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By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By W. A. Turcotte, A. D. Paananen

Introduction The large reserve of fine grained oxidized iron-formation at the Tilden mine has been the object of research and development efforts to concentrate the iron oxides as far back as 1949. Due to the nonmagnetic nature of the ore and the fine grinding required to liberate the iron oxide minerals, this crude ore was not amenable to concentration by conventional methods. The iron oxides of the Tilden, ore body have a grain size of less than 25 microns and recovery of the finer, well-liberated iron oxides is essential. Conventional methods of desliming employing cyclones or thickeners were not feasible because of the excessive loss of iron oxides in the finer fractions. Development of selective flocculation-desliming was a key to commercialization of the process. Operations started in late 1974 with Algoma Steel Corp. Ltd., J & L Steel Corp., The Steel Company of Canada Ltd., Wheeling-Pittsburgh Steel Corp., Sharon Steel Corp., and The Cleveland-Cliffs Iron Co. as participants. Cleveland-Cliffs operates and manages the operation. Development of the Tilden Flowsheet The geology and ore reserves of the Tilden mine have been detailed in a paper by Villar and Dawe (1975). A joint program was undertaken in 1961 with the US Bureau of Mines in Minneapolis using the flowsheet developed by the Bureau employing the selective flocculation-desliming and calcium activated anionic silica flotation method (Frommer, et al, 1966; Frommer, 1964; Frommer, Wasson, and Veith, 1973). During this time, parallel testing at Cleveland-Cliffs Research Laboratory and Pilot Plant centered on the same type of desliming but was followed by the cationic flotation of silica with amine collectors (Columbo and Jacobs. 1976). The cationic silica flotation system was eventually chosen for its overall efficiency and simplicity. Regardless of the flotation method chosen, the technique of selective flocculation-desliming prior to flotation is the key to the success of the process. The flowsheet is described in detail by Villar and Dawe (1975). [Figure 1] shows a simplified one-line flowsheet of the Tilden concentrator. A total tailings thickener has been added to the original flowsheet and was placed in operation in 1978. The total-tailings thickener overflow reports to the reuse water pond and the underflow is pumped approximately 8 km (5 miles) to a storage basin. A flowsheet of the reuse water system is shown in [Fig. 2]. Selective Flocculation-Desliming Data have been published on the mechanisms and factors affecting selective flocculation in iron oxide-silica systems. The intent of this paper is not to discuss the theoretical aspects of selective flocculation, but rather to present experience gained from the commercial Tilden operation and from bench and pilot plant testing of fine-grained oxidized iron ores. From the bench and pilot plant testing prior to plant startup, certain reagent combinations and rates for the commercial Tilden plant were established. In the experience gained from three years of plant operation at Tilden, some of these reagent dosage rates have required significant adjustments due to changes in reuse water quality and to meet the requirements of varying ore types. Reuse Water The process water quality is a major concern at the Tilden mine and is constantly being monitored for selected chemical and physical characteristics. This monitoring has continued on a regular basis in order to gain a more thorough understanding of the interactions taking place in a dynamic water system and particularly as water quality is influenced by seasonal variations. Control of the reuse water chemistry is essential to the Tilden process both in the selective flocculation-desliming and flotation stages of concentration. With roughly 75% of the reuse water used in grinding-desliming operations, it is readily apparent that the biggest "reagent" in the selective flocculation-desliming process is water. Not enough can be said about the close control that must be exercised on the overall reuse water system. Control of the chemical treatment of the feed to the total tailings thickener is of utmost importance in order to produce a reuse water for the concentrator that is compatible with all stages of the concentrating process. There are many analyses made which aid in judging the quality of the water. Some of these are shown in [Table 1]. Five are particularly important and are monitored daily so that reagent adjustments can be made as required: suspended solids, calcium hardness, pH, dissolved silica concentration and temperature.

Jan 1, 1981

By F. W. Jessen, R. W. Durie

The development in the laboratory of mall salt cavities illustrated that the rate at which salt dissolved was affected by the rate at which fresh water was injected into the cavity. Experiments carried out with small salt cores indicated, however, that the rate of salt removal with forced convection was not significantly different from that with natural convection, provided the flow was in the laminar range. The rate of salt removal was apparently controlled by the water salinity, which was indirectly determined by the rate at which fresh water was injected. With turbulent flow at the salt surface, the rate of salt removal could be increased several-fold with the same salinity in the cavity. A quantitative evaluation of the rate of salt removal under natural convection was attempted by using techniques developed for the analogous heat convection system. The values of the rate of salt removal obtained experimentally were considerably greater than the calculated values due to surface irregularities. To determine the effect of these irregularities, the rate of salt removal was found for a smooth surface by experimentally determining the rate of salt removal as an irregular surface developed and then extrapolating this trend back to initial time. Excellent agreement between the experimental and calculated values then were obtained. INTRODUCTION Underground cavities leached from massive salt formations have been used extensively for many years for storing LPG products. The development techniques for storing methane gases in the liquid state at a low temperature leads to speculation that underground salt cavities of controlled geometry may be quite important in this field. In any case, the increasing number of salt cavities used for storage indicates an impending need for a better knowledge of the washing process to efficiently develop maximum storage volumes within specified regions. It is the purpose of this paper to discuss some aspects of -the mechanism of the dissolution of salt in the formation of cavities of controlled geometry. Although no attempt is made to resolve the problems that may be associated with the storage of methane in the liquid state in salt formations, the fact that salt cavities can be formed at reasonable cost would appear to justify investigation in this direction. Further, underground cavities have the advantage of allowing storage at higher pressures (and hence higher temperatures) than surface installations. Although the thermal conductivity of salt is somewhat higher than frozen earths, 0.017 cal/(sec) (cm)(c) for salt at 32F vs 0.005 cal/(sec) (cm) () for ice at this temperature, this disadvantage is offset by the higher storage temperature in underground cavities. For example, at atmospheric pressure, the temperature of liquid methane would be —258F. In a storage cavity at 2,000 ft, the pressure would be approximately 1,000 psia, which would allow a storage temperature of -9OF. The formation temperature would be roughly 110F at this depth, hence the total temperature differential would be 200F. Under surface storage conditions the corresponding temperature difference would be some 333 F (75 F + 258 F). The results of this difference can be compared more readily by substituting the appropriate values of thermal conductivity, temperature difference, heat capacity and density into the solution of the diffusion equation for the unsteady linear conduction of heat. For the underground salt storage, the heat flux is 15cal/(sec) (sq cm), where t is the time in seconds from the initiation of the cooling. For the surface system, and using the thermal properties of ice at the average temperature, the corresponding figure is 21cal/(sec) (sq cm). Hence, the heat losses through ice under surface conditions would be some 30 per cent higher than the underground salt storage. This ratio would vary, considerablv. Of course, for other conditions, but it indicates that an advantage over surface facilities may be obtained by storage in underground salt cavities.

Jan 1, 1965

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

By E. B. Fitch, E. C. Johnson

The operating behavior of liquid-solid cyclones is outlined, together with the nature and range of the process results obtainable, to serve as a background for engineers wishing to consider application of this new process tool. BY now most engineers are familiar with the liquid-solid or Dutch State Mines cyclone. However, it should be helpful to know exactly what it is that the equipment does and what its limits are. Without going into cyclone theory, this paper will describe the operating characteristics of Dutch State Mines cyclones. These are manufactured under license in this country and sold under the trade-marked name of DorrClone. The physical construction of the liquid-solid cyclone has been covered in many papers,'-' the DorrClone in particular being described in some detail by Weems. Fig. 1 shows the unit in cross-section. The feed enters at C. The coarse, heavy particles are thrown centrifugally to the periphery and make their way down the wall to the apex where their rate of discharge as underflow is controlled by an adjustable rubber apex valve. As the apex diameter is decreased the solids build up behind the valve, producing a denser underflow. Meanwhile the fine particles are swept into the upward flowing vortex stream which exits as overflow through the vortex finder, F. Flexibility to produce the specific result desired in a particular process is achieved by providing means for varying the areas of the entrance, vortex discharge, and apex discharge. The entrance area may be varied by insertion of special shims. Vortex discharge area may be changed by use of different-sized vortex finders which are interchangeable. Similarly, the different sizes of apex valves are interchangeable and in addition each apex valve is variable down to about 60 pct of its maximum diameter. A most significant primary distinction to make is that although liquid-solid cyclones have been sometimes called thickeners, they actually are classifiers, and very potent ones. They are almost never thickeners in the special sense that many metallurgical engineers understand the term. There would be no profit in quibbling over the definition of a word, but when the application of cyclones is considered, it will help to understand the difference be- tween two mechanisms, one of which will be called classification, and the other thickening. In what is called thickening the fine solid particles present in the feed hold together by surface attraction during the sedimentation process. The loose network of particles thus held together constrains all particles to settle at approximately the same rate, the larger ones dragging the smaller ones down. As a result, pulp settles with a sharp line of demarcation between solids and a relatively clear supernatant liquid. Essentially all the solids, regardless of their fineness, pass into the thickened underflow, and a clear overflow is separated. In classification, on the other hand, the interparti-cle forces are relatively insignificant as compared to the settling force on the individual particles, and are insufficient to prevent independent movement of the particles. The coarsest, heaviest particles settle most rapidly through the pulp, passing more slowly settling fines. Particles coarser than the mesh-of-separation essentially all settle into the underflow, but if the feed contains any particles finer than the mesh of separation, at least part of them will appear in the overflow. A clear supernatant or overflow can be obtained only if there are no undersize particles present in the feed. Thus it will be seen that classification is impossible under ideal thickening conditions. The finer particles are pulled down at essentially the same rate as coarser particles, and there is no separation on the basis of particle size. The surface attraction holding the particles together in a thickener is usually feeble. Whenever the sedimentation force on any particle is strong with respect to the interparticle forces, that particle can pass through the tenuous structure and settle independently. There are at least four ways of making the sedimentation force strong, with respect to the interparticle forces, and obtaining classification. First, and most obvious, the particles may be large and heavy. Thus coarse sands settle out in a beaker or Dorr thickener ahead of the rest of the thickening solids. Second, the interparticle forces may be altered by physicochemical means; i.e., it is often necessary to add dispersing agents to destroy the interparticle forces and permit classification to take place. Third, the interparticle forces may be reduced by dilution of pulp. It is well known that to obtain the most efficient separation of

Jan 1, 1954

By E. A. Hopkin

Laboratory tests conducted by the author. together with actual field experience in Canada. have indicated the magnitudc of some of the factors affecting ability of drilling mud to clean the hole. A correlation was observed between funnel viscosity and particle slip velocity. A relationship was also observed between the Bingham yield value of the mud and the particle .slip velocity. Laburatury tests indicated little change in slip velocity with funnel viscosities up to ahout 80 sec/qt or to yield values of aboul 15 lb/100 .sq ft. The lip velocity of the partic1e.s. studied vuried from 160 ft/min with water to neerly zero for high mud viscositie. lncreasing the mud density, creating laminar annular mud flow or rotating the drill pipe Mlay also improve the carrying capacity of mud. Field tests indicated that during fast upper-hole drilling, the rate of cutting removal must he sufficien to maintain the concentration of cuttings in the annulus at less than 5 percent by volume to prevernt balled-up drill collars and .stuck drill pipe. INTRODUCTION In the Mid-Continent area, hole cleaning during rotary drilling normally involves the use of low-density drilling muds with funnel viscosities varying from 26 to 80 sec/qt. However, frequently it is necessary to raise the mud viscosity in excess of 200 sec/qt to clean the hole. In addition, field experience has indicated that during very fast upper-hole drilling, annular mud velocities considerably in excess of the maximum slip velocity of the cuttings (normally considered to be 120 to 150 ft/min) are necessary to prevent balling the bit and drill collars. In view of these variations in mud properties and circulation rates necessary to clean the wellbore, a study of factors affecting hole cleaning and the relative magnitude of each was undertaken. The study was also prompted by the knowledge that a drilling mud with properties close to those of water would drill at rates several times that of a viscous mud. The carrying capacity of these near-water muds was not clearly understood, however, and many drillers were reluctant to use them. DISCUSSION EFFECT OF MUD PROPERTIES ON DRILLING RATE The effect of mud properties on drilling rate has been studied by a number of investigators. 1t is clear from their work that mud properties close to those of water will significantly improve drilling rate and bit life. If the water-type mud will also effectively clean the hole and cause no logging or formation impairment problems, the choice of an appropriate drilling fluid is clear—use water. Often, however, a water-type drilling fluid is not capable of effectively cleaning the hole. THEORY OF PARTICLE SETTLING The forces acting on a particle that is allowed to settle through a fluid quickly reach equilibrium, and the particle settles at some constant velocity referred to as the slip velocity. The slip velocity of any particle depends upon a number of factors such as density and viscosity of the fluid, the volume, specific gravity, shape and roughness of the particle, and upon the shape and area of the projected face of the particle at right angles to the direction of relative fluid solid movement. Brown' expressed this relationship for spheres in Newtonian fluids in the following equation. where v, = slip velocity D, — diameter of sphere p, = density of spheye p, = density of liquid /a = friction factor g = constant. The friction factor f, varies as the size, shape, surface roughness and slip velocity of the body, and as the density and viscosity of the fluid varies. WaddelV ound experimentally that where dynamic similarity exists. f, was a function of the particle Reynolds number (NRe) of the sphere (Fig. 1). Fig. 1 shows that f, for spheres varies from over 10 for low NKe numbers to 0.44 for N,,. over 600.

By J. G. Balkestein, J. W. R. Baerts

During an attempt to develop a method for accurate, rapid, continuous analysis of ash content of wal, the Dutch State Mines Laboratory found that the absorption coefficient for X-rays was related to ash content. This relationship was utilized in the development of an apparatus called CendreX, used to measure the absorption and in turn the ash content. The principle, procedure, accuracy, and applications of the CendreX automatic determination of ash in coal are discussed in detail. Until recent years coal preparation research was concentrated on the possibilities and efficiency of preparation equipment. Ever increasing demands for quality in coal, however, have caused researchers to become concerned with quality control. One of the characteristics strongly influencing quality (calorific value) and, consequently, the price of coal is ash content. Both customer and producer require that the ash content be controlled. To make this possible it is necessary for the producer to collect samples from the coal stream in the washery and to determine their ash content. On the strength of the results obtained the production process can then be adjusted, if required. Until recently incineration was the only method for determining ash content. When coal is incinerated with oxygen, it takes at least 15 min to determine the ash content. Even then some time may be lost in passing on the data. Therefore, this discontinuous and time-consuming method does not make a suitable starting point for checking, re-adjusting, or modifying the production process. Since it was not possible to accelerate incineration by mechanization and automation, another type of rapid continuous analysis had to be found. This would have to depend on some coal characteristic closely linked with ash content. At the Central Laboratory of Dutch State Mines, Dijkstra and Sieswerda found that the absorption coefficient for X-rays was suitable for this purpose. An apparatus based on the measurement of this characteristic was developed. Named CendreX,* this patented equip- *A Stamicarbon N. V. registered trademark. ment, used in combination with a sampler and conditioning apparatus, permits continuous determination of ash content with satisfactory exactness to within 3 min.t At the American Mining Congress meeting of May 1961, Log A. Updegraff, surveying aspects of continuous analyaia, reported on the CendreX appartus (Mining Congress Journal, August 1961). Since the first Condition for correct ash determination, whatever the method used, is always a sample taken in the right way, some practical aspects of sampling will be discussed first. SAMPLING In coal handling operations, each grain has its characteristic properties. In both the cross-sectional and longitudinal direction of the product stream the mixture of these grains is imperfectly blended. The elimination of the factor of segregation between the cross-sections from the direction of the stream is the principal aim of continuous analysis. Therefore, the samples to be analyzed are withdrawn in various places from the segregated product stream in such a way that they form a semi-continuous flow. In order to be truly representative of the product stream, the sample flow must fulfil two conditions: 1) The sample flow must be sufficiently large to insure that adventitious differences between the composition of the product stream and sample flow will be as small as possible. 2) All grains through the entire cross section of the product stream must have an equal chance to get into the sample flow. Since there is always a segregation through the cross section the sample flow will have a bias if the sampler collects only part of this section. In order to prevent the volume of the sample flow from becoming too large, the cross sections are taken discontinuously. However, this discontinuity gives rise to the adventitious differences that arise between the composition of product stream and the sample flow, and these differences become greater and are more deranging as the fluctuations follow each other more quickly. Moreover, the intervals between the morrnents of sampling mean a delay in the analysis. The aim will, therefore, be to collect small samples, or in other words thin cross-sectional increments, taken at sufficiently high frequencies. The following points should also be taken into account: 1) The smallest dimension of the openings in the sample collector must be equivalent to at least 3 d in

Jan 1, 1962

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By Lewis E. Dr. Young

MINING engineers in the United States understand that mining conditions in the British coalfields are much more difficult than in most of the mines now being operated in the United States. We realize also that in the near future we must face some of these same difficult problems. Early Mechanization The progress made in mechanical loading in the United States is the result of a long struggle in many coalfields to mine with power tools safely and to increase output per man-shift. Attempts to use power to loosen coal and to transport broken coal in the U. S. may be said to date from the Stanly Header, or Entry-Driver brought from England in 1888. The principle of this boring machine was used in the McKinlay Entry-Driver, almost continuously used in the U. S. since 1920. Since 1888 experimental loaders, scrapers, and conveyors were installed with more or less success. Beginning in 1918, considerable progress was made with mobile loaders, and in 1920 the first wage agreement for the operation of mechanical loaders was made in Indiana. In 1923 the Pocahontas Fuel Co. loaded nearly 1 million tons of coal using 23 Coloders. Labor Policy The United Mine Workers of America have never officially opposed the Mechanization movement. On December 10, 1945, in a statement before the House of Representatives Labor Committee, John L. Lewis said, regarding the policy of the United Mine Workers of America: "We have welcomed progress; we have welcomed machines. We have told our people that they had to accept that condition; that it was the process of progress, and that they would have to take their chances." Recent Development In 1951 about 71 pct of the tonnage mined underground was mechanically loaded. Over 4000 shuttle cars are in service and it is estimated that much more than half of the tonnage loaded underground is produced by trackless mining. In 1947 roof-bolting was introduced extensively and it is estimated that more than 2 ½ million bolts are now being used per month in about 600 mines. The use of roof bolts has permitted the more effective and safer use of loaders and shuttle-cars. Continuous Mining The McKinlay Entry-Driver could have been used for continuous mining, but for many years it was used only .for entry driving. In 1946 the Silver machine was developed in Colorado, and in 1947 this was acquired by the Joy Mfg. Co. and called the Joy Continuous Miner. Other types of combination mining-loading machines which eliminate drilling and blasting operations are the Marietta Miner, the Colmol, the Lee-Norse Miner, the Junior Miner, the Goodman and the Konnerth machines. There are several other types in the process of development. Probably by January 1953 there will be about 250 continuous miners in operation in the U. S. Payment of Mine Labor One of the most important problems in mechanizing was the establishing of rates of pay that would be attractive to the best men. Prior to the installation of mobile loaders the hand loaders and cutters have been paid by the ton. It was felt that a system of a day's pay should be established and that piece and tonnage rates should be abolished completely. Without exception, all coal loaded in mines equipped with mobile loaders is prepared and loaded by men paid an hourly rate. Trends in Mining Research There are two diverse approaches in coal production research; to try to design a mining machine to fit current methods, or to adapt mining practice to take advantage of proven machines. A great deal of credit must go to the mine operators who have been enterprising and dynamic enough to use available equipment intensively and to discard it as soon as an improved or new machine is available. Effect of Changing Markets Formerly there was an important demand for lump and prepared coal in the larger sizes for domestic use. The use of bituminous coal for house heating has decreased so that not more than 19 pct of the annual tonnage goes to retail trade, only 12 pct is used by the railroads, and much of the retail and most of the railroad coal is in stoker size. As a result of this decline in the market for coarse coal most of the large mining operations have crushers installed in the tipples or preparation plants. Mass production at the face requires increased preparation facilities. Another important trend is in connection with complete seam mining with mechanical loading. In many mines where the immediate roof is apt to fall with the coal no effort is made to separate roof material from coal prior to

Jan 1, 1952

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By J. N. Ong, J. P. Ratledge, J. H. Boyce

SINCE German operators opened the Tsumeb mine in the early 1900's, continuous operation has been interrupted only by enforced shutdowns during two world wars and the depression of the 1930's. Original metallurgical practice was blast furnace smelting. This was applicable only to low zinc ore, leaving large tonnages of high zinc ore to be stockpiled on the surface. A gravity concentrator using tables, buddles, and jigs operated for several years, but differential flotation of the ore did not get beyond the experimental stage. When the property was put up for sale by the South African Custodian of Enemy Property there was an estimated 434,000 tons of ore on surface dumps. The dump material, assaying 4.48 pct Cu, 15.8 pct Pb, and 10.9 pct Zn, had become highly oxidized during a stay of many years on the surface. But these dump ores had to be used in evaluating possible metallurgy because the shaft became flooded after the 1940 shutdown and underground ore was unavailable. Many companies examined Tsumeb but quickly lost enthusiasm because of the formidable metallurgical problems presented by the dump ore. However, on the basis of extensive test work, the present company decided that differential flotation would be successful and purchased the property after competitive bidding. Geology and Mineral Association is Complex The Tsumeb mine lies near the northern boundary of South West Africa at an altitude of 4200 ft. The village of Tsumeb is 335 air miles northeast of Wal-vis Bay, territorial port of entry. The orebody is a hydrothermal replacement deposit associated with an irregular intrusion of aplite cutting folded pre-Cambrian dolomite beds. In plan the deposit is a lens of 250x600 ft maximum dimensions. In section the orebody dips 55" south from the surface to 2000 ft, below which there is a reversal in dip to 75" north. Mineralization is localized in the aplite and in the adjoining brecciated dolomite. In the upper levels the ore is largely confined to a single lens, but below the 1890 level massive sulphide ore forms north and south lenses that partially enclose a pipelike body of medium to low grade disseminated ore, part of which is of too poor a grade to mine. Drilling below the 24th, or bottom level, has disclosed that a high percentage of the mineralization from the 3000 to 3300-ft horizons is comprised of copper and lead oxides. The deep oxidation may be local, since it appears due to circulating waters in a major fault cutting the orebody. Tsumeb ranks as one of the highest grade base metal deposits in the world. It is geologically and mineralogically famous for 41 copper, lead, zinc, vanadium, and germanium ore minerals, but its complex mineral assemblage is not attractive to metallurgists. In addition, there is a gradual change in oxidation intensity from the upper levels to the lowest level now operating, which is the 24th. This is well illustrated by the copper minerals. In the upper levels malachite and azurite are predominant, in the intermediate levels chalcocite, and in the lower levels tennantite. Throughout the mine there are sufficient heavy metal soluble salts to activate zinc, and large amounts of depressants are required even for so-called clean sulphide ores. When the same sulphide ore is exposed to prolonged oxidation aboveground, as was the case with the dump ores, reagent requirements become fantastic. Plant Construction First staff members arrived at Tsumeb in March 1947, and by May essential services had been restored and mine unwatering began. In 2 1/2 months company employees built a temporary jig and sorting plant for treating existing dumps to provide a saleable product during high metal prices. Meanwhile, concentrator design and construction was contracted to a South African firm, with subcon-

Jan 1, 1956

By J. L. Lytton, T. E. Tietz

The recovery of flour stress of recrylstallized are-cast molyhdenum after 10 pet prestrain at 150°C was studied for recovery temperatures of 725o 801o and 901oC. The yield phenomenon observed after recovery was such that the yield drop diminished and disappeared as recovery proceeded. A fractional flow-stress recovery parameter fr, was developed and it was shown that, independent of recovery ternperatzwe, equal f, values of about 0.16 produced superposition of stress-strain curves except for the initial yield phenomenon. The activation energy for low degrees oj recovery was found to he 32,600 cal per mole, in close agreement with a reported valzie for difjzdsion of carbon in molybdenum. For values of fr greater than about 0.15 where recovery was thought to predominate over strain aging, the activation energy varied from 43,600 to 82,500 cal per mole and increased with increasing recovery and recovery temperature. A 10 pet pre-strain shifted the ductile-brittle transition temperature, as indicated by tensile elongation, from 10°C. to about -22"C. A 100-hr recovery anneal at 801oC was shown to shift the transition temperature to about —5oC, the major shift occurring during the first hour of recovery. ThE recovery of cold-worked metals is accompanied by changes in the arrangement of the dislocations generated during cold work. In recent years, the use of transmission electron microscopy has allowed direct observation of some of the dislocation configurations formed, such as "tangles", networks, cells, subboundaries, and loops. These observations have recently been reviewed by Keh and Weissmann.' Accordingly, some understanding has been gained concerning the nature of the dislocation rearrangements involved. The relationship between recovery and the decrease of mechanical strength, however, has only recently been explored. Previous efforts of the authors were directed toward investigating the decrease of tensile flow stress of aluminum and Al-1 pet Mg during recovery2 and the effects of concurrent elastic and plastic strain on the flow-stress recovery of aluminum.3 In addition, an investigation of the effect of four different solute additions on the tensile flow-stress recovery of aluminum has been made.4 Many important metals, however, have the bee crystal structure, e.g., iron, molybdenum, tungsten, vanadium, columbium, tantalum, and chromium. These metals might be expected to behave differently during recovery from those with other crystal structures for two reasons. First, the previous and present investigations of aluminum and its alloys have shown that tensile flow-stress recovery is strongly affected by foreign atoms in the lattice. In the bee metals, interstitial impurities are usually present and might be expected to have various effects upon both flow behavior and recovery. For example, heterogeneous yielding might occur during prestraining. The diffusion of these interstitials can also relock dislocations during recovery so that a yield point might be obtained upon restraining (strain aging). Second, some of the bee metals (e.g., iron, molybdenum, and tungsten) undergo the familiar structure-sensitive ductility transition and exhibit brittle fracture at suitably low temperatures. It is of considerable interest to determine the effects of recovery on the transition temperature of such metals. The purpose of the present investigation was to extend our knowledge of flow-stress recovery to the bee metals and to study the effects of recovery on the ductile-brittle transition temperature. Unalloyed recrystallized are-cast molybdenum was chosen as a test material, since it exhibits a well-defined ductility transition near room temperature. As in the previous studies, the degree of recovery was measured in terms of the decrease of tensile flow stress. Prestraining and restraining were carried out at 150°C to avoid the possibility of brittle fracture. EXPERIMENTAL PROCEDURE The are-cast molybdenum sheet used in this investigation was obtained from the Climax Molybdenum Co. of Michigan. It was 0.060 in. thick by 10

Jan 1, 1964

By A. E. Wraith, N. J. Petch, J. D. Embury, E. S. Wright

The two most important parameters controlling the fracture behavior of a solid are its intrinsic properties, e.g.,grain size, and the operative stress system. The latter may be modified in laminates by the presence of weak interfaces. This is studied in notch-impact tests on a mode1 system of mild steel laminates containing a variety of interfaces. The effect of these is evaluated in terms of the ductile/cleavage transition. Two laminate geometries are distinguished, here called "crack-arrester " and "crack-divider". In both, cleavage is inhibited. This arises because of relaxation of a state of triaxial tension. In the crack-avrester laminates, cleavage initiated at a notch is confined to the layer containing the notch. In crack-cliuider laminates, a thick specimen behaves as the Sum of a number of thinner ones. Additional benefit may derive from improved intritnsic propevties of- the lanlinate layers arising from greater deformation in their manufacture. It has long been recognized that the two most important parameters controlling the fracture behavior of solids are their intrinsic properties (e.g., grain size friction stress,3 distribution of second phase particles4) and the operative stress system under which fracture occurs. In solids that show a ductile/cleavage transition, cleavage is favored by the presence of a notch. This is because triaxial tensions, generated by the localized plastic constraint at the notch, are operative when fracture occurs.= Anything that suppresses these triaxial tensions will be unfavorable to cleavage. Such suppression may possibly occur in laminates containing weak interfaces and the purpose of the present paper is to explore this possibility. Two basic laminate geometries, here termed "crack-avrester" and "cvack-divider", are examined. They are illustrated in Fig. 1. With the crack-arrester laminates, there is the possibility that, when the fracture crack approaches the interface, this, if weak, may delaminate due to the tensile stress acting parallel to the plane of the crack.= If this happens, energy will be used in delamination, the crack will be completely blunted, and the triaxial tension associated with the crack will be relaxed. To fracture the second portion of the laminate, crack reinitiation will be necessary and, because of the relaxation of the triaxial tension, this reinitiation will occur under conditions of nearly uniaxial tension, which are unfavorable to cleavage. Thus there is the possibility of cleavage suppression in the second and subsequent subunits of a crack-arrester laminate. With the crack-divider geometry, there is again the possibility of delamination at the interfaces. This will divide the crack into a series of cracks propagating through the individual laminate subunits. If these are sufficiently thin, the triaxial tension will be relaxed towards a state of biaxial tension in each of them. Thus, with the crack-divider laminates, there is again the possibility of cleavage inhibition. In the present work, these possibilities are explored using a notched impact test on mild steel laminates bonded with soft solder, silver solder or copper. Even if delamination does not occur, it is still possible that cleavage may be inhibited in laminates. With the crack-arrester geometry, the cleavage crack in the first layer may be blunted and arrested by plastic deformation in the laminate bond, if this is ductile. Partial relaxation of the stress transmitted ahead of the crack into the second layer will then result and this will reduce the significance of this stress in the fracture of the second layer. With the crack-divider geometry, there cannot be much effect in the absence of delamination unless a large amount of energy is absorbed in rupturing the ductile material. EXPERIMENTAL DETAILS The composition of the mild steel (wt pet) was: 0.04 C, 0.29 Mn, 0.01 Si, 0.006 P, 0.008 S. "As-received" plate was annealed for 2 hr at 900°C and slowly cooled to give a grain size of 0.04 mm. The laminates were made by brazing or soldering together mild steel plates 8 by 3 in. by various thicknesses. These were obtained from the annealed plate by machining, so that the intrinsic material properties were .kept constant. Laminates containing two to six steel layers were studied using standard Charpy V-notch specimens cut from the bonded plates. Standard homogeneous specimens from the annealed plate and subsize ones from the laminate components

Jan 1, 1968

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell's Principles of Petroleum Geology' contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

By B. Ancker, E. R. Parker

The small-angle dislocation-boundary density of nickel and some of its alloys was investigated as a function of strength. It was found that the strength is a linear function of the density for pure nickel and for Ni-Ti alloys, but not for Ni-Co alloys. The results are interpreted in terms of dislocation theory. THE processes by which metals deform are still poorly understood, even though there has been a concentrated research effort in this field during the past fifteen years. Single crystals and individual grains in polycrystalline aggregates often develop a subgrain structure when deformed. Substructure formation occurs as a result of local plastic bending and its development is augmented by annealing at moderate temperatures.' Investigations made to date, largely qualitative in nature, have shown that the substructure is composed of a network of small-angle boundaries. The purpose of the present paper is to present some quantitative data on substructure (obtained by X-ray techniques) and to correlate the results with the strength of the metal in which the substructure existed. Nickel and some of its alloys were used for the experiments. The presence of certain kinds of foreign atoms greatly alters the formation and effect of the substructure. Polycrystalline tensile specimens were prepared from high purity nickel, two Ni-Ti alloys, and two Ni-Co alloys; the composition of these materials is given in Table I. Tensile specimens having a reduced section 1/4 in. diam by 3 in. long were machined from materials which were refined, cast, forged, and swaged in the authors' laboratories. The specimens were annealed for 1/2 hr at 1150°C, a treatment which produced grains having a diameter of approximately 0.5 mm. This rather large grain size was used to facilitate later examination of the substructure. Duplicate specimens of pure nickel and of each alloy were strained various controlled amounts in tension at room temperature and recovered for 1 hr at 800°C. (This strain induced prior to recovery will be referred to hereafter as the "prestrain.") One of each of the recovered specimens was pulled in tension at room temperature to obtain the stress-strain curves. The other bar was cross-sectioned in the gage length, carefully polished, and deeply etched to remove all cold-worked material. This specimen was then examined by the X-ray microscopic technique2 to determine the nature and magnitude of the substructure. The use of duplicate specimens permitted a direct correlation between tensile properties and substructure characteristics. X-ray microscopic studies were made with an apparatus constructed to have an average resolving power of about 4 microns. The monochromatic radiation reflected from grains which were oriented favorably was recorded on fine-grain photographic plates. These were examined at Xl00 which represents the true magnification, since there was essentially none in the X-ray system. This permitted detection of angular differences between subgrains of as little as 10 min. A very large number (over 100) of grains for each specimen was examined at this magnification and the number of substructure boundaries per grain was tabulated. An accurate relative measure was obtained under fixed experimental conditions, e.g., same grain size, resolving power, magnification, etc. The greatest source of error lay in counting the subboundaries, but this proved to be surprisingly small when repeated counts were made by different investigators. Furthermore, as the subsequent analysis indicates, whatever human error was introduced was not significant. Analysis of the Substructure Data When the number of substructure boundaries per grain was plotted against the frequency, skew (asymmetrical) distribution curves of the type shown in Fig. 1 were obtained. These are smoothed curves for the 1 atomic pct Ti in nickel alloy subjected to various prestrains and are representative of the curves obtained with all the metals. Since skew-distribution curves cannot be analyzed by elementary statistical methods, detailed investigations were undertaken in order to 1—test the consistency

Jan 1, 1955

By Louis Raymond, John E. Dorn

The object of this investigation was to analyze the recovery that arises when the stress on a specimen undertaking creep is reduced. For this purpose annealed specimens of high-purity aluminum were precrept under a stress of 1000 bsi to a strain of 0.08 following which the stress was reduced for various periods of time to 10, 250, 500, or 700 psi. When the original stress was reapplied the subsequent creep curve lay above that for the unre-covered state and below that for the original annealed state. Analyses on the kinetics of this recovery as a function of the temperature gave a stress-sensitive activation energy that decreased as the reduced stress was increased from a value of 64,000 cal per mole at 10 psi to 37,000 cal per mole at 750 psi. Recovery was also detected and measured during creep under the reduced stress. Following a short initial period, the creep rate under the reduced stress increased monotonically until it reached the secondary-creep rate for the reduced stress. The temperature dependence of this phenomenon was also shown to be correlatable in terms of the previously deduced activation energy for recovery. The activation energies for creep of most pure metals at high temperatures have been shown to agree well with those for self-diffusion.'j2 Since the true secondary stage of creep is usually due to the steady-state balance between the rate of strain hardening and the rate of recovery, it is generally thought that the activation energy for recovery of the creep-induced substructure equals that for creep itself. A shoft time ago, however, Ludemann, Shepard, and Dorn~ found that the activation energy for recovery of the creep-induced substructure in high-purity aluminum under zero stress was almost twice that for self-diffusion, namely about 65,000 cal per mole; obviously recovery under reduced stresses differs in some significant way from the recovery that accompanies the secondary stage of creep. The major purpose of this investigation is to study the effect of stress on the re- covery of the creep-induced substructure in order to provide a better understanding of the recovery mechanism itself. EXPERIMENTAL TECHNIQUE High purity aluminum, containing 0.004 pct Cu, 0.002 pct Fe, and 0.001 pct Si, used in this investigation, was in the form of 0.100-in.-thick sheet which has been cold-rolled to the H-18 temper. Creep specimens were milled from the sheet with their tensile axes in the rolling direction. All specimens were then heated at 686°K for 1 hr followed by air cooling in order to produce an annealed structure which exhibited a uniform equiaxed grain size of about 4 grains per mm. Tests were run in creep machines fitted with Andrade-Chalmers type of lever arms so contoured as to maintain the stress constant to within 0.05 pct of the reported values. Constant temperatures to *O.l°K were obtained by complete immersion of each specimen in a temperature-controlled and agitated bath of molten KN02-KNOs mixture. Where changes in temperature were involved, the change was effected in less than 2 min by manually replacing one bath by another controlled at the second temperature. Displacements over the gage section were sensed by linear differential transformers, the output of which was autographically recorded. The calculated strain measurements were sensitive to 5x EXPERIMENTAL PROCEDURE The following analyses are based on extensions of the previously announced effect of the temperature on the creep strain,2 namely for a = constant, where e = the total true tensile creep strain for a given applied true tensile stress, t = the duration of the test, R = the gas constant, T = the absolute temperature, Q, = the activation energy per mole for creep which is independent of the stress, / = a function of 8, = and of the stress, and a = the stress. The validity of this correlation for high-purity aluminum is demonstrated in Fig. 1 for temperatures in the near vicinity of 600°K; the activation energy for creep, Q,, which is approximately that for self-diffusion, is insensitive to the applied stress

Jan 1, 1964

By G. A. Vissac

MoIstuRe in coal must be considered as an impurity, just the same as ash, from the standpoint of utilization of the coal. Being incombustible, it reduces directly the heating value of the coal, and in addition absorbs heat for its evaporation. Its presence means useless expenditures in handling and transportation. In coke plants, extra moisture reduces capacity and may cause damage to brick work and equipment. Accordingly, the removal of extra moisture can be considered just as important as the removal of other impurities, such as ashes, in the modern coal preparation plant. Moisture, which can be removed by heating the coal up to a temperature of 100°C, may be retained in various forms: 1. As a film, on the surface of each coal particle, and in the interstices between particles, retained by capillary forces. 2. Or "occluded" inside the coal particles. This occluded moisture may be either free moisture (as in a sponge), or hygroscopic moisture which varies with atmospheric conditions, (also called "regain"). These latter forms of moisture are particularly common in "young" coals (subbituminous and lignites); bloom coals (seam outcrops); fusain; and carbonized products. In our study of coal drying, we shall consider only the removal of free moisture, exclusive from hygroscopic moisture. Dewatering If we reserve the name of drying to the removal of water by evaporation, we must consider the initial phase of the mechanical removal of free moisture as a distinct operation covered by the term dewatering. In all cases the free water carried over the surface of the coal particles or in their interstices, or in their pores, is retained by capillary forces. Dewater-ing is accomplished by breaking or counteracting these capillary forces; removal of as much water as possible by dewatering methods is usually advisable, as the cost of these operations is generally much less than by evaporation. The most common methods of me-chanical dewatering are: 1. "Pressure piling," which reduces the interstitial spaces, accomplished in dewatering bins or over dewatering screens. 2. Or dynamic methods, such as used in centrifuges or over vibrating screens. We shall only mention the " preferential wetting" method, in which surface water can be displaced by hydrocarbons, as offering possibilities, but which, to our knowledge, has not reached yet a practical development. But we must point out that the capillary forces retaining water on the coal surfaces, decrease considerably with increased temperatures. This is the principle used in all modern dishwashing machines; by using very hot water, dishes are extracted almost dry. In line with this development, we favor the type of dryers including a dewatering section; as the coal enters the dryer and is gradually brought up to higher temperatures, its dewatering ability is increased and advantage can be taken of this conditioning, resulting in increased drying efficiencies and reductions in drying costs. Heat Drying In the final phase, the remaining moisture must be evaporated. Coal and water must be brought up to the chosen temperature of evaporation, and heat must be supplied to fill the requirements of the latent heat of evaporation of the water to be removed. Accordingly, drying becomes largely a problem of heat transfer, and drying methods can be classified accordingly, namely: 1. Radiant transfer. 2. Transfer by surface contact and conduction. 3. Transfer by hot gas contact. The first method is not applicable to coal drying; the second method is used in the old type rotary dryer. The third method, the most commonly used in modern coal dryers, will be the only one considered here; and, of course, we shall deal with continuous types of dryers only. The mechanism of complete drying is really very complex-—several phases are involved: 1. The constant rate period. 2. The uniform falling rate period. 3. The varying falling rate period. As most of our practical coal drying problems deal with wet coals (over 6 pct of moisture), and do not require complete drying (under 1.5 pct), we shall deal with the first condition only, namely the constant rate drying. Dryer Calculations Instead of presenting the algebraic formulas, we believe a concrete example will provide a clearer illustration. Assume a feed of wet coal at the rate

Jan 1, 1950

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950