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By Charles Russell

PRESSURES developed by the coal during the coking process have been responsible for serious trouble to many companies that operate or build by-product coke ovens. The insidious nature of this trouble is indicated by the fact that oven operators, unless they have ascertained the charac-teristics of the coals they use, cannot determine the existence of dangerous pressures until after the damage has been done. A rather popular mis-conception is that ease of pushing of the charge at the completion of the coking period indicates that no dangerous pressure has been developed, but this is far from the truth; pressures developed during the coking period are often completely dissipated by the shrinkage of the charge in the completion of coking, and so any criterion based on the ease of pushing is futile. However, methods of testing coals are available that will definitely distinguish the dangerous coals from those that are safe, and such methods have been brought to a high degree of certainty. The operator should take no risk that involves either a lack of knowl-edge of the behavior of coals during coking or the failure to believe that certain of the coals or coal mixtures can cause damage to the oven struc-ture. This merely tends to minimize the problem and leads to claims that coking coals of all kinds may be carbonized with no danger of damage to the oven structure provided some particular kind of by-product oven is used. This lack of appreciation of the true situation is in itself one of the main factors leading to damage of coke-oven structures. Coals that develop more than a certain safe pressure cannot be used in by-product coke ovens without causing damage to the side flue walls. The following paper presents a highly certain method for the measure-ment of the pressures developed during the carbonization of coal-a method that is the culmination of many years of work on the problem in which a number of methods for the purpose were investigated and used. While actual pressures found may appear to be small when expressed in pounds per square inch, the number of square inches in each oven wall is so large that the total pressure on the oven wall becomes an enormous load.

Jan 1, 1939

By C. M. Nickerson

It is apparent that repressuring of the oil measures is becoming increasingly important to the oil industry, and is a matter that warrants the best efforts of the petroleum engineer charged with applying this method of operation to a producing property. Considerable attention has been directed to repressuring in various California oil fields, such as Dominguez and Seal Beach, which have served to sell the more progressive operator on this idea and also to keep him sold. The projects that have received most attention are in comparatively young fields where the fluid levels are high, the wells, perhaps, still flowing, where the wet gas production is of considerable volume, and where there is vital need of immediate conservation of gas, which otherwise would be blown to the air. The new State of California Gas Law, which prohibits the waste of gas, has served to interest the oil industry in means of conserving the gas that is now being blown to the air because of lack of markets. This vitally affects the operator in the older, well-depleted oil fields of the state, because in many cases he has a limited market for gas, on account of the flush production from the more active oil fields. While the waste of gas is relatively small in these older fields, such as the Midway-Sunset area, it now attains considerable importance, since under the new State Gas Law it must be put to some bcneficial use. Repressuring in the older fields of California has not received the attention of the petroleum engineers that is warranted by the present situation. This paper was prepared with the view of presenting the salient features connected with repressuring in the well-depleted oil measures of the older fields, and to show what results have already been obtained in these fields by injecting the unmarketable gas into the sands, particularly in the Midway-Sunset field in the San Joaquin Valley of California. Other projects in the older fields of the state offer some supporting data in this connection, such as the Shields Canyon and the Brea Canyon fields. Gas Storage and RepressuRing On account of the lack of market for a large portion of the dry gas produced in certain of the older, well-depleted oil fields of California, the

Jan 1, 1930

By T. T. Read

A short time ago, one of the large steel companies courteously furnished the author with detailed records of the operations of a considerable number of iron blast furnaces over a period of two months. These will be made the basis of a subsequent study, but in beginning this study one of the first points requiring consideration was the probable error of the records, for what otherwise might be regarded as significant differences of performance under different conditions were perhaps really due to errors of observation, or failure to observe and record variations. If it is assumed, in blast-furnace records and calculations, that known quantities or factors are constant, .when as a matter of fact they are variable, the effects of these variations may erroneously be ascribed to some other cause. This is quite clearly expressed in the following quotation from E. Buckingham:l Theory always operates on an ideally simplified picture of reality because real phenomena are unmanageably complicated. The results obtained are not exactly true for any real phenomenon, though they may be for an ideal one; and the approxi-mation with which a theoretical equation, however obtained, represents the actual facts, always depends on the approximation in essentials between the ideal picture and its real prototype. The purpose of dimensional reasoning is to find out how some quantity which is involved in the phenomenon under consideration is related to certain others; or to find the relation connecting two or more quantities which vary, or may vary, simultaneously during the course of the phenomenon. Since we know that we must have a complete equation to start with, we begin by thinking the matter over, to see whether the quantities we have in mind are the only ones involved. Usually it is evident that they are not; so we next make a list of all the quantities we can think of which might under any circumstances be important. Upon considering this list, which is often a long one, it is usually evident that under the actual circumstances a number of these quantities may safely be ignored; so we cross them off the list and thus pass from our most general conception of the phenomenon to an ideal simpler one, in which these quantities are not involved at all.

Jan 1, 1926

By Thomas C. Baker

The Fresnillo unit of the Mexican Corporation, S. A., is situated at the old historic mining town of Fresnillo, Zacatecas, Mexico, 33 miles north of the city of Zacatecas and 750 miles south of El Paso, Tex. It is connected with the Mexican Central Railroad by a broad-gage spur 5.5 miles long, belonging to the company. Fresnillo is surrounded by a broad semi-arid valley on the Mexican plateau at an elevation of 7300 ft. The monotony of the valley is broken by a number of low hills. Near the town of Fresnillo is the " Cerro de Proano," an elliptic-shaped hill of gentle slope, rising out of the plain to a height of 325 ft.; the base has a major axis of 4500ft. and a minor axis of 3000 ft. In this hill is the silver-bearing mineralized zone, which comprises past and present mining operations. (In this paper money values are expressed throughout in American currency and the dry short ton of 2000 lb. is used.) The discovery of ore at Fresnillo is credited to the Spaniards, soon after the conquest of Mexico. There are, however, no authentic records to show the amount of work done by them. In 1832, the State of Zacatecas took possession of the property and operated it. Evidently the rich ore above the horizon of the plain had been fairly well exhausted, as an old record states that thirty shafts were used for unwatering, requiring 300 men and 1500 animals. The cost of pumping alone amounted to $150,000 a year. In spite of the fact that cheap convict labor was used, mining costs were reported as $20 and treatment charges as $20 per ton. In 1835, the state was obliged to seek foreign capital, and a company formed in London secured a controlling interest in the property. This new organization sank two shafts, one 11 by 19 ft. and the other 10 by 15 ft., to unwater the mines and extract ore. Large Cornish pumps were purchased in England and hauled overland from Vera Cruz; engines also were installed to operate the arrastres (grinding mills) in the patio process of ore treatment. Substantial buildings were erected and operations were conducted on a large scale, for that period. The patio, the largest in Mexico, was 1150 ft. square. The costs for 1850 were:

Jan 1, 1925

By H. W. Straley, G. R. MacCarthy, J. C. McCampbell, W. R. Johnson

In the spring of 1935 the authors undertook to compare the geomagnetic and direct-current carth-resistivity methods of tracing a concealed dike along its strike. An area near Chapel Hill, North Carolina, was selected, where a diabase dike was known. For rapid reconnaissance the magnetic method offers several advantages ovcr the electrical. The resistivity method is useful in determining the position of underground water, a factor of consideration in regions where mining is contemplated. All factors considered, the coincidence between the positions of the dike as determined by the two methods is striking.

Jan 1, 1940

By W. R. Johnson, H. W. Straley, J. C. McCampbell, G. R. MacCarthy

In the spring of 1935 the authors undertook to compare the geomagnetic and direct-current carth-resistivity methods of tracing a concealed dike along its strike. An area near Chapel Hill, North Carolina, was selected, where a diabase dike was known. For rapid reconnaissance the magnetic method offers several advantages ovcr the electrical. The resistivity method is useful in determining the position of underground water, a factor of consideration in regions where mining is contemplated. All factors considered, the coincidence between the positions of the dike as determined by the two methods is striking.

Jan 1, 1940

By F. L. Misaqi

The total amount of radon-222 released into the atmosphere by the US uranium mines and mills is only an infinitely small fraction of the total amount of radon released by the top layers of soil with a high concentration of uranium, such as is found in Grants, N. M. Even when compared to areas where mineable deposits of uranium are unknown, the amount of radon released by all US mining and milling operations is still relatively insignificant. Of course, higher local concentrations of airborne radioactivity may be observed around stockpiled ore and

Jan 8, 1976

By O. Skiredj, J. F. Elliott

It has been necessary to collate the available data on the solubility of graphite in Fe-Si-Mn alloys for a study of slag-metal equilibria in ferromanganese production. That study will be reported later; the collation is reported here. The carbon content of graphite-saturated liquid iron above 1153ºC by Chipman and co-workers1 is: %C= 1.34 + 2.54 x 10~3t(°C) [l] For graphite-saturated manganese above 1322ºC it is: %C = 2.68 + 3.52 x 1CT3 t(°C) [2]

Jan 1, 1963

By C. Harries

The mechanism of blasting and the effect that blasting has on rock properties including the generation of new cracks and the opening of existing joints is discussed and compared with changes in seismic velocities. .Knowing the extent of blast induced damage and the overall stable slope angle it is shown that it is possible to design blasting so as not to induce any damage behind the toe of the blast area. Practical methods of blasting to meet this criterion and the results of these blasts are then discussed.

Jan 1, 1983

By Stanley C. Herold

TWENTY-FIVE years ago no distinction was made between water wells and oil wells except in the nature of the fluid produced. Water wells usually showed no decline in their rate of production; when oil wells showed decline something in the manner of handling them was considered wrong. Both water and oil were believed to be subject to the same physical laws in their underground movement toward the wells. Today a sharp distinction is made between them. Whereas water exists alone in the porous formations at depth, oil is usually accompanied by gas. This mixture does not behave as a liquid alone. It is a frothy, seething mass of foam which approaches and enters the wells. Different physical laws come into play. Twenty-five years ago attention was directed entirely to the well itself; today the well is accepted as a mere hole in the ground, a hole to be equipped properly for efficient service, yet without any value whatever unless it is backed up by a sufficiently prolific reservoir. Then, we were concerned with wells alone, 3000 ft. in depth; now commercial wells and their reservoirs are 10.000 ft. deep. Petroleum engineering concepts have necessarily therefore undergone a change in this last quarter century. What are they today?

Jan 1, 1937

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By Scott Turner

IT has been considered that the training of an engineer is too often vocational training; that it is a pity all engineers cannot have had a period of liberal training before taking up' pure engineering. Offhand, the so-called liberal courses should bring more ready adaptability to deal with the unexpected, to face with assurance situations which have had no parallel in one's experience, and to move without hesitation under conditions which were heretofore unknown to one, than the specialized course in mining engineering. We hear increasing talk as to the necessity of making the engineer articulate and bringing him into public life. The social implications, and responsibilities of engineering are pointed out, as of equal importance with the prodigious marvels of engineering ingenuity. You often read of this as the logical result of the in¬creasing consciousness of the engineer as to his rela¬tive position in our modern industrial civilization. , Some wag has noted that man is the noblest work of God, but that man is the only one who has said so. Perhaps engineers are the only claimants as to the necessity of their going in for public life and service; at any rate, some liberal educators' still maintain that a well-rounded general education is the better training.

Jan 1, 1930

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.' Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.' They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.' He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.' They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.' The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 ' who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult's law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.' The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

GWILLIAM H. CLAMER* (Philadelphia, Pa.).-Sulphur is not so detrimental in its effect if oxygen is also present, so that in sulphur-carrying bronzes and brasses, it is advantageous to maintain a certain percentage of oxygen. As a matter of fact, it would be possible sometimes to correct difficulties by actually adding oxygen. If the cathodes were charged directly into an electric furnace in a neutral or reducing atmosphere, a very high grade of copper would result by a simple melting operation. This would very largely eliminate the loss occasioned by melting in a reverberatory furnace. In such a furnace a large amount of slag is produced during the oxidizing stage of refining. Notwithstanding the fact that melting in an electric furnace might be somewhat more expensive than melting in a fuel furnace, the ultimate result would be a saving and the production of a very high grade of copper.

Jan 1, 1919

By Herbert Lang

Cord-wood, sawn into blocks of about a foot in length, is a regular constituent of our fuel-charge at Mineral, Idaho, our work being the matting of silver-ores by fusion in a blast-furnace. The furnace is a round water-jacket furnace, of 36 inches diameter at the tuyeres, and the charge of smelting-mixture weighs 950 Ibs., requiring 110 Ibs. of Connellsville coke to drive it. I replace half this coke with 135 lbs. of fir-wood, cut from dead and apparently perfectly dry trees. This mixtrire produces as high a sn~elting-temperature as all coke, whence I infer that the smel ting-effeot of a given weight of wood is to that of the same weight of coke as 11 to 27, or 1 to 25/11. A cord of wood sawed ready for use weighs 2840 lbs., costs $5.00, and is

Jan 1, 1892

By Mason J. Christner

Geology has become increasingly quantitative in the last 20 years. This trend has been accelerated by computer capability in the manipulation of data. The mining industry has been relatively slow to harness computer power, but the larger companies have moved in this direction in the past few years. Among the leaders in this progression is the White Pine Copper Co., and the following is a brief description of their computer system for processing, managing, and utilizing geologic data. Geology The White Pine mine is in the Upper Peninsula of Michigan, 6 miles south of Lake Superior and 80 miles west of the Houghton-Hancock area, center of the famous Copper country. The ore body of chalcocite, native copper, and minor native silver, is a tabular body in the basal 25 ft of the flat lying Nonsuch Shale and the top part of the underlying Copper Harbor Conglomerate. Twelve or more

Jan 1, 1972

By P. R. Gage, R. W. Bartlett

SILICIDE coatings on refractory metals are often applied by transporting a silicon halide vapor to a hot metal surface where dissociation or hydrogen reduction occurs. The subsequent chemical reaction to produce the coating requires diffusion of silicon or the refractory metal through the in situ silicide layer. This solid-state diffusion process step is often slower than the vapor-transport step and, therefore, rate controlling. This situation is analogous to the parabolic oxidation of metals in which the oxidation rate is controlled by diffusion through the oxide layer. The purposes of this study were to 1) measure the rate of formation of MoSiz and MoSi2 coatings under conditions such that the silicide diffusion process is rate controlling and lower silicide compounds are not formed and 2) determine by a marker experiment whether silicon or the respective refractory metals are the principal diffusing species in the disilicides.

Jan 1, 1965