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By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By J. M. Uys, T. B. King

WalSH, Chipman, King, and rant' have measured the water content (as hydrogen) of actual steel-making slags. An average water content of 290 ppm was found for basic open-hearth tapping slags and 114 ppm for acid open-hearth slags. Upon equilibration of these slags at 1550°C with a 25 pct H20-75 pct Nz atmosphere, the water content increased to about 410 and 300 ppm for the basic and acid slags, respectively. Walsh et al. concluded that an acid slag was thus relatively far removed from equilibrium, and that basic slags showed a closer approach to equilibrium, with the water vapor in the furnace atmosphere. Herasymenko2 contended that these conclusions were unjustified, as the oxygen pressure used in the equilibration experiments, ;bout 5 x X atm, was quite different from that found in the furnace. Consequently, during the experiments the slag composition would have changed due to oxidation of ferrous iron. As an extension of Walsh's work and to attempt to clarify this matter, the solubility of water in a basic open-hearth slag was measured as a function of oxygen pressure. Similar measurements were also made on synthetic silicates in the "Fe0"-Fe203-SiO, system. The experimental technique has been described previously by Walsh et a1.l and Uys and King.3 Samples of the basic open-hearth finishing slag, contained in 10-cc platinum crucibles, were equilibrated at 1550°C with atmospheres of different oxygen pressure but constant water-vapor pressure, Ph~o = 0.192 atm. Calculations, as well as measurements, indicate that this figure approximates the water pressure of the combustion gases in a steam-atomized, oil-fired open hearth. Oxygen pressures in the open hearth can vary from 10"2 atm in the combustion gases to between l0-' and 10" atm in the steel bath. The former figure depends on the combustion practice and the latter on the carbon content and temperature of the bath. The oxygen pressure of the slag should lie somewhere between these extremes and is expected to be closer to that of the steel bath than that of the combustion gases. Oxygen pressures were therefore varied between 10" and 6 x l0 atm. At the lowest pressure the slag "puffed up" when quenched (indicating possible loss of water) so experiments were not conducted at lower oxygen pressures. The results are shown in Fig. 1, which includes the water content of the slag "as sampled". The results show that the water content of the slag increased appreciably on equilibration with water vapor at 0.192 atm pressure and that the water solubility apparently decreases with increased oxygen pressure. The solubilities found are comparable to those of the Li20-Ca0-Si02 system.3 Work with synthetic slags in the "Fe0"-Fe203-SiOz system was performed at 1500" C, with Ph20 = 0.192 atrn and for oxygen pressures varying between 10"2 and 10-lo atm. Samples for chemical analysis were prepared as described by Larson.4 The results are shown in Fig. 2. Some low-silica melts tested at low oxygen pressures "puffed up" when quenched and analyzed less than 100 ppm water; these results are not included in Fig. 2. The melts containing 40 mol pct silica also showed a tendency to "puff up" during the quench, when they were tested at the lowest oxygen pressure. These results indicate that, at constant silica content, the solubility of water decreases somewhat with increased oxygen pressure. The effect is, however, small considering the wide range of oxygen pressures studied. Also, at constant oxygen pressure (above about lom5 atm) the solubility increases

Jan 1, 1963

By W. A. Hockings, D. W. Fuerstenau, A. L. Mular

This paper briefly describes a simple air pycno-meter and its use for rapid determination of the composition of mixtures of solid particles. Research on such problems as the pelletizing of solids, the mixing of solid particles, and the comminution of mixtures can be simplified by means of this analytical tool. THEORY OF OPERATION Liquid pycnometers1 are commonly employed to measure volumes. These devices are time consuming and sometimes give inconsistent results. The liquid used in the pycnometer may have an undesired influence on the material to be measured; moreover, complete displacement of air by the liquid is seldom

Jan 1, 1963

By A. M. Gaudin

THE purpose of ore dressing is to separate the rough ore into one or several valuable concentrates and a discarded tailing. The first step is to crush the ore so that the resulting particles may be individually valuable or worthless. The next step generally has to be a sizing operation, because the property by which concentration is effected depends on the size of the in-dividual mineral particles as well as on their physical properties. These two effects may cancel each other if a preliminary sizing is not resorted to. Sizing is accomplished by screening or classifying. Screening depends almost solely on the dimensions of the particles; classifying depends also on the specific gravity of the particles and the viscosity of the settling medium in which the classifying operation is conducted. Classification, therefore, is to a certain extent a con-centrating operation as well as a sizing operation. Before the days of concentration by flotation, the available screens were mechanically poor. As a result classification was employed for sizing in the range. of comparatively coarse sands (table feeds). In recent years, the advent of stage-grinding to flotation size has brought about the development of good screens, which are more economical than classifiers down to about 20, -mesh. With decreasing size at which separation is to be made, screens become increasingly uneconomical, while classifiers become increasingly economical. The line of demarcation between the respective fields of screening .and classification is, therefore, fairly sharp. With the development of processes of concentrating finely comminuted ore, the need for classifiers or other sizing devices operating so as to make efficiently a split at a very fine size has become increasingly apparent. Such classifiers might be termed de-slimers, from the fact that they separate a material having a slimy ap-pearance from one having the characteristics of a sand. Sizing-tests are carried on by means of testing sieves, the finest of which have apertures of about 1/500 of an inch. The 200-mesh sieve, which has an average open-ing of 0.0029 linear inches is generally considered the limit of practical test-sizing. As a result, little is known of minus 200-mesh material and the advantages of classifying concentrator feeds within the minus 200-mesh range has been overlooked. An extension of the -present sieve scale beyond the 200-mesh screen is given in Table 1.

Jan 2, 1927

Low Zinc Prices Close Alcoa Mine Alcoa Mining Co., announced that it will suspend operations at its Hutson mine, near Salem, Ky., because of low zinc prices, January 15. The Aluminum Co. of America subsidiary announced that the low market has made zinc mining un- profitable. About 70 men were employed at the mine, with a production of about 5000 tons of zinc annually. Alcoa said the shutdown would not affect other company operations, with most of the men at Hutson absorbed in the mining firm's fluorspar operations in the same area.

Jan 2, 1953

By Carl Heinrich

I HAVE read with particular interest that portion of the discussion by Anton Eilers referring to the high-lime (and also high-alumina) slags made by August Raht in 1881, while smelting the Horn Silver ores at Franklin, Utah. The two analyses of such slags, furnished by Mr. Raht to Mr. Eilers are: Horn Silver Slags Oxygen(b) Oxygen(b) Average of I and. II Slag I percentage Slag II percentage Oxygen Si02 33.9 18.1 .35.0 18.7 34.50 18.40 FeO 26.8 6.0 25.4 5.7 26.10 5.80 CaO 26.1 7.5 24.9 7.1 25.50 7.30 BaO 3.2 (a) 0.3 3.2 0.3 3.20 0.30 A1203 10.8 5.1 9.3 4.4. 10.05 4.75 100.8 37.0 97.8 36.2

Jan 10, 1916

By E. S. Moore

The Kolar gold field has been for a long time the most important gold-producing area of India. It is situated in the Skate of Mysore, southern India, and not far from the City of Bangalore. The productive field is about 3 miles long and in it a gold-bearing quartz vein varying in width from 1 in. to over 10 ft. is worked. The vein carries high values to great depths and many of the mines have paid large dividends. Geological Formations In KolaR Region The rocks of the Kolar region are pre-Cambrian in age and bear a close resemblance to some of the pre-Cambrian formations of America. The oldest rocks seen are basic lavas, now mostly altered to hornblende-schists, with which is associated some banded iron-formation; these rocks are similar to the Keewatin schists and iron-formation in the Lake Superior region. The schist is cut by the gold-bearing quartz vein. In certain parts of the area there is also a conglomerate containing pebbles of granite, jasper, and schist. The matrix resembles a hornblende-schist and is intruded by small granite dikes, which in some cases have been pinched off by squeezing of the rock. This has led Dr. W. I?. Smeeth, Chief Inspector of Mines of Mysore, to whom the writer is greatly indebted for information regarding this area and for his hospitality while visiting the field, to regard this conglomerate as a breccia due to crushing of granite dikes in the schist. Dr. J. W. Evans has regarded the conglomerate as probably a squeezed glacial boulder clay. From analogy with pre-Cambrian conglomerates in America, the writer regards it as a metamorphosed rock similar to our basal Huronian conglomerate. However, the main bearing which it has upon the problem under discussion is the apparent fact that it is younger than the schist and that it indicates the presence of a syncline in the rocks cut by the quartz vein. Surrounding the area of schist and conglomerate is a large mass of granite-gneiss resembling the Laurentian gneiss of the Lake Superior region. Still later than the rocks mentioned above are basic intrusions which cut the quartz and schists; in the mines these are known as trap. One dike of this type is 50 to 60 yd. wide.

Jan 1, 1920

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By Louis A. Carapella, William E. Shaw

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By M. L. Fuller

OWING to the nature of the die-casting process, freshly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effect of reaching a state of equilibrium at the aging temperature, beyond which no further change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (1) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time.

Jan 1, 1934

By Goerge F. Weaton

Since 1909, when an agreement between Minnesota's Tax Commission and the University of Minnesota's School of Mines was worked out, it has been the annual responsibility of the School to evaluate and classify the iron ore deposits within the State. These unique duties of an academic institution have provided School officials with an excellent view of the past, present and probable future of the mining industry in Minnesota as the average grade of iron ore (excluding taconite) * diminishes while at the same time it competes with beneficiated taconites and foreign high-grade ores for use in America's eastern blast furnaces. SYSTEM OF EVALUATION In the latter part of November of each year, the Mining Division of the Department of Taxation makes a preliminary study of the active mines which the Department wants the School of Mines to review. These are discussed with the engineers of the Ore Estimate Division of the School of Mines and with the mining companies. After these discussions, a list of the mines of each of the major operating companies is submitted to the Ore Estimate Division of the School of Mines with the request that these properties be reviewed by them as of the next assessment date (May 1st). At the same time, a letter is sent to the mining companies requesting that they submit to the Division their own estimates on the selected mines operated by them, together with all computations, drill records, maps and cross-sections. The mining companies are re- quested to send in this information during the first half of the year, and, as far as is possible, they have always complied with this request promptly. Much of this information received by the School of Mines is of a confidential nature and is treated as such.

Jan 1, 1965

By R. E. Hummel, J. W. Koger

IT is generally accepted that the martensitic start temperature (Ms) can be determined by resistivity measurements and is that temperature where the resistivity vs temperature curve on cooling first deviates from a straight line.1-4 Both Titchener and ever' and pops5 have used resistivity measurements to follow the martensitic transformation in b1 Cu-Zn and ternary Cu-Zn-based b-phase alloys, respectively. Actually because of the nature of their measurements the temperature of minimum resistivity (M) was used by these authors to determine "Ms" . Also, due to experimental difficulties in detecting M, with resistivity measurements, Pops and Massalski 8 determined M, by optical microscopy. The present communication is concerned with high-precision, low-temperature resistivity measurements which reveal a definite M, temperature which differs from the temperature of minimum resistivity (M). It is also shown that M is merely the result of the geometry of the percent-transformation curve and the temperature coefficient of resistivity of the alloy. In other words, it will be demonstrated that M has no apparent significance (except that it denotes a temperature at which some percent of martensite can be detected in a given alloy). Alloy specimens were made by melting 99.999 pct Cu and 99.9999 pct Zn in sealed and evacuated quartz tubes and homogenizing them at 601PC for 300 hr. After the alloy was cold-rolled into foils suitable for resistivity measurements, it was quenched in ice water from 871PC. The chemical analysis showed a zinc content of 38.8 wt pct. The cooling rate during the martensite transformation was 1°C per min and was controlled with a thermistor. Electrical resistivity measurements were made using a K-3 type potentiometer; the reproducibility of the resistivity values was better than 0.03 pct. Temperatures were measured with a thermocouple to an accuracy of better than 0.2° C. Fig. 1 shows the resistivity vs temperature curves of the martensitic transformation in B1 Cu-Zn for both cooling and heating. The starting point of the martensitic transformation (M,) was taken as that

Jan 1, 1968

By R. S. Montgomery

Laboratory experiments simulating rock drilling were conducted on a number of commercial grades of tungsten carbide in order to determine their wear rates when they are used as inserts in percussive rock drill bits. The test rock was Barre granite and tests were made at conditions similar to those of the carbide buttons near the periphery of a large, down-hole, button bit. In addition, some wear rate measurements were made at a low blow energy. Wear rates of these carbide buttons were an extremely sensitive function of their cobalt contents and hardnesses and were proportional to e-°.57Hup to a hardness of about 91 RA. The point of minimum wear rate, which occurs at about 92 RA, corresponds to the point of maximum compressive strength. Modern percussive rock drill bits have inserts of cemented tungsten carbide on their wear faces. These inserts have drastically reduced bit wear in comparison to that of earlier all steel bits. The most common cemented carbide grade used in percussive rock drill bits contains about ten weight percent cobalt, although grades containing more or less cobalt are also used. Contrary to the case with carbide in metal-cutting tools, alloying materials are rarely used in mining grades. There are a number of designs of rock bits in current use. The most common form is an X bit which has four chisel-form radial wings. The button bit is another important design and one which has been recently developed. This design uses a flat steel face studded with relatively small hemispherically tipped carbide buttons. These types are illustrated in Fig. 1. Studies have been made of the sliding wear of cemented tungsten carbide on rock 1-4 and multiple-impact fracture', 5-6, b~t there has been comparatively little published on the percussive wear of this material although the wear of the impact face is the most important. There is some available data on the rate of dulling of rock bit inserts in actual drilling 7 but no laboratory studies. Sliding wear studies are useful for understanding the wear of coal and mineral cutting tools and gauge wear of percussive drill bits. but the

Jan 1, 1970

By Bruno KERL

THE list of deaths reported during the year 1905 comprises the following names (the figures in parentheses indicating the year in which the persons named were elected to membership:- Honorary Member.-Dr. Bruno Kerl. Members and Associates.-Charles Christy Adams (1903), John Wesley Anderson (1898), William Burton Barber (1901), Thomas A. Bennett (1900), Luke W. Bryan (1901), Edwin S. Daugherty (1905), William Scott de Camp (1875), George H. Eldridge (1889), B. W. Frazier (1871), John Broome Guinn, Jr. (1897), Dana C. Irish (1900), Harry Hugh Lee (1899), William Alfred Lindsay (1902), Roland C. Luther (1884), James MacNaughton (1890), Gordon McLean (1899), Herbert Holmes McNamara (1902), August R. Meyer (1886), William Orr (1897), William J. Parker, Jr. (1898), Joseph Phillips, Jr. (1895), Charles O. Ripley (1902), Emmerich J. Schmitz (1883), Ludwig Philip Seeger (1900), Jacob Johnston Sperry (1900), Gustavus H. Stoiber (1902), William L. Study (1905), Robert Macnair Wilson Swan (1900), Richard Henry Terhune (1886), Joseph Thiry (1892), John N. Tisdale (1903), Alfred Isham Totten (1897), Walter H. Virgoe (1902), Charles H. Wellman (1890), Harvey L. Williams (1903). Of these, Dr. Bruno Kerl and Prof. B. W. Frazier have been made the subjects of special Biographical Notices in the Bi-Monthly Bulletin 1 the former in No. 4, July, 1905, p. 743, and the latter in No. 5, September, 1905, p. 1097. Concerning the remainder of the list, the following paragraphs comprise such information as could be obtained by the Secretary. Charles Christy Adams, who had been a member of the Institute since 1903, died in Johannesburg, South Africa, August 31. 1905. He was born in New York City, July 13, 1849, and received his technical training at the Colorado State School of

May 1, 1906

By G. Gabra

The kinetics of acidified thiourea leaching of pyrite concentrate was investigated at temperature ranging form 20 °C to a 60 °C. The effect of various parameters on the dissolution rates are discussed. The gold extraction was found to be zero and first orders with respect to Fe (111) and thiourea concentration, respectively. The order of the reaction with respect to sulfuric acid was found to be zero. The activation energy was determined from the Arrhenius plot as 2,039 kcal mole -1 (for a freshly prepared acidic solution containing Fe (111) as the oxidant and at 800 rpm stirring speed. This relatively low activation energy value suggests that the gold extraction is controlled by a-physical phenomenon. Under optimum conditions, more than 90% of gold has been dissolved in about 30 min. and 95% in 60 min. Attempt to recover gold from thiourea solution using active carbon is also discussed.

Jan 1, 1984

By C. W. Spencer, J. Singer

A PARTIAL phase diagram for the As-Te system is given in Hansen.' The only compound reported is As2Te3, melting at 362°C. Stoichiometric quantities of reagent-grade elements were reacted in evacuated quartz and directionally cooled. The resulting ingot consisted of very thin threadlike crystals from which only very small single-crystal fragments were isolated. A powder diffraction diagram disclosed nonisomorphism with the analogous V-VI compounds insofar as these have been reported; Sb2S3, As2S3, Bi,S,, and Bi2Te3 data in the ASTM index of powder patterns, together with the single-crystal data on Sb2Se3,2 were used for the com- parison with the observed spacings. Single-crystal data confirmed the uniqueness of the As2Te3 structure. Single-crystal Weissenberg diagrams have so far yielded the following data: As2Te3 is monoclinic, space group C-m (OkO data still lacking), a = 14.4A, b = 4.05A, C = 9.92A, ß = 97". The cell volume is about 5802. The set of isomorphous ortho-rhombic cells of Sb2Se3, Sb2S3, and Bi2S, are apparently related to As,Te, in having one lattice constant close to 4.0 and with cell volumes as large as 540A8. Assuming Z = 4 for As2Te3 also, the density is calculated as 6.1 which agrees well with a roughly determined value of 6.0. A complete structure analysis is under way.

Jan 1, 1956

By J. C. Martin

Stmplified equations are developed for the flow of fluids in gas drive reservoirs in which the effects of gravity can be neglected. The results show that the pressure distribution is governed by a nonlinear heat flow type of equation, and the saturation distributions are related to the pressure by the same equations QS those developed by Muskat for the average pressure and saturations in gas drive reservoirs. Unrler certain conditions the equation for the pressure can be approximated by the linear form of the heat flow equatlon. This equation tk analogous to the equation for the pressure in single-phase compressible flow The analysis reveals that the equation for the pressure in n~ultiphase flows can be obtained directly from the equation for the pressure in slngle-phase flows by simply replacing the single-phase compressibility by the total compressibility and the single-phase mobility by the sum of the mobilities of all the fluids present. Perrine's method of pressure buildup analysis for multiphme flows is based on these same substitutions. Thus, the development presented in this paper constitutes a theoretical justification for Perrine's method of pressure buildup analysis. One of the most difficult problems associated with the production of oil is the determination of the flow of the fluids within the reservoirs. One purpose of this paper is to present the development of simplified equations for the flow in gas drive reservoirs. The other purpose is to present some of the needed theoretical foundation for the methods currently being used in the analysis of multiphase pressure buildup data. The analysis presented in this paper makes use of a partial linearization of the equations governing multiphase flows. It is felt that the process of linearizing or partially linearizing the nonlinear equations of multiphase flows can lead to useful results since this process has proved extremely valuable in the study of other fields of science and engineering where nonlinear equations are encountered. Pressure buildup data of shut-in wells have been used for many years to estimate the static reservoir pressure. These data have also been used in studying the aver- age permeability both away from and close to the well-bores. The majority of the buildup data are obtained from wells producing two or three fluids. As yet the theoretical foundations for the methods of buildup analysis used in connection with rnultiphase buildup data have not been established. A number of methods of analysis of pressure buildup data have been developed." Most of these methods apply only to single-phase flows, and almost all of the theoretical analysis is confined to single-phase flows. Perrine' developed a method of analysis for rnultiphase flows from the method for single-phase flows of Miller, Dyes, and Hutchinson.' He did this by simply replacing the single-phase compressibility by the multiphase compressibility and replacing the single-phase mobility by the sum of the mobilities of the fluids in the rnultiphase flows. Obviously, such a procedure lacks a certain amount of theoretical justification, and such practices can lead to erroneous results. Fortunately, Perrine's results have a theoretical justification, and this justification is presented in the following discussion. It is assumed that gravitational effects and the cornpressibility of the rock can be neglected. Under these assumptions the equations governing the simultaneous flow of gas, oil and water in porous media areo* The preceding equations can be expanded into the following expressions.

By G. Thodos, R. B. Grieves

A method has been developed for the accurate calculation of the cricondentberm and cricondenbar temperatures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain any number of components including paraffins and isoparaffins, olefins, acetylenes, naphthenes and aromatics. This approach is based upon the mole fraction of the low-boiling component in the mixture and graphically presents the ratios of the cricondentherm and cricondenbar temperatures to the pseudocritical temperature as {unctions of a boiling-point parameter. The only requirements are the critical temperature, normal boiling point and the approximate vapor pressure behavior of each component. For mixtures of more than two constituents a stepwise calculation procedure is necessary where the pseudocritical temperature is based upon the critical temperature of the pure low-boiling component and upon the actual cricondentherm or cricondenbar temperature of the mixture of all the remaining higher-boiling components. From an analysis of 22 binary systems (123 compositionsl, the average deviation of calculated cricondentherm temperatures from reported values is 0.87 per cent, based on degrees Rankine; and for 10 multicomponent mixtures containing from three to six components, the average deviation is 0.98 per cent. From an analysis of 18 binary systems (104 compositions) the average deviation of calculated cricondenbar temperatures from reported values is 0. 79 per cent; and for 15 multicomponent mixtures, 1.47 per cent. Equations, derived from the graphical relationships, are presented which enable rapid calculations for both binary and multicomponent systems. INTRODUCTION With the increasing tendency towards the use of high pressure processes, the need for an accurate method of calculation of the properties of a multicomponent hydrocarbon mixture in the critical region is becoming more essential. Critical region phase relations are also significant in gas condensate reservoirs, for which a knowledge of the fluid phase boundaries and regions of retrograde condensation make it possible to evaluate optimum operating conditions. The possibility of liquefaction in the underground structure may be established, and information on the feasibility of the use of repressurizing may be determined. A typical phase diagram for a multicomponent hydrocarbon mixture is presented as Fig. 1. This figure also shows the regions of retrograde behavior encountered by following lines AB and AC. If accurate methods of calculating the temperatures and pressures at the critical, cricondentherm (maximum temperature) and cricondenbar (maximum pressure) points of multicomponent hydrocarbon mixtures of known composition were available, it would be possible to estimate closely the entire phase diagram of any mixture. Several methods have been presented in the literature for the estimation of the critical temperatures and pressures of multicomponent mixtures containing all types of hydrocarbons and including the fixed gases.4-8,21 Considering the cricondentherm and cricondenbar points, the work is more limited. Etter and Kay5 have developed rather complex equations for