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By J. F. Myers, F. M. Lewis

The paper reports the development of a large, slow speed ball mill closed circuited with a hvdro-scillator. This increased grinding efficiency 28 pct over conventional units. AS the title indicates, this is a progress report for the first year of experimental operation of a relatively large diameter, slow speed ball mill with 1-in. balls, with and without various classifiers, and including a hydroscillator. Several years ago the authors came to the conclusion that if any further progress were to be made in our flotation process, an understanding of the chemical and physical reactions and the control thereof, in the grinding circuit, was essential. It may be stated, at this point, that the preparation of a correct feed for the flotation process is still the number one objective of our grinding studies. This progress report deals with grinding "per se," and not with the chemical and physical reactions as the result of grinding. Prior to this time we had taken the naive position, that since grinding had been practiced by the industry for some fifty years or more, it had been well exploited and developed by a host of investigators. Consequently, we had given the matter only superficial attention. At the start of our study, we were aware of the fact that some difference in opinion existed, but we were not prepared for the controversial evidence that developed nor for the extent to which the experts differed in their viewpoints. There seemed nothing else to do but to tour the continent and decide for ourselves what was right and what was wrong, read all the published literature and visit with anyone who had ideas about the matter. This we did over the next few ensuing years. Since our study has met with some measure of success, we report, herewith, these data that ultimately they may be of help to other investigators. In 1944 it became necessary to increase our grinding capacity and at the same time to grind the sulphide portion a little finer. This provided the impetus to put our ideas into effect. As has been previously described, our grinding flowsheet at that time consisted of a 6x12 rod mill, followed by two 5x10 ft, and one 6x12 ft trunnion overflow ball mills, with conventional rake classifiers. Naturally, we first considered all the possibilities of altering or adding to the existing equipment. It became evident that if any appreciable increase in grinding efficiency could be obtained, it would pay to scrap the existing small mills and classifiers and install one big mill with adequate classification. Trying to determine just how much more efficient a big mill could be, in which were incorporated all

Jan 1, 1951

By G. W. Binkley, G. K. Dumbauld, F. A. Brooks, B. E. Morgan

In recent years, oil well cementing compositions have been developed with low densities, controlled set strengths, and satisfactory thickening times. With the introduction of the permanent-type well completion method for cementing wells, another property—that of rate of filtration or water loss to permeable formations— has become important. Laboratory data show that cement slurries prepared with oil, water, bentonite, and calcium lignosulfonate possess satisfactory thickening times, strengths, and filtration properties for primary cementing of casing and for squeeze cementing with the permanent-type well completion technique. Cementing compositions have been prepared with oil-in-water emulsions varying in composition from 60 cc water and 20 cc oil per 100 gm cement to 90 cc water and 45 cc oil per 100 gm cement. These compositions have contained from 0.4 to 5.0 per cent calcium lignosulfonate by weight of dry cement. Slurries prepared from these compositions weigh 11.4 to 13.1 lb/ga1 and have filtration rates of from 10 cc to approximately 100 cc in 30-min API tests at room temperature. The unfiltered emulsion cements develop one-day tensile strengths of 60 to 220 psi; and the filtered mass sets to tensile strengths of 60 to 150 psi in 12 hours and develops strengths of 320 to 515 psi in seven days when cured at 125° F. Field experience gained from 13 field mixing jobs demonstrates the utility of the emulsion cement for permanent-type squeeze cementing operations. INTRODUCTION In recent years, research in oil well cementing composition has been directed toward the development of cements having low densities, controlled set strengths, satisfactory thickening times, and low rates of water loss by filtration. Two well cementing compositions that have been developed with these properties are the modified cements containing, respectively, 12 and 25 per cent bentonite clay and various concentrations of calcium lignosulfonate1,2 In a search for other ways to incorporate these characteristics in a cementing composition, consideration was given to the rheological properties of oil-emulsion drilling fluids. Many of the desirable properties observed in oil-emulsion drilling fluids are equally advantageous in a cementing composition. For example, low water loss by filtration and low density, which are inherent characteristics of these oil-in-water emulsions, are desirable for many oil well cementing operations. Furthermore, oil-emulsion slurries have lubricating properties similar to those of oil-emulsion muds, a factor which should provide ease of rotation of casing during primary cementing operations. The properties of lubrication and low filtration may be of special value in both primary and squeeze cementing operations encountered in slim-hole drilling. Studies in the preparation of oil emulsion systems have pointed out the need for violent agitation in order to disperse the oil into the water phase. It was thought, therefore,

Jan 1, 1957

By Nathaniel Arbiter, Arthur F. Taggart

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Alec M. Crowell, Thomas D. Bailey

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By Konrad Stern

The terms asphalt and bitumen have been applied interchangeably, although incorrectly on occasion, for centuries to various bituminous materials that were found in nature. Native bituminous materials of only the solid types, deposits of which are found on or near the surface of the ground, together with the principal asphaltic type petroleum bitumens will be considered in this chapter. The international dictionary compiled by the "Permanent International Association of Road Congresses" still gives the full name as "Asphaltic Bitumen" but of recent years the word "Bitumen" has been recognized as most appropriate and is defined by the American Society for Testing Materials as follows: "Mixtures of hydrocarbons of natural or pyrogenous origin, or combinations of both, frequently accompanied by their nonmetallic derivatives, which may be gaseous, liquid, semisolid or solid and which are completely soluble in carbon disulfide." Asphaltic pyrobitumens, as defined by Abraham,2 is a species of pyrobitumen, including dark-colored, comparatively hard and nonvolatile solids; composed of hydrocarbons, substantially free from oxygenated bodies; sometimes associated with mineral matter, the nonmineral constituents being infusible and largely insoluble in carbon disulfide. Deposits of native bituminous materials are found scattered over the entire world, but many are relatively unimportant as far as commerce is concerned. No attempt has been made to cover all of the known deposits. The principal bituminous materials of commercial interest are: 1. Native asphalts, solid or semisolid, associated with mineral matter such as Trinidad Lake asphalt, Rock asphalt and Selenitza, Boeton and Iraq asphalts. 2. Native Asphaltites, such as gilsonite, grahamite and glance pitch, conspicuous by their hardness, brittleness and comparatively high softening point. 3. Asphaltic bitumens obtained from nonasphaltic, semi-asphaltic and asphaltic crude petroleum by distillation, blowing with air and the cracking of residual oils. 4. Asphaltic pyrobitumens of which wurtzilite and elaterite are of chief interest industrially as they depolymerize upon heating, becoming fusible and soluble in contrast to their original properties in these respects.2 5. Mineral waxes, such as ozokerite, characterized by their high crystallizable paraffine content. Native Lake Asphalt At Brighton situated in the southwestern part of the Island of Trinidad is one of the largest deposits of native asphalt in the world.3 The lake is oval in shape, covering an area of 114 acres and having a depth of 285 ft at its center. The material forming this deposit is an emulsion of water and bitumen with a suspension of mineral matter consisting of impalpably fine clay dispersed by nature in the asphalt, and small quantities of silica and vegetable matter. The entire mass of asphalt is in slow but constant motion as evidenced by the migration of islands of vegetation from one place to an-

Jan 1, 1960

By Thomas D. Bailey, Alec M. Crowell

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

Copper ores from small mines in the area south of Tucson, where the Twin Buttes mine is located, were first operated in the 1880's. Today this area is one of the great copper mining centers of the world. In 1963, Anaconda Company acquired the property from Banner Mining Company and in recent years joined with AMAX in a 50/50 partnership to work the Twin Buttes property. From the beginning, Anaconda had relied on conveyors to remove overburden, oxide material for eventual leaching, and ore from the open pit. In the large st preproduction stripping program in mining history, Anaconda in a four-year period (1965 to 1969) removed 266 million tons of overburden of an average depth of 500 ft (152 m) lying over the ore body. The alluvium overburden was stripped by scrapers carrying 70 to 80 tons and push-loaded by two D9 tractors operating in tandem. The scrapers delivered their loads to bins which fed a 60 in. (1.52 m) conveyor having a capacity of 8500 tph. The 25% slope belt conveyor, which was 2100 ft (640 m) long, transported the material to the brow of the pit, where it was transferred to an 8300 ft (2530 m) surface belt to a 1000 ton loadout bin. At this point, the overburden was trucked to the sites of the tailings ponds, where it was used for dam construction. During 1976, the one billionth ton of overburden was removed from the Twin Buttes mine. The Twin Buttes quartz monzonite porphyry contains only scattered mineralization of which chalcopyrite is the most abundant mineral, associated with chalcocite, covellite, minor bornite, and several oxide minerals. Oxidation has progressed to variable depths of up to several hundred feet below the base of the alluvium. Because of the depth of the sulfide and oxide ores and hard rock waste, two in-pit crushers and conveyor systems were also installed for their transport out of the pit; and in 1976 a third crusher and conveyor system was installed lower in the pit for waste rock only. The two initial crushing and conveying systems were designed to handle any of three functions: crushing waste to be disposed of by a rail-mounted stacker -conveyor, crushing oxide ore for conveyor and then truck transport to stockpiles for future leaching, and primary crushing of sulfide ore for conveyor transport to the two 30 in. by 70 in. (0.76 by 1.78 m) secondary crushers and the two 7 ft (2. 13 m) standards and four 7 ft shortheads in the third and fourth stage crushing plant. A third standard crusher has been in- stalled recently. Mining is done by 15 yd (11.5 cum) shovels which load 100- and 150-ton

Jan 1, 1978

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By G. D. Van Arsdale

THE paper of Mr. Posnjak presents a laboratory confirmation of the well known facts that air ox-idation of pure solutions of ferrous sulfate is slow and difficult and that, like many other similar reactions, the speed, may be greatly accelerated by the presence of other substances, often in very small amounts, the effect of the presence of copper being determined ex-perimentally in this case. However, it should not be. overlooked that copper is always present in heap leach-ing solutions in amounts equal to or greater than those in the experiments described; therefore the paper may be considered as an explanation of present results rather than a possible improve-ment to be added to present practice. It is not practicable and it does not pay to precipitate copper by ce-mentation below a point about 5 lb. per 1000 gal., equivalent to about 0.0005 mol. Cu. per liter, compar-ing with the approxi-mately 0.0009 mol. per liter of curve 2 in the diagrams given of course, also, in the heaps local concentrations are usually very much higher than this, which is also true of the effluent li-quors, so that I feel that it is safe to say that copper is already present in amount sufficient to realize, as large an accelerating effect as is practicable. Too much im-provement or refinement cannot be expected in a method of this kind, due to commercial limitations. It should be remembered that chemically and physically there is no sharp dividing line between leaching in place, heap leaching, and the usual tank leaching practice, practi-cally the same reagents being used in all three. From the viewpoint of extractions, etc., it is not common sense to apply leaching in place to an orebody carrying enough copper to pay for mining; and the same is true of heap leaching, for an ore carrying enough to pay for the crushing, handling, etc., of ordinary leaching. That is to say, leaching in place should properly be consid-ered only for an ore too low-grade to pay for mining, and heap leaching for the next higher grade, still how-ever too low-grade to pay for crushing and other re-finements. There is no advantage in leaching without mining or in heap leaching except lower cost of in-stallation and handling; on the other hand there are very distinct disadvantages which are inherent and which should prohibit their use except where necessity requires. The object of metallurgy is to make money out of the handling of ore, and it is purely a question of money as to how far we can go in "improving" or

Jan 7, 1927

By A. M. Gaudin

IT is only in recent years that substantial progress has been made in developing a physico-chemical picture of the solid state. The molecular concept, so useful in dealing with gases, was naturally carried over to the field of crystalline solids; it has resulted in the firm implanting of erroneous concepts that only now are being eradicated successfully. Two simply written and effective books on the subject are Crystal Chemistry by Stillwell1 and An Introduction to Crystal Chemistry by Evans.' A more complete treatment of the subject is available in a book by Wells.' The monograph by Hückel4 also touches on a subject most easily perceived by reference to the brief introduction by Bragg,5 that master of the field. These texts make it clear that while some solids are built of molecules, many are built of ions, others of atoms connected in the form of giant molecules, and still others of cations and electrons. The various lattices in which these entities are systematically arranged, the joint use of several of these entities, and the transitional character of some of the bonds make for the great variety of crystalline solids. The purpose of this paper is to point out a most important corollary of present views on the structure of solids. In this connection the classification of solids in Table I is helpful. Atomic crystals are those formed by the noble gases, e.g., helium and argon. They are soft, sublime at very low temperature, of very low specific gravities, and not encountered in ores. Molecular crystals are uncommon among inorganic materials, common among organic materials. Typical examples from both inorganic and organic fields are sulphur, iodine, naphthalene, benzene, and carbon tetrachloride. These crystals are soft and have low specific gravities; where the molecules are small, the sublimation temperature is low. Filament and sheet crystals are rare. They are typified by elemental selenium and elemental arsenic, respectively. Graphite and molybdenite come near being sheet crystals. These crystals are soft in some directions, tough in others, sublime at various temperatures. Diamantine crystals, typified by diamond, are very few in number, stable at high temperatures, and extremely hard. Ionic crystals are common. Most salts, acids, and alkalies belong in the two classes of ionic crystals; examples are rock salt, fluorite, calcite, and angle-site. The salts, acids, and alkalies that do not belong in these classes are more properly regarded as transitional between ionic crystals, framework crystals, and diamantine crystals, e.g., ice and quartz. Fiber crystals are relatively uncommon mineral-ogically speaking, but common in the fields of living processes. Examples are asbestos, silk, cellulose, and wool. Many fiber crystals are so little known even now that their crystallinity may be doubted. Layer crystals, among the more interesting and useful of solids, include a wide variety of substances

Jan 1, 1956

By Nathaniel Arbiter, Arthur F. Taggart

THE fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. EXPERIMENTAL Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,' and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: 1. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. DISCUSSION OF RESULTS Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether

Jan 1, 1943

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By G. W. Nabor, M. Mortada

The effects of anisotropic or directional permeability on the areal sweep efficiency and the flow capacity are examined. The paper points out the importance of taking directional permeability into consideration in planning a flood. It analyzes the two-dimensional flow pattern associated with the skewed line drive for a unit mobility ratio. The direct and staggered line drives are treated as special cases of the skewed line drive. Analytical expressions are developed for the areal sweep efficiency at breakthrough and the flow capacity. They are related to the spacing between like wells, the distance between a row of injectors and the nearest row of producers, and the degree of skewness of the line drive. The latter quantity is defined such that it is equal to zero for the direct line drive and equals one-half for the staggered line drive. The areal sweep efficiency and the flow capacity depend also on the orientation of the flood pattern with respect to the principal axis of anisotropy. The paper provides a simple method for determining the areal sweep efficiency and the flow capacity for a formation in which the permeability in the bedding plane is anisotropic. INTRODUCTION Directional or anisotropic permeability is manifested by the ability of the formation to conduct fluids more readily along certain preferred directions. This situation occurs in many producing formationsl-4 and is usually attributed to depositional features in which the sand grains are oriented in a preferred direction. In some cases it results from the formation of a major and a minor fracture system. 4 Directional permeability should be taken into account in many phases of the production and exploration activities. Recognizing its existence in the formation of interest and planning accordingly can lead to increased recovery and substantial savings. For instance, the areal sweep efficiency in a water flood depends to a great extent on the orientation of the flood pattern with respect to the principal axis of permeability. Anisotropic5 permeability is specified by the directions of its three principal axes and the permeability along each axis. The principal axes of permeability are mutually perpendicular. This paper deals with the areal sweep efficiency at breakthrough and the flow capacity for formations with aniscltropic permeability. The flood pattern considered consists of alternate rows of injecting and producing wells. The rows of wells are parallel and form a developed, skewed line drive which is illustrated in Fig. 1. The staggered and direct line drives are treated as special cases of the skewed line drive. PRELLMINARY CONSIDERATIONS The formations considered in this paper are assumed to be of uniform thickness and porosity. The permeability is uniformly anisotropic, with each principal axis of permeability maintaining

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature1135°C. (2095°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm, at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.'-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1' for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T', the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

ONE of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing of the A.S.T.M., 1938. The work of Mann,1 Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserve especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by [P OL, plotting So = Ao as a function of eo = Lo] where A o and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors' It was shown that the true physical behavior of the material in the tension test could best be represented [by plotting the average true stress, S = P as a function of e = q' = log o = log Log] where P, A, L, S, e, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximum load point to fracture. The construction of such- curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain difficulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece

Jan 1, 1941

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.'-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1' for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T', the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947

By L. J. Demer, W. W. Walker

AMONG several variables of the indentation hardness test is the effect of loading time on the measured hardness of a material. The most generally recommended duration of loading is 10sec.1-3 Although this short loading duration is undoubtedly satisfactory for harder metals, it is questionable that it is sufficient for very soft metals,4 or for certain plastics.5 The effect of duration of loading on the measured hardness of ionic crystals is largely unknown, although Onitsche and Mitsches found that the indentor (under a very low load) had not yet reached equilibrium after 60 sec in a variety of ionic crystals. To extend further the data of Onitsche and Mitsche, a systematic study was made of the effect of duration of loading for longer periods, up to 50,000 sec, on the 136 deg Dph of synthetic lithium fluoride. For comparison, less extensive tests were made on synthetic magnesium oxide and copper single crystals. The general procedure used was to indent a cleaved and polished (100) face of a lithium fluoride crystal using a Leitz Durimet microhardness tester. In certain cases, the indentor was so oriented as to align the diagonals of the 136 deg diamond pyramid indentation parallel to a (100) edge. In other cases the diagonal of the indentation was aligned at 45 deg to a (100) edge of the crystal. After indenting, the surface tested was etched in the acid etchant recommended by Gilman and Johnston.' This revealed the position of dislocation lines which intersected the surface tested. At these points of emergence were formed the usual sharp, pyramidal etch pits as shown in Fig. 1. The specific procedure used in studying duration of loading was as follows. The surface of the crystal was indented, and the load was left on the indentor for a predetermined time. This duration of loading was varied systematically from 1 to 50,000 sec. After the desired amount of time had elapsed, the indentor was removed from the crystal and the size of the resulting indentation was determined using a micrometer eyepiece. The surface was then etched to reveal the dislocation etch pit pattern around the indentation. Procedures used for lithium fluoride, magnesium oxide, and copper were similar. Preliminary studies revealed that, although an indentation was enlarged by increasing loading time, no corresponding changes occurred in the surface etch pit pattern. Since no evidence of dislocation movement was observed on the surface, it was assumed that the plastic deformation indicated by the indentor sinking into the surface was a result of dislocation movement inside the crystal. This movement was studied bf making a series of surface indentations in a crystal corresponding to various lengths of time, cleaving the crystal vertically through the indentations, etching the freshly

Jan 1, 1964

By O. L. Culberson, J. J. McKetta

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

The external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied. The theory that has received the most attention recently—that of dislocations—postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped. Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc. Whatever the precise mechanism, the concept of growth is in itself consistent both with the observed low values of critical shear stress and with the experimental observation that slip bands frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleation 2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed 5,6 to precede slip but also predicts certain transient effects in the deformation process. The existence of these transients apparently has not hitherto

Jan 1, 1949