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By Frank Riddle

PRODUCTS made from the ores of the sillimanite group, and synthetic substitutes for them, have unique properties, and service tests prove that they are playing, and will continue to play, a major part in improvements in metallurgical processes. Also, they are examples of how comparatively useless, rare, or "museum" minerals have been made available in commercial quantities. Until research developed uses for them, the minerals had been observed only in small, scattered masses, or crystals. Improvements in ceramic processes and compositions have come about very gradually. In the last 10 or 15 years, several outstanding developments have been made. Of greatest interest to the mining and metallurgical engineers are those affecting the composition, necessitating the mining of new minerals, and improvements in ceramic products used in metallurgical processes.

Jan 1, 1932

By B. L. Landrum, J. Simmons, J. M. Pinson, P. B. Crawford

Patentiometric model data have been obtained to estimate the effect of vertical fractures on the areas swept after breakthrough in water flooding and miscible displacement programs such as gas cycling where the mobility is near one, The data are presented for the case of the fire-spot pattern in which the cemer well is fractured various lengths and orientations, the data indicate that for 10-acre spacing, fractures extetidirrg over 1300 ft in either directior1 from the fractured well may re.srrlt in reductions in sweep efficiencics from 72 to approximately 34 per cent. However. the area swept after break through may be quite largr and only 10 or 12 per cent 1ess than would be obtained if the reservoir were trot fractured. For the specific case when the volume of fluid injected is equivalent to 100 per cent of the pattern vol-unie, the swent area may vary from 80 to 88 per cent, depending on the lenght of the fracture. The former value is that which occurs when the break through or sweep efficiency was orrly 34 per cent and the latter figrrre of 88 per cent is that which is obtained if the reservoir were unfrac-ttm'd. It is pointed out that although the sweep efficiency may he very low in vertically fractured five-spot patterrz.s, the area swept at low water-oil ratios may be only 5 to 10 per cent less than those achieved if the reservoir were unfractured. INTRODUCTION Since the initiation of commercial reservoir fracturing techniques it has been desirable to determine the effect of fractures on the areas swept after breakthrough. Most water flooding or gas cycling projects are continued for substantial periods after the brcakthrough of the injected fluid. Although the sweep efficiency serves as one criterion for rating various flooding patterns. the area swept after breakthrough for various water-oil ratios or percentage wet gas, if cycling. is of perhaps more importance than the sweep efficiency alone. Sweep efficiency data on the vertically fractured five-spot have been presented3. Previous work on the line-drive pattern has shown the effect of vertical fractures on the area swept after breakthrough for the case in which the distance between injection and producing wells divided by the distance between adjacent input wells was equivalent to 1.5 (see lief. 2). The data indicated that for the line-drive pattern it may be desirable to flood or cycle substantially perpendicular to the fractures in order to achieve the greatest recovery for the smallest volume of fluid injected. For this study the center well of a five-spot is assumed as the fractured well. All fractures were assumed to originate at this well and extend into the reservoir for various distances and orientations. All the fractures are straight and are of large permeability compared to the matrix proper. These data are presented to aid the engineer in estimating fractured five-spot pattern performance. ANALOGY The potentiometric model was used in making this study. The model used was 20 20 in. by approximately 1-in. deep. For certain portions of the study one corner of this model was considered to be an injection well and the opposite corner a production well. To simulate vertical fractures a copper sheet was soldered to the wire well and made to conform to the desired length and orientation. In other studies the same model was used except that the four corners of the model might be considered as the corner wells of a five-spot pattern and a fifth well was placed in the center of the model. The well placed in the center of the model was fractured. The total fracture length is L and the well spacing. d. The complimentary fracture angles will be obvious from Figs. 3 and 4. The data obtained on the potentio-metric model assumes the pay to be uniform and homogeneous, the mobility ratio is one, steady-state conditions exist and gravity effects arc neglected. The permeability of the fractures is very great compared to that of the matrix proper. The po-tentiometric model has been used widely both in water flooding and gas cycling projects, and may be used for miscible displacement; how-ever. it is believed that the poten-tiometric model data are more properly applicable to gas cycling than water flooding because the model as-

By W. S. Keyes

(Read at the Amenia Meeting, October, 1877.) EASTERN NEVADA. THE State of Nevada, known par excellence as "the Silver State," occupies the major portion of the wide plateau, or so-called Great Basin, lying between the Sierra Nevada range on the west and the Wahsatch range of the Rocky Mountains on the east. It extends from the 114th degree to the 120th degree of longitude, west of Greenwich. It is limited, on the north, by the 42d degree of latitude, and on the extreme south by the 35th degree of latitude. Its general shape is that of an irregular parallelogram, from which the lower or southwestern portion has been cut off by a diagonal southeasterly line; the missing portion forms a part of the State of California on the west. The Great Basin is made up of a succession of low hills, or minor mountain ranges, running very nearly north and south, with long valleys between them. All of these mountains are more or less metalliferous. On the western rim, marking the eastern flank or foothills of the Sierra, we find granites, porphyries, and propylites. Here we note the great Comstock lode, with its free-milling gold and silver ores, and still further south the once prominent and the now reviving gold and silver-bearing districts of Esmeralda County, Nevada, and of Morro County, California. Next, at some distance to the east, we find the mining districts at and near Unionville, in Humboldt County. Still further to the east we find the Battle Mountain copper-silver district, north from the railroad, and southerly therefrom the Austin or Reese River, Belmont, and other districts. Still further east and north of the railroad, we find the Tuscarora, a new district of very

Jan 1, 1878

By John H. Hollomon, C. Zener

It is commonly recognized that a given material may be described as ductile or brittle only with reference to the conditions of test. Thus under the usual test conditions quartz is brittle, but under high pressures it is ductile. Salts that are brittle at room temperature become ductile at elevated temperatures. Pitch, brittle with respect to rapid loads, flows at low rates of loading. Pearlitic steel, ductile under the usual conditions of test, may be embrittled under the proper conditions of combined stresses, temperature, and rate of loading. Earlier Investigations A clear analysis of the conditions necessary for plastic flow and for fracture was first given by LudwikI1 who introduced two types of stress, the "flow stress" and the "stress at fracture." These stresses may refer to tensile or to shear stresses, or, in fact, to any type of stress. Ludwik considered these two stresses to be independent of one another, functions of the conditions of test and of the prior history of the material. For the purpose of analysis. both a Flow stress and a stress at fracture can be envisaged as functions of strain over the entire range from zero to infinite strain. Thus, the material is brittle if the stress at fracturc is less than the flow stress and ductile if the reverse is true. According to Ludwik's analysis, the problem of determining the effects of combined stresses, of temperature and of strain rate upon the behavior of metals reduces to a problem of determining the effect of these variables upon the flow stress and upon the stress at fracture. In the present paper, methods are described for determining the effects of two of these variables, temperature and strain rate, and examples are given of the dependence of tlow stress and stress at fracture, upon these two variables. The effect of combined stresses will be discussed in a succeeding paper. The flow stress may be determined from a load-diameter curve. Load-diameter curves were obtained over a wide range of temperature and over the limited range of strain rates obtainable with the lever-type Riehle machine used. The curves were then converted to an extremely wide range of strain rate by making use of the equivalence of the effects of changes in strain rate and changes in temperature, previously proposed2 and demonstrated3 by the authors. According to this principle of equivalence, strain rate e and temperature T affect the flow stress only through a single parameter-p of the form: p = eeQ/RT 111 In this equation, R is the gas constant (2 cal. per gram mol per deg. C.), and Q is a heat of activation, which varies from material to material, and may depend upon the strain, but not upon the strain rate or the temperature. There is associated with every value of p a flow-stress curve. article of strain rate and of temperature that give the same p have the same flow-stress curve. Therefore, merely by changing the temperature of test, the effect of changing the strain rate may be obtained. Thus, under isothermal conditions, the material will behave the same at

Jan 1, 1944

By C. Zener, John H. Hollomon

It is commonly recognized that a given material may be described as ductile or brittle only with reference to the conditions of test. Thus under the usual test conditions quartz is brittle, but under high pressures it is ductile. Salts that are brittle at room temperature become ductile at elevated temperatures. Pitch, brittle with respect to rapid loads, flows at low rates of loading. Pearlitic steel, ductile under the usual conditions of test, may be embrittled under the proper conditions of combined stresses, temperature, and rate of loading. Earlier Investigations A clear analysis of the conditions necessary for plastic flow and for fracture was first given by LudwikI1 who introduced two types of stress, the "flow stress" and the "stress at fracture." These stresses may refer to tensile or to shear stresses, or, in fact, to any type of stress. Ludwik considered these two stresses to be independent of one another, functions of the conditions of test and of the prior history of the material. For the purpose of analysis. both a Flow stress and a stress at fracture can be envisaged as functions of strain over the entire range from zero to infinite strain. Thus, the material is brittle if the stress at fracturc is less than the flow stress and ductile if the reverse is true. According to Ludwik's analysis, the problem of determining the effects of combined stresses, of temperature and of strain rate upon the behavior of metals reduces to a problem of determining the effect of these variables upon the flow stress and upon the stress at fracture. In the present paper, methods are described for determining the effects of two of these variables, temperature and strain rate, and examples are given of the dependence of tlow stress and stress at fracture, upon these two variables. The effect of combined stresses will be discussed in a succeeding paper. The flow stress may be determined from a load-diameter curve. Load-diameter curves were obtained over a wide range of temperature and over the limited range of strain rates obtainable with the lever-type Riehle machine used. The curves were then converted to an extremely wide range of strain rate by making use of the equivalence of the effects of changes in strain rate and changes in temperature, previously proposed2 and demonstrated3 by the authors. According to this principle of equivalence, strain rate e and temperature T affect the flow stress only through a single parameter-p of the form: p = eeQ/RT 111 In this equation, R is the gas constant (2 cal. per gram mol per deg. C.), and Q is a heat of activation, which varies from material to material, and may depend upon the strain, but not upon the strain rate or the temperature. There is associated with every value of p a flow-stress curve. article of strain rate and of temperature that give the same p have the same flow-stress curve. Therefore, merely by changing the temperature of test, the effect of changing the strain rate may be obtained. Thus, under isothermal conditions, the material will behave the same at

Jan 1, 1944

By Francis Lucas

EACH year we gather in this auditorium to honor the memory of a. distinguished American metallurgist and educator. I cannot bring to you reminiscences of Prof. Henry Marion Howe as other lecturers have done. It was not my good fortune to enjoy the-privilege of studying and working under his direction. As I have reflected on the published works of Professor Howe, it has seemed to me that his mind was trained on the nature of metals and on the mechanism which produced known but unexplained effects. He was interested in controlling and regulating the causes so as to produce specific effects, useful in serving mankind. I recall an afternoon in May, 1925, when, at the invitation of Mrs. Howe, I visited his former home, Green Peace at Bedford Hills, N. Y. The purpose of my visit was to receive at the hands of the widow an engraving of Professor Howe, a reproduction of a painting from life. Mrs. Howe showed me his study. The walls of this large attractive room, brilliantly illuminated by the spring sunshine, were literally covered with the scrolls of honors and of decorations which had been conferred on Professor Howe by governments, academies, universities, societies and institutions the world over. As we walked about the room, she pointed out the significance of each honor and recited a few details of each occasion. I sensed the pride with which Mrs. Howe, then in the late autumn of her life, told me of her husbands' achievements, of his struggles, of his disappointments and of his successes. There was a surprisingly familiar note in the recital to which I was listening. I 'have found the same theme running as a disconnected thread through the written accounts of the lives of most men of science. We then went to the drawing room to chat for a few minutes before I said my farewells. As we seated ourselves, Mrs. Howe turned to me and asked: "Mr. Lucas, what of this great microscope of yours? Cannot it be applied to the study of disease? What a great blessing it would be if it could be directed to relieve the suffering of mankind."

Jan 1, 1931

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By C. W. Binckley, F. R. Burgess, E. R. Haymaker

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well's actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2'' O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well's actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2'' O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By J. L. Bruce, G. W. Nicolson

THE country rock of the Mavrovouni mine of the Cyprus Mines Corp. is hydrothermally altered, disintegrated pillow lava, with very little tensile strength ("short" ground). In places, especially when wet, it is heavy ground, though not extremely heavy except where movement has been caused by underlying or nearby stoping operations. Damage by caving from roof or sides of galleries is not sudden but progressively faster when the size of the cave increases as a result of the fall of small pieces. CEMENT AND CONCRETE LININGS During early operations, galleries in the country rock were supported by customary mine-timbering methods. Available timber, however, was of poor quality and of relatively high price, and replacements were frequent and expensive. Furthermore, the massive sulphide ore bodies required large volumes of fresh air for ventilation and cooling, and it was therefore desirable to provide smooth-lined galleries with low resistance for the introduction of air to the ore bodies. It was also desirable to eliminate hazards of fire in shafts and underground workings insofar as this would be practical. Cement and concrete were relatively cheap, and plans for using these in support of shafts, underground galleries, raises, and chutes, were developed steadily. Circular shafts with diameters ranging from 10 to 15 ft were adopted for all permanent shafts and airways. In places these were lined with concrete poured behind sectional pressed-steel forms especially constructed for this purpose. In other places, they were lined with precast-concrete blocks. It was found that such precast concrete of good quality could be produced on mass production scale and delivered at the mine from most favorable point of manufacture, at a cost of about 25 cents per cubic foot of concrete. This refers to prewar costs. As the use of concrete blocks in circular lined galleries was developed, it was found that there were very great advantages in the reduction of air resistance as compared with customary timber supports. After best methods had been developed, it was found that breakage and replacements were extraordinarily low, averaging only about 1 ½ pct per year during a period of about 15 years. Furthermore, it has been possible to reclaim for re-use a very large percentage of the concrete blocks from abandoned galleries. During the history of the operations precast-concrete blocks have been used for lining shafts, raises, ore chutes, galleries, and shaft stations, ranging from 3 to 16 ft id. The thickness of lining has varied from 5 to 10 in.; with I2 in. thickness in a few cases. Junctions of two galleries at angles ranging from about 30 to 60° are usually made of poured concrete behind sectional forms, or of a combination of poured concrete and precast blocks. In nearly all cases it has been found advisable to make the point of the wedge at the junction, of

Jan 1, 1947

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962

In a straight caving system, the ore is first undercut and then broken down by its own weight or .by the weight of the overlying rock, or by a combination of both. Operations that involve the caving of the material overlying an orebody as an essential part of the work are also classed as caving, though practically all the ore is broken by drilling and blasting. Actually there are two distinct methods—sublevel caving and block caving, and modifications thereof. The mines described are Miami and Alaska Juneau.

Jan 1, 1925

By Alexander L. Field

The rate of elimination of carbon largely controls the time required to make a heat of steel by the basic open-hearth process and to an important degree determines the cost of refining. Practical experience has led to the generally accepted belief that the use of slags relatively high in iron oxide, such as are required to bring about rapid refining, leads to a certain sacrifice of quality in the product. As a consequence, a compromise must be made between the exceedingly slow rate of carbon drop which would correspond to the ideal case and the rapid rate which would best satisfy the condition of minimum cost. An increase in rate of refining necessarily implies an increase in the concentration of iron oxide dissolved in the metal. However, even for the infinitely slow rate that corresponds to slag-metal equilibrium, the metal would contain a certain definite concentration of dissolved iron oxide. It is a matter of great practical importance, therefore, to determine the quantitative relation between the minimum or equilibrium concentration of iron oxide in the metal and the higher concentrations which must actually obtain in practice. The present paper is devoted to the development of certain equations, derived from the established laws of physical chemistry, which will enable this relation between rate of refining and the degree of oxidation of the metal bath to be computed from operating data. So attempt is made to exhaust the possibilities of this general method of treatment. In considering rate of refining, attention is mainly confined to rate of carbon elimination. However, the equations are of a more general nature and their application may readily be extended. The results of the preliminary calculations given herein indicate that increased rate of refining may have a decided effect in increasing the concentration of iron oxide dissolved in the metal. The uncertainty which attaches to the calculated value for this relationship arises in part from probable errors in experimental data on which the calculations are based, and in part from the lack of complete or favorably disposed information on basic open-hearth practice. When the relation between rate of refining and degree of oxidation of the metal has been more accurately established than has been done in the present paper, it will then become possible to consider what comprises

THE following paper has been prepared to meet a demand for a concise review of the California oil industry. It is based largely upon information secured during the course of the senior, author's professional activities, and upon data obtained during the course of investigations for the U. S. Geological Survey and the U. S. Bureau of Mines. Considerable information has been obtained from other sources, and to those who by publication or otherwise have contributed, the writers extend their thanks. GENERAL STATEMENT In 1912 the United States produced 63.25 per cent. of the world's production of petroleum, Russia, its nearest competitor, yielding only . about 19 per cent. The production in 1912 reached 222,113,218 barrels (or 29,615,096 metric tons), compared with 220,449,391 barrels in 1911. The average price per barrel in 1912 was nearly 74 c., as against nearly 61 c. in 1911. The total value, therefore, increased 22.20 per cent., or $163,802,334 above the value for the previous year. These figures of production include pipe-line runs, independent railroad shipments, oil piped direct to refineries, and the crude oil consumed as fuel in oil production. The production does not include oil in storage in the field which has not been sold.

Jan 3, 1914

By C. H. Stewart, R. A. Fagin

A two-dimensional, three-phasereservoir simulator was programmed for a large memory digital computer. It was designed to provide a practical solution to describing the complex physical relation between the natural forces and the physical properties of a heterogeneous reservoir when subjected to a specific set of conditions. A reservoir study is briefly described to illustrate application of the model. A full volumetric account of three phases (oil, gas and water) is performed simultaneously throughout an integration net representing the reservoir. Absence of one or two of the phases is treated as a special case of the more general situation. Expansion (or contraction) of all phases, including rock expansion, is performed so that the pressure calculation is the general unsteady-state case. To account for the large variations of subsurface elevation encountered in some reseruoirs, and to allow for segregation of the various phases, a gravity head term is included in the basic drive potential. Appropriate fluid and rock properties are used in polynominal surface form (functions of pressure and/or depth) or they can be entered as space variables at each position of the integration net. An unsteady-state water influx calculation, based on the method of van Everdingen and Hurst, l was connected to the boundary of the matrix to simulate aquifers of various sizes. In addition to reservoir calculations, three-phase fluid flow from the producing depth to the wellhead, including provisions for gas lift, was incorporated in the simulator. A workover routine was also built which can automatically switch to a different set of production relations when a gas-oil ratio or water fraction reaches a limit; or it can shut-in the well if prescribed. INTRODUCTION This paper describes a reservoir engineering mathematical simulator used to represent the complex interaction of natural forces and physical properties of a reservoir during natural depletion or with various injection schemes. The simulator, which was programmed for a large memory digital computer, is a two-dimensional calculation which handles three mobile fluid phases simultaneously (oil, gas and water). Basic requisites for the method are individual well production and pressure data, hydrocarbon fluid properties, geological data (producing depth and net sand), capillary pressure data, relative permeability data and permeability and porosity information. Matching the past performance of a combination drive reservoir often has yielded information concerning continuity and the validity of basic data. Detailed predictions of future performance can be made for continuation of current depletion methods (natural depletion) as well as for various types of recovery by gas or water injection. Combination injection cases and pattern studies can also be performed. Workover programs, gas lift and different types of artificial lift programs have been investigated using a technique similar to that described by Kern and Nicholson2 except that conditions of pressure and saturation at the block within which the well is located are used rather than average reservoir conditions. Drilling additional wells to optimize profit was explored, both as to number and location, by placing wells at different spots within the reservoir matrix. Special depletion processes can be examined, such as upstructure drainage and lateral (or strike) waterfloods in thin oil columns. In one case the mathematics of the simulator were modified to calculate the displacement in the vertical plane rather than in the horizontal plane. In this manner specific reservoir problems can be studied, such as coning of gas and/or water around production points, fingering along permeable stringers or, more generally, frontal advances in a heterogeneous section.

Jan 1, 1967

By R. A. Burmeister, P. E. Greene

Two methods for the synthesis and growth of single crystals of B6 P are described: a solution-growth process employing nickel as the solvent, and a vapor-growth process employing BBr3 and pH3 as the reac-tants. Relevant portions of the Ni-B-P phase diagram have been examined and liquidus data are presented for an isobaric section at an equivalent P2 pressure of 3.8 Torr, and an isothertnal section at 1300°C. Solution-growth techniques are described and the purity and crystalline perfection of the resulting material is discussed. Epitaxial growth of BeP on &P substrates has been obtained using the vapor-phase system. Evidence is presented which supports the assignment of the stoichioknetry B6P to boron sub-plwsphide. THE B-P system differs from other III-V systems in that it contains two distinct compounds. The existence of the monophosphide (BP) has been known for some time,' whereas the subphosphide (B6P) was reported only recently.' Both of these compounds are large bandgap semiconductors (Eg = 2.0 ev for BP~ and 3.3 ev for B6P4), and are therefore of interest for optoelectronic applications. The crystal structure of B6P is quite different from those of most semiconductors, being derived from that of a-rhombohedral boron by the incorporation of the two phosphorus atoms in the intericosahedral sites of the a-boron unit cell?76 B6P also exhibits a number of unusual characteristics, including a high degree of chemical inertness, hardness, and high-temperature stability. No information concerning other physical properties is available in the literature. The present study is part of a broader investigation of the preparation and properties of B6P. This paper considers methods of growing single crystals of B6P of suitable size and quality for physical-property measurements. A detailed discussion of the electrical and optical properties of B6P will be given elsewhere.' GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP' according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .'" It is therefore possible, in principle, to apply several of the reactions reported for the synthesis of BP to the synthesis of B6P merely by selecting lower phosphorus pressures or higher temperatures, in accordance with the equilibrium data. Other techniques for the direct synthesis of microcry stalline B8P have also been reported.1°

Jan 1, 1968

By J. Paone, S. Tandanand

This paper studies the behavior of rock at the initial state of crater formation resulting from stresses created under a drill bit. The purpose of this study is to determine which mechanical properties of rock are important in rock fragmentation by drilling. Although a definite relation between the drilling strength and relevant mechanical properties has not been established, maximum yield strength or hardness of rock is apparently a parameter of drillability of rock. The strengths of rock were considered from the Mohr-Coulomb criterion from which the surface of failure was constructed. The results from previous triaxial tests on Solenhofen limestone were adopted in establishing a limit of failure. Inelastic behavior of Solenhofen limestone was observed under a low velocity impact of a hemispherical bit and under static indentation with a similar bit. Permanent set at low applied loads in the indented area was measured with an interferometric technique. A quantitative determination of strengths of the rock was made under static indentation. The maximum yield strength estimated from the average stress over the contact area for plastic deformation was used as the crushing strength of rock under a drill bit. Much research has been done on energy requirements and mechanisms of energy dissipation to perfect rock fragmentation by a drilling process. But more needs to be done. More needs to be known about the mechanisms of energy dissipation or failure criteria of rocks in the drilling process in order to evaluate the efficiency of energy requirements in specific rock fragmentation. This paper examines some published studies on rock failure and energy dissipation and presents some findings in that phase of research concerned with rock fragmentation by drilling. This work is specifically concerned with rock behavior at an early stage of failure induced by a concentrated load. Consideration is limited to the primary phase of the crater formation under drill bit, i.e., before chipping takes place. Failure Phenomena of Rocks: Failure of rocks can be classified into two types, fracture and plastic flow. Both involve separation of material to form new surfaces with complete or partial loss of cohesion. Fracture is further classified as extension (or cleavage) fracture and shear fracture. Extension fracture involves separation in a plane without shear stress component, while shear fracture involves slippage along a plane as a result of combined stresses. Then, shear fracture inclines to the axes of the principal stresses. Plastic flow occurs under combined stresses, especially at high confining pressure and temperature, and denotes macroscopically irrecoverable deformation of rocks. Flow mechanisms have been classified as in-tergranular failure, intragranular gliding, and re-crystallization of mineral constituents.6 Failure phenomena in rocks are complicated because they include fractures and plastic flow as well as a friction process developed intrinsically as the internal stresses increase. All can occur in one rupture process, depending on the varying stress conditions. Both fracture and plastic flow are encountered in rock drilling. Rock failure under a drill bit as observed in drop tests simulating a single blow of a percussion drill, consists of two types, crushing and chipping. Crushing is considered as a separation of material particles by many fractures resulting from the application of high compressive stresses exceeding the strength of rock at the contact area. Chipping results from subsurface fractures extended to the face surface; this phase is preceded by crushing or surface deformation. The state of stress under the drill bit and the strength of rock create and control these two types of failure. The state of stress under the bit and in the vicinity of the contact area depend on the bit configuration and the magnitude of applied force. The strength of rock, characterized by its ability to resist penetration, depends on its composition and structure. However, the term "strength" quantitatively defined, is still ambiguous and may or may not correspond to the tensile, compressive and shear strength obtained from simple tests. Rock Failure Criterion: Rocks are weak in tension, their tensile strength being many times less than their compressive strength. This characteristic excludes

Jan 1, 1967

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith' while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith's experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours' exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By Walter Mathesius

The use of high blast heats on furnaces melting Mesaba ores is still the exception, the average blast temperatures carried on Mesaba stacks seldom reaching 1,100" F. Some 15 years ago, when the use of fine Mesaba ores in larger proportions to the total burden first came into practice, it was found difficult to employ even those blast heats which it had been possible ' to carry with the Old Range ores. The furnaces refused to "take" high heats, and would persistently labor with irregular stock movement, which impaired the practice and increased the coke consumption. By lowering the blast temperature, the working of the furnace became smoother, and experience taught that with the softer and more easily reduced Mesaba ores, satisfactory practice could be obtained with comparatively low blast heats. Therefore a large number of Mesaba furnaces have ever since been operated on very low blast temperatures, ranging between 800" and 1,000" F. In the face of these difficulties, furnace men were slow to recognize that furnaces could be so designed as to permit a free movement of the charges in combination with the use of higher heats. Since higher blast temperatures did not seem to offer great advantages in the smelting of Mesaba ores, investments in hot-blast stoves were not as attractive to the furnace man as labor-saving devices and means of obtaining greater tonnages. The effect of this preference is keenly felt at the present time. It has brought about the peculiar situation, that the majority of our furnace plants (among them some of the most progressive) lack modern and efficient stove equipment. The result is that, even where the proper furnace lines have been adopted and conditions are now favorable to the successful employment of higher blast temperatures, the heats required for the greatest fuel economy are not available. In an endeavor to obtain results, even with inadequate equipment, we find that, at many plants, the stoves are worked far beyond their capacity. This leads, in many instances, to a situation in which the coke saving in the

Jan 1, 1915