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By Murray F. Hawkins

Horner1 and van Everdingen8 ave shown that the pressure drop within the wellbore, as a result of having produced the well at a constant rate q for time t, where t is sufficiently large, is: van Everdingen observed that better agreement between theory and well performance can be obtained if, instead of assuming the permeability is kc everywhere about the well, it is assumed the permeability near the well-bore is substantially reduced as a result of drilling, completion and/or production practices. In order to account for the additional pressure drop he introduced the dimensionless quantity S, the skin effect factor, so that Eq. 1 becomes: Eq. 2 might have also been obtained as follows. Assume a zone of altered permeability k, exists about the well out to a radius r and beyond that the unaltered, external permeability k. The additional pressure drop required to overcome this skin of reduced permeability may be calculated with sufficient accuracy using the incompressible flow equation; for Browns-combe and Collins1 have shown almost no difference between compressible and incompressible steady-state flow, in the vicinity of the wellbore, and the small volume of fluid in the vicinity of the wellbore makes unsteady-state mechanics unnecessary. Then. The sign of this skin pressure drop will be positive or negative depending upon whether the altered permeability k, is smaller or larger, respectively, than the external permeability k... Adding the pressure drop of Eq. 3 to Eq. 1 to find the total pressure drop: Comparing Eq. 4 with Eq. 3 it is seen that the skin effect may be defined by: be determined from pressure build-up tests1,3,4,5,6,7,8 The average permeability kavg including the altered and external permeabilities, can be determined from PI tests, and may be defined approximately on the basis of steady-state flow, as was done by Thomas' in defining the damage factor, by: The productivity ratio is the ratio of the average to the external permeability, kavg/ke or This equation shows that the productivity ratio and the skin effect are not uniquely related, because of the uncertainty in the drainage radius, and also, in many instances, the wellbore radius. Fortunately, they enter in the logarithm. The curves of Fig. I are plots of Eq. 8 for values from 100 to 50,000. The points represent the skin effects and corresponding productivity ratios from a large number of well tests, taken from Fig. 15 of Ref. 5 or Fig. 13 of Ref. 9. While some of the data

Jan 1, 1957

By D. M. James, J. C. Martin

The results are presented of a study of the application of analytical methods to the solution of two-phase flow into single wells. Approximate analytical expressions for the pressure distribution in two-phase flow are found ;;; a number of conditions. The results obtained from the analytical solutions me found to be in good agreement with results obtained by finite difference techniques using a high speed digital computer. Mathematical solutions for four sets of boundary conditions are presented. All of these solutions are composed of a short-term transient plus a steady or quasi-steady state. The rates of decay of the short-lived transients are analyzed. It is found that the durations of the short-term transients may be characterized by a parameter defined as the time constant which can be determined from simple relations. It is shown also that if the outer radius is much greater than the radius of the well. the short term transients decay at rates which are proportional to the square of the exterior radius, and the rates of decay are only slightly dependent upon the radius ratio. Numerical solutions based on finite difference techniques are presented for a number of conditions. The numerical solutions are in good agreement with the predictions based on the theoretical analysis for small and moderate drawdowns. Examples involving large drawdowns indicate that the nonlinearities in the equations of flow do not appreciably alter the longevity of the short-term transients. In all cases the time required for the short-tern transients to disappear is predicted satisfactorily. INTRODUCTION The mechanism by which oil and gas flow into a single well is of vital interest to the petroleum industry. The fundamental equations of two-phase flow which describe this mechanism are nonlinear partial differential equations. Numerical solutions of these equations describing pressure transients have been obtained with the aid of electronic computers. Although solutions obtained in this manner take into account a large number of effects, the reduction of this information to useful generalities is difficult. One method of obtaining generalities is the use of linearized approximations of the nonlinear equations. Since it is possible to obtain explicit solutions of the linearized equation, general properties of the role of pressure in the flow mechanism may be ascertained. Results obtained from this approach are limited to some extent by the linearizing assumptions. The severity of these limitations may be evaluated by comparing solutions of the linear equation with numerical solutions of the more exact nonlinear equations of two-phase flow. In the past considerable amount of work has been devoted to studying pressure build-up using the single-phase flow theory. Unfortunate1y, most prep sure build-up tests involve multiphase flow. A small amount of work has been done studying pressure build-up where the flow is two-phase. The encouraging results of these studies suggest that useful results may be found from additional studies of not only pressure build-up, but also the rapid transients associated with placing a well on production. This paper presents the basic theory of the pressure transients associated with placing a well on production and with closing it in. The paper is concerned chiefly with two-phase compressible flow; however, the results also apply to single-phase flow. The results are based on analytical solutions of the flow equations, and they are verified by numerical solutions using finite difference techniques. Much of the previous work on compressible flow into wells has been confined to single-phase flow. Some work has been done on compressible two-phase steady state flow, and solutions of the equations of flow have been found by finite difference techniques using high-speed computers. Muskat1 presents some rather general solutions to the equations of single-phase compressible flow into wells. Much work has been done on pressure build-up in wells (see, for example, Refs. 2-6). Almost all of the work on pressure build-up concerns single-phase flow with the exception of Ref. 5 and part of Ref. 2. Some work has been done on pressure fall-off in injection wells.718 Muskat9 presents the solution of the equations for radial steady state two-phase compressible flow. Handyl0 extends Muskat's solution to obtain

By Francis P. Sinn

LOW prices have made 1938 a difficult year for the zinc industry of the world. Particularly in the United States, output had to be radically curtailed to bring production into line with consumption. Despite these unfavorable conditions, some additional plant construction is contemplated. In Jugoslavia, through co-operation with the Government, Trepca Mines is lo build a zinc plant to produce 10,000 metric tons annually, the plant to be ready for operation in July, 1941). Cerro de Pasco is proceeding with its plans for an electrolytic plant in Peru. A pilot plant, to be ready next summer, is under construction. In eastern Canada an electrolytic plant is planned in Quebec to treat concentrates from Yoranda and other mines but no defi-

Jan 1, 1939

By B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By A. E. Powers, J. F. Libsch

THE simultaneous influence of time and temperature upon the tempering process in steel is well known. Hollomon and Jaffe¹ have expressed the effect of time and temperature upon the progress of tempering by a single parameter, T (c + log t); where T is the absolute temperature; t, the tempering time; and c, a constant characteristic of the steel and treatment. It was found that when hardness data for plain carbon and low alloy steels were plotted vs. this parameter, a master tempering curve was obtained which satisfied all the data for a given steel and a given hardening treatment. Roberts, Grobe, and Moersch² successfully applied the tempering parameter to various tool steels, including high speed steel for tempering times ranging from 6 min to 100 hr. The influence of tempering time and temperature upon the physical properties of high speed steel has also been extensively investigated.'" Recently, the use of induction heating for very rapid tempering treatments has received attention. The authors% have shown that tempering treatments of only a few seconds duration may be successfully applied to plain carbon and low alloy steel. However, the influence of such short tempering treatments in high speed steel has not been explored. Since high speed steel is a highly alloyed steel exhibiting physical reactions during tempering that are often relatively slow and large in magnitude, it is an interesting steel for the study of tempering reactions. It was the purpose of the present investigation, therefore, to study the early progress of reactions leading to secondary hardness in high speed steel, type 6-5-4-2, and to determine if induction-tempering treatments of a few seconds duration are able to produce results equal to those of more conventional long-time tempering cycles. Experimental Details The chemical compositions for two different heats of W-Mo high speed steel used in this study are given in Table I. Table II summarizes the heat treatment given various groups of specimens cut 21/2 in. long and centerless ground to ¼ in. diam. Hardening treatments consisted of preheating to 1600°F (870°C) for V2 hr and then oil quenching from 2250°F (1230°C). Heat I was subjected to the high temperature in a salt bath for 3 min, while specimens of heat II were austenitized in a carbon-block muffle furnace for 10 min. Specimens of series E were immediately refrigerated to — 318°F (— 195°C) in liquid nitrogen following the hardening treatment to transform the major portion of the retained aus-tenite. Specimens of series F and G were subzero cooled to — 100°F (-75°C) in a dry ice-alcohol mixture. Induction tempering was performed with a Lepel high frequency converter operating at a frequency of approximately 300,000 cycles per sec. Heating cycles were controlled and recorded for each specimen using a chromel-alumel thermocouple, percussion welded to the surface of the specimen, and a modified high speed instrument with a timer previously used and described.' Temperature oscillation of the specimens, while being held at the tempering temperature, was ± 15°F (8°C). Tempering Treatments: After hardening, specimens were tempered between 900" and 1500°F (480" and 815°C) to study the progress of retained austenite decomposition and secondary hardening. The specimens tempered in salt for 1 hr (series C, G, and I) were considered to represent conventional treatment and are used for comparison with rapid tempering treatments. Several induction-tempering cycles were employed: 1—flash tempering, i.e., induction heating to the tempering temperature and immediately cooling (series A, E, and F); 2—induction heating for 60 sec at temperature (series B); and 3—double-induction tempering by two successive heating and cooling cycles (series D). All specimens tempered by induction were heated at an initial rate of 450°F (250°C) per sec except those of series E, which were heated at an initial rate of 1300 °F

Jan 1, 1952

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Thomas M. Dr. Drown

REMARKABLE as have been the direct results of Danks's puddler, there are some indirect and incidental results, which are well worthy of study for their intrinsic value and suggestiveness. The success of Danks's machine is due mainly to the nature of the lining and the manner in which it is attached to the walls of the revolving chamber. Herein lies Danks's merit and good fortune. Given such a lining, and the success of the machine, as far as puddling iron is concerned, could easily be predicted. Other important results have, however, been obtained with this machine, which, though clearly explicable, were, nevertheless, unanticipated. These are the increased yield of bar-iron over the pig-iron charged, and the elimination of phosphorus, which, though not absolutely complete, is yet more decided than in the case of hand-puddling. As regards the increased yield, this is merely what we have a right to expect if we consider the puddling process to consist in the oxidation of the carbon and silicon of the pig by the oxygen of the oxide of iron. That this result is attained, nearly to the extent that the theory requires, in Danks's puddler, and has never been more than partially attained by the most careful experiments in hand-puddling, points clearly to the fact that the contact of the molten pig-iron with the oxide of iron is much more intimate and complete in the one instance than in the other. The action of puddling in Danks's machine may be considered to be twofold first, the removal of the carbon, silicon, and phosphorus of the pig, which is the primary object, and, second, the production of wrought iron direct from the ore, which is entirely an incidental result. Intelligent metallurgists were not long in recognizing in this latter result a fact of deeper import and greater value than the attainment of a perfect puddling process. A new method

Jan 1, 1874

By E. Breinan, M. Salkind

Al3Ni whiskers were chemically extracted from unidirectionally solidified Al-A13Ni eutectic ingots, bent into loops, and heated for 0.1 to 10 hr at 320°, 415", and 510°C. The initial strains ranged from 0.003 to 0.055. In all cases, permanent plastic deformation was noted after heat treatment. The deformation consisted of relatively uniform bending at low stresses and temperatures and short times and kinking followed by fracture at high stresses and temperatures and long times. After kinking, the whisker segments adjacent to the kinks were found to have straightened, which is evidence of a dislocation condensation mechanism. The range of temperatures and strains at which time dependent plastic deformation was found indicates that creep of whiskers probably plays a role in the creep of A13Ni whisker-reinforced aluminum. WHISKERS may be defined as nearly perfect single crystals which exhibit high strength. Because they can support high stresses at relatively low strains, they have been successfully employed in reinforcing metals at both ambient and elevated temperatures. In studying the creep behavior of A13Ni whisker-reinforced aluminum at elevated temperatures,1,2 it was noted that the composites exhibited measurable creep deformation. This investigation of the creep relaxation of individual A13Ni whiskel, extracted chemically from the composite was initiated to determine if creep of whiskers could con. "bute to the overall creep of the composite material. Many observations of plastic deformation of metal and halide whiskers have been made. Brenner3-8 noted that copper, silver, and iron whiskers exhibited heterogeneous plastic deformation at room temperature when strained beyond their yield points. Gyulai9 and Gordon10 observed plastic deformation of relatively large (>3 µ) NaCl and KC1 whiskers, although the smallest, most perfect whiskers were completely elastic. Eisner" noted plastic deformation and microcreep of iron and silicon whiskers at room temperature after straining beyond the yield point. Whiskers reported to exhibit creep at stresses below the yield point were zinc1'-" and Silicon.15 Cabrera and price" observed some zinc whiskers which crept at room temperature after a short incubation period but then stopped creeping after a short time. Because some of their specimens exhibited no creep, they concluded that those whiskers that crept were relatively imperfect. Pearson, Reed, and Feldman15 observed similar creep behavior of silicon whiskers at 800°C. They also concluded that creep of the whiskers was a result of imperfections in their crystals. Brenner16 observed delayed failure of A12O3 whiskers at elevated temperatures but found no evidence of plastic deformation up to 2030°C (99 pct of E.EREINAN and M.SALKIND,JuniorMembers AIME,are Research Scientist and Chief, respectively, Advanced Metallurgy Section, United Aircraft Research Laboratories, East Hartford, Conn. Maunscript submitted April 5, 1968. IMD the melting temperature). Brenner also noted7 that some copper and iron whiskers exhibited delayed kinking above 350°C while others did not. One can conclude from these observations that small relatively perfect whiskers could exhibit completely elastic behavior during sustained elevated-temperature loading of composites. Since A13Ni whiskers tested in both bending and tension were found to exhibit no evidence of plastic deformation at room temperature'7'18 this study was initiated to determine whether or not creep of A13Ni whiskers occurred at the elevated temperatures at which creep in the composites was observed. Whiskers were chemically extracted from ingots of unidirectionally solidified A1-A13Ni eutectic, constrained in bending to various elastic strains and heat-treated. The bending constraints were removed after heat treatment and the amount of permanent set was taken as a measure of the time-dependent plastic deformation. EXPERIMENTAL PROCEDURES Ingots of eutectic Al-A13Ni containing nominally 6.2 wt pet Ni were unidirectionally solidified at approximately 11 cm per hr using a process described elsewhere.19,20 The starting materials were 99.99 pct pure. Cylindrical sections cut from the center of each ingot were placed in a 3 pct aqueous solution of hydrochloric acid and the whiskers were extracted as described previously.17 The whiskers nearest the surface were blackened somewhat due to overexposure to the acid while the center of the ingot was being dissolved These partially attacked whiskers were discarded. An intermediate zone of silver-gray-colored whiskers was collected and stored in methanol for use in relaxation experiments. Individual long pieces of A13Ni whiskers were placed on Fisher Precleaned Microscope Slides. These normally straight whiskers were bent elastically into arcs or loops of varying radii by manipulating their ends with a slender probe. The mass attraction between the whisker and the probe was sufficient to cause the whisker to follow the probe. The whiskers were retained in the elastic bend by the surface tension of a fine residual film on the slides. By using long whiskers, the action of the surface tension on the unlooped ends of the whisker allowed high elastic strains to be maintained in the loops. After each whisker was bent, a photomicrograph was taken for use in measuring the bending strain. The range of strains studied was 0.003 to 0.055. The bent whiskers were then encapsulated in Pyrex tubes at pressures between 10"6 and 5 x 10"6 mm of mercury and heat-treated at 320°, 415°, and 510°C (respectively 53, 61, and 70 pct of the peritectic decomposition temperature). After each heat treatment, the liquid film on the slides was found to have dried, but the whiskers were held in their original shapes by a residue on the slide. The minimum radius of curvature of each bent whisker was measured before and

Jan 1, 1969

FRED. MACCOY, Raton, N. M. (written discussion *).-In the review of the Chilean nitrate industry presented by Messrs. Rogers and Van Wagenen, the most critical point relating to the future of the industry has been summed up in the last paragraph: when nitric acid can be produced synthetically cheaper than from the Chilean deposits, the Chilean industry will cease. A study of the prevailing mining methods and extraction process leads one to suspect that much can be done to reduce the present cost of the finished product; and a reasonable reduction of the cost would make available immense reserves of low-grade caliche, the locations of which are fairly well delimited. In a study of costs, one finds that actual data are very hard to procure. The average operator does not know, with any degree of reliability, his "head assay," what percentage of the caliche is lost in mining, nor what tonnage of caliche he is putting into the maquina. One manager remarked to me, "We are not concerned in what it costs to treat a ton of caliche, we are interested only in what it costs to, produce a quintal of' finished nitrate." Apart from the crude methods of mining, and the inefficient work in extraction, attention is at once drawn to the fact that the 40d., stated as the cost of the nitrate at the plant, has become 80d. by the time it is on board ship. Of this 100 per cent. increase in value, 70 per cent. is

Jan 4, 1918

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By A. Perry Thompson

I- GeneRal Distribution, AppeaRance, and Relations ........ 563 11. Data fRom MicRoscopic Examination............... 568 1. Criteria for Distinguishing Primary from Secondary Minerals...... 568 2. The Leonard Vein Filling..................... 574 Quartz............................ 575 Pyrite............................ 575 Enargite............................ 576 Covellite............................ 578 Bornite............................ 581 Chalcocite........................... 583 Chalcopyrite.......................... 586 3. The Fault-Vein Covellite..................... 587 The Speculator Ore........................ 587 The East Gray Rock Ore.....,.............. 589 4. Other Occurrences of Covellite.................. 591 111. Conclusions........................... 592 1. The Replacement of Minerals..................592 2. The Character of Mineralizing Solutions .............. 594 I. General Distribution, Appearance, and Relations Mining in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,' it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 1, 1916

By Homer W. Riley

ANTHRACITE SMALL power-driven, toothed, cast-iron rolls were used first to break anthracite in 1844. Prior to that time, men with hammers, who stood on perforated cast-iron plates, broke the large lumps into commercial sizes. In order to convert run-of-mine into the various sizes required by the anthracite industry, about 20 million tons must be broken, annually, into smaller sizes. This phase of anthracite preparation is of major importance, because the degradation accompanying reduction in coal sizes should be kept at a minimum. The exclusive use of toothed rolls for that purpose indicates that comminution by rolls is the best solution of the problem. Many improvements have been made in tooth design, but the most important was a reduction of the peripheral speed of the rolls from 1000 to 300 ft. per minute. The higher speed was based upon and approximated the velocity of a falling piece of coal when it entered the rolls, Exhaustive roll tests at the slower speed showed that the same size reduction could be affected with less degradation. The adoption, therefore, of slow-speed, compound geared rolls, especially for breaking the larger sizes, became quite general after 1912. A high-speed roll is shown in Fig. 1 and a slow-speed roll in Fig. 2. Anthracite Crushing Problems.-Crushing anthracite presents the problem of selecting a series of rolls that will produce the greatest percentage of the prepared sizes of nut and over. The size distributions to be expected are shown in Table 1. Coal breaking and crushing practices in anthracite breakers involve the use of equipment for comminuting the following classes of material: 1. Run-of-mine-plus 6 ½ -in. coal. 2. Sized coal-steamboat, broken, egg, stove, nut, and pea. 3. Flat coal--coal that is flat and hence not suitable for the market. 4. Bone--a piece of laminated coal and slate, crushed for the purpose of reclaiming the coal. 5. Breaker refuse, reduced to a size suitable for flushing into a mine for back-filling purposes.

Jan 1, 1950

By C. Ernest Birchenall, Robert F. Mehl

APPLICATION of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion coefficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner1 derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smiths on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 ACTIVITIES IN BRASS9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by azn = Pza/Pzn° [I]

Jan 1, 1947

By M. R. Tek, F. H. Poettmann, M. L. Grove

The general problem of single-phase natural gas flow through porous media has been considered both by mathematical analysis and field experiments. Theoretical studies on the fluid dynamics of natural gas wells resulted in derivations of expressions which permit a ber-ter understanding of the flow mechanism for conditions under which Darcy's law is no longer valid. In applying these results to natural gas production and testing technology, special emphasis war placed on the study of low permeability, slowly stabilizing formations. These applications resulted in a method of predicting the performance coefficients of tight natural gas wells. The calculation of the performance coefficient requires the determination of the "test-index", pkh/µ, the drain- age radius, R, and the effective wellbore radius, rw. Methods for estimating these parameters from field data were also developed. Field data from 15 wells were collected and analyzed. The measured values of the performance coefficients were compared with the predicted values. This statistical evaluation gave a bias of 7.14 per cent and a standard deviation of 11.6 per cent. INTRODUCTION The performance of a natural gas well is determined by the physical properties of the reservoir rock, the extent and the geometry of the drainage area, the properties of the flowing fluid, and the conditions of pressure distribution within the drainage matrix. The relation between the quantity of gas delivered and the pressure drop within the reservoir is characteristic of the behavior of each well and is often referred to as the back-pressure behavior of the well. It is well established that for normal, single-phase gas wells the relationship between the gas delivery rates and the bottom-hole pressure take, in general, the form, Q = c(P3 8 -P2 1)n. ,.......(1) where C is the performance coefficient, and n is the exponent corresponding to the slope of the straight-line relationship between Q and (P2 s, — P2 l) plotted on logarithmic coordinates. The determination of a well's performance by the back-pressure behavior not only permits the production engineers to analyze many operating problems, but also provides necessary information useful and essential to predict the future development of the field.' Important engineering and production problems such as calculation of gas deliverability into a pipeline at a predetermined line pressure, design and analysis of gas-gathering lines, determinations of spacing and number of wells to be drilled during field development to meet future market or contract obligations, etc., all depend, at least in part, on the availability and use of reliable back-pressure curves.' In the past the behavior of gas wells was evaluated

Jan 1, 1958

By H. J. R. Way

THE work to be described was undertaken at various periods from 1937 to 1939 on the Busia gold field, in the eastern province of Uganda. It was decided to examine the possibility of reef prospection by the resistivity method, for it was not known how far the usually disintegrated nature of most reefs in the ubiquitous laterite near the surface would obscure indications obtained by resistivity traverses. The work at the commencement was therefore largely experimental, but the results obtained thereby were satisfactory, and a survey was started at the Government closed area at Amonikakine. With the limited time and resources at the writer's disposal, it was not possible to complete the survey to his satisfaction or to follow up exhaustively all the geophysical indications, but some of the results of the experimental work and the survey were of sufficient interest to be worth recording; in particular the relation between the width of reef, electrode separation and shape of the curve, and the interference effect of constant separation curves over zones of float are significant and useful. Three new veins were located, but only one contained sufficient gold to warrant detailed prospection. This was called the Geophysical reef, and was uncovered over a strike distance of 1140 ft., and there are indications that it extends over a distance of 1990 ft. These results and the recommendations consequent therefrom were embodied in a special report to the Uganda Geological Survey. HISTORY OF THE FIELD The Busia field is in the southeastern corner of Uganda near the Kenya-Uganda border, and is about 17 miles north of the northeastern corner of Lake Victoria. Gold was first discovered in the area in the stream beds by Davies1,2 in 1932. Subsequently numerous small alluvial claims were worked by prospectors and the area was prospected for reef by a company for periods varying from three to nine months, but was finally abandoned, as the results were considered unfavorable. Further prospecting by the Geological Survey in 1935-1936 under Davies3 and later under the writer4 uncovered three reefs with sufficient gold values to be of economic interest. These were finally taken over by a company known as Borderland Syndicate, which still owns the area, and from September 1937 to the end of 1941 about 13,000 oz. of gold was extracted from reefs of the area proved by the Geological Survey. Opencast mining operations are still proceeding (February 1943). The Amonikakine area lies to the immediate north of that of Borderland Syndicate. A certain amount of prospecting had been done when the writer started work there. As a result of his report, this area was taken over by another syndicate, but little further work was accomplished before it ceased operating because of difficulties of wartime working.

Jan 1, 1944

By Thomas M. Drown

Remarkable as have been the direct results of Danks's puddler, there are some indirect and incidental results, which are well worthy of study for their intrinsic value and suggestiveness. The success of Danks's machine is due mainly to the nature of the lining and the manner in which it is attached to the walls of the revolving chamber. Herein lies Danks's merit and good fortune. Given such a lining, and the success of the machine, as far as puddling iron is concerned, could easily be predicted. Other important results have, however, been obtained with this machine, which, though clearly explicable, were, nevertheless, unanticipated. These are the increased yield of bar-iron over the pig-iron charged, and the elimination of phosphorus, which, though not absolutely complete, is yet more decided than in the case of hand-puddling. As regards the increased yield, this is merely what we have a right to expect if we consider the puddling process to consist in the oxida tion of the carbon and silicon of the pig by the oxygen of the oxide of iron. That this result is attained, nearly to the extent that the theory requires, in Danks's puddler, and has never been more than partially attained by the most careful experiments in band-puddling, points clearly to the fact that the contact of the molten pig-iron with the oxide of iron is much more intimate and complete in the one instance than in the other. The action of puddling in Danks's machine may be considered to be twofold: first, the removal of the carbon, silicon, and phospho rus of the pig, which is the primary object, and, second, the produc tion of wrought iron direct from the ore, which is entirely an inci dental result. Intelligent metallurgists were not long in recognizing in this latter result a fact of deeper import and greater value than the attainment of a perfect puddling process. A new method

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) Members and guests who called at Institute headquarters during the period Jan. 10, 1917 to Feb. 10, 1917: Victor C. Alderson, Denver, Colo. G. Komar, New York, N. Y. Arthur W. Allen, New York, N. Y . H. H. Lauer, Allentown, Pa. George S. Blair, Pittsburgh, Pa. Frederick MacCoy, Antofagasta, Chile. F. J. Brulé, Toronto, Canada. E. P. Mathewson, Toronto, Canada. W. M. Corse, Buffalo, N. Y. Douglas Muir, San Antonio, Tex. John J Croston, Cullasaja, N.' C. F. W. Osborn, Ajo, Ariz. W. A. Deane, Waxhaw, N. C. Mortimer A. Sears, Washington, D. C. P. H. Dudley, New York N. Y. W. H. Selden, Jr., Iron River, Mich. J. D. Gilchrist, Denver, Colo. W. H. Staver, Yonkers, N. Y. L. Hoffman, Pottersville, N. J. Ralph H. Sweetser, Easton, Pa. Guy R. Johnson, Florence, Wis. Benjamin F. Tibby, Salt Lake City, Utah. W. McA. Johnson, Hartford, Conn. Carl J. Trauerman, Butte, Mont. John S. Kennedy, Philadelphia, Pa. H. C. Wilmot, Arequipa, Peru. D. C. Bard has become a member of the geological department of the Chicago, Milwaukee & St. Paul R. R., with headquarters at Seattle. Jay A. Carpenter has resigned his position as metallurgist for the West End Consolidated at Tonopah and has been appointed superintendent of flip. Nevada. Packard mines it Rochester.

Jan 3, 1917

The Sub-committee on Safety of the Industrial Organization Com-mittee of the Institute has been asked to cooperate with the National Safety Council, and has made certain recommendations to the Board of Directors of the Institute regarding ways and means of bringing about this cooperation. The National Safety Council has been in existence seven years. Its inception was at a meeting of the American Iron and Steel Electrical Engineers held in Milwaukee in 1912. The first annual congress was held in New York City in October, 1913, at which time the Council was definitely organized. Its membership now consists of nearly four thousand members, representing industrial plants, railroads, public utility companies, insurance companies, state labor commissions, Chambers of Commerce, manufacturers' organizations, etc. These members are in all states of the Union and in eleven foreign countries, and through them the National Safety Council reaches more than six million workers.

Jan 7, 1919

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1' of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967