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By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

By B. A. Eaton, R. H. Jacoby

This paper presents the depletion-performance correlations developed using data from PVT studies and well-completion tests of 27 rich gas-condensate and volatile-oil reservoir fluids. The PVT behavior for each fluid war determined experimentally in the laboratory, and the depletion performance of each fluid was then calculated. Well-completion test data consisting of reservoir pressure and temperature, initial total gas-oil ratio, and stock-tank oil gravity were used with the depletion-performance data to develop general performance correlations. Three correlations are presented. The first equation shows the empirical relation of gas in place per barrel of hydrocarbon pore space with reservoir pressure and temperature, and initial total gas-oil ratio. The second equation is the correlation of stock-tank oil in place per barrel of hydrocarbon pore space. The third equation relates stock-tank oil production (to 500-psia depletion pressure) with pressure, temperature and oil gravity. All three correlations are also presented in convenient graphical form. Gas production to 500-psia depletion pressure is approximately 92.6 per cent of the gas in place for each fluid, so no correlation was developed for gas production. INTRODUCTION The rate of discovery of shallow, low-pressure and low-temperature oil reservoirs in the United States has been declining in recent years. For this reason, the search for oil has gone to greater depths where high pressures and temperatures are encountered. A high-pressure and high-temperature reservoir is the environment in which many rich gas condensates and highly volatile oils are found. Because of this trend, the performance prediction of such reservoirs has become an important task of the reservoir engineer. The need and usefulness of a performance correlation based on field data that are available from the usual well-completion tests have previously been established. These earlier attempts have shown that the phase behavior of rich gas-condensate systems and volatile-oil systems can be correlated with fluid properties, pressure and temperature. However, very little information on gas-condensate depletion performance5 was available at the time of these earlier attempts. The availability of more recent data has made possible the development of an improved correlation. The data, as listed in Tables I and 2, are for 25 gas-condensate and two volatile-oil systems that were studied. The problem was to correlate the data for in-place fluids and the production data with the initial total gas-oil ratio, initial reservoir pressure and temperature, and stock-tank oil gravity. These correlations were obtained by multiple regression analysis, whereby the data were fitted to an equation by the method of least squared error. BASIS OF THE CORRELATIONS 1. The data used in the development of these correlations were obtained from depletion-performance calculations6 and well-test or production measurements. 2. All of the independent variables used in the correlations are available from the usual well-test completion data. 3. The reservoir volume considered is 1 bbl of hydrocarbon pore space (HCPS). 4. The gas-oil ratio used is the total standard cubic feet of gas (at 14.7 psia, 60F) coming off the entire separator train per barrel of stock-tank oil. This minimizes the effect of separator conditions which might vary from system to system. 5. The correlated pressures are the actual reservoir pressures which might or might not be the saturation pressure of the reservoir fluid.

Jan 1, 1966

By E. C. Skinner

Cardox, which consists essentially of a steel tube containing carbon dioxide compressed to the liquid state, is a trade name designating a device used principally in coal mines to break down coal. The use of Cardox to break down coal was developed in the Middle Western coal fields around 1927 or 1928. At first, a large, heavy tube was used, requiring many parts. Through experimentation and technologic improvement, the weight of the tube has been brought down from 88 lb. to 20 lb. and the new, light tube makes use of larger volumes of CO2 at lower pressures than formerly was thought possible. This blasting method is extensively used today in coal mines and probably one tenth of the bituminous coal produced in the United States is prepared with Cardox. Construction and Application As used in the coal mine, Cardox looks like a piece of steel pipe 2 to 3 in. in diameter and 3 to 5 ft. long. When it is necessary to fire a shot, the tube is wired with two leg wires that are long enough so that when the tube is pushed the desired distance into the hole the wires will protrude 5 to 6 in. It has been found that No. 18 insulated copper annunciator wire is the best material for leg wires. A two-conductor rubber-covered shot-firing cable of sufficient length is then attached to the leg wires. A 2 to 6-volt current is applied, either by means of shot-firing batteries or the standard type of shot-firing generator. Upon the application of the current, the charge in the cartridge is set off. Because the breaking action upon the coal is supplied by the relatively slow physical expansion of the carbon dioxide gas rather than by the rapid chemical formation of gases as in more familiar explosives, the result is a slow heaving action, somewhat similar to that produced by black powder, rather than a shap detonating effect. Permissible powder does its work at roughly ten times the pressures in use with Cardox. The escaped gas from a Cardox shot apparently works along the planes of weakness in the coal face, such as the coal cleats, the edges of the cut, and along the top of the seam, breaking off the coal toward the free faces and heaving the mass of coal outward. Cardox tubes are manufactured in various sizes to take care of variable conditions of seam size, undercut depth, cleatage, coal hardness, and so forth. The tubes range in diameter from 2 to 3 in. (Table I) and the normal CO2 charge is from 24 to 96 oz. For any one tube size, several sizes of shear disks are available, thus excellent control of the type of shooting desired is possible. In general, local experience and experimentation dictate the size of tube chosen for any particular job. For high coal, and deeper or wider cuts, a larger size is chosen to start with, and the opposite is true for low coal, softer coal, or small cuts. After the tube size has been experimentally selected, tests are run in the mine to determine how many shot holes are needed and where the holes should be placed. The size of the disk,

Jan 1, 1944

By E. C. Skinner

Cardox, which consists essentially of a steel tube containing carbon dioxide compressed to the liquid state, is a trade name designating a device used principally in coal mines to break down coal. The use of Cardox to break down coal was developed in the Middle Western coal fields around 1927 or 1928. At first, a large, heavy tube was used, requiring many parts. Through experimentation and technologic improvement, the weight of the tube has been brought down from 88 lb. to 20 lb. and the new, light tube makes use of larger volumes of CO2 at lower pressures than formerly was thought possible. This blasting method is extensively used today in coal mines and probably one tenth of the bituminous coal produced in the United States is prepared with Cardox. Construction and Application As used in the coal mine, Cardox looks like a piece of steel pipe 2 to 3 in. in diameter and 3 to 5 ft. long. When it is necessary to fire a shot, the tube is wired with two leg wires that are long enough so that when the tube is pushed the desired distance into the hole the wires will protrude 5 to 6 in. It has been found that No. 18 insulated copper annunciator wire is the best material for leg wires. A two-conductor rubber-covered shot-firing cable of sufficient length is then attached to the leg wires. A 2 to 6-volt current is applied, either by means of shot-firing batteries or the standard type of shot-firing generator. Upon the application of the current, the charge in the cartridge is set off. Because the breaking action upon the coal is supplied by the relatively slow physical expansion of the carbon dioxide gas rather than by the rapid chemical formation of gases as in more familiar explosives, the result is a slow heaving action, somewhat similar to that produced by black powder, rather than a shap detonating effect. Permissible powder does its work at roughly ten times the pressures in use with Cardox. The escaped gas from a Cardox shot apparently works along the planes of weakness in the coal face, such as the coal cleats, the edges of the cut, and along the top of the seam, breaking off the coal toward the free faces and heaving the mass of coal outward. Cardox tubes are manufactured in various sizes to take care of variable conditions of seam size, undercut depth, cleatage, coal hardness, and so forth. The tubes range in diameter from 2 to 3 in. (Table I) and the normal CO2 charge is from 24 to 96 oz. For any one tube size, several sizes of shear disks are available, thus excellent control of the type of shooting desired is possible. In general, local experience and experimentation dictate the size of tube chosen for any particular job. For high coal, and deeper or wider cuts, a larger size is chosen to start with, and the opposite is true for low coal, softer coal, or small cuts. After the tube size has been experimentally selected, tests are run in the mine to determine how many shot holes are needed and where the holes should be placed. The size of the disk,

Jan 1, 1944

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

COMMITTEE IN CHARGE SPENCER PENROSE, Chairman A. E. CARLTON, Chairman Finance Committee GEORGE M. TAYLOR, Vice-Chairman J. DAWSON HAWKINS, Secretary DENVER Arrangement DAVE G. MILLER FRANK BULKLEY GEO. E. COLLINS Entertainment F. H. BOSTWICK F. E. SHEPARD HOWLAND BANCROFT B. P. MORSE J. G. PERRY Finance T. B. STEARNS RICHARD A. PARKER T. B. BURBRIDGE

Jan 7, 1918

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

NITROGEN is becoming recognized as one of the important elements in ferrous physical metallurgy. Several investigations indicate that nitrogen plays a significant part in such phenomena as strain aging and temper brittleness. Nitrogen is known to be a powerful austenite stabilizer and may be a useful alloying element in stainless steels. The hard-enability of steels has been found to be increased by nitrogen. The nitriding and carbonitriding pro- cesses are examples of successful industrial application of nitrogen in ferrous materials. For a complete understanding of the various roles played by nitrogen in ferrous metallurgy a knowledge of the phase relations in the binary iron-nitrogen system is essential. The literature contains a variety of iron-nitrogen phase diagrams. Those suggested by Fry, Sawyer,² Epstein and his coworkers,³,4 Lehrer,5 Eisenhut and Kaupp, and Hägg7,8 differ significantly from one another. Moreover, the most recent of these investigations dates back about twenty years. A re-determination of the entire diagram, therefore, appeared desirable. In addition to the published phase diagrams, investigations have been carried out on portions of the iron-nitrogen system. Bramley and Haywood determined the composition and temperature of the iron-iron nitride eutectoid. The maximum solubility of nitrogen in a iron was investigated by Portevin and Seferian10 and by Diikstra. 11 Several investigators have determined the crystal structure of the various iron-nitrogen phases. In fact, Eisenhut and Kaupp6 and Hägg7 based their entire phase diagrams on the results of such studies. Epstein' and Emmett12 reported lattice-parameter measurements on the E (hexagonal close-packed) phase. Osawa and Iwaisumi13 also studied the change in lattice parameters of the a, ? and E phases with nitrogen content. Brill" and Hägg7 showed that the y' phase has an ordered structure, and Hendricks and Kostingsl5 suggested a structural relation between the E and phases. In a recent investigation Jackl6 arefully studied the super-lattice reflections from the y' and phases. Experimental Procedure A large variety of experimental methods has been used by previous investigators in studying the iron-nitrogen system. These methods include thermal analysis, microscopic examination, X ray diffraction, magnetic measurements, dilatometric analysis and anelastic experiments. Thermal analysis is of low accuracy in determining changes in the solid state. This accuracy is further decreased for iron-nitrogen alloys since composition changes will occur during heating or cooling unless extreme care is taken to use a proper atmosphere. Metallographic methods are of small value . because homogeneous iron-nitrogen alloys of sufficient size can be produced only with great difficulty. The dilatometric method is open to the same objections as thermal analysis in that changes in composition may occur during heating and cooling. Lattice parameter measurements by X ray diffraction can be used satisfactorily for determining phase boundaries if cooling is fast enough to prevent structural changes. In view of the limitations of the various other techniques two methods only were adopted in this investigation, (1) X ray diffraction measurements, and (2) a controlled nitrogenizing method. The second method is an innovation for investigating the iron-nitrogen system, and will be described at length. Materials: All iron-nitrogen alloys were prepared from carbonyl iron powder of the analysis shown in table I. The average particle size was about 20

Jan 1, 1951

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

By F. W. Lee

Historical-From the beginning of time, all ingenuity of mankind has been concentrated upon the methods of finding gold and unusual deposits in the earth. An illustration (Fig. 1) from the old treatise by Agricola, "De Re Metallica," published in 1580, will serve to show the im-plicit faith of that generation in divining methods. However, it was not until 1920 that real progress was made in prospecting by using the latest advances of the physical sciences. The public interest was stimulated by the successes of these methods on the part of commercial oper-ators, and governmental agencies received many requests for information concerning their relia-bility. There were also, in the late 1920's.high- pressure mine-promotion schemes which used geophysical methods in a very questionable manner, symbolized in Figure 2 as of 1928 by an elec-trified forked stick. Authoritative information concerning such practices for public protection was needed to curb such notorious undertakings. Dr. Scott Turner, then Director of the United States Bureau of Mines, thoroughly understood the situation and was first in the governmental de-partments to recognize the possible value of a study of modern prospecting methods. The Bureau of Mines began this investigation by employing Drs. A. S. Eve and D. A. Keys of McGill University for short periods in the summer in 1927. Their first publication [see 1 of "References" at end of paper] served to illustrate the fundamental scientific principles which underlie geophysical prospecting. This was followed by a second publication [21 giving the results of field-tests. In the light of the rapid improvements during the intervening ten years, these two papers take a historical position. Later a full-time position under Civil Service was planned by the Bureau of Mines for con-tinuous investigations and research concerning geophysics and its applications to prospecting. It was Turner's idea that. since the oil-industry had been making very rapid progress with good results, if mineral mining could also benefit to the same degree, it would be of great help to that industry.

Jan 1, 1940

By D. G. Westlake

NUMEROUS hydride habit planes in zirconium, Zircaloy-2, and Zircaloy-4 have been observed by various researchers and have been compiled by Louthan and Angerman.1 While only partial agreement exists on the identification of these habit planes, there is a growing consensus that a tensile stress applied on a polycrystalline rod during slow cooling will cause the hydride platelets to lie perpendicular to the tensile axis. walters2 agrees with Louthan and Angerman who reason that "The particular plane on which precipitation will occur is the plane that will result in the maximum relief of stress by precipitation of the low-density hydride." The experiment described below was initiated to test this hypothesis on a single crystal of zirconium. A single-crystalline tensile specimen of zone-refined zirconium, designated number 13 in a previous study,3 had a square cross section with one pair of parallel faces only 4 deg from the basal plane of the hcp structure. The tensile axis was about 86 deg from the (0001) pole, 14 deg from the (1010) pole, and 16 deg from the (1150) pole. The specimen was charged to 50 ppm H by allowing reaction with the correct amount of hydrogen at 1073°K, homogenizing at this temperature for 2 hr, and cooling in the furnace. Two- surface analysis revealed that hydride platelets had precipitated parallel to the three {1010} prism planes. The specimen was heated to 673°K, in air, for 16 hr to bring the hydrogen back into solid solution, and furnace-cooled to 573°K.* It was then stressed in ten- sion at 1.2 kg per sq mm. (This produced a resolved shear stress of 0.6 kg per sq mm for glide on the prism plane with the highest Schmid factor. A higher stress would have produced significant strain at this temperature because the critical resolved shear stress for prism-plane glide in this crystal was only 1.0 kg per sq mm at ambient temperature.) The poles of the three prism planes were at angles of 14, 46, and 74 deg to the tensile axis so that an applied stress would exert normal stresses on the three planes in the approximate ratios 10:5:1, respectively. As soon as the stress was applied, the sample was furnace-cooled to room temperature. It was ground on wet Sic paper and chemically polished in 50 parts HNO3, 50 parts water, and 7 parts HF before examination. The result of the experiment was negative; i.e., the three (1010) planes were of equal importance as hydride habit planes.* It must be admitted that the ex- periment is not entirely comparable to those performed by walters,2 Louthan,5 and Louthan and Marshall6 on polycrystalline materials. They have found that some critical stress (below the macroscopic yield stress) is required for stress-orienting the hydrides. The applied stress in the present experiment was, by necessity, smaller by an order of magnitude than the critical stresses they report for the various materials. If the critical stress was related to the microstructure, one might postulate that it should be decreased by increasing the degree of perfection of the metal lattice and by increasing the grain size. But the experiment above suggests that, for the extreme case of a zone-refined single crystal of zirconium, the critical stress lies above that which one can apply without introducing gross plastic strain as another variable.

Jan 1, 1967

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3' of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:' basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,'-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6'7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5' of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

By John S. Alexander

By L. S. Allen, R. L. Caldwell, W. R. Mills

Borehole models used in the study of nuclear well logging are reviewed and the merit of heterogeneous us homogeneous formation simulation is discussed. .A heterogeneous model for simulating sandstone formations of variable porosity is described. Simulation adequacy was checked by steady-state and pulsed-neutron measurements. INTRODUCTION In the course of developing new methods of nuclear well logging, the problem of testing new logging instruments under controlled conditions always arises. This testing is usually done in wells of known lithology, porosity and fluid saturation, or in laboratory test facilities which simulate the borehole environment. Although the former approach is possibly more satisfying, it is frequently difficult or inconvenient to find wells with enough variation in the cited parameters for a truly comprehensive study, On the other hand. laboratow- test facilities can simulate a wide variety of formation and borehole conditions if care is exercised to maintain adequate simulation under all conditions. Workers concerned with the development of nuclear well logging methods have reported several types of research facilities in the past. Tittle, et a1 used cubical tanks filled with Ottawa silica sand to study the steady-state behavior of thermal and epithemal neutrons in simulated sandstone logging environments.1 In addition to the effects of fresh vs salt water, a wide variety of casing sizes and compositions were investigated. Tittman also used a large tank of Ottawa sand to measure the slowing down length of sio2;2 for making the same measurement in CaCO3, however, an assembly of solid Vermont marble blocks was used. More recently a very useful and carefully planned test pit for nuclear logs was constructed under the auspices of the API.3 This facility consists of three massive limestone sections, each 6-ft thick and more than 5 ft in diameter. The blocks are buried, one on top of the other, in a concrete- lined pit having a total depth of 24 ft. Each section is made of a different limestone to achieve porosity variation, the selection being Carthage (2 per cent), Indiana (19 per cent) and Austin (26 per cent). The blocks are traversed by a 7 7/8-in. diameter borehole and are saturated with fresh water. Great care was taken to insure total saturation of the stone. Homogeneous mixtures and materials have not been used exclusively for simulating earth formations. Tittle, et a1 4 showed that a heterogeneous lattice of water and graphite could be used to simulate Liquid furfural with very little effecton measured thermal and epi thermal neutron distributions. Subsequently, a lattice-type model for simulating limestone earth formations was designed and built by Berry This limestone model was constructed of 7/8- x 11/4- x 36411. marble rods glued together with a plastic resin to form a 36-x 42- x 42in. cube. The cube was honeycombed vertically with 7/8- x 7/8- x 3641-1. holes for porosity and had a 111/2-in. diameter hole in the center to serve as the borehole. Lower porosities were simulated by placing marble rods in the square holes. The finished cube was used with the borehole vertical and set in a tank to hold liquid for filling the holes in the rock matrix. A second type of heterogeneous borehole model has been proposed by Kukharenko, et a1.6= In this concept the model is composed entirely of solid material. The hydrogen equivalent of formation fluids is simulated by making the model of alternating layers of dense rock and celluloid. Additional hydrogen is included by drilling vertical holes in the rock sections and filling them with solid forms of hydrogeneous material. The volume of the holes is equal to the volume of the celluloid layers, so an axial and radial dispersion of the hydrogeneous material is thus obtained. One such model was composed of alternate 50 mm-thick sand layers and 2 mm-thick celluloid sheets. Approximately 200 appropriately spaced plastic tubes were used in each sand section. The plastic tubes were filled with paraffin for additional hydrogen concentration. This arrangement yielded a model with a water-equivalent hydrogen concentration of 10 per cent. Experimental data taken in this model and in a model consisting of the same material but homogeneously dispersed showed that the heterogeneous system adequately

Jan 1, 1966

By Richard P. Rothwell

THOUGH coal has been mined in this country for more than a century, no systematic effort was ever successfully made to ascertain the total amount produced. The production of the Cumberland Basin, Md., and the shipments from the anthracite fields of Pennsylvania, have been placed upon record, thanks to the intelligence sand foresight of Mr. C. Slack in the former case, and to the late Mr. B. Bannan in the latter. For some of the years between 1822 and 1842, the production of the Richmond Basin was reported by Mr. R. C. Taylor, but since that date till the author undertook this work it was impossible to obtain any statement of the production of this field. A few of the newer fields, such as that of Mt. Diablo, Cal., have been fully reported, and a few of the newer States have also had this service performed by some intelligent private individuals.; but no statistics of coal production have ever been collected either by the State or General Government, if we except the returns for the years 1869-70 of the census report. During the year 1875, by great exertions, I succeeded in obtaining, and July 3d, 1875, gave in the Engineering and Mining Journal what, "though not an accurate statement of our coal production," was " by far the most full and reliable that had ever been published." Though that report showed the production of bituminous coal to be 23,630,094 gross tons, or about six million tons more than had ever before been reported, it was in reality two and a half million tons below the actual output. The more full returns I obtained for 1875 gave many figures for 1874

Jan 1, 1877

By A. Adiassevich

PETROLEUM has been found in Russia in various localities from north to south, as may be seen from the list given below: (a) In the basin of the Petchora river, Northern Russia. (b) In the basin of the Volga river, in the governments of Samara and Saratoff. (c) In the government of Astrakhan and in the Uralsk territory, close to the northern and eastern coast of the Caspian sea. (d) At Grozny in Northeastern Caucasus. (e) In the Daghestan territory, Eastern Caucasus, on the Caspian sea. (f) On the Apsheron peninsula (Baku and other districts) close to the Caspian sea shore. (g) On the island of Tcheleken in the Caspian sea, also on the island of Sviatoi. (h) In the Transcaspian territory on the Neftianaia Gora (Oil hill) and on the surrounding hills. (i) In the Ferghana valley in Russian Central Asia. (j) On the Kertch and Taman peninsulas on the Black sea. (k) In Siberia it has been discovered in the Transbaikal territory and on the island of Sakhalin. In the above-mentioned districts petroleum has been found to exist under different geological conditions and to vary in its chemical and physical properties. At the present time petroleum is produced in Russia at Baku, Grozny, on the island of Tcheleken, in the Ferghana district, and in the Uralsk territory. The yearly production in 1912 throughout the Russian Empire amounted to 69,400,000 barrels, of which the Baku fields were responsible for 52,000,000 barrels. This shows that the Baku fields on the Apsheron peninsula are the chief oil-producing centers in Russia, being at the same time the oldest of all our oil fields.. In this paper I shall discuss the Baku fields only, leaving all the others until a later date.

Jan 5, 1914

By R. Schuhmann, O. W. Moles

at temperatures of 1150°, 1250°, and 1350°C for liquid copper sulphides ranging in composition from saturation with Cu to about 21.5 pct S. From the experimental data, activities of Cu, S, and Cu2S in the melts were calculated. Also, the results furnish a new determination of the location of the curve showing the compositions of Cu-saturoted sulphide melts in the CU-S constitution diagram. THE "white metal" made as an intermediate L product in converting copper matte to blister copper is a matte approximating Cu2S in composition. It has long been known that liquid Cu-S mattes can exist at a given temperature over an appreciable composition range, with S:Cu ratios ranging up from a lower limit corresponding to equilibrium of the matte with a liquid Cu phase. The Cu-saturated matte has somewhat less S than Cu2S, although previous measurements of the compositions of Cu-saturated mattes are not in good agreement.'" As the S:Cu ratio approaches and slightly exceeds that for Cu2S, the partial pressure of sulphur gas over the liquid matte rapidly approaches atmospheric pressure,5 so that Cu-S melts with much more S than Cu2S can be made and handled only in pressure apparatus. Accordingly, the liquid copper sulphides of interest in copper smelting and readily studied experimentally fall in a relatively narrow composi- tion range about Cu2S. The freezing points of Cu-S mattes show a maximum of 1129°C near the composition Cu, dropping to 1105oC for Cu-saturated mattes having less S and dropping under 1100°C for higher S mattes.' Estimates of the sulphur pressure and other thermodynamic properties of liquid Cu,S were made by Kelley; based on extrapolations from equilibrium measurements on solid Cu,S. More recently, Cox and coworkers' studied equilibria in the reaction: Cu,S + H, e 2Cu + H,S over the temperature range 700" to 1250°C. They measured equilibrium H2S:H2 ratios presumably with both the sulphide and the metal phase present, so that their data above the melting point of Cu,S should measure the S pressure of Cu-saturated sulphide melts. The sulphur pressures of liquid copper sulphides of several S:Cu ratios at their freezing points can be estimated from data given by Posnjak, Allen, and Merwin." However, beyond these few data, no systematic study seems to have been made of the relations of sulphur pressure and other chemical properties of liquid copper sulphides to composition and temperature. The measurements of the sulphur pressures of liquid copper sulphides reported in this paper represent a first step in the quantitative study of the chemistry of mattes. Similar work is planned on

Jan 1, 1952

By H. H. Taft

IT has long been known that the volcanic area south of Belmont, Nye county, Nevada, had mining possibilities. Some of the old-time prospectors knew that gold existed there. Its remoteness from any source of supplies, its long distances from water, the absence of game, and more, perhaps, the lack of grass for animals to subsist upon, has made this an unattractive region in which to search for mines. The decline of the Comstock mines, the exhaustion of sun-dry large and rich ore-bodies, the high cost of mining, marketing, and particularly the ruinously high freight-charges upon refractory ore that had to be shipped to distant smelters, have kept investors out of Nevada for the last few years; and mining people have hardly yet awakened to the importance of Tonopah, Goldfield and perhaps the newer and less developed districts. The discovery of Tonopah by J. L. Butler, who located the Mizpah Claim in May, 1900, and the fortunes soon realized there, attracted many people. As the boom declined, many went away, some scattering out into the surrounding country, and the population is now about 7,000. In the fall of 1902 a discovery of gold was made 23 miles south, in what is now known as the Sandstorm group, 4 miles NW. of Goldfield. In the winter of 1903-4 the Combination, January and Florence mines were discovered, and shipments of high-grade ore soon followed. In January, 1905, there were 10,000 people in Goldfield. In June, 1904, rich gold-ore was found 85 miles SE., at the foot of the south end of the Kawich mountains, but this discovery was kept quiet until a re-location could be made. On August 10, 1904, the Bullfrog claims, and a month later the Ladd mountain and neighboring claims, were located. The Shoshone group was located September 24. This district is

Nov 1, 1905

By J. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953