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By N. T. Cotman, C. H. Pickering, P. B. Crawford

A beat-conduction model has been developed to study the flow of fluids in a stratified oil reservoir which is being subjected to unsteady-state depletion. To simulate stratification, plates of different metals were joined together so that cross flow could occur between strata. A description of the model, plate construction and necessary instruments is included. The data indicate that stratified oil reservoirs experiencing cross flow may be treated as a single, homogeneous, producing sand having properties intermediate between those of the layers making up the system. A technique for averaging core-analysis data to arrive at the proper average value of rock permeability and porosity is presented INTRODUCTION Although oil has been produced from reservoirs for 100 years and reservoir injection processes have been undertaken for 40 years, the industry is still inadequately informed on the problem of reservoir inhomogeneities. Stratification is perhaps the best-known type of reservoir heterogeneity. Urenl discussed the possible significance of this nonuniformity in his 1927 paper on the theoretical aspects of water flooding. Since this time the problem of vertical permeability variations has been the subject of much discussion and numerous papers. Levorsen2 simply describes the origin of layered beds in his Geology of Petroleum. Some beds are field-wide and may be traced from well to well, while others apparently pinch-out and become discontinuous. In addition, the physical characteristics of a layer may vary from place to place. For these reasons, a stratified system is not easily defined. In calculations involving oil reservoirs in which permeabi1ities vary, methods presently used contain many simplifying assumptions. The reservoir frequently is considered as consisting of permeable layers, each of uniform vertical and lateral permeability and each behaving as if separated from adjacent layers by thin impermeable layers. Other assumptions frequently made in reservoir calculations are steady-state flow conditions, unit mobility ratio, linear geometry, average or homogeneous porosity, and negligible capillary-pressure and gravity effects. Muskat3 has. developed solutions to the stratification problem for mobility ratios other than unity for both linear and exponential permeability distributions. He assumes lateral uniformity and continuity of all productive strata and does not consider porosity. This study will take into account transient effects, cross flow and varying porosity, as well as the variations in permeability, by means of a heat analogy. Muskat5 has shown the similarity of the equations which describe the flow of fluids in a porous medium to the flow of heat through a solid. Landrum, et al,6 made an analogy between the flow of fluid in an unsymmetrical reservoir and the conduction of heat in a similarly shaped metal plate. This analogy is summarized briefly as follows. If fluid is produced from an oil reservoir above the bubble point, the resulting pressure distribution will be identical to the temperature which would result in a metal or heat-conducting plate if heat were similarly removed. This means that a study of heat flow in stratified thermal models will behave like fluid flow in stratified oil reservoirs. For mathematical correspondencies, set- Ref. 6. The fluid mobility k/p is proportional to the thermal conductivity, and the porosity-times-compressibility product is proportional to the density times specific heat of the thermal plate. EXPERIMENTAL EQUIPMENT AND PROCEDURE The stratified reservoir model used in this study is illustrated schematically in Fig. 1. A Leeds and Northrup Speedomax Type G temperature recorder

By J. W. Putman, N. J. Grant, D. S. Bloom

SEVERAL recent determinations of the melting S point of pure chromium have been reported which give values of 1845°C1; 1895°C,² 1930°C,³ 1860°C,' and 1890°C.5 because of this wide spread of values, it appeared desirable to make one additional attempt to obtain a more accurate, reliable figure. bloom and Grantx recently reported a phase transformation in chromium:.--- it was desired to check this, too, in the course of checking the melting point. To accomplish this, a much higher purity chromium was required. Electrolytic chromium containing about 0.5 pct 0 was crushed to a finer size and was then annealed in highly purified, dried hydrogen at 1375°C for 100 hr. This treatment produced chromium with about 0.008 pct 0, 0.002 pct N, and negligible carbon. The balance of the impurities was 0.3 pct Fe, 0.03 pct Si, 0.004 pct S, and less than 0.001 pct Mo. This chromium was melted in a stabilized zirconia crucible under pre-purified argon, using induction heating. Temperature measurements were made with annealed wolfram-molybdenum thermocouples and a Leeds and Northrup Speedomax Recording Potentiometer. The thermocouples were annealed for 1 min in hydrogen at a temperature of about 2400°C. Each leg of the thermocouple was immersed in an ice-water mixture using mechanical connectors to the lead wires. The thermocouple tip was immersed in the molten chromium in a zirconia protection tube which introduces an error of about 3°C as a temperature drop through the walls of the tube. The weight of chromium was about 183 g. The dimensions of the melt in the crucible were about 1.25 in. diam x 2 in. high. The tip of the thermocouple was held about ½ in. from the bottom of the crucible. Two new thermocouples were used with the above set-up giving the results shown in Table I. Since this chromium is purer than that used by Greenaway, Johnstone and McQuillan,' by Carlile et al.,4 and other investigators,²,3 it is believed to be the more accurate. Thermocouple aging effects which are believed responsible for the high value of 1930°C³ were avoided in this work. This value of 1903°C is correct to about ±10°C. The right hand column lists the temperature of the a ? ß transformation on heating and the ß ? a on cooling.3 A sample curve is shown in Fig. 1. The value so determined is 1840°C + 15°C. Fig. 1 gives adequate evidence that there is a transformation in chromium at high temperatures.' References 'H. T. Greenaway, S. T. M. Johnstone, and M. K. McQuillan: High Temperature Thermal Analysis USing the Tungsten-Molybdenum Thermocouple. Journal Inst. Metals (November 1951) 19, p. 109. ²J. W. Putman, R. D. Potter, and N. J. Grant: The Ternary System Chromium-Molybdenum-Iron. Trans. A.S.M. (1951) 43, p. 824. ³D. S. Bloom and N. J. Grant: Chromium-Nickel Phase Diagram. Trans. AIME (1951) 191, p. 1009; Journal of Metals (November 1951). ' S. J. Carlile, J. W. Christian, and W. Hume-Rothery: The Equilibrium Diagram of the System Chromium-Manganese. Journal Inst. Metals (1949) 76, p. 169. 5G. Grube and R. Knabe: Ztsch. Elektrochemie (1936) 42, p. 793.

Jan 1, 1953

By Karl F. Peterson, H. K. Najarian, Robert E. Lund

R. E. Powers (Mellon Institute of Industrial Research, University of Pittsburgh, Pittsburgh)—Several of the processing methods at the Josephtown smelter might well be considered by plants producing iron blast furnace sinter. In making blast furnace sinter the objectives are much the same as at Josephtown: To produce a strong yet porous agglomerate which has a size consist in a preferred range. The emphasis however is on production rate rather than on the size or other quality characteristics of the sinter. Therefore the technique is entirely different. Blast furnace sinter plants attempt to make their product in one pass with a minimum recirculating load and without sizing treatment after the sinter leaves the machines. Many plants are beginning to feel that more attention paid to quality characteristics would make the product a more desirable blast furnace material. The pelletizing of very fine material before placing it on the bed is not deliberately done at iron sinter plants, although the installed equipment sometimes gives a simila; action. Such pelletizing seems to be a promising way of accommodating the down-draft sintering Drocess to very fine materials. he recirculating load at Josephtown is extremely high. Two plants' producing blast furnace sinter from raw material of comparable size have a recirculating load of about 100 pct of production. At Josephtown it is notable that the size and the rate of feeding of return fines are under control. This is not the case in most blast furnace sinter plants. The sinter slicer appears to be a worthwhile aid in effecting such control. It is similar in action to rakes and plows used at a number of plants, but it has the advantage that the sinter dislodged is positively removed and not left to the inefficient action of a stationary grizzly screen. Blast furnace size specifications for sinter are not at present so rigid as the Josephtown specifications. If the sizing of blast furnace sinter does become important, then the Josephtown crushing practice, in which a large recirculating load is maintained on the crusher in order that minimum fines be produced, may be of interest. H. K. Najarian (authors' reply)—We note that Mr. Powers appreciates some points that we tried to emphasize in our paper as being of importance in making zinc sinter of good quality and which may well be applied to iron blast furnace sinter. Fig. 2 shows the pelletized nature of the feed going on to a Dwight-Lloyd type sintering machine in our plant. Practically, the entire feed consists of more or less rounded particles which permit more uniform air passage through the charge, while the larger particles in the charge roll on to the surface of the grate, which helps to keep the grate openings from being clogged by excessive fines. An agglomerated charge of this character may preferably be made by rolling action while being mixed in a rotating drum and wetted by water sprays to bind the fine particles together and give the charge the desired moisture content. From our observations of several iron ore and blast furnace flue dust sintering operations, we believe that if the fines from the sinter discharged from the machines were to be recirculated and agqlomerated with the new feed, not only sinter of better quality but larger capacity from the machines may be realized.

Jan 1, 1952

R. E. Powers (Mellon Institute of lndustrial Research, University of Pittsburgh, Pittsburgh)—Several of the processing methods at the Josephtown smelter might well be considered by plants producing iron blast furnace sinter. In making blast furnace sinter the objectives are much the same as at Josephtown: To produce a strong yet porous agglomerate which has a size consist in a preferred range. The emphasis however is on production rate rather than on the size or other quality characteristics of the sinter. Therefore the technique is entirely different. Blast furnace sinter plants attempt to make their product in one pass with a minimum recirculating load and without sizing treatment after the sinter leaves the machines. Many plants are beginning to feel that more attention paid to quality characteristics would make the product a more desirable blast furnace material. The pelletizing of very fine material before placing it on the bed is not deliberately done at iron sinter plants, although the installed equipment sometimes gives a simila; action. Such pelletizing seems to be a promising way of accommodating the down-draft sintering Drocess to very fine materials. he recirculating load at Josephtown is extremely high. Two plants' producing blast furnace sinter from raw material of comparable size have a recirculating load of about 100 pct of production. At Josephtown it is notable that the size and the rate of feeding of return fines are under control. This is not the case in most blast furnace sinter plants. The sinter slicer appears to be a worthwhile aid in effecting such control. It is similar in action to rakes and plows used at a number of plants, but it has the advantage that the sinter dislodged is positively removed and not left to the inefficient action of a stationary grizzly screen. Blast furnace size specifications for sinter are not at present so rigid as the Josephtown specifications. If the sizing of blast furnace sinter does become important, then the Josephtown crushing practice, in which a large recirculating load is maintained on the crusher in order that minimum fines be produced, may be of interest. H. K. Najarian (authors' reply)—We note that Mr. Powers appreciates some points that we tried to emphasize in our paper as being of importance in making zinc sinter of good quality and which may well be applied to iron blast furnace sinter. Fig. 2 shows the pelletized nature of the feed going on to a Dwight-Lloyd type sintering machine in our plant. Practically, the entire feed consists of more ,or less rounded particles which permit more uniform air passage through the charge, while the larger particles in the charge roll on to the surface of the grate, which helps to keep the grate openings from being clogged by excessive fines. An agglomerated charge of this character may preferably be made by rolling action while being mixed in a rotating drum and wetted by water sprays to bind the fine particles together and give the charge the desired moisture content. From our observations of several iron ore and blast furnace flue dust sintering operations, we believe that if the fines from the sinter discharged from the machines were to be recirculated and agqlomerated with the new feed, not only sinter of better quality but larger capacity from the machines may be realized.

Jan 1, 1952

By I. Havenaar

EXPERIMENTAL DATA In an article by C. K. Ferguson and J. A. Klotz,1 experiments on the filtration of drilling muds under borehole conditions are discussed. Experimental data on mud filtration through the wall and the bottom of the hole are presented. From the data on bottom-hole filtration it was concluded that the filtrate does not flow freely into the formation, but that the pores of the formation are plugged by the mud. A quantitative interpretation of the data can be civen, by using a formula for bottom-hole filtration, dehved below. This formula is based on the following assumptions, 1. Each time a blade of a drag bit, or a cone of a roller bit, moves along the bottom of the hole, the mud cake is completely removed. 3. A new mud cake is immediately formed on the freshly produced surface, and losses of "whole" mud into the formation are negligible (this is equivalent to an immediate plugging of the pores). 3. The filtration of the mud on the bottom of the hole follows the classic law: V = A +1—(Eq. I), where t is the time required to yield a volume of filtrate V, A is the surface area of filter cake, and C is a constant. The application of this equation means that any eroding effect of the mud stream on the mud cake is neglected. The formula for the calculation of the volume of filtrate, Q,, flowing in one second through the hole bottom (diam. d cm), when using a bit with n cones or blades rotating at a rate of rn revolutions per second, is derived as follows: The mud cake is formed on the bottom of the hole in the time t =1; the filtrate volume V which passes n through the bottom In this time 1s given by Eq. 1: After1/nmsec the mud cake is removed. In one m second this process takes place nm times. Therefore the volume of filtrate, obtained in one second is given by This equation has now been applied to the experiments of Ferguson and Klotz. The constants C were derived by means of Eq. 1 from the API filter losses of the muds used by the authors (t = 1,800 sec; A = 45.16cm2). A three-cone bit was used (n = 3) at 90 rpm (m = 1.5). The calculated figures are compared with the experimental data in the table below. The calculated values of Q, are usually lower than the experimental values. This may be due to the following causes. 1. The value of C used in the calculation is based on the API filter test (filtration pressure of 100 psi), whereas the experimental data were obtained with a filtration pressure of 200 psi. Although the effect of the pressure on C is not large, C decreases somewhat with increasing pressure, and this leads to a higher filtration rate. 2. Mud losses and the eroding action of the mud stream on the cake are not entirely negligible. 3. The values of Q, derived by Ferguson and Klotz from their experiments are too high, because of their assumption that all pore liquid within the formation drilled is picked up by the drilling mud. It is found, however, that the calculated values of Qf, except in the case of oil base muds, are of the right order of magnitude. ACKNOWLEDGMENT The author wishes to thank the management of the Koninklijke/Shell-Laboratorium, Amsterdam, for permission to publish this note.

Jan 1, 1957

By Nick Holonyak

Halogen vapor-transport synthesis of Ga(As,-,Px) and its preparation into laser junctions are described. Electrical and optical properties of Ga(As,-,PX) laser junctions are discussed. The present limitations in these properties are related to material proble?vzs and the very early state of development of Ga(As,-,PX), and are discussed in this context. Inhonzogeneity problems, fluctuation of As :P ratio, and problems with deep-level contaminants are described and related to Ga(As,-,PX) junction performance. Laser junctions are demonstrated which operate to wavelengths as short as 6470 A (77°K). The prospect that Ga(As,-,P,) will operate to wavelengths perhaps 100A shorter is mentioned. IN this paper we wish to describe some of the more important features of almost 1 year of experience in the preparation and properties of Ga(As,-,P,) p-n junction lasers. Because much data so far available are far from complete, some of the results still must be considered tentative and subject to correction and revision as work on Ga(As,-,P,) crystal problems progresses. Although the electrical, optical, and device properties of Ga(As,-,P,) junction lasers are understandably of considerable interest, the work to date points out that by far the most serious problems extant and those deserving first attention are problems involving the growth, doping, and perfection of Ga(As,-,P,) crystals. One of the most formidable of these is to grow Ga(As,-,P,) sufficiently free of deep levels, either due to contaminants or to structural imperfections, to allow fabrication of laser p-n junctions which can be cooled and not suffer from "freeze-out" of carriers on deep levels (and consequent double-injection behavior). In addition to the problems of growing crystals adequately free of deep levels and generally of the highest perfection, so that the best possible laser junctions can be realized, the further goal remains of increasing the phosphorus content well beyond 40 pct in an attempt to determine the practical lower wavelength limits of laser action in the Ga(As,-,P,) system. Even though the laser junctions prepared in Ga(As,-,P,) are of importance in their own right, we have considered them at this point mainly a means to study the growth and crystal problems of the material. It can be concluded that the laser junctions now available are almost completely limited by the purity and structural deficiencies of Ga(As,-,P,) crystals, and cannot be fairly compared with, for example, GaAs p-n junction lasers until Ga(As,-,P,) crystal growth has been more extensively developed. The basis for the statements above will become evident in the following sections which describe Ga(As,-,P,) crystal and junction preparation, and laser-junction properties. G(As,-,P,) CRYSTAL GROWTH As previously reported,2 we have found it convenient to employ the halogen vapor-transport process3 for synthesizing Ga(As,-,P,) crystals for use in laser junctions. Commercially available GaAs and Gap, separately prepared by halogen vapor tranport, are sealed in the desired ratio in a quartz vessel with a quantity of column-VI donor and a small quantity of metal halide which supplies the halogen for transport. The sealed ampoule, as shown in Fig. 1, is heated at a temperature in the range from 1025" to 1100°C at the position of the source GaAs and Gap. The GaAs and Gap are simultaneously vapor-transported and deposited as Ga(As,-,P,) at one end of the ampoule

Jan 1, 1964

By David Phillips, George Jura

WHEN Bridgman1 determined the volume-pressure relationships of bismuth to 100 kg Cm-2, he found two small volume discontinuities at 45 and 64 kg em-2. Probably every investigator in high pressures has determined the electrical resistivity of bismuth in this pressure range. Until Zeitlin and Brayman2 reported discontinuities in the resistance of bismuth at these pressures, no one had found resistance discontinuities

Jan 1, 1968

The Keweenaw Peninsula in the Upper Peninsula of Michigan is plagued with abandoned prospectors' test pits and mine shafts, the result of exploration and operation of mines for over 100 years. The Fort Wilkins State Park in Keweenaw County alone has three open prospectors' pits within its boundaries, protected by wooden fences and maintained by the (Michigan State Conservation Department as a tourist attraction.

Jan 1, 1967

By J. Murray Riddell

The method of treating hazards wherein value is decreased, is cited by R. D. Parks. Quite properly, the theory of probabilities is made use of when multiple hazards are under consideration. E. F. Fitzhugh, Jr. $ deals with the enhancement phase graphically and uses percentage of expectancy as derived by a study of conditions and the selection of a chance factor. It is believed that both of the authors referred to fully recognize the part which human judgment plays, and as coupled with experience, training, and the application of the theory of probabilities; in that respect the composer of this paper is in accord. Within the past year, the task of arriving at a mathematical method for handling the enhancement phase, and, additionally, coupling the negative and positive phases, was explored. In citing the hazard, or negative phase, reference is made to the text by Parks. Types of Items far Consideration On the hazard, or negative, side some of the common items to be considered are: 1. Subsidence and resulting damage. 2. Flo wage of water above that anticipated. 3. Geological. (a) Decline in quality of probable ore, and/or (b) Decline in quantity of probable ore. 4. Depressed economic conditions. 5. Litigation. Similarly, on the enhancement, or positive, side common items to be considered are: 1. Flo wage of water below that estimated. 2. Geological. (a) Increase in quality of probable ore, and/or (b) Increase in quantity of probable ore. 3. Elevated economic conditions. 4. Litigation. 5. Technological advance in the art. Tn all of the above items no consideration is given to placing a value on, or giving consideration to, possibilities. For example, referring to Table 1, the estimated normal present value (Vp) of a property, exclusive of risk consideration, is taken as $100,000. If subsidence affects the usefulness of the shaft, the present value of the property will decrease to $60,000, and it is judged that there is a 1 in 4 chance that the shaft will be impaired;, consequent.ly, if subsidence took place, the present value would be reduced ($100,000-$60,000) $40,000, but since the chance is 1 in 4, the allowable reduction would be only one-fourth of $40,000, or $10,000, or a discount of 10 pct (hazard factor) of the original value; the related safety factor is taken as unity minus 0.10, or 0.90. Thus, the original Vp, $100,000, multiplied by the safety factor ($100,000 X 0.90) gives $90,000, which is the adjusted present value of the property in this single instance. Additionally, there is a water hazard, which, if encountered, will reduce the present value to $85,000. The chance is 1 in 3. Following through with the same reasoning as shown above, the derived safety factor will be 0.95. To arrive at a single multiplying factor which will express the combined risks, the two safety factors are multiplied together, 0.90 X 0.95 = 0.855. That factor when multiplied by the origirial Vp will give the adjusted, and

Jan 1, 1950

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By Marcus A. Grossman

THE institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it," All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we should review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks.

Jan 1, 1946

By B. H. Bergstrom, D. D. Crabtree, C. L. Sollenberger

Experimental data is given for several natural minerals on the load required for the fracture of single specimens over a very wide size range. The experimental results are compared with published data, such as for coal specimens from 30 to 64 in. in size. Correlations of the specific energy (per unit mass) required for fracture with specimen size are given as functions of specimen shape and the experimentally observed load-size relationships. These correlations are discussed with reference to comminution theory. Comminution, through compression or impact, can result only if sufficient force, or energy, is applied to a specimen of a given size. The relation of specimen size to force requirements has not been adequately considered previously. For single particle fracture, it was previously shown 1 that the specific energy (energy, e, per unit mass, M) at fracture of single glass spheres was inversely proportional to the product size modulus, k, as indicated in the equation: e/M = C/k [1] This was found true not only for numerous glass specimens of the same nominal size but was true for all nominal sizes tested from 1/8 to 1 in. Also, it was observed that the smaller spheres required a greater specific energy at fracture than the larger spheres and consequently had a smaller product size modulus. However, the relationship giving the required fracture energy as a function of specimen size was not further elaborated upon. This paper will extend the development of the feed size effect on specific fracture energy for brittle materials. SPECIFIC ENERGY-FEED SlZE RELATIONSHIPS FROM PREVIOUS DATA For the particular glass spheres tested in the previously described experiments,' it can be shown, as on Fig. 1, that the specific energy varied inversely as the 4/3 power approximately of the feed size, F, in the span of nominal sizes ranging from 1/8 to 1 in. The load at which a 3-in. diam glass sphere (a crystal gazer's ball) was broken was within the range predicted by an extrapolation of this energy-feed size relationship. The product size distribution from this

Jan 1, 1963

By Shiro Ban-ya, John F. Elliott, John Chipman

The activity of carbon in Fe-C austenite at 1150°C has been determined for concentrations up to about 2.1 pct C using the equilibrium: C + COz = 2CO; equations have been derived expessing the activity as a function of carbon content on the basis of twelve mathematical models. Several of these represent the data satisfactorily. ACCURATE information on the thermodynamic properties of austenite in the binary system Fe-C is needed as a basis for studies of transformation and precipitation in steels of all sorts, alloy as well as plain carbon. The many attempts to approach this problem through statistical thermodynamics require sound and dependable experimental data in order to evaluate the several models which have been suggested. In this paper we are concerned with the experimental determination of the activity-composition relation in austenite at the temperature of its widest range of stability, approximately the eutectic temperature (1153°C). Accurate investigation of the activity of carbon in austenite may be said to have begun with the work of Dunwald and wagner.' A more detailed study was carried out by R. P. smith2 on the two equilibria: More recent work on these two equilibria has been reviewed by Chipman,3 who pointed out the experimental hazards associated with studies of Eq. [I]. Studies of this reaction involve rather small values of the ratio these are susceptible to errors due to traces of moisture in the apparatus according to the reaction: Ellis, Davidson, and Bodsworth4 evaluated K, for their experimental temperatures and used desiccants to control water vapor pressure. While they were able in this way to obtain consistent values for K1 it cannot be said that all of the uncertainties of the method have been overcome. Results by both methods reported by Schurmann, Schmidt, and wagener5 appear to be consistent except at very low carbon content. Reaction [2] was employed in the experimental work reported here. It is to be recognized, however, that it is not applicable to projected studies of certain alloy steel compositions involving stable oxide-formers.

Jan 1, 1970

By Paul M. Tyler

MINOR industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz (Iceland spar, tourmaline, fluorite, selenite, mica), and nonfuel gases (air, helium, carbon dioxide). ALUM MINERALS The alums comprise a series of double sulphates (or selenates) isomorphous with potash alum, which, according to a ruling of the Pennsylvania courts, is the only product commercially described simply as "alum." Common alum occurs in nature as kalinite (K2SO4- A12 (SO4) 324H2O). The mineral mendozite (Na2S04) 3.A12 (SO4)3- 24H2O) is soda alum; tschennigite (NH4)2SO4.Al2 (SO4)3.24H2O) is ammonium alum; and there are about a dozen other native alums and related double sulphates. Alunite (alumstone or alum rock) has the formula Al2(SO4) 3.K2S04.4A1 (OH)3 and alunogen, Al2(So4) 3.18H20. Saline residues, found wherever natural water is evaporated, may contain sulphate of alumina, which for most uses is the essential ingredient of alum. Mineral wells and springs that emerge from beds of pyritiferous shale are typically astringent and at times form local deposits of alum, generally as incrustations. Acid waters acting upon aluminous rocks may form sulphates of alumina. The alums of commerce, as well as aluminum sulphate (concentrated alum), are produced principally by treating bauxite with acid, but they have been made also on a substantial scale from clay, cryolite, pyritic slates, schists, lignites, alunite, and leucite. Alum shale-chiefly clay, pyrite, and (usually) carbonaceous matter-was extensively used in England as a source of alum for more than two centuries. In France, pyritic lignites mixed with sand and clay were burned in heaps to red ash, the leach Liquors from which, after treatment with ammonia, yielded alum and copperas. Processes have been developed for making alum or aluminum sulphate from such diverse materials as feldspar, aluminous phosphate minerals, greensand, and mixtures of mica and

Jan 1, 1949

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal etfect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24s-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to inter-crystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot he accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. Review of Previous Work In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknalll demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K • io"^ (i) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-~/m (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver.rich copper alloyZ and of duralumin.3

Jan 1, 1946

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal etfect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24s-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to inter-crystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot he accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. Review of Previous Work In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknalll demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K • io"^ (i) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-~/m (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver.rich copper alloyZ and of duralumin.3

Jan 1, 1946

INTRODUCTION Porphyry copper deposits have been reported from the Caribbean area by Pease (1966), Cox, et al. (1973), Guild (1974), Kesler, et al. (1975), and others. This chapter summarizes the most widely known characteristics of those deposits. Only one deposit that conceivably can be classed as a porphyry copper occurrence is in production (Pueblo Viejo, Dominican Republic), but others are known whose tonnage and grade are of economic interest. Deposits in this province may be classified as copper-gold or copper-molybdenum types (Kesler, 1972), but deposits associated with quartz-rich plutons that have high Na2O:K2O and high gold:copper but low molybdenum: copper ratios dominate. Porphyry copper occurrences are reported in the literature from Puerto Rico, Haiti, the Dominican Republic, Jamaica, and Cuba. Only the porphyry copper deposits from Puerto Rico are extensively described in the literature; consequently the Caribbean porphyry copper province in general is not as well documented as the southern Cordilleran orogen. Because past published technical descriptions are incomplete, some data presented here are new to the literature. The Caribbean includes the island arcs between North and South America. Porphyry copper occurrences are known from the Greater Antilles, the generally east-west trending group of islands that lies south of North America. Fig. 48, therefore, only covers the Greater Antilles portion of the Caribbean. Porphyry copper deposits in this area are not described by the Lowell and Guilbert (1970) model in details of metallization (general paucity of molybdenum), alteration (scarcity of orthoclase), or petrography (preponderance of quartz diorite). Therefore, this model should be modified to include deposits associated with quartz-bearing plutons such as those found in the Caribbean. In the Meme deposit on Haiti ore occurs in skarn adjacent to the quartz diorite phase of a composite quartz monzonite-granodio-rite-quartz diorite pluton (Kesler, 1968). This deposit, with a K-Ar 66 m.y. date, is not included in Fig. 48 as a porphyry copper deposit because metallization is restricted largely to the intruded rocks. Although the intrusive rocks at the Meme deposit may contain sulfide near skarn contacts they are otherwise essentially unaltered. Porphyry molybdenum deposits as defined by Clarke (1972) have not been reported in the Caribbean area.

Jan 1, 1978

By Paul A. Farrar, Felix Ermains, Harold Margolin

The systems Ti-Crand Ti-Vhave been reinvesti-gated in the region up to 40 wt pct alloying addition using both conventional and rapid quenching techniques. The Ti-Cr eutectoid temperature was determined to be at 667° & 10° C and 14.5 wt pct Cr. The solubility of the Cr in a Ti was found to be less than 1 pctat 700"C. The P transus of the Ti-V system was found to be depressed to 510°C at 40 wt pct V and the solubility of V in a Ti was found to be less than 2 wt pct at 700°C. Investigation by a. d. McQuillan1-3and m. k. McQuillan4 on the systems Ti-Co, Ti-Cr, Ti-Cu, Ti-Fe, Ti-Mn, Ti-Ni, and Ti-V has cast doubt as to the position of the ß/a + ß boundaries in many of these systems. Their investigations were carried out using hydrogen pressure and/or rapid quenching experiments, as opposed to the conventional quartz capsule techniques employed by most other investigator.'" By these methods, the ß/a + ß boundary was found to be lower than that obtained by conventional techniques in all except the Ti-Fe system. In the latter, the ß/a + ß boundary was essentially the same as the boundary obtained by conventional technique.7' On the basis of rapid quenching results in the Ti-Cr system, M. K. McQuillan4 placed the eutectoid temperature below 550°C whereas other investigations using conventional techniques had placed the eutectoid variously as between 650' and 700°C,5 between 675' and 700°C,6 between 650" and 675°C,7 at 670°C,8 and above 625"C.la9l3 In order to check these results, a reinvestigation of four of the systems was undertaken using both conventional and rapid-quenching techniques. The Ti-Fe and Ti-Mn systems will be dealt with in anoth er paper, with only the Ti-Cr and Ti-V systems being discussed here. EXPERIMENTAL TECHNIQUES Alloys employed for the delineation of the systems under investigation were prepared from iodide titanium sheet capsules containing the alloying materials,

Jan 1, 1962