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By Samuel Storchheim

IT was noted that variations existed in the magnetic properties, namely, coercive force, He, and rema-nence, Br, of 18/8 stainless steel wires of the same analysis when these wires were given the same percentage of reductiori of area at different rates of reduction. In order to determine the extent of these variations, a program was initiated whereby commercial 302 and 304 stainless steels were drawn with a wide variation of speeds. Ultimate tensile strengths and specific resistances, as well as the Hc-BT measurements, were determined. If variations of considerable magnitude were found, it was thought that the knowledge accrued from the investigation could probably aid in determining the particular drawing speed required to obtain desired properties for a given specification for a particular analysis of wire. Drawing Procedure Two specimens (set I, No. 302 and No. 304), the chemical analyses of which are given in Table I, were drawn at different speeds, namely, 45 to 3900 ft per min, directly from 0.016 in. diam wire to 0.004 in. diam wire, a 93.7 pct reduction of area. To obtain this high percentage of reduction, the wire at 0.016 in. was softened by annealing at 1150°C. It was then strung in a No. 16CF variable speed Vaughn drawing unit and passed through 13 B.&S. gage dies of successively smaller diameter, as shown in the accompanying table. Following this step, several hundred feet of the wire was drawn, at a particular speed, through the dies and wound upon a spool. Once the sample of wire was drawn at the desired speed, the spool with the finished sample was removed, tagged for later identification, and an empty spool was placed in the machine. Another wire sample was drawn at a different speed, after making the necessary adjustments upon the Vaughn unit. At the greater speeds, several thousand feet of sample were drawn to insure that the wire to be used for testing would be uniform. This was done because the desired speed was not reached instantly; the wire taking a short while to attain the required drawing rate. All speed measurements were made by placing a tachometer against one of the machine's pulleys during the actual drawing of the specimens. 84.4 pct reduction of area. The 0.072 in. diameter wire was also annealed at 1150°C. The process of obtaining samples was the same as described above. The only difference between the two was that the rates involved were not as extensive, set II covering a range of 625 to 1150 ft per min. Tensile tests were carried out for the 0.004 in. diam wires on a horizontal Scott Tensile Tester, while tensile tests for the 0.028 in. diam wires were made on a vertical Scott Tensile Tester. Each value listed in the tables represented the average of five samples with a maximum deviation of approximately 3 pct among the samples. Resistance per foot of the wires was determined by use of standard bridges accurate to the nearest hundreth of an ohm for the 0.004 in. wire, and to the nearest thousandth of an ohm for the 0.028 in. wire. The resistances per foot were then converted to resistivities by use of the following equation: P = RxCM where R is the resistance per ft in ohms per ft; CM, the area in circular mils; and P, the resistivity in ohms—CM. The values listed in the tables likewise

Jan 1, 1952

By P. G. Meikle, C. T. Holland

The effect of the condition of friction upon the ultimate unit compressive strength as determined between the compressed faces of precisely machined coal specimens and specially prepared testing platens has been examined. Reductions of 30 to 40% in the ultimate unit compressive strength of these model coal pillars have been verified when lubricants areused between the faces as compared to non-lubricated faces. Increase in unit compressive strength due to confinement at each of three levels of friction appears to follow generally the widely accepted "1/2 power law", i.e. S - C (L/T)1/2 where S is the unit ultimate strength, C is a constant dependent on the coal being tested and the coefficient of friction acting at the compression surfaces and L and T are the least width and thickness of the specimen, respectively. Results suggest that the surface condition of both the specimen and platens should be mentioned in detail in conjunction with compression testing, for although the term (L/T)1/2 is adequate for all practical purposes, the coefficient C is directly dependent on the condition of interfacial friction, all else remaining constant. One phase of the investigation of the confining effect of friction on the ultimate unit compressive strength of small coal specimens has recently been completed at the School of Mines of West Virginia University. The efficient control of ground is of fundamental importance to successful mining operations and the design of support pillars has always presented the mining engineer with a difficult and intriguing engineering problem. Since about the turn of the century, many investigators have performed extensive laboratory tests on small coal specimens in efforts to solve some of the perplexing problems of strata control and pillar action in coal mines. A detailed review of this work would serve no purpose here, but a brief mention of the more significant contributions is in order. Muller16 was perhaps the first to illustrate the effect of confining pressure on the strength of coal specimens in compression. His work has recently been more carefully expanded by the experiments of Murrell17 in Great Britain. Rice and Enzian l9 observed that as the size of cubical test specimens increased, the unit compressive strength decreased. These observations were later supplemented by Lawall and Holland, 13 by Greenwald4,5 et a1 at the U. S. Bureau of Mines, by Gaddy3 as well as by Steart,22 Millard15 et a1 and Evans2 et al. Gaddy3 seems to have been first to quantify this relationship with his equation: S = K/vd , where S - ultimate unit compressive strength (psi), K = a constant dependent on the coal, and D =edge dimension (in inches). Holland7 concluded that the strength of coal as affected by lateral dimensions and thickness could be expressed as where K = a coefficient dependent upon the coal, L = least width of pillar (in.) and T = thickness of pillar (in.). Data supplied by this formula have been compared to the estimated stresses in pillars that had been standing for long periods in coal mines and in the cases so far studied the results indicate that the formula predictions are sufficiently accurate for engineering purposes (Holland11 ). This equation therefore is believed to be the simplest and most accurate tool available at the present time for approximating the strength of a coal pillar (over a specified range of L/T) in situ. However, Holland7,9 has indicated that friction between the coal pillars and the top and bottom rock

Jan 1, 1965

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 A. G. Metcalfe

Observations at temperature are used to investigate the phase changes in alloys containing more than 50 pct Co and above 1000°C. The nonsuppressible transformations in cobalt above 1120°C and in the intermetallic compound Co2Cr3 are studied. The liquidus and solidus surfaces are determined. Insufficient data is obtained to complete the constitution diagram. A REVIEW of some of the earlier work on cobalt' and on the binary systems with chromium2-4 and with molybdenum,5 showed that one likely source of differences might be attributed to the presence of phases at high temperatures which could not be retained by quenching. Consequently, the decision was made that only methods of examination at temperature should be used in this work. The correctness of this decision was confirmed during the course of the work by the investigation of the martensitic nature of the transformation in cobalt- and by the decomposition of the high temperature form of the phase Co2Cr3 on quenching.' The use of high temperature methods, including dilatometry and thermal etching led to the postula-tion of the existence of a high temperature form of cobalt with a probable hexagonal close-packed structure, transforming from cubic cobalt over a range of temperature from 1119° to 1145°C.8 One of the important pieces of evidence for this transformation was that it was observed in alloys with chromium and molybdenum which were nonmagnetic at this temperature so that confusion with magnetostriction effects was impossible. These results were not reported in this earlier paper, so that the data given here supply further evidence for the existence of a second allotropic transformation in cobalt. High temperature observations are necessarily much slower in producing results than the examination of quenched specimens at room temperature by conventional means such as X-ray diffraction or microexamination. The investigation has only covered a limited part of the field, as a result, extending from the liquidus down to about 1050°C and from the cobalt corner up to 50 pct alloying elements. The differences between the various reported diagrams for the constitution of the Co-Mo and Co-Cr systems have already been mentioned. The best available diagram in the first system is due to Sykes and Graff' which is shown in Fig. 1. Fig. 2 shows the latest Co-Cr diagram due to Elsea, Westerman, and Manning.' A comparison reveals that these are incompatible because of the disagreement with regard to the number of allotropes of cobalt. Elsea, Westerman and Manning took their liquidus and solidus curves from Wever and Haschimoto.2 The temperature horizontal in the two-phase field beneath the eutectic was placed 35" to 39°C higher than in earlier work2,4 with a new interpretation of the nature of this transformation. This interpretation also required a peritectic horizontal at about 1470°C, which has been confirmed here for an alloy with 53 pct Cr. No investigation had been made of the ternary system until after this work had been terminated, when a section at 1200°C was published." In this work a ternary compound was found by the X-ray diffraction examination of quenched alloys. This compound contained less than 50 pct Co, and was thus outside the field investigated here. However, some reactions were found dilatometrically which could not be fitted on the diagram and are now believed

Jan 1, 1954

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 M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By A. J. May

THE Star shaft is near the north boundary of the group of mining claims belonging to the Ground Hog Unit of the American Smelting and Refining Co., near Vanadium, N. Mex. The shaft bins and surface plant are served by a siding from the Atchison, Topeka and Santa Fe railroad, and this factor of railroad transportation influenced the choice of site. This paper describes the shaft sinking only, and does not cover the surface plant or other parts of the mine or its equipment. Experience with this shaft seems of interest because of the mechanical mucking, good rate of progress, and the costs obtained at the present level of labor and material costs. The shaft has four compartments, as shown in fig. 1. Equipment: Riddell Mucker: The mucking was done by a clamshell bucket and a Riddell mucker, which, as in other shafts sunk with this machine, consisted of a carriage mounted on axles with double flanged wheels that traveled back and forth on a swinging track, parallel to the long axis of the shaft (fig. 2 to 6). Three air motors were mounted on the carriage; one hoisted the clam, one operated the bucket opening and closing device, and the third moved the carriage along the track. The carriage was designed with guide shoes and could be hoisted to the surface in either skip compartment without trouble (fig. 4). During blasting operations the clam was tied on the rails and the carriage was hoisted up a few sets to protect it from flying rock. No attempt was made to hoist the carriage and clam together lest the clam catch in the timbers. The track on which the carriage operated was built of extra heavy 6 in. pipe with 1x2 in. strap welded on top for rails. A 1/2x4 in. angle was welded on the bottom of the 6 in. pipe with a 1 in. round rod welded in the angle for a filler and additional strength. The end or cross pieces of the track which kept the track to gauge, were also made of reinforced, heavy 6 in. pipe and were bolted to the long members on which the carriage traveled (fig. 2 and 3). This section of track was used, instead of heavy railroad rails, for two reasons: (1) this section would bend before it snapped and was much safer for the men in the bottom; and (2) it was a better blasting shield, and protected the timbers better, in fact, only five wall plates were broken by blasting in 1926 ft of shaft, although 150 to 225 lb of 40 pct powder was loaded per round, depending on the ground conditions. The swinging track was supported by four 5/s in. hoisting cables anchored to the end plates. There were also four safety cables fastened two to three sets above the carriage, which would catch the carriage if one of the supporting cables should fail for any reason (fig. 7). Clamshell Buckets: Two clams were used, each of 3/s yard capacity, both manufactured by Blaw Knox, Nos. 662 and 663. The No. 663 clam was 4 in. wider and 5 in. shorter than the No. 662, but seemed to dig and load more satisfactorily. It was easier to hoist and lower when it came up for repair. It did not turn over as easily, had less spill

Jan 1, 1950

By P. E. Baker

An improved method of logging formation density has been developed in which the formation is bombarded with a collimuted beam of gamma rays. By means of a scintillation detector and pulse height discriminator, the gamma-ray energy band is accepted and recorded which corresponds to deepest penetration into the formation. Laboratory tests on a field tool revealed no borehole diameter effect for smooth holes and no effect of formation chemistry, except insofar as chemistry affects density. In extensive field tests, the density log has exhibited satisfactory agree-ment with core measurements and has correlated accurately with other logs. INTRODUCTION This paper describes an improved method of logging formation density by means of back-scattered gamma rays to penetrate the formation together with energy discrimination to select only that energy (or frequency) range corresponding to deepest penetration into the forma- tion. This method of density logging was developed at the La Habra laboratory of California Research Corp.* Field instruments have been built and tested by McCullough Tool Co. and commercial service has begun in some areas. All of the data discussed here were obtained for the original field tool. The density log can be a valuable adjunct to existing logs because of its use in determining porosity quantitatively. It is useful also in connection with seismic and gravity surveys where formation density information is of interest. PHYSICAL PRINCIPLES The intensity, I, of a beam of gamma rays after traversing a distance, x, in an absorbing medium is given by I = loe -ax where I, is the intensity of the beam entering the medium and a the attenuation constant or macroscopic cross section of the medium for gamma-ray absorption. The macroscopic cross section depends on the number and types of atoms per unit volume and the gamma-ray energy. In brief, it is the sum of the atomic cross sections of all atoms per cubic centimeter. The density of the material is the sum of the masses of all atoms per cubic centimeter. Thus, the density and the macroscopic cross section for gam-ma-ray absorption vary in propor- tion to the number of atoms per cubic centimeter. The density of the material increases, of course, if the atomic masses increase without a change in the number of atoms per cubic centimeter. When the density increases in this latter way, the macroscopic cross section increases also, but disproportionately. This results from the fact that part of the gamma-ray absorption arises from the photoelectric effect and the pair-production effect**, which are proportional to the sixth and to the second power, respectively, of the atomic number of the absorber. The remainder of the absorption results from the Compton effect, and is directly proportional to the atomic number. The gamma rays that undergo Compton scattering are not immediately absorbed. Since these rays are scattered in all directions, a fraction will emerge from the face of the medium at which they entered. If a gamma-ray shield is placed between the source and detector, most gamma rays reaching the detector will be those scattered out of the medium. The intensity will depend on absorption and scattering in the medium, and so indicates the density of the medium. For gamma rays for which Compton scattering prevails, the intensity

Jan 1, 1958

By Robert L. Bates

Definition An industrial mineral, says the Glossary of Geology, is "any rock, mineral, or other naturally occurring substance of economic value, exclusive of metallic ores, mineral fuels, and gemstones; one of the nonmetallics." Probably most geologists and engineers would accept this simple and straightforward definition, at least as a general statement. On analysis, however, certain anomalies crop up. For example, it may be considered arbitrary to include industrial diamond and corundum and to exclude their precious varieties, gem diamond and sapphire. So the present volume has a section on gems and gem materials, in spite of the definition. Another problem arises when we try to define precisely what is metallic and what is nonmetallic. Bauxite and ilmenite certainly qualify as metallic ores, but both are also raw materials of important nonmetallic substances; hence they are included in the book, A third anomaly is that, by common consent of geologists, engineers, mineral economists, and others concerned, the term industrial minerals may include not only rocks and minerals but also certain manufactured products like cement and lime, and even mixed groups of natural and artificial products, such as abrasives and refractories. Thus the central realm of the industrial minerals is clear enough, but its boundaries tend to be indefinable. Since a definition that allowed for every irregularity in the outer fringes would be excessively unwieldy, the one quoted above may be considered satisfactory. The expression industrial minerals is commonly equated with nonmetallics, and with the somewhat more precise phrase industrial minerals and rocks as in the title of this book. Characteristics of the Field The industrial minerals as broadly interpreted are a highly diverse group of materials; indeed, we may say paradoxically that diversity is about all they have in common. At one end of the spectrum are ordinary earth materials such as gravel and crushed stone, with a value of perhaps $3 per st; at the opposite end are industrial diamonds, which sell (by the carat) at the rate of roughly $18,000,000 per st. Neither the metals nor the fuels, and few if any categories of manufactured products, include items that differ in value by more than six orders of magnitude. Most gravel and stone are of no value unless close to a market; diamonds and other exotic substances possess such unique and desirable properties that their occurrence in remote corners of the earth is no deterrent to their use. The broad range of industrial minerals falls between these extremes of unit value and place value. The industrial minerals penetrate the entire fabric of modern industrialized society, from such fundamental operations as drilling for oil and smelting iron ore to the manufacture of virtually the whole array of consumer products. There is no industrial-minerals industry; there are many industries. The simple term field is convenient as an all-inclusive expression. An industry is considered to belong in the industrial-minerals field if its operations consist of extraction and processing, but not manufacturing. Thus the mining and beneficiation of feldspar is a mineral industry, but the manufacture of ceramic products is not. In the cement and lime industries, processing merges into manufacture, and the line is less distinct. It disappears altogether in a plant that extracts salt as artificial brines, and makes sodium and chlorine chemicals, all under the same roof. An aspect of some industrial minerals that differentiates them from the metals is that their physical properties carry over into ultimate use of the product. Such minerals as mica, asbes-

Jan 1, 1983

By O. P. Quist, S. H. Carpenter

The internal friction of single-crystal LiF has been investigated as a function of crystal orientation, while simultaneously applying a static compressive load. Three different crystal orientations were used, these being samples with the (100), (110), and (111) directions along the sample length. Results show the internal friction measured to be similar in appearance but different in magnitude for the (100) and (110) samples. With both orientations, application of a static stress caused an increase in the amplitude-independent damping, which recovered with time. The amplitude-dependent damping was found to first decrease with load up to the yield stress and then increase rapidly. Samples of the (111) orientation were found to have no measurable internal friction even when loaded up to 3.0 kg per sq mm. These results are discussed in terms of current theories of internal friction in ionic crystals. This paper presents the results of an investigation of the dislocation mobility and dislocation motion in high-purity single-crystal LiF at applied stress levels up to the yield stress. Internal friction measurements of the dislocation damping while simultaneously applying a static compressive load was the experimental technique used. LiF crystals much prefer to slip on the (110) set of slip planes. However, with a suitable stress distribution they can be forced to slip on the {100} set of slip planes.' For both sets of slip planes the slip direction is the same, namely (110). The object of this investigation was to try and learn more about the dynamical properties of dislocations on the different slip systems in LiF crystals. EXPERIMENTAL PROCEDURE Dislocation damping was measured, in terms of the log decrement, using a five-component marx2 composite piezoelectric oscillator. The apparatus used allows one to measure the dislocation damping while simultaneously applying a static compressive load on the sample. A schematic of the apparatus used is shown in Fig. 1 and a complete discussion of its construction and operation is given elsewhere.3 All measurements were made at room temperature with a longitudinal resonant frequency of approximately 50 kc per sec. Damping measurements were made using longitudinal vibrations with strain amplitudes from up to 10. Static loads up to 3.0 kg per sq mm were applied to the sample while the damping was being measured. Samples used in this investigation were high-purity single crystals of LiF purchased from the Harshaw Chemical Co. All samples were approximately of an in. square and were hand-ground in length to one-half wavelength to match the resonant frequency of the driver and gage quartz crystals. Samples of three different crystallographic orientations were used, namely, crystals with the (loo), (110), and (111) direction parallel to their length. The magnitude of the damping is a direct measure of the area on the slip planes swept out by dislocations during a complete oscillatory cycle. With a sample of the (100) orientation the maximum applied shear stress, due to longitudinal vibrations, is on the (110) slip planes with zero shear stress on the (100) slip planes. Thus, damping measured from a (100) sample is due entirely to dislocation motion taking place on the (110) set of slip planes. Similarly, for a sample of the (111) orientation there is zero shear stress on the (110) set of slip planes and the damping measured from a sample of this orientation is due entirely to dislocation motion on the (100) set of slip planes. Samples of the (110) orientation will have a component of shear stress on both sets of slip planes and

Jan 1, 1969

By Murray Pezim

In the good old days of the folklore of the mining industry, grizzled prospectors obtained a few loose dollars from friends and neighbours then wandered off to eventually return with the great discovery which became the core of the new corporate empires. Alternatively, merchant banking barons obtained exclusive rights to just about anything of future value over hugh nation-size territories. Some of this probably still goes on, likely with about the same ineffectiveness and waste of effort and money as in the past. CURRENT CONCERNS IN MINING In today's difficult climate in the mining industry, for that matter in all industry, effectiveness is the vital consideration. Cost effectiveness -- more bang for the buck -- is especially important in such an area of high risk as mineral exploration. And there are other factors to consider. Since minerals are depleting resources, the mining inddustry is constantly confronted with the reality that those resources extracted today must be immediately replaced if a resource enterprise is to continue. And if growth is to be achieved, even more resources must be found to support future expansion. The current and immediately foreseeable climate internationally for the mining industry creates a special need and urgency for aggressive and successful exploration, certainly in Canada, if not also in the United States. Depressed world markets and prices have turned yesterday's economic reserves into today's waste, hopefully to be converted into economic ore again in some distant time. One way of replenishing reserves and maintaining a viable mining industry is to find and develop mines which are economic under short-term depressed price and market conditions. This probably means higher grades. A new copper discovery with the right combination of characteristics to be an attractive investment even at today's pices for copper would still merit development into production. Exploration is the only way to find such mines for the difficult short-term conditions. Another important consideration is that normally many years stretch from the first thought of conducting exploration to production -- in those rare instances where an economic discovery is made. If discoveries are not made today, then there will not be any projects to develop when business conditions are more attrative. This industry and the vast number of skilled professionals who are part of mining, are faced with two key problems that underlie the need for a junior exploration segment. One consideration is how to maintain exploration during those years, indeed eras, of recession and depression. We are in such a time now. Throughout the world, major companies have sharply cut back, if not eliminated completely, exploration expenditures other than what is vitally necessary and easily and inexpensively done at the known and producing deposits. And related to that consideration, even more important today than during happier times, is how to finance such necessary ongoing exploration if major companies and governments back away because of financial stringency. CANADIAN SUCCESS In Canada, such problems are being tackled with a success which is capturing worldwide attention. The ability of mineral explorers to obtain willing, eager, high-risk capital is achieving even more outstanding results than in the past. These results are reflected in the widespread continuing exploration ativity in Canada which even spreads into the United States, with some outstanding discovery successes. The most notable exploration success from junior mining activity is the discovery of the Hemlo gold camp in northwestern Ontario, a source of gold which promises to rank with the South

Jan 1, 1985

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

[THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle ? is determined only by the reagent&apos; and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox2 showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0° to the equilibrium value of 60°. Further, Gaudin and Vincent&apos; showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, ? varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher4 were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by, the difference of the free surface energies (surface tensions) of the respective phases ?1 and ? 2 before contact and the interfacial free surface energy ?12 after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation5 of W from the surface tension of the liquid ? and the contact angle ?: [W = y (1 + cos ?)[1]] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are ? and ?3. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: [W,,,=x•W2+ (1-x).WR[2] .] in which Wm is the work of adhesion of the composite surface. Eq 1 can be introduced into W2 and W3 but in the case of Wm some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle ?m, calculated from Wm, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that ?m would have aphysical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically]

Jan 1, 1952

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production. Introduction During the past 10 years there has been a growing interest within the industry regarding the movement of fluids through oil reservoirs. A number of research projects have been directed toward the development of the physical laws governing this movement. In the period 1933 to the present, correlations between laboratory analysis of cores, reservoir fluids and well performance have been established and have been applied to successful secondary water-flooding recovery operations; and to the completion, production, reconditioning and evaluation of wells in new fields. The application of these data to water-flooding, either natural or artificial, is comparatively new, but the principlcs involved were set forth in 1880 by John F. Carll,1 who said: The flooding of an oil district is generally viewed as a great calamity, yet it may be questioned whether a larger amount of oil cannot be drawn from the rocks in that way than by any other, for it is certain that all the oil can-not be drawn from the reservoir without admission of something to take its place. If one company owned all of the wells drawing upon a pool, and had accurate records of the depth and characteristics of the oil producing stratum in each well, it is quite possible that some system might be devised by which water could be let down through certain shafts, and thus the rocks be completely voided of oil and left full of water. As it is, however, no systematized plan of action can be adopted. The careless handling of one well. by which water is let down to the oil rock, may spoil several others belonging to different parties. A clashing of interests at once arises and is likely to result in disaster to the whole district. In judging of the probable effects of the intro-duction of water into any particular oil district several things are to be considered. (1st) The time of flooding—whether early in the progress of development, while yet a large percentage of oil remains unexhausted or at a later period after the supply has suffered from long continued depletion. (2nd) The structure of the rock—whether regular and homogeneous throughout, or composed of fine sand inter. bedding connected and irregular layers of gravel, sometimes lying near the top and at others near the bottom. (3rd) The shape of the area being flooded. (4th) The position of the point at which water is admitted. in relation to the location of the surrounding wells still pumping oil. (5th) The height (which governs the pressure) of the column of water obtaining admittance. (6th) The duration of the water supply. Although we may take exception to part of Carll&apos;s reasoning, particularly " and thus the rocks be completely voided of oil and left full of water," we must give him credit for pointing out the increased effectiveness of water encroachment in displacing oil from a sand and for his recording six of the present seven considerations necessary for evaluation of production of oil by water

Jan 1, 1942

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10&apos; cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;&apos; the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson&apos;s equation is

Jan 1, 1965

By R. C. Edwards, Will Mitchell, T. G. Kirkland

A scrubber of new design has been invented for the beneficiation of glass and chemical sands. The machine is described and its capacity and metallurgical efficiency compared with the performance of other sand cleaning devices. THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.&apos; The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry.&apos; The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5" to 35" from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180" apart. Each successive set is mounted 90" from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, lx1 1hx9 in. long, which is attached about Yz in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1953

S. Tandanand, Twin Cities Mining Research Center, U. S. Bureau of Mines As an addition to the fine reviews on drilling presented in the foregoing papers, we feel it would be appropriate to mention briefly some work in this area by the U. S. Bureau of Mines. The Bureau has had under way for several years at its Twin Cities Mining Research Center studies directed toward a better understanding of basic drilling mechanisms. The work includes drillability investigations with diamond rotary, and with percussive drilling systems, as well as fundamental studies of rock behavior under drill bit types of loading. Results of our work to date have contributed the following to the state of the art. MECHANISM OF ROCK FAILURE-Rock fragmentation through use of mechanical energy systems, including drilling systems, consists of two major components-machine and rock. The two components are related to each other by their functional behavior and their resultant motion which the components mutually influence. Forces in the systems are transmitted directly to the bit which in turn induces stresses in the rock. When the induced stresses exceed the strength of the rock, the rock fails resulting in penetration. Rock strength is a function of the forces applied to the rock. Stresses under a drill bit, regardless of bit configurations, are essentially compressive, resulting in a condition where the rock has the highest resistance to failure. The ratio of principal stresses induced under drill bits is an indication of the mode of failure in the rocks. Initially, compressive stresses under the drill bit cause rock to undergo inelastic deformation. The impression observed at the first stage of crater formation under the drill bit shows that rock is no longer elastic. Associated subsurface failure at this stage precedes total rupture which subsequently appears at the rock surface. Thus, explanation of crater formation, by applying theory of elasticity alone, is likely to be over-simplified. ENERGY VERSUS VOLUME OF ROCK REMOVED-Experimental results show that energy per unit volume of rock removed is constant for a particular rock and bit type. Rock offers a definite resistance to penetration, depending on the method of the energy application; this may be defined as the drilling strength of a rock. Energy consumption in a drilling system may be divided into two components: 1) Energy required to move the machine parts; and 2) energy consumption in breaking rock. Component 1 is dependent on the type of the machine. Component 2 is dependent on the strength properties of rock and the efficiency of the bit in rock cutting. The sum of the energy required in both components determines the total energy required in breaking rock. Our work in this area has included consideration of both diamond and percussive drilling systems. PENETRATION RATE-For a drilling rate expression to be useful in predicting field performance, it should include the operating characteristics of the drilling machine. Eq. 37, for example, is simply a statement of the fact that the drilling rate is determined by the power output of the machine (2pNT) and the power requirements to break the rock in the hole (AER). In order to predict the performance of a particular drill and the effect, for example, of the rotary speed, on the drilling rate, R, Eq. 37 must be modified to include the

Jan 1, 1967

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965