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By Allen Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND. GENERAL COMPOSITION OF CLAYS AND SHALES Clays, shales and- surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust, has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales.

Jan 1, 1939

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By A. M. Kivari

OPERATIONS at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials Closed-circuit grinding, classification, hydroseparation, flotation, agitation, and thickening are familiar terms at this cement plant These methods make it possible to process refractory limestone into suitable materials for the manufacture of modern cements Construction of the plant, haying originally a design capacity of 7000 bbl of cement per clay, was started in June 1939, and the first clinker was ground on the following Christmas Day At present the capacity is about 12,000 bbl of finished cement per 24 hr , most of the production being low-heat cement † About 3130 tons of limestone, 620 tons of clay and 100 tons of gypsum are required daily for this output Occasionally iron oxide is added to the clay to obtain the desired composition This, together with the gypsum, is purchased from outside sources Up to the present time, the corporation has produced low-heat, normal, moderate¬ heat, moderate-sulphate-resisting, high-early-strength, oil-well, modified-oil-well, and plastic cements Most of the present production is for Shasta Dam, near Redding, Calif , the told demand being 5,800,000 bbl of cement Following are sonic of the cement requirements of the Shasta D [im] specifications [ ] The average specific surface in the bin s sampled shill be not less Ulan 1800 sq cm per gram and no individual sample less thin 1600 sq centimeters Compressive strength The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2 75 parts fine testing sand, by weight, shall be equal to or greater thin the following

Jan 1, 1941

By A. N. Holden

A DISLOCATION mechanism has been described by Cottrell' by which metals can yield locally, I. form Liiders bands, giving rise to a characteristic stress-strain curve with a sharp yield point and appreciable strain at constant or decreasing stress. It is undoubtedly the best mechanism that has been suggested to date." In its present development, however, the dislocation mechanism provides a more satisfying explanation for the sharp yield point than for the extensive localized flow occurring at the lower yield stress. The primary objective in this paper is to extend the dislocation mechanism to account for localized cataclysmic flow by a dislocation collision process and to give experimental evidence to support such a process. Only the yielding of iron containing carbon -will be discussed, although other metal-solute systems are known to behave similarly. Cottrell Mechanism In brief, Cottrell explains the yield point in the following way: The dislocations in iron which must propagate to produce slip usually lie at the center of local concentrations of carbon atoms, since segregation about these dislocatlons relieves some of the local stress resulting from them. A dislocation surrounded by a "cloud" of carbon atoms is thus anchored, and a higher stress is required to set it in motion than to move a free dislocation. Considering all available dislocatlons to be anchored in this fashion, the iron exhibits a yield point when the first dialocations break free and move through the lattice causing slip. This first breaking away of a dislocation enables other dislocations to break loose by "interaction" and the process becomes a cataclysm producing local deformation or Luders bands. The yield point in the stress-strain diagram for iron is absent in freshly deformed material, but returns gradually with time; the phenomenon is one aspect of what is called strain aging. The rate at which the yield point returns following straining depends on the temperature of aging. According to Cottrell the rate of return of the yield point in strained iron is limited by the rate of diffusion of carbon at the aging temperature, the mechanism is onr: of reforming the solute atmospheres around carbon-free dislocations that had stopped moving coincident with the removal of stress. If the specimen is retested immediately after straining and unloading, carbon will not have had time to diffuse to, and re-anchor, dislocations and the yield point will not occur. The carbon diffusion limitation for the rate of strain aging apparently applies if the criterion for strain aging is either the change in hardness" or the change in electrical resistance" of the strained speci- men with aging time. The possibility exists, however, that the yield point actually returns to strained iron at some rate other than that deduced from hardness or electrical resistance data. Therefore, as a preliminary experiment, the rate of yield point return in a rimmed sheet steel strained 6 pct in tension was measured at 27°, 77°, and 100°C. A plot of yield-point elongation for each of these temperatures against aging time appears in Fig. 1. The aging process is described by curves which rise to a plateau value of elongation that seems independent of temperature, but at a rate that depends on temperature. Very long times lead to a further rise in the yield-point elongation above the plateau value. However, if the later increase in yield-point elongation is ignored and the log of the time to reach half the plateau value of elongation is plotted against 1/T, a straight line results for which an activation energy of about 25 kcal pel- mol may be assigned. Within the accuracy of this sort of experiment this is approximately the activation energy for the diffusion of carbon in iron (20 kcal per mol), and the carbon diffusion limitation suggested for the yield-point return on strain aging is valid. The Cottrell mechanism thus explains in a qualitative manner the occurrence of a yield point in iron and its return with strain aging. It fails, however, to explain some of the other experimental observations that have been made of the yielding behavior of iron. For example, it is known that the yield point in iron becomes less pronounced with increasing grain size. Annealed single crystals of iron have very small yield-point elongations .if indeed they have any,' compared to a polycrystalline steel. If the only requirement for a yield point is that the dislocations in the lattice of the annealed. material be anchored by carbon atoms, the difference in the behavior of single crystals and polycrystals is not explained. That a dislocation mechanism may be entirely consistent with little or no yield point in an annealed single crystal will become apparent later when dislocation interaction is discussed. Strain aging produces a definite yield point even in single crystals. This accentuation of the yield-point phenomenon in single crystals after strain

Jan 1, 1953

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

By Strathmore R. B. Cooke, William F. Stowasser

RESULTS presented in a previous paper1 have shown that the strength of fired pellets made from eastern Mesabi magnetite concentrates containing 8 to 9 pct Si02 as quartz and silicates is due to several processes which occur during firing. These are: l-recrystallization and cementation of the fragmented magnetite grains; 2-formation of slag from reaction between the quartz, silicates, and available ferrous iron, followed by slag-bonding of the magnetite grains; and 3-oxidation of the magnetite to hematite and subsequent recrystallization and grain growth of this constituent. Microscopic examination of all magnetite pellets fired in one operation in small and large-scale pilot plant furnaces and possessing normal strengths shows that the processes 1,2, and 3 have taken place; where strengths are low and the pellets are otherwise sub- normal, one or more of the processes has not occurred. For example, soft and friable red pellets may contain a central core of slag-bonded recrystallized magnetite which is strong enough in itself, but the shell contains only slightly recrystallized hematite, indicating that the maximum temperature reached was too low. Processes 1 and 2 can occur only under reducing conditions, as for example, when coal is intention- ally added to the original pellets; under neutral conditions, when pellets are fired in an inert atmosphere; or when pellets are brought so rapidly to temperature in an oxidizing atmosphere that oxygen diffusion to the core lags behind the recrystallization and slagging effects. This last-mentioned process has occurred in all pilot-plant shaft fur-

Jan 1, 1952

By K. L. Ludeke, A. D. Day

For many reasons, it appears that deep rooted, perennial shrubs offer potential for improved stabilization and provide maintenance free vegetative cover to harsh sites where perennial grasses have not been successful. The major objective was to select various shrub species of arid plants for initial soil stabilization of disturbed mining areas. The very fact that a drought-adapted shrub has a massive root system that can use moisture from a greater volume of mineral waste soil materials suggests that arid environment disturbed soils may be vegetatively stabilized using desirable forage shrubs. A secondary effort is underway to assemble information and plant materials of promising species from many arid regions of the world for reclamation of mined lands. Surprisingly, many of the better plants for arid sites are quite high in protein content. With proper management, breeding, and selection, they may prove to be very desirable livestock feed when mined lands are used in range land areas. Advancements in arid land solid waste stabilization hold favorable promise for many industries that mine and mill in arid regions for effective reclamation of disturbed areas. Particularly exciting is the possibility of establishment of high density maintenance free vegetative cover of climax vegetation that reclaims the disturbed area back to its original land use. Due to high shrub productivity, stabilization potential, nutritional quality, and reclamation success, greater use should be made of shrubs in disturbed land reclamation associated with mining and milling operations in harsh aril environments.

Jan 1, 1986

By George D. Graffin

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3500°C and sublimes at about 4500°C. It is combustible in the presence of oxygen between 620° and 670°C, but is stable and chemically inert at ordinary temperatures.

Jan 1, 1975

By Charles H. Eldridge, Robert J. Anderson

When a metal or alloy is poured into a mold, internal stresses are set up by the cont,raction in volume on passing from the liquid state at the temperature of pouring to the solid state at the ordinary temperature. It is assumed by the writers that all castings are internally stressed. That any casting is internally stressed is shown by its warping or distortion on maturing at the ordinary temperature, by warping or cracking on heating, or by cracking or distortion on machining. In the investigation made by the writers, the internal stresses in cast non-ferrous alloys were studied with a view to examining the effects of heat treatment (i.e., simple anneal) on the release of such stresses. Data have been obtained that show quantitatively that internal stresses can be removed by appropriate heat treatment. The investigation was limited to a study of the effect of heat treatment on stress release in cast rings of the 87:7:5:1 copper-tin-zinc-lead alloy. The writers are indebted to E. G. Fahlman for the method used for inducing stress in cast rings; to M. E. Boyd for microscopic examination and for other aid; and to G. B. Dalrymple for the chemical analyses. General Information While casting stresses have been discussed considerably, they have usually been treated in a general way, and so far as the writers know no measurements of the magnitude of internal stresses in castings have been reported. It has been suggested by many investigators, particularly in the case of steel castings, that castings are internally stressed, and that these stresses can be removed by annealing. In a casting, the internal

Jan 1, 1923

By Robert J. Anderson, Charles H. Eldridge

When a metal or alloy is poured into a mold, internal stresses are set up by the cont,raction in volume on passing from the liquid state at the temperature of pouring to the solid state at the ordinary temperature. It is assumed by the writers that all castings are internally stressed. That any casting is internally stressed is shown by its warping or distortion on maturing at the ordinary temperature, by warping or cracking on heating, or by cracking or distortion on machining. In the investigation made by the writers, the internal stresses in cast non-ferrous alloys were studied with a view to examining the effects of heat treatment (i.e., simple anneal) on the release of such stresses. Data have been obtained that show quantitatively that internal stresses can be removed by appropriate heat treatment. The investigation was limited to a study of the effect of heat treatment on stress release in cast rings of the 87:7:5:1 copper-tin-zinc-lead alloy. The writers are indebted to E. G. Fahlman for the method used for inducing stress in cast rings; to M. E. Boyd for microscopic examination and for other aid; and to G. B. Dalrymple for the chemical analyses. General Information While casting stresses have been discussed considerably, they have usually been treated in a general way, and so far as the writers know no measurements of the magnitude of internal stresses in castings have been reported. It has been suggested by many investigators, particularly in the case of steel castings, that castings are internally stressed, and that these stresses can be removed by annealing. In a casting, the internal

Jan 1, 1923

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

THE subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for 10 years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. I). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, nonmetallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to 100 mg. per sq. cm. per day, the corrosion rate of high-purity magnesium is 0.15 ± 0.05 mg. per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in combination, in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called "tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable. In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0.001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. While the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1941

By N. D. Gerald

The mathematical analysis, which is an essential part of this paper, has revealed the interesting fact that contrary to the opinions of many, determinate and measurable economic factors are largely responsible for the price of crude oil. It should, however, be well understood that the results of this analysis are applicable, without qualification, only to the particular period and market studied. There are certain peculiarities of the petroleum industry which make the consideration of its economics very difficult, and at times practically impossible. Noneconomic factors often become highly important and have serious economic effects, which make unqualified predictions based on economic data extremely hazardous and ill advised. However, in spite of the attendant difficulties there are many problems, especially in price analysis, to which approximate solutions must be made for the proper guidance of public and private policy, but their limitations should be kept clearly in mind. An understanding of the nature of prices is of fundamental importance for a number of purposes. Measurement of the motivating factors giving rise to trends and other price movements is essential to forecasting for the intelligent engineering and financial administration of the industry. The fixing of prices, maintenance of an intelligent industrial dictatorship, or the making of other industrial adjustments, demand, for success, an accurate understanding of their probable consequences. The establishment of a system of equitable relations within an industry, or between industries, by methods other than the natural competitive ones, requires a thorough knowledge of the price structures and the nature and trends of the normal and basic prices of their products. This research has shown that in this case, even though the statistical records are only fair, quantitative economics offers a direct and satisfactory approach to the problems of economic consequences dependent on the reactions of mass intelligence. A consideration of commodity prices naturally leads to costs. The true cost of petroleum is so complex and elusive that its accurate deter-

Jan 1, 1934

By L. C. Graton

Although marked by numerous well-known attributes of its own, gold does not possess a kind and range of physical, chemical and geological characteristics wholly different and apart from those of other metals. Instead, it is merely one of the family of metals, with its individual and distinctive traits subordinate to the underlying family relationships and resemblances. The geologist concerned with pure science will pursue, therefore, the same general course and will examine the same broad kinds of facts and interrelations when studying the occurrence of gold as when studying that of copper or cadmium, or any other metal. But when we come to consider the use and economics of the metals, we discover that gold differs strikingly from all the others. Gold, in short, is unique, not by virtue of its inherent characteristics, but because of a peculiar and concerted psychological regard in which it is held. It will be evident, therefore, that the geologist who would deal with gold supply must give far greater weight to economic considerations than is required in his contacts with any other metal. If the geologist be called the scientist of occurrence, and the economist the scientist of use, the economic geologist stands as the necessary link between them. Perhaps it is in part because the economic geologist has made himself more familiar with the science of occurrence than with the science of use and has thus in some degree failed to bridge effectively the gap between the two fields, especially with regard to gold, that the usen1 of gold now appear to be in a state of general concern and even of alarm for the security and adequacy of future supplies. In the case of no other mineral commodity do the users, as a rule, trouble themselves greatly about the adequacy of supply except in so far as that may affect the price which they shall have to pay for the commodity. Oversupply, with resulting low price, they regard as a gift of good fortune. As to long-term undersupply, they are generally content to go ahead on faith, leaving the producer to discover as best he may the means for meeting their requirements or the inventor to find a substitute. But history has shown that for gold a different situation exists. While

Jan 1, 1931

By Anthony Anable

The definite trend to stricter specifications with respect to hydraulic concrete has become increasingly manifest in the last six years or so; but it remained for the vast reclamation projects of the Bureau of Reclamation of the Department of the Interior of the last few years to focus attention on this trend, and to demonstrate how thousands of tons of concrete-making aggregates can be produced continuously and automatically with a control of fineness comparable with that obtained with small samples in well equipped private and governmental laboratories. Pioneer work in this direction was done, to be sure, by private companies, notably the Kaiser Paving Co. of San Francisco, prior to the present vast public works program. Then in 1931 came the first great aggregates-preparation plant of the Six Companies, Inc. to supply construction materials for Boulder Darn1 in Nevada, and now, in 1936, the aggregates plant of the Mason-Walsh-Atkinson-Kier Co., general contractors on the Grand Coulee darn in Washington. At Boulder dam and to an even greater degree at Grand Coulee dam, sand production is recognized as probably the most important single element affecting the physical characteristics of the concrete. For in the construction of dams accurate grading of the fine aggregate has considerable bearing on the attainment of a uniform and homogeneous concrete of a high degree of workability and placeability and, at the same time, combining high density and low cement content. Low cement content is of value not only from the standpoint of ceonomy but also because the use of an unnecessarily rich concrete causes certain undesirable characteristics to develop. This paper will relate how at Grand Coulee dam methods that are more advanced than ever before are producing four sizes of gravel and a sand having a fineness modulus of 2.5-3.0. The design capacity is 1000 tons an hour. Significantly, the methods and equipment employed arc broadly those that have been used for a generation in metallurgical mills for accurately sizing and grading both precious

Jan 1, 1938

By Anthony Anable

The definite trend to stricter specifications with respect to hydraulic concrete has become increasingly manifest in the last six years or so; but it remained for the vast reclamation projects of the Bureau of Reclamation of the Department of the Interior of the last few years to focus attention on this trend, and to demonstrate how thousands of tons of concrete-making aggregates can be produced continuously and automatically with a control of fineness comparable with that obtained with small samples in well equipped private and governmental laboratories. Pioneer work in this direction was done, to be sure, by private companies, notably the Kaiser Paving Co. of San Francisco, prior to the present vast public works program. Then in 1931 came the first great aggregates-preparation plant of the Six Companies, Inc. to supply construction materials for Boulder Darn1 in Nevada, and now, in 1936, the aggregates plant of the Mason-Walsh-Atkinson-Kier Co., general contractors on the Grand Coulee darn in Washington. At Boulder dam and to an even greater degree at Grand Coulee dam, sand production is recognized as probably the most important single element affecting the physical characteristics of the concrete. For in the construction of dams accurate grading of the fine aggregate has considerable bearing on the attainment of a uniform and homogeneous concrete of a high degree of workability and placeability and, at the same time, combining high density and low cement content. Low cement content is of value not only from the standpoint of ceonomy but also because the use of an unnecessarily rich concrete causes certain undesirable characteristics to develop. This paper will relate how at Grand Coulee dam methods that are more advanced than ever before are producing four sizes of gravel and a sand having a fineness modulus of 2.5-3.0. The design capacity is 1000 tons an hour. Significantly, the methods and equipment employed arc broadly those that have been used for a generation in metallurgical mills for accurately sizing and grading both precious

Jan 1, 1938

By Charles Legrand

(San Francisco Meeting, September, 1915) THE problem of mine pumping is so much affected by local conditions, and those conditions are so liable to changes during the life of a mine, that the best system to use is difficult to determine. The experience of the;, writer has been that, in general, for copper mines, electric pumping is most satisfactory unless the quantity of water to be pumped is great or. the mine does not use electric power for any other purpose. As a rule, however, figuring on the cost of necessary power plant, the total cost of: installation is greater with electric pumps than steam- pumps. As the water is liable to be gritty, outside-packed plunger pumps are to be recommended, and if the water is not acid, or only slightly so, chilled cast-iron plungers pay for their extra cost very quickly in diminished cost of packing. With chilled plungers it is possible to use metallic, packing instead of soft packing, if the water, is not too gritty nor the lift too high. In vertical pumps this packing is satisfactory for lifts up to 400 ft., in the experience of the writer; and may be found satisfactory for higher lifts. For water slightly acid, cement-lined pump bodies have given good satisfaction. For acid. water, both plungers and pump bodies should be made of acid-resisting bronze. For high lifts, especially with gritty water, a satisfactory pump valve is difficult to find. To reduce the unbalanced pressure on the valve at time of opening it is advisable to have narrow seats; this, however, brings high pressure on the seats when the valve is closed. On large valves for lifts of 600 to 1,000 ft. we have used leather, hard rubber, vulcanized fiber, and soft brass; for clear water the latter has given best satisfaction. The difficulties due to grit make it advisable to have large sumps where water can settle, and if possible, to have two of them so that they can be cleaned alternately. At the mines of the Old. Dominion Copper Mining ,& Smelting Co.; Globe, it was found that a small air. ejector discharging into a mine car is a very convenient way to clean mud and sand from a sump. .

Jan 9, 1915

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a&apos;) transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

By Charles Stuart

A PAPER on this subject can cover but a limited range. A thorough visualization of the subject would contemplate a comparative analysis of haulage machines and batteries of various types; the relationship of the storage-battery locomotive to other types of mine haulage should be considered and limiting factors in each case should be carefully developed. This paper will briefly deal with these factors. So far as the writer has been able to determine, the first storage-battery locomotives for mine haulage were manufactured in 1897 or 1898 and were tried out in the Pocahontas coal field, but they were not sufficiently satisfactory to justify their continued use. Battery explosions were frequent and caused serious damage to the wiring, electrical equipment, and the clothing and bodies of the motormen. Sulfuric acid was used as the electrolyte. Experiments were then conducted with locomotives bearing reels of flexible cable through which connection between the motors of the locomotive and the trolley wire was maintained. At first, these reels were turned by hand. Later, the reels were revolved by contact with the wheels of the locomotive, being raised out of contact with the wheels, by a lever, when necessary. About 1902, the plan of operating the reel, by chain and sprocket wheels, from one of the locomotive axles, as is still the practice, was devised. The popular floating motor-driven reel had its inception in the Pocahontas fields prior to 1906. The maximum radius of operation of the reel-type locomotive is about 500 ft. (150 m.) from point of connection with trolley wire. This is ample for room work and certain entry work, but the need for a machine that would operate entirely independently of the trolley wire was so great that, with the development of the storage battery, renewed efforts were made to manufacture a successful storage-battery locomotive. About 1908, the gasoline locomotive was introduced. In spite of many objections to this type of machine for such work, the fact that hun¬dreds of these machines were purchased was proof of the need for a machine operating independently of the trolley.

Jan 1, 1922

By Charles Pack

EXTENSIVE progress has been made in the metallurgy of alloys for die castings. Enthusiastic proponents of some alloys are inclined to make extravagant claims for their materials, which may be justified by physical tests on test bars made from the respective alloys but are seldom justified by the results obtained with commercial die castings made from those alloys. Chemical analysis of the test bars and castings fails to determine the cause of these variations, since they are due to other physical factors entering into the commercial production of die castings. In this paper, an attempt will be made to outline some of the factors in commercial die-casting practice to which these variable results may be attributed, in the hope that the manufacturer of die castings, recognizing the importance of these factors, will devote more attention to them in the design and construction of dies and equipment. In 1914,1 the author defined die castings as "metal castings made by forcing molten metal, underpressure, into metallic molds or dies." This definition was given in order to differentiate die castings from other molded metal products such as "permanent-mold" castings, "slush" castings and similar products that are sometimes erroneously termed die castings. The term "die casting" could be interpreted to include all castings made in metal molds or dies; but since this term, like most of our technical nomenclature, has been developed by commercial practice we must look to this practice for its proper definition. The Germans, with their usual devotion to descriptive names, have adopted the name of spritzguss (squirt cast) for die castings. Undoubtedly this name is more descriptive of the die-casting process, where the metal is literally squirted into the die and serves to differentiate this process from other metal mold processes, where the metal is poured into the die. In the earlier paper mentioned, the author also emphasized the fact that the definition given for die castings indicated clearly that the satisfactory operation of the process must comprise three factors, all of which must be considered of vital importance to the successful operation of the die-casting process:

Jan 1, 1930