio as a function of normalized PV injected.

Jan 1, 1967

By R. E. Cook

This work presents the development and application of equations of the form developed by Martin1 to describe gravity segregation performance during natural depletion. One-dimensional depletion analyses are applied to several hypothetical reservoirs. Considerable attention is given to the changes in saturation distribution in the dip direction resulting from depletion at various rates. Vertical gas saturation distribution within a sand having vertical permeability is studied to illustrate conditions which provide For low gus-oil ratio production from wells selectively completed away from sand tops, as observed from well performance. Results of performance calculations are shown graphically and illustrate the rate sensitivity of the gravity segregation mechanism and the influence of reservoir geometry and withdrawal distribution. It is shown that for sufficiently high depletion rates gas saturation distribution in the dip direction is characterized by the formation of two discontinuities, or saturation "fronts"; the updip front being the gas-oil contact of the secondary gas cap and the downdip front occurring at a position dependent upon the reservoir depletion rate, withdrawal distribution and reservoir geometry. The gas saturation in the region between fronts is shown to continually increase with time, while that downdip from the lower front remains very low and relatively stable. The effect of increased depletion rate is to reduce the region of stable gas saturation and thus enlarge the portion of the reservoir producing with continually increasing gas saturation. Special attention is given to the performance of reservoirs having sufficient vertical permeability to permit liberated gas to segregate vertically within the sand section before proceeding in the updip direction. It is shown that reservoirs of this type are far less sensitive to depletion rate due to the mechanical control of producing gas-oil ratios afforded by selective well completions away from sand tops. It is shown that gravity segregation performance is adversely af- fected by decreasing reservoir cross-section area in the updip direction. It is also shown that down-dip withdrawal concentrations can restrict gas segregation rates in the dip direction. INTRODUCTION The natural depletion performance of several large producing reservoirs in Western Venezuela has unmistakably shown the significant role that gravity forces play in governing the gas-oil ratio behavior of individual wells and the over - all pressure-production performance of the reservoirs. Analysis and prediction of the natural depletion performance of these reservoirs is of great importance in determining the economics of pressure maintenance operations. In 1957, a method for the analysis of pressure maintenance performance was presented by Martin1 which, in the original and more general form of the equations involved, provides a physically sound basis for the analysis of one-dimensional gravity segregation performance during natural depletion. The work reported herein is an application and extension of Martin's outstanding developments to a series of hypothetical reservoirs in an attempt to explain the general behavior of the gravity segregation mechanism and the influence of such parameters as depletion rate, reservoir geometry and withdrawal distribution. The study considers two types of flow: "distributed flow", where vertical permeability in the reservoir is zero and fluids flow only in the dip direction while uniformly distributed over the sand thickness; and "segregated flow", where vertical permeability is sufficient to permit gas to segregate against the sand top before proceeding updip. This latter type of flow has been recognized as an important mechanism active in the massive sand reservoirs of Western Venezuela. ANALYSIS OF ONE-DIMENSIONAL DISTRIBUTED FLOW SYSTEMS For an inclined reservoir having zero vertical permeability, the velocities of oil and gas flow at any point in the reservoir can be derived from Darcy's equations as

By D. L. Harris

Chemical upgrading testwork on Stillwater chomite concentrate shows that reduction roasting and leaching (sulfuric acid and/or ferric sulfate) can provide upgraded feed to ferrochromium furnaces for making upgraded ferrochromium. Two-stage reduction smelting in electric arc furnaces can make upgraded ferrochromium also. Sulfating roasts and leaching (acid and/or water) results using gaseous SO2—SO3 or solid ammonium sulfate were not satisfactory for upgrading chromite. Chemical upgrading of domestic Stillwater (Montana) chromite has been considered at various times1'2' to provide a material with higher chromium to iron ratio, more like foreign high grade ore, for the production of standard grade ferrochromium. Physical bene-ficiation of Stillwater chromite ore can provide a ratio, Cr/Fe, no higher than the ratio in the chromite mineral, which is approximately 1.7. For comparison the analyses of a foreign metallurgical grade chromite ore, a high grade electrostatic process Stillwater concentrate and a stockpile concentrate from the Stillwater ore are noted in Table I. Single stage smelting of the high grade foreign ore with a ratio, Cr/Fe, of 3.37 can provide a ferrochromium of over 65 pct chromium content. Similar smelting of the Stillwater concentrate with a ratio of 1.7 can provide a ferrochromium of 50 to 55 pct chromium content.' It has been demonstrated on a pilot plant scale that chemically upgraded Stillwater chromite having a ratio, Cr/Fe, of 3.0 also can be smelted to provide a ferrochromium containing over 65 pct chromium.5 Two major considerations for an upgrading process are the ratio, Cr/Fe, in the product and the chromium recovery. A minimum ratio, Cr/Fe, of 3.0 is required in the product but for economic reasons a higher ratio is desirable for blending purposes as long as the recovery is satisfactory. Data from different kinds of chemical upgrading testwork are presented in this report. Some of the testwork was conducted to make a product which was not intended to be feed for ferrochrome smelting, but the data are considered pertinent to chemical upgrading. Results reported by others are noted also for comparison. WORK REPORTED BY OTHERS The U. S. Bureau of Mines has contributed much to the literature on chemical upgrading of chromite and a summary is given in Table 11. Reduction roasting and acid leaching were reported by Boericke and Bangert,1 by Lloyd and Gorst, et a1,2 and by Boericke3 to demonstrate very good success on a laboratory scale and only fair success in pilot plant tests for Stillwater (Benbow) concentrates. This work included basic studies on thermodynamic properties to explain the reduction and leaching results. Canadian workers, Downes and Morgan,9 have reported experimental success in upgrading a low grade Bird River chromite, similar to Stillwater material by the same process. Russian workers1' have noted results on reduction tests of high grade chromite which may apply to low grade ores and which help in understanding the reduction process. The use of flux additives in the reduction process was an innovation of their work. The Canadian workers9 also reported other kinds of experiments, including autoclave leaching of the chromite in a limited amount of sulfuric acid. An insoluble basic chromium sulfate was formed and separated from soluble iron, magnesium, and aluminum sulfates to provide an upgraded material. U.S. Bureau of Mines workers, Lloyd, Rosenbzum, Home and Davis,' reported on autoclave leaching of Benbow concentrates as a means of obtaining chromium alum for electrolysis. This last work required selective crystallization of alum to separate iron from chromium. Chloridizing roasting of Benbow and Mouat concentrates has been reported by Hunter and Banning6 and others8 to show that the iron chloride could be volatilized from the chromite to provide upgraded residues.

Jan 1, 1964

By C. K. Eilerts

Finite difference equations were programmed and used to integrate the second-order, second-degree, partial differential equation with variable coefficients that represents the transient linear flow of gas-condensate fluids. Effect was given to the change with pressure of the compressibility factor, the viscosity, and the effective permeability and to change of the absolute permeability with distance. Integrations used as illustrations include recovery of fluid from a reservoir at a constant production rate followed by recovery at a declining rate calculated to maintain a constant pressure at the producing boundary. The time required to attain such a limiting pressure and the fraction of the reserve recovered in that time vary markedly with properties of the fluid represented by the coefficients. Fluid also is returned to the reservoir at a constant rate, until initial formation pressure is attained at the input boundary, and then at a calculated rate that will maintain but not exceed the limiting pressure. The computing programs were used to calculate the results that would be obtained in a series of back-pressure tests made at selected intervals of reservoir depletion. If effect is given to the variations in properties of the fluid that actually occur, then a series of back- pressure curves — one for each stage of reserve depletion — is required to indicate open-flow capacity and related flow characteristics dependably. The isochronal performnce method for determining flow characteristics of a well was simulated by computation. INTRODUCTION The back-pressure test procedurel is based on a derivation of the equation for steady-state radial flow of a gas, the properties of which are of necessity assumed to remain unchanged in applying the test results. The properties of most natural gases being recovered from reservoirs change as the reserve is depleted and pressures decline, and the results of an early back-pressure test may not be dependable for estimating the future delivery capacity of a well. The compressibility factor of a fluid under an initial pressure of 10,000 psia can change 45 per cent and the viscosity can change 70 per cent during the productive life of the reservoir. There are indications that the effective permeability to the flowing fluid can become 50 per cent of the original absolute permeability before enough liquid collects in the structure about a well as pressure declines to permit flow of liquid into the well. The advent of programmed electronic computing made practicable the integration of nonlinear, second-order, partial differentia1 equations2.3 pertaining to flow in reservoirs. Aronofsky and Porter4 represented the compressibility factor and the viscosity by a linear relationship, and integrated the equation for radial flow of gas for pressures up to 1,200 psi. Bruce, Peaceman, Rachford and Rice5 integrated the partial differential equations for both linear and radial unsteady-state flow of ideal gas in porous media. Their published results were a substantial guide in this study of integration of the partial differential equation of linear flow with coefficients of the equation variable. The computing program was developed to treat effective permeability as being both distance-dependent and pressure-dependent. In this study all examples of effective permeability are assumptions designed primarily to aid in developing programs for giving effect to this and other variable coefficients. The accumulation of data for expressing the pressure dependency of the effective permeability is the objective of a concurrent investigation. FUNDAMENTAL DIFFERENTIAL EQUATIONS DIFFERENTIAL EQUATION OF FLOW Linear transient fluid flow is represented by the partial differential equation,

Jan 1, 1965