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By K. A. Slagle

Hydraulic analysis of the wellbore has become increasingly inzportant for designing cementing operations and selecting equipment, materials and techniques to complenzent modern well-c-ompletion practices. Non-Newtonian fluid technology has advanced beyond the point where former empirical methods of analysis adequately define the hydraulic system and fluid properties. In view of these factors, this paper describes a series of rheological calculations which have been found practical, through field usage, for assistance in selecting a cementing program. A relatively simple laboratory method using standard viscometric equipment is suggested for determination of the rheological properties of slurries, and clrrta are presented on some of the more common cementitrg conzposition.A. A criterion for divergence from laminar-flow characteristics has been proposed. Usefulness of the calculations is indicated by examples of cementing operations where they have been used. INTRODUCTION With the changing aspects of well-completion practices during the past few years, it has been increasingly important to have a relatively simple method of analyzing the flow conditions existing in the well during cementing operations. This is particularly true in view of the improved economics toward which most of the changes have been directed. Rheological characteristics of slurries used for cementing should be a major consideration in the trend toward smaller casing sizes, either single or multiple strings. Receiving increased attention is the practice advocated in 1948 by Howard and Clark' of attaining turbulent flow with the fluids circulated during a primary cementing operation. While there may still be a difference of opinion concerning this technique, most available information indicates that superior primary-cementing results are generally obtained when high displacement rates are employed. Fluid properties of the slurry to be used must be available, as well as calculation methods, to determine what flow rates should be attained and the probable consequences in terms of frictional pressure and horsepower utilization. It would certainly be inappropriate to attempt high displacement velocities if sufficient pressure might be developed to create lost circulation. Since cementing slurries are non-Newtonian fluids, it is not possible to define their rheological or fluid properties by the single factor of viscosity and then make calculations for the quantities just described. Because the shear stress-shear rate ratio is not constant: it becomes necessary to establish at least two parameters for adequate fluid-flow calculations. It is not the purpose of this paper to delve into the mathematical development of non-Newtonian technology, nor to discuss the arbitrary classification system under which a single fluid may resemble two or three different classes depending upon experimental conditions. Rather, the intention is to present a useful series of calculations based on a concept applicable to both Newtonian fluids and to the preponderance of non-Newtonian fluids encountered in the oil-producing industry. Development of this approach was begun some 32 years ago,' and has most recently been brought to fruition by Metzner and his co-workers at the U. of Deleware. Some non-Newtonian fluids encountered in the petroleum industry, other than cementing slurries, have also had the benefit of this method of analysis."' The two parameters required to define the fluid are usually denoted by the symbols n' and K' and, for the purposes of this discussion, are called "flow behavior index" and "consistency index", respectively. These two slurry properties permit calculation of the Reynolds' number and the "critical" velocity, or the velocity at which departure from laminar flow begins. EXPERIMENTAL DETERMINATIONS The two principal instruments used for rheological studies are the pipeline (capillary-tube) viscometer and the rotational viscometer. When conveniently possible, a capillary-tube viscometer (where the pressure drop and flow rate of the material can be measured) is the better method for rigorous determination of the flow behavior index and consistency index for non-Newtonian fluids. With pressure-drop data at various flow rates, it is then possible to prepare a logarithmic plot of shear rate as the abscissa-shear stress as the ordinate. For fluids which do not exhibit time-dependency, these data will usually produce a straight line. The flow behavior index n' represents the slope of this line, while the consistency index K' becomes the intercept of this line at unity shear rate in accordance with the mathematical derivations associated with this concept of rheology. Due to the difficulties anticipated in maintaining a uniform, pumpable cement slurry for the time interval required to obtain measurements from the pipe viscometer, the n' and K' data reported herein were obtained using a direct-indicating rotational viscometer (Fig. 2). The

By H. H. Otto

COMPARED with 1939, the year 1940 has seen no material change in the production of anthracite. Many factors seem to indicate a stabilized anthracite production of approximately 50 million tons per year. The present war has stimulated demand in the Cana¬dian and New England markets, which were formerly furnished with a portion of their needs from Great Britain and other European countries. Neither has there been any material change in the "bootleg coal" situation. This problem is more serious in the Southern anthracite field than in the Hazleton, Wilkes-Barre, and Scranton areas. One reason for this is the nearness of the Southern field to the large anthracite markets in Philadelphia, Washington, Baltimore, and Harrisburg. During the past year no new large

Jan 1, 1941

By A. C. Richardson

Troughs or launders are probably the oldest machines used for ore concentration, and their development was suggested no doubt by the natural segregation and stratification of materials that take place in the bed of a stream. Trough washers for coal cleaning were first used in France and Germany about one hundred years ago and have been used in some form or other ever since. The early launders were intermittent or batch machines, and only comparatively recent developments have made them continuous. The chief disadvantage of early launder systems as applied to coal has been that when a satisfactorily clean coal was produced the loss of good coal in the refuse was excessive. Other disadvantages have been the large quantities of water and the great lengths of troughs necessary to treat moderate tonnages of feed. One of the most widely used types of trough washers is the Rheolaveur, which has been developed in the last 25 years. Fig. 1 shows a more or less standard arrangement for fine coal. In this there are four trouglis placed one below the other and sloped a few degrees from the horizontal. Rheo-boxes or draws are provided at intervals in the bottom of the trough for the removal of material deposited from the stream. These draws are spaced substantial distances apart. Some of the rheo-boxes are provided with upward currents of water to modify the horizontal current stratification. In operation it is the function of the first two troughs to remove all refuse material and permit only clean coal to be discharged over the end. In order to accomplish this, large quantities of coal are drawn through the rheo-boxes. The third and fourth troughs are used to recover the coal discharged through the boxes of the first two troughs as a middling product and to discharge a clean refuse. The middlings are returned to the first launder and are usually about equal to 40 per cent of the raw coal being fed to the launder. In considering launder processes, one would reason that the conditions of extreme crowding under which stratification takes place in a flowing stream should effect complete separation in a single pass down a launder.

Jan 1, 1938

By A. C. Richardson

Troughs or launders are probably the oldest machines used for ore concentration, and their development was suggested no doubt by the natural segregation and stratification of materials that take place in the bed of a stream. Trough washers for coal cleaning were first used in France and Germany about one hundred years ago and have been used in some form or other ever since. The early launders were intermittent or batch machines, and only comparatively recent developments have made them continuous. The chief disadvantage of early launder systems as applied to coal has been that when a satisfactorily clean coal was produced the loss of good coal in the refuse was excessive. Other disadvantages have been the large quantities of water and the great lengths of troughs necessary to treat moderate tonnages of feed. One of the most widely used types of trough washers is the Rheolaveur, which has been developed in the last 25 years. Fig. 1 shows a more or less standard arrangement for fine coal. In this there are four trouglis placed one below the other and sloped a few degrees from the horizontal. Rheo-boxes or draws are provided at intervals in the bottom of the trough for the removal of material deposited from the stream. These draws are spaced substantial distances apart. Some of the rheo-boxes are provided with upward currents of water to modify the horizontal current stratification. In operation it is the function of the first two troughs to remove all refuse material and permit only clean coal to be discharged over the end. In order to accomplish this, large quantities of coal are drawn through the rheo-boxes. The third and fourth troughs are used to recover the coal discharged through the boxes of the first two troughs as a middling product and to discharge a clean refuse. The middlings are returned to the first launder and are usually about equal to 40 per cent of the raw coal being fed to the launder. In considering launder processes, one would reason that the conditions of extreme crowding under which stratification takes place in a flowing stream should effect complete separation in a single pass down a launder.

Jan 1, 1938

By W. McA. Johnson

The object of this paper is to describe the several necessary characteristics of the zinc-retorting charge and to show how by certain improved methods, the large excess of coal, over that theoretically required, can be reduced, thereby effecting an increase in the smelting capacity of a retort plant as well as other economies. In the southwestern zinc works a charge of roasted zinc ore with a side mixture of carbonates and silicates, analyzing on the average 50 per cent. Zn, is mixed with 55 or more per cent. of its weight of a mixture of coal and coke analyzing 60 to 70 per cent. fixed carbon. The ore is of varying fineness and the coal and coke are usually crushed in a semi-moist condition through a 3/8-in. screen. With ores of a slaggy nature, this coal proportion is increased, sometimes to as much as 100 per cent. of the weight of the ore. With carbonate ores, or where anthracite screenings with higher carbon content are cheap enough, the percentage of reducing agent is cut to 45 per cent. or even somewhat lower. The average charge per retort for a monthly run of a plant on ore, as distinguished from retorts on blue-powder, ladle-skimmings and other between-products, runs from 60 to 66 lb., with a mean of 63 lb. for the Southwest with standard retorts of 8 1/2-in. inside diameter and 50 in. long inside, using roasted sulphide ores. Conditions will change these figures, but 40 lb. of ore per cubic foot of retort space is, I believe,'an average in the better-operated plants. Since the rise in the price of spelter, the tendency has been to overcharge. To remove the slag that is formed when retorts are overcharged, extra men are put on to "gum-chisel" the retorts to prevent "set" furnaces and "butchered retorts." Taking the above conditions as premises, we find that from four to six times the amount of coal necessary for the reduction is used, as is evidenced by the fact that the residues analype as high as 35 per cent, fixed carbon. There are good reasons why this excess of fixed carbon must be used and perhaps these can be best explained by a description of the metallurgical requisites of a zinc charge. We may enumerate these as follows: 1. High reducing power, especially at the end of the shift, to reduce any carbon dioxide to monoxide and bring about a good condensation

Jan 1, 1918

By L. Graydon Carpenter, Donald E. Garrett

Probably the largest single tungsten deposit in the U. S. is one that has yet to produce any tungsten; it is not even listed in tables showing U. S. reserves. This deposit is at Searles Lake, Calif., where the brine contains about 70 ppm WO3. Small though the concentration is, the amount of brine in the lake is so great that it is estimated at 170 million lb of WO3 (8.5 million units), equaling the total of all other known reserves in the U. S. This dry lake is located in the basin formed by the Argus and Slate ranges in the northeastern corner of the Mojave Desert (Fig. 1). It consists of a massive salt body some 35 sq miles in extent, varying in thickness from 0 to 120 ft and containing more than 3 billion tons of salt. A central section of about L. G. CARPENTER and D. E. GARRETT are with the Research Dept., American Potash & Chemical Corp., Trona, Calif. TP 47881. Manuscript, Nov. 4, 1958. AlME Trans., Vol. 214, 1959. 8 sq miles is exposed salt; the remaining area is overlain by mud. Except for the exposed sodium chloride (10 to 15 ft thick) the body consists of a very complex and heterogenous mixture of soluble crystals, containing at least eight major phases. It is only about 53 pct solid, the voids being occupied by a dense brine which is the raw material for two chemical companies operating in the valley.

Jan 3, 1959

By J. R. Guard

Development of electrical power in coal mining has been an outstanding example of adaptability. It has accommodated itself to new inventions, changing mining methods, increasing demands, increasing safety requirements and many other new conditions. With the appearance of the continuous miner in the mining machinery picture, those engineers interested in the application of electricity to mining have been thinking about what new combination of electrical apparatus will best suit this newcomer. It is the purpose of this paper to discuss the relative costs of supplying d-c versus a-c power to mining equipment with particular reference to continuous miner setups. Assume that a-c power will be delivered to the mine at some high voltage suitable for transmission to the various substation locations. Typical voltage for this purpose is 4000 volts. The problem then is to change the power to some kind of power suitable for driving the motors of mining equipment. For safety and other reasons the voltage to be delivered to the motor terminals must be under 600 volts.

Jan 1, 1950

By Neil H. Bostick

A specialized electronic data system processes data taken from normal gologic maps and stratigraphic tables to yield predictions of uranium resource location for an area such as much of the United States. Strata underlying specific quadrangle cells of the earth are evaluated for uranium favorability on the basis of selected criteria of lithology, structure, and stratigraphy but not specific past production in the area. Stored data are computer processed to yield volume of likely host rock beneath each cell to a given depth and at a given favorobility level. Results are plotted by machine directly as maps. A specialized and simplified procedure for predicting approximate uranium resources has been devised at Stanford Research Institute (SRI). The prediction is based on general geology beneath specific area cells of the earth in order to provide complete volume coverage; the strata underlying these areas are evaluated for uranium mineral favorability on the basis of a few selected geologic criteria in order to allow rapid data input. In order that the predictions be generally applicable, they are based on geological factors only, not past ore production of a given cell. Since the bulk of U.S. resources are in elastic host rocks, only such strata are considered in this work. This paper describes the structure and some details of the resource system and how it was tested in an area of the western United States.

Jan 1, 1971

By A Guinier

RECIPITATION in alloys is undoubtedly one of the most essential phase transformations in metallurgy and, besides, it is a phenomenon of great interest to physicists. It seems then that it can be chosen as a topic for an Annual IMD Lecture. Of course, the subject is a very wide one and I shall discuss here only a very restricted part of it. I should like to show why it is now considered that there is, at the beginning of the process, a stage distinct from the real precipitation, which is the pre-precipitation. We shall be chiefly interested in the atomic structure of the metal in this preprecipi-tation stage. Numerous reviews on this subject have been published recently.', ' The latest was given by H. K. Hardyh t the last meeting of the Institute of Metals in London. One of the most complete articles has been written by the late Dr. Geisler." I should like, at the beginning of this lecture, to pay a tribute to the memory of our friend Arthur Geisler. Some of the ideas which will be developed here are different from those advocated by him. But everybody knows the considerable progress in experiment and in theory which we owe to him and, personally, I deeply feel how fruitful have been the long discussions which we have had during many years. Experimental Basis of the Precipitation Problems Let us recall the essential facts pertaining to the problem of the precipitation. The starting point and the final one are well known. The initial stage is the supersaturated solid solution before quenching. The dissolved atoms replace some of the atoms of the solvent at the points of a definite lattice. It is generally considered that the distribution of the atoms is completely random, and that the lattice distortions are relatively weak. These assumptions are only an approximation. It has now beenproven", that, in some cases, the dissolved atoms have a tendency to segregate to form very small nuclei. These fluctuations of composition are greater than the normal statistical fluctuations in a purely random alloy. We shall see the role played by these nuclei later. The final state is obtained by a very long annealing at such a temperature that an equilibrium is reached in a reasonable time. The alloy is then composed of a matrix which is a saturated solid solution, much poorer than the initial one. Imbedded

Jan 1, 1957

By Matthew J. Hrebar

SINCE the first installation in 1936, the use of rubber-tired equipment for secondary mine haulage has increased rapidly. From August 1936 to January 1944, approximately 750 rubber-tired units were placed in operation. Of these, 650 units were installed after January 1940. During the year 1941, it per cent of the mobile loaded bituminous tonnage was hauled by rubber-tired equipment. This percentage increased to about 20 per cent during 1943. The first rubber-tired units were battery-powered tractor-trailer types. In the year 1938 the battery-powered self-contained car was introduced. In 1939, the cable-powered self-contained car made its appearance. These self-contained units are our modern "shuttle cars." By the end of 1941, approximately 15 per cent of the shuttle cars in operation were cable-powered. Installations made during 1942 and 1943 increased the proportion of cable-powered cars to about 40 per cent of the total number of shuttle cars in use. There is a marked trend toward cable-powered cars, although one need not make many trips to mines where both types are used to discover that opinions are highly controversial as to the relative advantages and field of use of each type. It is natural for mining engineers in the coal-mining industry to have diversified opinions regarding the use and application of coal-mining machinery. Coal mining is not a standardized industry; natural conditions vary from mine to mine. However, it is surprising how many operations in scattered fields arrive at the same conclusions and adopt similar methods. This happens not so much through cooperation and exchange of ideas as through hard, costly experimentation, involving months of low production and relatively high costs. What then, are the reasons for increased use of cable cars? Could it be that present scarcity of materials is forcing their use? True, battery cars require considerably more auxiliary equipment, but during 1942 it was no more difficult to obtain than shuttle-car cable. Furthermore, the trend toward cable cars started before curtailments on mining equipment took effect. Undoubtedly, cable-reel shuttle cars were introduced to produce coal at a lower cost by simplifying trackless mining through the elimination of auxiliary equipment, and by reducing the first cost on equipment. The theory of cable-powered shuttle cars is well based, as can be proved by successful operations. Many operators have weighed the advantages and disadvantages of each type carefully before choosing the type most suitable to their operation. Others have taken much for granted and accepted one or the other without much thought. At many small operations, low first cost is apt to be the deciding factor. One large company, with considerable experience in the use of battery locomotives, preferred to use cable cars even though it was neces¬sary to reduce the section voltage from

Jan 1, 1944

By A. W. Faheneald, Lewis S. Prater

By taking advantage of the fundamental difference between screening and classification—namely, that specific gravity has no effect on screening but is one of the important factors in classification—a combination of the two may be used as a process of mineral concentration. Although this fact is not new, so far as is known it has had little or no commercial application. The scheme is not presented now as a process for producing finished products but rather as a preliminary operation rejecting part of the barren material from an ore before it is subjected to more costly treatment. That is largely the function of the new heavy-media concentration processes that have been widely accepted. Original installation costs for the present sink-float processes are relatively high, however, which confines their use to operations where large tonnages are handled. Sink-float has been successful on only the relatively coarse (approximately plus 10-mesh) portion of an ore, and it is in this same range that classification screening can function most satisfactorily. Theoretically, there is no upper limit to the size of particles that can be handled in a sink-float operation, but the degree of liberation in the very large pieces usually limits this. With classification screening, particles from % to % in. would be the largest that could be handled, but the lower range could be extended somewhat below 10 mesh. In order to take full advantage of the difference in specific gravities of the minerals being separated, sorting in the classifier should be under as extreme hindered-settling conditions as possible. Laboratory tests have been made on a galena ore and on an artificial mixture of quartz and magnesite to determine the separations that may be expected. Although more than one scheme may be followed, in these tests the separations were made by cutting the underflow from the classifier as a concentrate and then screening the overflow. The screen oversize was rejected as a tailing. Classification was done in a hindered-settling teeter column and screening was done by hand, using the standard 4 2 series. The accompanying flowsheet gives the testing procedure followed.

Jan 1, 1947

By A. W. Faheneald, Lewis S. Prater

By taking advantage of the fundamental difference between screening and classification—namely, that specific gravity has no effect on screening but is one of the important factors in classification—a combination of the two may be used as a process of mineral concentration. Although this fact is not new, so far as is known it has had little or no commercial application. The scheme is not presented now as a process for producing finished products but rather as a preliminary operation rejecting part of the barren material from an ore before it is subjected to more costly treatment. That is largely the function of the new heavy-media concentration processes that have been widely accepted. Original installation costs for the present sink-float processes are relatively high, however, which confines their use to operations where large tonnages are handled. Sink-float has been successful on only the relatively coarse (approximately plus 10-mesh) portion of an ore, and it is in this same range that classification screening can function most satisfactorily. Theoretically, there is no upper limit to the size of particles that can be handled in a sink-float operation, but the degree of liberation in the very large pieces usually limits this. With classification screening, particles from % to % in. would be the largest that could be handled, but the lower range could be extended somewhat below 10 mesh. In order to take full advantage of the difference in specific gravities of the minerals being separated, sorting in the classifier should be under as extreme hindered-settling conditions as possible. Laboratory tests have been made on a galena ore and on an artificial mixture of quartz and magnesite to determine the separations that may be expected. Although more than one scheme may be followed, in these tests the separations were made by cutting the underflow from the classifier as a concentrate and then screening the overflow. The screen oversize was rejected as a tailing. Classification was done in a hindered-settling teeter column and screening was done by hand, using the standard 4 2 series. The accompanying flowsheet gives the testing procedure followed.

Jan 1, 1947

By Douglas L. Gerner

In the early 1950's fishermen and their families around Minamata Bay in Japan were stricken with a mysterious neurological illness. The Minamata disease, as it came to be called, produced progressive weakening of the muscles, loss of vision, impairment of other cerebral functions, eventual paralysis and in some cases coma and death. The victims suffered structural injury to the brain. Minamata seabirds and household cats which, like the fishermen, subsist mainly on fish, showed signs of the same disease. This led to the discovery of high concentrations of mercury compounds in fish and shellfish taken from the bay, and the source of the mercury was traced to the effluent from a factory. Since then there have been other alarming incidents. In 1956 and 1960 outbreaks of mercurial poisoning involving hundreds of persons took place in Iraq, where farmers who had received grain seed treated with mercurial fungicides ate the seed instead of planting it. Similar outbreaks occurred in Pakistan and in Guatemala. In Sweden, game birds and other wildlife, apparently poisoned by mercury-treated seeds, began to be noticed in 1960. The Swedish Medical Board in 1967 banned the sale of fish from 40 lakes and rivers after it was found that fish caught in those waters contained high concentrations of methyl mercury. In 1970 alarm rose in North America. Following the discovery of mercury concentrations in fish in Lake Saint Clair by an investigator working in Canada, restrictions on fishing and the sale of fish were imposed in many areas in the U.S. and Canada. Government agencies in both countries began to take action to control the discharge of mercury-containing wastes into lakes and streams.

Jan 6, 1973

By Carl H. Samans

The attention of physicists and metallurgists has been directed toward the study and explanation of the deformation textures in metals for the past 15 years. In 1920 N. Uspenski and S. Konobejewskil were first able to show that the symmetrical X-ray diffraction effects that had been previously reported by E. Hupka2 and others in metal foils were caused by a directed arrangement of the crystallites. Since then, the systematic study of textures resulting from the application of the pure forces of tension or compression to polycrystalline materials has been supplemented by many investigations on deformed single crystals, which have greatly added to our knowledge of deformation. However, despite the valuable information secured from these comparative studies only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature. This lack of quantitative data is especially unfortunate because of the much greater practical significance of rolling textures and their effects in both cold-rolled and annealed materials. This investigation was undertaken for the purpose of specifying the deformation of rolled single crystals in the hope that such information might later facilitate the explanation of polycrystal-line textures. Of the four studies that have been made upon cold-rolled single crystals, only two are of any quantitative value. S. Tanaka,3 working

Jan 1, 1934

By P. M. Kelly

TWO analytical methods for calculating the positions of matrix and twin reflections on electron-diffraction patterns of a twinned cubic crystal have recently been published.1,2 Meieran and Richman1 considered the case of twinning on (1 12) in a bcc structure, while a more general treatment, capable of analyzing twinning on any plane in a cubic crystal, was developed by Johari and Thomas.2 The latter authors applied their general rotation matrix to both (111) twinning in face-centered crystals and {112} twinning in body-centered crystals and they derived separate expressions for these two cases. This separate treatment masks the fact that in a holosymmetric cubic crystal a (111) twin is crys-tallographically equivalent to a {112} twin.3 This is analogous to the crystallographic equivalence of rotation and reflection twins in centrosymmetric crys tals. A particularly simple example of this equivalence occurs when the two twin planes are perpendicular to each other—for example (111) and (112). Then, if twinning on (111) moves a point P to a new position P1, and twinning on (112) moves P to P2, P1 and P2 will be related to each other by a 180-deg rotation about [110]— the direction normal to both (111) and (112). Since there are diad axis axis along (110) direction in a holosymmetric cubic crys tal the two positions P1 and P2 must be crystallo-graphically equivalent. In other words if a particular pole (hk l) is in a position P1 after twinning on (Ill), then after twinning on (112) a pole of the type {hkl}—but not the particular pole (hk1)—will also be in the position P1. As a result, when only the general (as opposed to the particular) indices of poles after twinning are required, twinning on (111) gives the same results as twinning on (112). To convert the results for a (111) twin to those applicable to a (112) twin, when the particular (as opposed to the general) indices of poles after twinning are required, all that is necessary is to multiply the indices of the twin poles by the matrix for 180-deg rotation about [lie], i.e., The analytical methods suffer the disadvantage that a new set of calculations must be performed for each different diffraction pattern or, as is done in the Meieran and Richman treatment,1 a lengthy list of the location of the twin spots in reciprocal space must be prepared. All the tedious computation involved in these analytical approaches can be avoided by simply plotting, on tracing paper, a stereographic projection of a crystal twinned on say (112). By superimposing this twin stereogram on a standard (001) projection (preferably with the points and indices in a different color from those on the twin stereogram) the relative positions of both matrix and twin reflections can be determined by inspection. Alternatively, a composite projection can be

Jan 1, 1965

By A. A. Collins

When we speak of high copper on a lead blast furnace we think in terms of 4 to 5 pct, or. any lead charge carrying over 1 pct. Any copper on charge will produce its corresponding troubles such as lead well, extra slag losses, drossing problems, and the working up of the dross. This is indeed a very interesting subject and one that used to give the old-time lead metallurgists such as Eiler, Hahn and lles many worries, not so much in the actual operation of the hlast furnace but in the working up of the copper. When the American nletallurgists commenced with the American rectangular-shaped lead blast furnace in the 1870's and got away from the reverberatories such as were in use in Germany and other parts of the world, they went to greater tonnages, as 80 to 100 tons per day in comparison to the 20 to 30 tons per day in the other processes. With the greater tonnages along with insuficient settling capacity, the silver losses in some cases were increased. Hence the lead-fall was low, for there were no leady concentrates in those days to assist the metallurgist to gain lead or an absorber for the precious metals; and in some cases copper sulphides were added intentionally to the charge to produce a copper matte to lessen the silver losses through the dump slag. The operators in those days thought that where some copper was always present in the lead ores the copper should not enter into the reduced lead and alloy with it. This, by the way, is just the reverse of our present-day practice, when we try to put all of the copper into the blast furnace lead and to remove the same through the drossing kettles. Therefore the furnace was operated to produce a certain amount of matte or artificial sulphides, since, due to the great affinity of copper for sulphur, any copper present would enter the matte almost completely. Thus, the lead bullion produced was practically free from copper. The products of the furnace were metallic lead or lead bullion, containing 05 to 95 pct of the lead and about 96 pct of the silver which were in the ore—a lead-copper-iron matte which contained nearly all the copper in the ore and the slag, the waste product. In the United States, up through the year 1092, we find the small furnace 100 X 32 1/2 in. with 12 tuyeres, some 6 on each side, plagued with a small amount of poorly roasted sulphides— either from heap or hand roasters that produced matte. This matte was roasted and if poor in copper was returned for the ore smelting. Otherwise it was smelted either alone or with additions of rich slags or argentiferous copper ores, the products being lead and a highly cupriferous matte, the latter being subsequently worked up for its copper. The lead metallurgists kept trying and improving on furnace and roasting equipment designs until we find blalvin W. Iles constructing at the old Globe Plant at Denver what came to be the modern furnace. That is, in 1900 he built a furnace of 42 in. width by 140 in. at the tuyeres with a 10 in. bosh and a 16-ft ore column. This type has been more or less standard to the present time, though modified in width and length to meet the demand for large tonnages and improvements in structural details. In 1905 at Cananea, Mexico, Dwight and Lloyd developed the present down-draft sinter machine that has meant so much in producing a well-processed material for the lead blast furnace. In 1912 Guy C. Riddell came forth with double roasting at the East Helena Plant of the American Smelting and Refining Co., which removed the "zinc mush plague." Incidentally, with the introduction of double roasting, which most lead plants were forced into after 1924, when lead flotation came into its own, less matte or no matte was produced. When this stage arrived, the copper was forced into the dross and the casting of lead at the blast furnace lead-wells was stopped. In plants with a fair copper carry 1 pct or better on the blast furnace charge, the lead wells became inoperative once the production of matte stopped. The copper drosses clogged the lead wells and even with bombing, either water or dynamite, the operators could not keep them open. Thus, the lead wells were abandoned in some plants, such as at the El Paso and Chihuahua smelters of the American Smelting and Refinillg Co., and all lead taken out through the first settlers. The elimination of sulphur, espccially sulphide sulphur, from the blast furnace charge and the nonproductiori of matte resulted in a great saving of tinie, energy and equipment in the recirculation of the copper, With the copper content in the dross and dross-fall ranging in quantities from a few percent up to 60 pct, such as at El Paso, a drossing problem was created. As the old-time operators hated dross and buried the same in the shipping bullion, the modern metallurgists from 1925 on decided that with increasing dross-falls they would have to adopt the lead refiner's ideas of drossing kettles with subsequent treatment of the lead with a sulphur addition to have the shipping lead of 0.01

Jan 1, 1950

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at '750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By E. H. Lancaster, M. E. Mitchell

A MUD-conditioning program found to be very effective for drilling and completion operations on routine field wells requiring relatively short drilling time involves a moderate alkaline-tannate-bentonite treatment resulting in an ultimate filtration rate of 10.0 cc or less (API test). Mud weight schedules are planned from pressure information on completed wells in producing reservoirs and drill-stem test data obtained on other zones not being produced at present. In general, terminal mud viscosities average 45 sec (Marsh). This value has been found to be sufficient to remove cuttings from the well bore on the average well, with the slush pumps in general use on the rigs. On field wells requiring drilling times in excess of approximately 30 days, an alkaline-tannate-lime-bentonite treatment has been effective in maintaining desirable viscosities and filtration rates with a substantial reduction in chemical costs. This system has shown particular advantage on heavily weighted muds and those with abnormal flow-line temperatures. For the most part, the chemical treatment utilized in wildcat drilling follows closely the program used on field wells, depending on depth and duration of drilling operations. Wildcat mud programs are planned from information available from various geologic and operational sources, taking into consideration the possibility of encountering mud problems of a special nature in the wildcat area. Careful planning of wildcat mud pro- grams has proved to have definite value in avoiding most serious mud problems. An analysis and recommended treatment are presented on several special. mud problems which have been encountered in the area in the past. Those problems discussed are lost circulation, blowouts, sloughing shale, excessive chloride contamination, sulphate contamination, and prevention and correction of cement contamination. Introduction Drilling-mud control in the Southwest Texas area, in general, does not involve the multiplicity of problems encountered in other coastal areas. For instance, it is rare that a mixture of problems such as lost circulation, abnormal pressure, severe sloughing shale, and others, occurs on one well within close enough limits in vertical depth not to be taken care of by a sensible casing program, together with a relatively clear-cut mud program. There are conditions such as the fairly widespread occurrence of abnormal pressure in the lower Frio and Vicksburg zones, and the tendency for sloughing shale in the Jackson section which make for rather expensive mud control. However, the availability of fairly accurate geologic and operational information makes possible a reasonable degree of standardization on mud treatment over a relatively large area. It may be said that, over most of this area where drilling is currently in progress, the natural mud made is very poor in quality, but responds readily to moderate chemical treatment to yield very good wall-building characteristics. AS far as field development drilling is concerned, the mud engineer's principal job, once the routine treatment best

Jan 1, 1949