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By Thomas M. Dr. Drown

IN experimenting in connection with Mr. P. W. Shimer (now chemist of the Thomas Iron Company, Hokendauqua, Pa.) on methods for the determination of silicon in pig iron, in order to find one which should be accurate and yet give results in a few hours, I have adopted the following procedure, which, as far as my experience goes, leaves nothing to be desired. About one gram of pig iron or steel is treated in a platinum or porcelain dish with 25 cubic centimeters of nitric acid (sp. gr. 1, 2). When action has ceased, 25 to 30 cubic centimeters of dilute sulphuric acid (one of acid and three of water) are added, and heat applied until the nitric acid is nearly or quite driven off. The heat of a water-bath is sufficient, though the process may be hastened by heating higher on a sand-bath. Water is then cautiously added (as soon as the free sulphuric acid is sufficiently cool) and the contents of the dish heated until the crystals of ferric sulphate are completely dissolved. The solution is then filtered as hot as possible, the residue washed first with hot water, then with 25 to 30 cubic centimeters of hydrochloric acid (sp. gr. 1, 12), and finally with hot water. After drying and igniting, the silica will be found to be snow-white and granular. The following are some results obtained by this method compared

Jan 1, 1879

By David E. Hyatt, Christopher H. Cox, Franklin T. Davis

INTRODUCTION The composition of water used in the flotation process has always been of primary interest to the flotation metallurgist. It is by alteration of the chemistry of the water introduced to the process that flotation separation is effected. In only a few cases has it been necessary to treat available water prior to use in the process. In the past, flotation tailings were treated for the removal of solids via the tailings dam and water decanted from the dam was either recirculated to the process or discharged to the surface water system. The choice of recirculation or discharge was based upon water availability, effect of recycle water on the process, and economic considerations. The Federal Water Pollution Control Act Amendments of 1972 have charged the United States Environmental Protection Agency with establishing effluent limitations from point sources of discharge into the navigable water of the United States. A detailed study, sponsored by EPA, of the water of ore processing plants took place in 1974 and 1975 and guidelines for these plants will presumably have been published by the time this paper has been presented(1). The action of many of the individual states preceded the EPA in this attempt to regulate the quality of the water discharged from industrial point sources. Even with recycle of tailings water, some water is discharged from tailings dams into the substrata and at least one state is currently preparing guidelines for the quality of water discharged into the substrata.

Jan 1, 1976

By C. H. Jr. Herty

IRON oxide .(Fe0) plays an extremely important part in the manufacture of steel. In the open-hearth furnace and the Bessemer converter it is the chemically predominant compound and controls to a large extent both the operation of the furnaces and the composition and quality of their products. Almost all of the refining action is carried out through the medium of FeO, which oxidizes carbon, manganese, silicon, and phosphorus. At the end of any open-hearth or Bessemer heat the steel contains dissolved iron oxide, which must be wholly or partly eliminated. The type of deoxidation product depends on the amount of dissolved iron oxide and on the deoxidizer used. After the heat has been deoxidized and while it is being teemed, iron oxide diffuses from the ladle slag into the metal, causing losses of deoxidizer and increase in iron oxide content of the steel. It is generally believed that non-metallic inclusions are responsible for a great many failures of steel in service and for decreased yield of steel during rolling. The basis of most non-metallic inclusions is dissolved iron oxide. This investigation was undertaken in order to determine the amount of iron oxide that will dissolve in iron under various conditions. Steel-making slags are complex and it has been thought best to determine solubility under simple slags as a first step. The study is being continued under slags whose compositions approach those of operating. slags.

Jan 1, 1928

By J. P. Hirth, C. S. Hartley

A simple graphical technique is presented for rapidly determining the ratio of resolved shear stress on slip systems in single crystals to the applied stress (Schmid factor) for various simple states of stress. Master plots are presented which, when used in conjunction with an appropriate stereo-graphic projection, allow one to determine the Schmid factor for all slip systems in a crystal of given orientation. It is shown that one such plot suffices for simple tension or compression, flex-ural bending, and biaxial compression, while a combination of two different plots must be used for torsion and simple shear. STUDIES of the deformation behavior of single crystals are most valuable when the applied stresses are resolved onto the various slip systems of the crystal. A careful study of the available slip systems and proper selection of the state of stress used and the specimen orientation can then yield quantitative information about the probability of specific dislocation reactions, the strength of barriers to plastic flow, and the mechanisms of yielding and flow in general. It is the purpose of this work to analyze some common states of stress used in deformation studies and to present a simplified way of determining for these cases the ratio of the resolved shear stress on the slip systems to the applied stress (Schmid factor). I) CALCULATIONS We first define two orthogonal coordinate systems: one based on the specimen geometry (a right circular cylinder of radius, R, is considered here) and one based on the particular slip system of interest. The unit vectors and angles specifying the two coordinate systems and the relationship between them are listed in Table I. The relationships among the various angles and unit vectors are shown on a stereographic projection in Fig. 1. The transformation matrix between the (XI X2 X3) and (x'1 x'2 x'3) system is x1 x2 x3 X'1 a11 al2 a13 x'2 a21 a22 a23 x'9 a31 a32 a33 where in this case the direction cosines aij are given by a11 a12 a13 aij = a21 a22 a23 a31 a32 a33 sin 0 cos F cos 0 sin F cos 9 = -cos 0 cos F sin 0 sin F sin 6 [1] 0 -sin F cos (p In terms of Eq. [I.], the stresses sij, referred to the slip system, are determined from oij, referred to the specimen axes, by1,2

Jan 1, 1965

By M. Tsunekawa, T. Takamori, T. Hirajima

In spherical agglomeration in water, the pattern of the growth behaviour of agglomerates is essentially determined by the surface chemical properties of the particles and the oil-water interface. When particles are suitably hydrophobic and oil-water interfacial tension is not too low under an adequate condition for agglomeration, large agglomerates are formed in the initial stage and micro- agglomerates do not appear. When particles are poorly wetted by oil and the interfacial tension is low, initially micro-agglomerates are formed and, after certain aging time, they grow to large agglomerates in a relatively short time without formation of intermediate size agglomerates. Under adequate conditions, the amount of oil and power input do not produce any remarkable effect on the pattern of growth.

Jan 1, 1980

By C. V. O. Hughes

Florida phosphate operations are unique in the ways standard mining equipment is made to meet specialized problems. Hydraulic mining and transportation has evolved in meeting three such special problems: 1) surface mining of a shallow, poorly consolidated but wet material; 2) high pro¬duction rates, necessary because of low prices for phosphate rock in a highly competitive market; and 3) preparation of the value-bearing rock, or matrix, for washing and flotation. The magnitude of the problems is better appreciated if the reader understands the size of operations in the area. The Florida phosphate field produces and ships about 10 million tons per year of phosphate rock. All of this has to be concentrated to its shipping grade, either by scrubbing and screening or by flotation.

Jan 1, 1956

By Eugene S. Perry

The oil and gas industries in Montana continued through the year of 1937 with but little change. No new fields were discovered, and production of old fields did not vary greatly. No outstanding wildcat wells were drilled. Perhaps most notable were extensions in the western part of the Kevin-Sunburst field. Acid treatment of wells in the Kevin and Pondera fields continued with gratifying results.

Jan 1, 1938

By Walter R. Hibbard, Harold Margolin

DURING preliminary tests on the aging of a Cu-plus 5 pct Ag alloy,' a specimen which had been overaged 24 hr at 550°C was annealed in a nitrogen-hydrogen atmosphere first for 2 hr and then for an additional 28 hr at 600°C. After each anneal the specimen was cooled to room temperature in about ½ hr and X-ray photograms were made. The first film, Fig. la, revealed two sets of copper-base lines, one intense and corresponding to the parameter at 550°C, the other fainter and shifted away from the beam, corresponding to the larger parameter at 600°C (see arrows). The 30-hr film, Fig. lb, revealed the same two sets of copper-base lines with a reversal of intensity. In neither case do the copper lines form a broad band which would be indicative of a range of compositions. This phenomenon is thus a "discontinuous" type of solution. A similar phenomenon was observed in a Ag-rich Cu-Ag alloy.' Finlay and Hibbard9 have suggested that directional rather than random solution of precipitate occurs in some alloys. Conceivably, for Cu-Ag alloys, the matrix-transition-precipitate precipitation sequence is reversible for the re-solution of the precipitate caused by rapidly raising the annealing temperature of an overaged specimen. A copper-base transition structure supersaturated with solute might be formed around the precipitate as it dissolves, thus obviating the necessity for a gradually changing solute composition of the matrix. The solute atoms then might be transferred rapidly and locally from the transition to the matrix phase in the proper amount and at the proper location to obtain directly the new ex- panded solid solution. The theory implies a minimum of diEusion of solute in the matrix (i.e., no significant range of matrix composition) and possibly suggests that the composition of the transition structure will vary with the conditions of re-solution. A transition copper phase found in aged Cu-Ag alloys1 might fulfill this function. Evidence regarding this suggestion could be obtained in Cu-Ag alloys by overaging a specimen until no trace of the expanded copper lattice is present and then subjecting the specimen to a retrogression treatment. Re-appearance of the transition copper phase would confirm the theory. Additional details could be secured by varying both aging and retrogression temperatures. References 'H. Margolin and W. R. Hibbard, Jr.: Effect of Ternary Additions on the Age Hardening of a Copper-Silver Alloy. Trans. AIME (1951) 191, p. 174; Journal of Metals (Feb. 1951) TP 3002E. 2 W. Ageew, M. Hansen, and G. Sachs: Decomposition and Changes in Properties of Super-saturated Silver-Copper Alloys. Ztsch. Physik (1930) 66, p. 350. 3W. L. Finlay and W. R. Hibbard, Jr.: Some Effects of Applied Stresses on Precipitation Phenomena. Trans. AIME (1949) 180, p. 255; Metals Technology (Sept.

Jan 1, 1952

By William Loblowitz

A simplified system of flotation testing has been developed recently at the Bureau of Mineral Research of Rutgers University. The technique involves the known principle of skin flotation and can be used with minute quantities of sample and reagents in a beaker. A vessel containing the conditioned sample with added water and flotation reagents is held inclined and rotated slowly. Water-repellent particles come in contact with air and float on the surface of the liquid, while wettable particles are submerged. The float is poured off and filtered whereas the nonfloat remains in the beaker. The filtrate may be returned to repeat the process. This procedure can be made quantitative. Separations are obtained and are remarkably complete and repeatable. The effect of different reagents, optimum quantities, pH and other variables can be determined in a fraction of the time required for conventional testing. However, the method gives no information on the effect of frothers and the quality of froth to be expected in a cell, and it is not practical for particles finer than 200-mesh. Unlike other preliminary tests, separate float and nonfloat products are obtained, and their contents can be determined quantitatively by chemical analysis or grain counts. After the optimum reagent combination has been determined, the effect of fines and frothing may be verified in the conventional flotation cell. On the other hand, agglomeration-tabling can be directly duplicated from beaker tests. Procedure: Five to ten grams of sample are weighed into a 100-ml beaker. Flotation reagents and a small initial quantity of water are stirred together; additional water is then added to produce the proper water-solids ratio. The beaker is then tilted to 45" and rotated slowly. After three to five rotations, liquid and float are poured off and filtered; the filtrate may be recycled until the separation is completed. One test generally requires less than 10 min. Reagent concentration and pH remain quite constant because of the recycling of the filtrate. Two to four tests may be made simultaneously, and the effect of varied conditions may be observed by comparison. Considerable time is saved in preparation and handling since small quantities of sample suffice for a series of systematic tests. Repeatability One test was repeated four times under constant conditions. The sample used was a quartz sand containing approximately 24 pct feldspar and some clay aggregates. The +28-mesh grains had been screened out, and most of those finer than 100-mesh had been removed by hydraulic classification. The results are presented in Table I. For comparison, 500 g of the sample were separated by agglomeration-tabling using the same reagent combination and quantities as given in Table I. The weight percent float was 18.3 pct, composed almost entirely of feldspar and with only traces of quartz. Most of the remaining feldspar was recovered in a middling product with 2.2 pct by weight.

Jan 1, 1952

By Richard R. Klimpel

The role of dispersion is described in the wet grinding of ores using tumbling media mills and the flotation of coal, sulfide, and non-sulfide ores. Emphasis is placed on characterizing the effects of dispersion in laboratory tests using engineering models which provide information useful for the improvement and control of existing plant operations. Significant economic gains in the above named operations have been realized using these models as guides for full- scale plant testing.

Jan 1, 1980

By Nicasio del Castillo

INTRODUCTION The tax structure of foreign mining investment into the United States has a significant impact on the financing and the profitability of the operation. For these reasons, it is critical for the foreign investor to develop and implement a well planned tax strategy that will enable its venture to: (1) reduce its U.S. income tax liability (2) lower U.S. withholding taxes when funds are transferred from the United States, and (3) decrease or defer home country taxation on its U.S. earnings ALTERNATIVE FORMS OF INVESTMENT A threshold business and tax consideration is the form in which the investment is to be made. The most common alternatives include: forming or acquiring a U.S. mining corporation, directly establishing a branch mining operation, or entering into a joint venture or partnership with a U.S. mining company. U.S. Corporations The most common structure through which foreign mining companies engage in business in the United States is to form a U.S. mining corporation. Forming a U.S. Corporation. If the investor decides to establish a new U.S. corporation the organization is relatively simple. No distinctions are made in the United States between "public" and "private" forms of incorporation. Minimum share capital is not usually required and share capital may consist of shares with no par value. Since corporate law is the responsibility of the individual states, the foreign investor must choose a state in which to incorporate. If appreciated mining property is transferred to a corporation solely in exchange for stock or securities in that corporation, and the transferors have control of the corporation (defined as at least 80 percent of all voting shares and at least 80 percent of all other shares) immediately after the exchange, no gain or loss will be recognized. However, if the transferors receive cash or other mining properties in addition to stock, any resulting gain may, in certain situations, be taxed to the extent of the cash and the fair market value of other property received. Acquiring an Existing U.S. Corporation. Acquiring an existing U.S. mining corporation is not as straight-forward as forming a corporation. This alternative may be accomplished through either a stock or an asset acquisition. Generally, with a stock acquisition the purchaser inherits all of the business and tax attributes of the former mining corporation. If the investor is able to acquire mining assets, however, the purchaser will usually be able to avoid any unknown or hidden liabilities that could be attached to an existing corporation. Another principal advantage in acquiring assets is that the purchase price may be directly allocated to the acquired mines or other mineral-related assets with the result that the assets' depreciable base may be increased. Assuming the domestic seller and the foreign purchaser can agree, it is generally advisable to allocate the purchase price in the sales agreement to specific individual assets. From the foreign investor's standpoint, it is preferable to allocate the purchase price to depreciable assets such as buildings and equipment versus an allocation to mineral land holdings or intangibles such as goodwill, which are generally not depreciable. It is not uncommon, however, for a seller mining company being acquired to insist for tax reasons that the investor purchase shares rather than assets. If the foreign

Jan 1, 1985

By J. W. Axelson, J. N. S. Kwong, J. T. Adams, E. L. Pire, J. F. Johnson

CRUSHING has always been a major operation in the chemical and metallurgical industries, yet little is known about the theory of crushing, and today, the design of crushers is still based almost entirely on empirical knowledge and accumulated practical experience. In view of the increasing national need for the economic working of poorer grades of ores, the lack of a fundamental understanding of this unit operation hardly presents a satisfactory situation. Basic investigations of crushing have been concerned mainly with three phases of the problem, 1—the mechanism of the fracture process itself, 2— the particle size distribution of the crushed product, and 3—the relationship between the energy input and the amount of new surface produced. Probably adequate information on these phases will be required for a comprehensive understanding of the process of crushing. A bibliography covering these phases will be given as well as a review of the work done in recent years at the University of Minnesota on the relationship between the energy input for crushing and the amount of new surface produced. Fracture of Solids This phase of the crushing problem is the most fundamental because it is concerned with the actual mechanism of fracture. The main problems in a study of the fracture process are concerned with the questions of why and how fracture occurs and why there is such a discrepancy between the actual and theoretical energies needed in a fracture process. In considering the how of fracture, Poncelet40 carried Out experiments On the crushing of glass under compression. Actual photographs were taken of the glass plates in various stages of fracture-From these experiments Poncelet was able to postulate a probable mechanism of fracture. Probably because of the quantitative nature of the problem, considerable effort has been expended to find an explanation for the low tensile strength of materials and the conversely high energy for crushing. Tensile strengths are often only 1/500 of the theoretical while the energy for crushing is usually at least 500 times the theoretical. A review of the work to explain the low strength of glass is given by Weyl,52 in which the work of Griffith," Joffe,32 and Powell and Preston " are discussed. In a recent paper Seitz46 holds that the presence of flaws and fissures, as originally expounded by Griffith, is the most probable reason for the low strength of metals. Since a mass of data has been accumulated on the fracture strength of materials, several investigators have attempted to correlate this data in the form of an equation. Glathart and Preston," Taylor,40 Ponce-let,40 Machlin and Norwich," and Frederickson and Eyring,20 have all considered this problem, and the final relationship has always been that the stress for fracture is proportional to the logarithm of time. Murgatroyd30 arrived at a very similar relationship by a different method. The study of the fracture process has used many methods. Among some of these are the thermody-namic approach used by Furth21 which was based on the work of BornxL and later used by Saibel,43 and the statistical method applied by Fisher and Hollo-mon.10 In recent years metallurgists have concerned themselves with the problem of brittle .fracture as opposed to the usual plastic failure of metals. The great amount of interest shown is reflected by the number of contributors to the recent symposium on the fracture of metals.' Repeated failures of welded ships during World War II have accelerated these Studies.31,50,34 The shifting of thought from an emphasis on the

Jan 1, 1952

By T. J. Neil, C. B. Manula, O&apos

This paper describes a simulation model developed to analyze truck haulage problems as they are found in the open pit mining and construction industries. The model, using a computer, cycles trucks between their assigned loading and discharge points over a measured haulage route. Required parameters for model operation include the number and type of operating trucks and loading units, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each origin. Equipment performance characteristics, system profile characteristics, and service time distributions are also included. Records are kept of all waiting times at the loading and discharge points and of any truck interference on the haulroads (moving queues), and a current journal of ore and waste production is maintained. In the pursuit of reduced truck haulage costs, management is confronted with three particular problems in truck and shovel mines. 1) What is the best assignment of trucks to shovels in the system? 2) If new equipment is needed, which new shovels and trucks will operate most effectively in the system? 3) Are any physical changes in the haulage layout warranted to increase productivity? For small open-pit mines the answers to these questions may be obvious. However, for larger operations complex problems are encountered with production and system configuration relationships usually being unknown. The mining simulator discussed here was developed to aid management in evaluating alternative pit-haulage schemes to reduce the risk involved in the selection and assignment of equipment in open-pit truck and shovel mining systems. There are two fundamental differences between this model and other truck haulage simulators: one is a difference of degree, the other a difference of kind. This model can simulate more complex systems than previous models by allowing transportation of material from multiple mine faces to multiple mine destinations and by being readily adaptable to a wide variety of mine layouts. The second difference that characterizes the model is the standard simulation of truck movements. This technique enables each vehicle to perform according to its mechanical capabilities and the physical profile of the haul road. Among the similarities between other truck haulage simulators and this model are the recognition of the probabilistic nature of certain service times in the system and the use of a digital computer to operate the model. The computer inherits the staggering computational and bookkeeping work loads and provides a means for compressing the time scale by allowing several days' operations to be simulated in a matter of minutes. DISTRIBUTION SYSTEM Basic aspects of the system analyzed here may be brought into focus by referring to Fig. 1, a schematic of the typical open pit truck-shovel operation programmed into the simulation model. A single stage materials handling scheme is employed to transport both ore and waste. Loaded trucks are directed to a crusher or stockpile if ore is being mined, while overburden is conveyed to a waste dump. Each shovel has a given number of assigned trucks and has two associated haulage routes, one for waste and one for ore. Up to 5 shovels and as many as 10 trucks per shovel (or a total of 50 trucks) can be operated in the model. Essentially the model, using a computer, cycles trucks between their assigned shovels and the proper discharge points over measured haulage routes. Required input parameters for model operation include the number of shifts to be simulated, operating time per shift, number and type of operating trucks and shovels, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each shovel. Equipment performance characteristics, system profile characteristics, and service time distributions are

Jan 1, 1968

By M. Perišic

Requirements concerning determination of geometric characteristics and estimate of reserves and grade may in various mineral deposits significantly differ and by no means can be completely envisaged. Therefore, program writing which would in advance meet all requirements is from a practical point of view impossible. Programming for each particular project is also unacceptable solution, due to many facts, among which is ever growing scope of work and the terms to be met. Therefore, conventional method of programming proved to be ineffective. The team of the Mining Institute experts came to the conclusion that the solution of facing problems lies in the idea of introducing specialized programs, instead of complex ones. Each of them represents a functional entirety. Procedure of complete mineral deposits computer processing is described by a problem-oriented programming language which was designed for that particular application. One or more than one specialized programs are called by one instruction so that the program in that language can have a few hundred time less instructions than an equivalent FORTRAN program. Besides description of the program system and programming language the paper also covers some aspects of its application in solving complex problems.

Jan 1, 1977

By E. W. Johnson, M. L. Hill

The dijfusiuity D was determined at 25° to 780°C- from hyd?-ogen evolution rates. Anomalous evolution from air-melted iron was att~zbztted to residual hydrogen, which is interpreted as a hydrogen compound that decomposes at a strongly temperature-(Ieperzdent rate above 500°C. Above 200°C, D = 0.0014 cm2sec-1 exp (-3200 cal per g atom/RT). Below, 200°C the diffusivity is anomalously low and represented by D = 0.12 cm2sec-l exp (-7820 cal per g atom/RT). It is postulated that at low temperatures the hydrogen in the metal is "trapped" with an energy 4.8 kcaL per g atom below- that of the interstitial hydrogen. 1 HE purpose of the present experimental study was to determine the diffusivity of hydrogen in a-Fe over an extended temperature range. As certain anomalies were encountered, attempts were made to understand the anomalies themselves. This research was in progress both before and after a determination of the diffusivity of hydrogen in nicke1.l The latter system was found to exhibit none of the anomalies of hydrogen in iron, and its description was far simpler. The experiments on nickel also

Jan 1, 1961

By H. O. Hofman

The object of refining copper in the reverberatory furnace is to obtain a metal which will have the highest attainable degree of malleability, ductility and electric conductivity, and present at the same time a level surface when it solidifies in the mold after casting. These desirable physical properties are governed by the character of the impurities and the forms in which they are present, by the amount of cuprous oxide retained by the copper, by the quantity of gas held in solid solution, by the casting-temperature, and by the thickness of the casting. The effects of impurities, of cuprous oxide and of gases upon the mechanical properties of copper have been studied by Hampe1 in his classical paper " Colitributions to the Metallurgy of Copper." The most recent research into the effect of metals upon the electrical conductivity of copper is that of Addicks. 2 The influence of cuprous oxide upon the electrical conductivity has been investigated by Walker3 and Addick. 4 The absorption of gases has received attention by Hampe: Stah16 and Heyn 7 The effects of casting-temperature have been noted by Stahl.8

Jan 1, 1908

By Milton E. Jennings

On May 11, 1977, the SAMARCO 508-mm (20-in.), 396-km pipeline was placed in service. This system represents the latest thinking in slurry pipeline design and is one of the main contributors to the viability of the SAMARCO project. This paper presents the background, description, and latest information on the system's operation. Special attention is given to the handling limitations of the slurry and to the unique hardware requirements.

Jan 1, 1982

By W. C. Browning

The influence of the hydroxyl factor is more damaging to formations penetrated and causes greater consumption of drilling mud additives than previously realized. This hydroxyl effect on clays is essentially independent of the cations present in the drilling fluid and thus differs from the base exchange reactions that have preoccupied mud chemistry with sodium and calcium bentonite concepts for nearly two decades. The new organic polyelectrolyte-con-ditioned muds haw made it possible to use materials other than sodium hydroxide to maintain the alkalinity of such muds. The properties of silicates, as indicated by their dissociation characteristics and buffering action, are such that they can control he pH and alkalinity of drilling muds at the desired level and, at the same time, minimize undesirable hydroxyl effects associated with sodium hydroxide. This use of silicate compounds is different and distinct from prior applications of silicates as deflocculants or shale preservers. Laboratory and field data presented in this report show that silicate compositions can be utilized to adjust the alkalinity of drilling muds and, at the same time, minimize hydmxyl-promoted clay cleavage. INTRODUCTION Studies for improving the efficiency of rotary drilling techniques must consider the chemistry of drilling fluids and of the formations being penetrated. The chemical aspects of drilling must be studied in conjunction with and in relation to the mechanical factors if, for example, penetration rates are to be optimized. Drilling fluid technology has been largely influenced by chemical reactions of the montmorillonite (bentonite) clay minerals. Most of the literature of mud chemistry concerns the properties of bentonite. Clays of the kaolin or illite type, which are nonswelling, are not generally regarded as sources of drilling mud problems. If these nonswelling shale clays are considered, they are commonly regarded as inert solids. Particularly noteworthy is the fact that the relation of surface and colloid chemistry to massive shale bodies has received only scant attention from drilling technologists. Clay studies reported in the drilling mud literature have dealt, for the most part, with the properties of clays in a finely divided state, and often in very dilute suspensions. Yet frequently during drilling, shale problems not related to the rheology of clay suspensions develop in massive non-bentonitic shale sections of zero or near zero permeability. This paper is concerned with surface chemical reactions that can influence the behavior of these non-bentonite clay masses in such a manner as to adversely affect drilling operations. Browning and Perricone1,2 have pointed out that some of the most troublesome shales to drill, such as the Atoka, contain no montmorillonites. They also pointed out that mud problems can frequently be mitigated by reduction of clay cleavage achieved by using drilling fluids with a minimum of available hydroxyl ions. If pronounced clay cleavage occurs during drilling, the borehole may soften, increasing the possibility of sloughing. In addition, the resulting increased incorporation of high-surface-area clay solids into the mud system can reduce penetration rates and necessitate greater chemical treatment. This increase of shale, of colloidal or near-colloidal dimensions, into the drilling mud is due to clay aggregate cleavage and not to base exchange or swelling reactions, such as occur with bentonites. Searle and Grimshaw3 point out the difference between cleavage or slaking reactions of nonswelling clays (such as illite and kaolinite) and the swelling of bentonite. They further state that the speed of slaking is increased in alkaline water. Eitel1 cites Salmang and Becker, who recognized that clay surface reactions impart plasticity and workability to clay masses. Their results clearly show that all liquids which contain hydroxyl groups in their molecules favor the workability of clays. The ancient technique of aging clays in the moist condition to increase their "workability" is evidence that these clay cleavage phenomena are of considerable importance. The same hydration cleavage that occurs during the aging of nonswelling clays for ceramic use also acts to break up cuttings and soften the borehole during drilling operations. The mechanism of cleavage of the crystalline aggregates of illitic, kaolinitic and other nonswelling clays; and the chemical means of controlling this cleavage are therefore of considerable significance to the drilling mud chemistry. Inasmuch as there is little reference in the drilling mud literature to the cleavage reactions of nonswelling clays, the structure of these clays and certain properties that relate to the mechanism of clay cleavage will be reviewed briefly. STRUCTURE OF NONSWELLING CLAYS Clays such as kaolinite, illite and montmorillonite are compmed of alternate layers of (1) silicon-oxygen tetra-

Jan 1, 1965

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By William P. Blake

The importance to the growing steel industry of the United States of a domestic supply of ferro-manganese or "spiegel" of a high grade, induces me to bring to your notice some details of the method by which a superior article is produced in the Austro-Hungarian Empire. At Reschitza, Hungary, and probably at Laibach also (the Krainische Industrie Gesellschaft), ferro-manganese is made in a blastfurnace, with charcoal as fuel, and limestone as the flux. The ore is a ferruginous mixture, containing about 37 per cent. of sesquioxide of manganese. It is silicious, and somewhat, resembles, in its appearance, the manganese ore from Red Island, in the Bay of San Francisco, California. It contains about 29 per cent. of silica and some alumina, shown by the subjoined analysis: