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By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By M. Kaufman, D. Rosenthal

IT would be of great importance to our understanding of the phenomena of fracture in metals if a unique relationship could be established between stress and some easily measurable parameter of deformation up to the fracture. It is known that no such relationshir, has been found when the parameter was the mechanically measured strain,' the major part of which is plastic. The present investigation was initiated to determine, among other things, if the X-ray or lattice strain" might be a • For the definition of lattice strain see ref. 2. more suitable parameter. To this end, annealed stress free*' specimens of 61s aluminum alloy were ** Freedom of stress in this particular case means absence of those stresses which can be checked by the technique employed. tested at room temperature and liquid nitrogen temperature (—195OC), by first maintaining the same temperature from the beginning until the end of the test, and then with crossovers from one temperature to the other. Three major factors had to be taken into consideration in designing the specimens and testing equipment. The test setup must allow X-ray pictures to be taken while the specimen is under load (for as much as 2 hr at a given load). Provision must be made for maintaining the test specimen at the temperature of liquid nitrogen as well as at room temperature. In addition, the specimen must be able to rotate to allow the X,ray beam to take in as large a sample of grains as possible, to maintain centering, and to correct for effects of large grains. The final design of the specimen and equipment is shown in Figs. 1 and 2. The specimen and grips are hollow, enabling liquid nitrogen to be poured in through a funnel-container arrangement while the specimen is rotating. The diameter of the specimens at the 2 in. gage section is 5/16 in. with a 3/16 in. diameter hole through the center. A small pilot valve in the lower grip allows a very small stream of liquid nitrogen to escape, thus assuring circulation of the liquid at all times. A low temperature silicone grease-tissue paper packing is used to seal all joints. The specimen is held in the grips by a pin. Spherical socket joints at top and bottom are used to allow for proper alignment. The grips are connected to the thrust bearings by means of plastic couplings to decrease the heat flow. Rotation is accomplished by means of a motor which drives a plastic gear (integral with the lower coupling) through a semiuniversal joint to allow for deforma- tion of the specimen. The torque applied to the specimen is very small. The maximum stress caused by this torque at the highest loads reached was found to be less than 200 psi, The whole unit was mounted in a 10,000 Ib testing machine. An insulation cage was placed around the specimen to cut down air circulation, and consequent frosting of the specimen, and also to reduce radiation and convection heat losses. A narrow window, covered on both sides with a thin plastic materiai allows the X-ray beam to reach the specimen. Thermocouples placed just outside the pilot hole at the lower grip, in the bottom of the funnel container and near the top of the funnel container permitted checks of the

Jan 1, 1955

By P. E. Schauer

During the initial nine-year deple-tion of the McKamie-Patton pool gas-condensate reservoir, the pressure behavior and fluid analyses indicated pressure maintenance by gas injection would be attractive relative to continued pressure depletion. As a result, a gas cycling program was inaugurated in Aug., 1949, which has since maintained reservoir pressure. In order to evaluate the benefits of this program, the recoveries for natural depletion and for cycling followed by blowdown were determined by calculating the fractional balance of the molar quantities of vapor and liquid remaining in the reservoir and produced at the surface for various stages of depletion. The results of the investigation show theoretical ultimate recovery due to the cycling program will be 42 per cent greater than would be realized under pressure depletion type operation. INTRODUCTION The benefits of gas injection pressure maintenance programs in condensate reservoirs have been recognized and qualitatively described in several papers1-8 during the past 15 years. Some of these papers also describe methods for calculating the increased recovery realized from cycling; however, as a rule, hypothetical reservoirs were used as examples".'.. This paper presents an evaluation of the pressure maintenance program for the McKamie-Patton condensate reservoir and includes a description of the fractional balance method employed to determine the benefits. Reservoir Development and Characteristics The McKamie-Patton pool, Lafayette County, Ark., was opened in June, 1940, with production obtained from the oolitic Smackover lime at a depth of approximately 9,300 ft. The structure is an anticline 8 miles long by 1 to 2 miles wide, and is one of many productive Smackover structures in Southern Arkansas. Of predominant importance is the condensate-bearing gas cap portion of the reservoir, which covers approximately 4,000 acres, attains a maximum thickness of some 200 ft, and has an average thickness of 90 ft. Development of the cap was accomplished with 21 wells drilled on 160 acre spacing. An isopach map of the cap is shown in Fig. 1. In addition, an oil rim is present along most of the periphery of the pool. Production practice includes field separation of black oil, and a high pressure gathering system which carries total well stream from gas cap wells to a plant where condensate is separated and the gas is processed for recovery of natural gasoline, butane, and propane. Since the gas contains appreciable hydrogen sulfide, it is removed by amine contact, after which free sulfur is produced by the Claus process. Core analyses from 1,767 gas cap formation samples averaged 14.2 per cent porosity and 379 md dry air permeability. Connate water was restored on seven samples of gas cap rock by air-brine capillary techniques, from which the interpreted water saturation averaged 28.17 per cent. During the early life of the field, it was believed the recovery mechanism, based on several of the other regional Smackover reservoirs, might be a natural water drive. However, subsequent production and pressure history revealed that the gas cap would not be produced by water drive, but would behave as a closed reservoir. In this respect, during the nine-year period of natural depletion from initial production to Aug., 1949, the cap production of 84.3 billion

Jan 1, 1958

By H. H

This paper describes the milling practice and operating results of the recently installed heavy-media separation plant of Barton Mines Corporation, the world's largest producer of garnet. This pioneer application of heavy-media separation (sink-float) processes for the beneficiation of a nonmetallic ore is unique in many respects, the details of which will be apparent from the following presentation. Characteristics of the Ore The property is on Gore Mountain, 5 miles west of the village of North Creek, New York, and 11 miles by road. The altitude of the mine is approximately 2800 feet. The valuable mineral, garnet, occurs in a surface deposit, the ore body being about ¾, mile long and varying in width from 50 to 300 ft. The garnet, principally almandite, Fe3Al2 (SiO4)3, occurs in a metamorphic rock of uncertain origin. The gangue mineral is principally hornblende, which constitutes from 40 to 80 per cent of the rock. The remainder of the gangue is divided between plagioclase feldspars and hypersthene, with smaller amounts of biotite, apatite and pyrite. The garnet content of the ore body varies from 5 to 20 per cent of the mass and averages about 10 to I2 per cent. The garnet occurs as crystals, mostly imperfectly developed, known locally as "pockets." These crys- tals vary in size from a fraction of an inch to a foot or more in diameter. Occasionally crystals have been found up to 30 and 36 in. in diameter but they average 4 to 6 inches. Nearly every crystal of garnet is surrounded by a rim of coarsely crystalline hornblende. The quarry faces are striking in appearance, showing crimson-red garnet crystals with their coal black rims scattered over a grayish black background. The specific gravity of the garnet is 3.8 to 4.1 while that of the hornblende ordinarily is 3-07 to 3.24. Some specimens of very dense hornblende have been found with a specific gravity as high as 3.40. The garnet crystals are laminated in structure, and readily cleave into flat, tabular pieces with sharp, chisel-like edges. Even when crushed to a very fine size, the garnet retains this flat, sharp, slivery grain shape. This characteristic, together with its hardness and toughness, gives it its value as an abrasive- Former Operations Mining operations have been carried on for 60 years. Until 1923, only the oxidized (soft rock) section of the ore body was mined. The oxidation, which affected the garnet only slightly, made possible the removal of the garnet from the rock by hand after it was blasted down, using small hand picks. In 1923 a mill was erected on the property, and was rebuilt and redesigned in 1928. Before the adoption of heavy-media separation, concentration was effected by

Jan 1, 1943

By H. H

This paper describes the milling practice and operating results of the recently installed heavy-media separation plant of Barton Mines Corporation, the world's largest producer of garnet. This pioneer application of heavy-media separation (sink-float) processes for the beneficiation of a nonmetallic ore is unique in many respects, the details of which will be apparent from the following presentation. Characteristics of the Ore The property is on Gore Mountain, 5 miles west of the village of North Creek, New York, and 11 miles by road. The altitude of the mine is approximately 2800 feet. The valuable mineral, garnet, occurs in a surface deposit, the ore body being about ¾, mile long and varying in width from 50 to 300 ft. The garnet, principally almandite, Fe3Al2 (SiO4)3, occurs in a metamorphic rock of uncertain origin. The gangue mineral is principally hornblende, which constitutes from 40 to 80 per cent of the rock. The remainder of the gangue is divided between plagioclase feldspars and hypersthene, with smaller amounts of biotite, apatite and pyrite. The garnet content of the ore body varies from 5 to 20 per cent of the mass and averages about 10 to I2 per cent. The garnet occurs as crystals, mostly imperfectly developed, known locally as "pockets." These crys- tals vary in size from a fraction of an inch to a foot or more in diameter. Occasionally crystals have been found up to 30 and 36 in. in diameter but they average 4 to 6 inches. Nearly every crystal of garnet is surrounded by a rim of coarsely crystalline hornblende. The quarry faces are striking in appearance, showing crimson-red garnet crystals with their coal black rims scattered over a grayish black background. The specific gravity of the garnet is 3.8 to 4.1 while that of the hornblende ordinarily is 3-07 to 3.24. Some specimens of very dense hornblende have been found with a specific gravity as high as 3.40. The garnet crystals are laminated in structure, and readily cleave into flat, tabular pieces with sharp, chisel-like edges. Even when crushed to a very fine size, the garnet retains this flat, sharp, slivery grain shape. This characteristic, together with its hardness and toughness, gives it its value as an abrasive- Former Operations Mining operations have been carried on for 60 years. Until 1923, only the oxidized (soft rock) section of the ore body was mined. The oxidation, which affected the garnet only slightly, made possible the removal of the garnet from the rock by hand after it was blasted down, using small hand picks. In 1923 a mill was erected on the property, and was rebuilt and redesigned in 1928. Before the adoption of heavy-media separation, concentration was effected by

Jan 1, 1943

By E. T. Dumble

For many years there have been occasional reports of the discovery of gold from a belt of the coast country of Texas which is underlain by deposits belonging to the lower Eocene. For the most part they have been treated as newspaper reports and no examination or record of them has been made. Among such, it may be mentioned that in 1896 there was a flurry over reported gold-discoveries west of Luling and elsewhere in this belt, and in 1903 some prospect-shafts were sunk on the Gon-zales branch of the Galveston, Houston & San Antonio railway, 3 miles below Harwood. During 1912, further discoveries have again brought the matter to our attention, and it may be of interest to record the facts as we have found them. Some years ago specimens were sent me, which were said to have been taken from certain beds on Gazley creek, and concentrated by washing in a rocker. In them were several particles of gold sufficiently large to be visible to the eye. Under the microscope they showed to be, with few exceptions, sharp cornered, and not rounded as is usual with placer-gold. They were not filings, however, but their sharpness seemed rather to be due to a recent freeing from their matrix. One or two grains were rusty, and one copper-hued, but the most of them were tolerably bright. On examining the material of the samples small grains or fragments were found, of a yellowish brown color, which seemed to be of a finely-granular structure—possibly a sandstone. In these fragments I found particles of gold, one of them being large enough to be visible without a lens. Gazley creek empties into the Colorado river just north of Smithville, and for a few miles north of that place its banks show, beneath the deposits of more recent materials, the sands and clays of the Lignitie division of the Eocene, with lignite, shells of iron, etc.

Jan 1, 1913

By G. Czupryna, S. Natansohn

Electrowinning is the prevalent technique for recovering silver from wastes generated in silver-tungsten electrical contact fabrication. Such scrap is placed in a permeable plastic basket, which constitutes the anode compartment, and is suspended in a larger cell where the cathode is mounted. A silver nitrate solution is used as the electrolyte and, upon application of an electric field, the silver migrates to the cathode where it deposits. At times, there is tungsten migration to the cathode compartment and consequent co-deposition with the silver. This W contamination, which may amount to several thousand mg/L (oz per gal), necessitates additional purification of the deposited Ag and its removal would, therefore, be advantageous. Eliminating the W impurity also extends the operating period of the cell with corresponding increases in the Ag output and savings in labor costs. The solution to this problem lies in the selective removal of the W from the AgNO3 electrolyte either by liquid-liquid or liquid-solid extraction. Although W extraction in the liquid-liquid mode with a quaternary amine or other reagents as extractants appears feasible, particularly in view of the low pH (about 1.5) of the system, this approach was not considered because it is essentially a batch-type process. It is a more elaborate industrial operation than extraction by ion exchange resins. Implementing the latter process consists of passing the electrolyte from the electrowinning cell through an ion exchange column which would extract the tungsten selectively and returning the tungsten-free stream to the cathode compartment. This process continues until the W extraction efficiency decreases (as a result of resin loading) below an acceptable value. The electrolyte is then directed through another, similar column while the W values are eluted off the first one and the resin is regenerated for another cycle. Thus, two columns in a parallel flow pattern provide the means for continuous processing of the electrolyte feedstock.

Jan 1, 1984

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By F. H. Buttner, H. Udin, J. Wulff

Using a modified Udin, Shaler, and Wulff technique, the surface tension of gold Udin, purified helium was found to be 1400 ± 65 dynes per cm for the temperature range 1017° to 1042°C. IN the original Udin, Shaler, and Wulff technique for measuring the surface tension of copper: variously weighted wires were allowed to extend or contract in a copper cell held at elevated temperatures in vacuum. By plotting stress vs. strain for a wire array in one test, the stress at zero strain is obtained. This is the point where the contractile forces resulting from surface tension are balanced by the applied load, according to the expression: y = e=o r [1] where y is the surface tension in dynes per cm; a,,,, the stress at zero strain in dynes per cm; and T, the radius of the wire in cm. The assumption that the wires deform viscously permits the drawing of a straight line through the points on the stress-strain plot. Justification of the assumption has received further experimental support recently.'-' The presence of grain boundaries in the wires requires a correction to the original expression used." Thus: y = d4=T [l- (dl) (ar)Y1 [2] where, n/l is the number of grain boundaries per unit length, and a, the ratio of grain boundary tension to free surface tension. Alexander, Kuczynski, and Dawson in studying the creep of gold wire in vacuum were unable to obtain reproducible values of the surface tension of gold. In plotting stress vs. strain for progressively longer times, they found that the stress at zero strain drifted with time from positive stress values to negative values. Similarly, for the surface tension of silver, reproducible values were obtained only when a purified helium atmosphere was substituted.' Evidently the evaporation rate of silver in vacuum is too high at the temperatures employed to obtain solid-gas equilibrium even in a similar metal enclosure. Thus reproducibility of results is lost. Experimental Procedure The experimental procedure was much the same as that originally developed by Udin, Shaler, and Wulff with a few modifications and improvements. For greater accuracy in strain measurements, knots gave way to cut gage marks as shown in Fig. 1. These were made with a hand-driven lathe in which razor blades serv'ed as cutting tools. Also a more precise cathetometer with a screw accurate to 0.00015 cm was used. The tests were conducted in an atmosphere of purified .helium rather than in vacuum in order to avoid possible evaporation difficulties. Five mil wire of high purity gold (99.98 pct) was used. After cutting in the gage marks, each wire of a series of about 12 was differently loaded by welding a gold ball to one end. This was done by dipping the end of the wire in a cooling gold droplet, previously melted on a charcoal block with a No. 2 acetylene torch. The other end of the wire was strung through a hole in a gold lid and twisted over the edge to hold the wires fixed and in suspension from the lid. The lid and mounted wires were then dipped in pure ethyl alcohol to dissolve any skin oils and dirt on the surface of the wires due to handling. Finally the lid was put in place on an alundum crucible lined with gold so that the wires hung freely within the gold-lined chamber. This whole assembly was next heated in a quartz nichrome wound tube furnace and heated for a few minutes at 600°C to soften the wires. After this anneal the wires were easily straightened with tweezers. The wire assembly was finally annealed 10" to 25°C above the subsequent test temperature for 2 hr. This treatment allowed the grains to grow to equilibrium size and shape. After the anneal, the lid was mounted in front of the cathetometer. The gage length was measured by sighting the 40 power microscope on the upper lip of the lower gage mark for the first reading, then traveling up to the lower lip of the upper gage mark for the final reading. This procedure was repeated four times to give an average gage length value. In this manner the annealed gage length and the final gage length could be measured to determine the strains. During all measurements, grain counts were made.

Jan 1, 1952

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers' as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By T. W. Healy, P. Somasundaran, D. W. Fuerstenau

The flotation behavior of quartz in the presence of alkyl ammonium acetates as a function of alkyl chain length has been interpreted in terms of hemi-micelle formation at the solid-liquid interface. The van der Waals cohesive free energy that is responsible for hemi-micelle formation has been found from these results to be 1.0 kT per CH2 group. This is in excellent agreement with literature values obtained from research on the properties of micelles in bulk systems. Collectors of the type CH3(CH2)n-2CH2-P, where P is a polar group and n is the number of carbon atoms in the straight alkyl chain, will induce flotation of an appropriate mineral at lower concentrations as n increases. This reduction in collector concentration with increasing n has been reported for such systems as xanthates on sulfides1,2 and amines on quartz.' The effect of chain length of alkyl surfactants on such solution properties as conductivity,' surface tension,' and solubility6 and such interfacial properties of solids as contact angle7 and electrokinetic potential8 have received considerable attention, but only limited quantitative descriptions of the effects have been given. The electrokinetic studies of alkyl amine salts on quartz indicated that the solution concentration of collector at which the marked change in electrokinetic potential of quartz occurs decreases systematically as the length of the alkyl chain increases. The aim of the present work was to obtain a quantitative description in terms of current theories of flotation of the effect of the hydrocarbon chain of alkyl ammonium acetates on the flotation behavior of quartz. BASIC PRINCIPLES The marked changes in electrokinetic potentials of quartz in dodecylammonium acetate (DAA) solutions were postulated to result from the association of adsorbed collector ions into two-dimensional aggregates, called hemi-micelles.9 Subsequently, the rapid increase in flotation rate of quartz was shown to coincide with hemi-micelle formation." We would like to discuss briefly the concept of hemi-micelles in terms of recent interpretations of micelles in bulk solution. Micelle hypothesis: In dilute solutions, alkyl ammonium and related salts behave as ordinary strong electrolytes, but at a certain concentration there is a marked change in physical properties of the solutions, e.g., in equivalent conductance, transport number, freezing point lowering and viscosity. To account for these phenomena, McBainl1 introduced the concept of micelles, which are aggregates of long-chain ions. It is believed that the ionic heads of the constituent ions of the micelle are in contact with water, whereas the nonpolar groups turn away from it and are in contact with each other. Work must be done to bring these charged polar groups together, but energy is gained (i.e., so called van der Waals cohesive energy) when hydrocarbon chains are expelled from the water and allowed to associate. For a given polar group, the tendency to form micelles will therefore strongly depend on the hydrocarbon chain length. Theoretical treatments of micelle formation by Shinoda12 and Phillips13 and others lead to the following expression for the concentration at which micelles form (the critical micelle concentration or cmc) in aqueous solutions of long- chain electrolytes

Jan 1, 1964

By Morris Muskat

It is pointed out that the application of capillary pressure curves obtained by drainage or desaturation processes to the calculation of the fluid distribution in interphase transition zones involves a number of difficulties; namely: (I) the development of very low nonwetting phase saturations appears to be in contradiction with the lack of mobility of such distributions indicated by permeability-saturation curves, (2) dispersed nonwetting phases are thermodynamically unstable, and (3) discontinuous phases should not be subject to hydrostatic equilibrium requirements. While these difficulties could be obviated by assuming that the capillary pressure drainage curve has an initial horizontal segment, they are automatically circumvented by application of the imbibition capillary pressure curve to the lower part of the water-oil transition zone. These generally show zero displacement pressure at only partial wetting-phase saturations. The countercurrent upward flow of oil into the main oil-saturated pay and downward drainage of water also suggests that wetting phase imbibition processes will control the saturation distribution immediately above the water-saturated section. Similar considerations, with a generalized interpretation of the apparent wetting-phase behavior of the oil and gas phases, provides a basis for constructing the curve for fluid distribution in the oil-gas transition zone. In the transition zones so derived, the oil begins with a nonvanishing saturation at the water-oil contact and terminates with a similar saturation at the top of the gas-oil contact. The gas-oil transition zone begins with an equivalent nonvanishing gas saturation. Introduction It has been a common assumption for some years that the nature of the fluid dis- tribution in virgin reservoirs, and in particular that in the transition zones between the oil and water and between the oil and gas sections, can be computed by a simple application of capillary pressure data. The results of such calculations appear to have been first reported by Leverett.' The latter, however, indicated only the numerical values of the parameters used in the computations, without explicitly describing the procedure. Leverett's illustrative calculated transition zones are reproduced in Fig I. Although no critical study of the apparently obvious method of calculation has been published, one cannot proceed very far in the computation without encountering some rather fundamental questions not yet answered in the literature. This paper is not written under the pretense that the whole transition-zone problem has been fully and satisfactorily solved. Its purpose, rather, is to discuss suggestions for its treatment, much of it admittedly hypothetical, and emphasize the nature of the uncertainties arising therein; for the literature, as now available, gives little indication that there are any problems still outstanding. The Transition-zone Equation The basic equation, which presumably gives directly the fluid distribution without recourse to any further consideration, is: Ap = (r1 - r2)gh [1] where r1, y2 are the densities of the two contiguous fluids, h is the height above the "capillary-free" zone of complete saturation with fluid I, g the acceleration of gravity, and Ap is the capillary pressure across the average interface at the height

Jan 1, 1949

By H. M. Chance, T. M. Chance

The term 'Llow-sulfur coal," as used in this discussion, is limited to coals containing less, or very little more, than 1 per cent. sulfur. For certain purposes it might be advantageous to include coals that contain as much as 1.25 per cent. sulfur, because such coals have been considered as available for making metallurgic coke of fair grade; but the same reasoning might apply to coals containing as much as.1 1/2 per cent. sulfur, if facilities exist for utilizing such coal by admixture with coal containing less sulfur. , In Pennsylvania, it is not possible to define the exact geographic limits of the areas in which coals relatively low in sulfur exist, because variations in the percentage of sulfur occur irregularly and often abruptly. It is not uncommon to find areas, more or less circumscribed in extent, in which the coal is relatively high in sulfur although all the surrounding territory contains low-sulfur coal; and, similarly, small areas of low-sul. fur coal exist in districts where the coal is normally high in sulfur. These generalizations apply, with few exceptions, to the whole area underlaid with bituminous coal in the State of Pennsylvania, and also to each of the individual beds of coal in this state. Pennsylvania is poorly supplied with coals of the low-sulfur class. We find, however, as an offset to this condition, very large areas in which coal ranging from 1 to 2 1/2 per cent. sulfur exists in beds of good workable thickness. This coal, by washing, can be reduced in sulfur low enough to make coke of a high grade. While a considerable tonnage of workable low-sulfur coal remains in the Pennsylvania bituminous districts, it has been necessary to turn to the areas of higher sulfur coal for the supply of metallurgical coke. This utilization of the higher sulfur areas has been made possible either by washing or by selective mining. Washing.—Fine crushing of the entire feed is not generally necessary to the successful washing of Pennsylvania coals. This is due to the fact that the pyrite is rarely finely and uniformly disseminated throughout the coal but is usually confined to high-sulfur benches in the bed or to concentrations on the cleavage planes of the coal. Hence, by graded crushing and sizing it is frequently possible to at once reclaim those portions of the coal bed containing coal that is relatively free from pyrite.

Jan 1, 1920

By G. R. M. Del Giudice

The term "slime-coating" is not new in the art of flotation; the phenomenon has been observed and described by Taggart;(l)† Taggart, Taylor, and Ince;(2) and by Ince.(3) Notwithstanding that flotation was introduced for the treatment of finely crushed ore, the adverse effects of slimes have been recognized since the earliest days of the process, and the Elmore, Delprat, Potter, and other processes actually specified desliming of the ore prior to treatment. The cause of this trouble has been studied and described by Taggart;(1) Taggart, Taylor, and Ince;(2) Ince;(3) Morrow and Griswold;(4) and by Gaudin and Malozemoff.(5) Old Theory of Slime-coatings At present, so far as published work shows, there seems to be but one theory for the mechanism of slime-coatings. Ince(3) states that they are due to attraction between electrostatic charges of opposite sign on the sulfide and on the slime particles, supporting this theory by migration experiments in the Burton tube. He also used the microscope in conjunction with a glass cell employed by Beans and Eastlack(6) in studying migration, but met with interference from endosmosis. Several attempts have been made in the Department of Mineral Dressing at Columbia University to duplicate Ince's experiments with the Burton tube, but the results have never been convincing. Formation of precipitates which settled through the pulp levels, and evolution of gas at the electrodes, which disturbed the interface between the pulp and the distilled water above it, seriously interfered with observations. However, by use of the migration cell shown in Fig. 1, endosmosis effects and the disturbances due to precipitation and gas evolution were avoided, and distinct and reproducible migrations or absence of migration were observed. The cell was made of bakelite and had platinum electrodes. Objectives were employed which had a working distance of at least three millimeters,1 and the parts of the mounting which came in contact with

Jan 1, 1935

By L. W. McKeehan

The occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note.' This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. Method of Preparation The material in which the crystals here dealt with were grown was made from 1/8in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400" C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of traveling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, as nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection. Measurements The wire in the etched state was next mounted in a goniometer of special form which allowed the measurement of the spherical coordinates of the normals to any plane surfaces left by the etching. These coordinates were most conveniently a polar distance, 8, from one direction of the wire axis, and an azimuth or longitude, ?, from an arbitrary prime meridian. The region to be described more particularly is shown at a low magnification in Fig. 1, which gives two different views, differently illuminated to show the spatial relationship of a crystal occupying most of the part shown and of an inclusion, or rather a series of three inclusions suspected of being twins based on the principal crystal.

By L. W. McKeehan

THE occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note.1 This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. METHOD OF PREPARATION The material in. which the crystals here dealt with were grown was made from 1/8-in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400° C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of traveling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, ass nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection. MEASUREMENTS The wire in the etched state was next mounted in a goniometer of special form which allowed the measurement of the spherical coordinates of the normals to any plane surfaces left by the etching. These coordinates were most conveniently a polar distance, ?, from one direction of the wire axis, and an azimuth or longitude, [ø], from an arbitrary prime meridian. The region to be described more particularly is shown at a low magnification in Fig. 1, which gives two different views, differently illuminated to show the spatial relationship of a crystal occupying most. of the part shown and of an inclusion, or rather a series of three inclusions suspected of being twins based on the principal crystal.

Jan 1, 1928