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By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By G. M. Schwartz, G. A. Thiel

THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snelling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipestone and elsewhere in southwestern Minnesota: The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation, in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowled and by Thiel and Dutton.2 The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.3 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on' the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1-Central Minnesota in the region of the city of St. Cloud, 2-the upper Minnesota River valley region, 3-the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in. their dis-

Jan 1, 1952

By Harlan W. Nelson, James B. Purdy

A study of data obtained during laboratory tests to determine the suitability of bituminous coals for use in residential underfeed stokers of the clinkering type has led to the following general conclusions: 1. Performance data obtained during the test furnish useful and practical information upon which to judge the performance of stoker coals. 2. Conclusions derived from the results of evaluation tests are in general agreement with use experience of the coals in the field. The method is of practical use in this regard. 3. Few direct relationships were found between data furnished by the evaluation test and determinations by standard laboratory tests. This is particularly true with regard to coke formation and clinker formation, two of the most important factors in determining the degree of satisfaction to be obtained in applications of the small underfeed stoker. It has not been the intention in this paper to prescribe this evaluation test as the best method for the evaluation of coals for use in residential stokers. That there are other test methods having similar objectives serves to point out the necessity for full-scale laboratory tests. At the present time, a standard test procedure for the evaluation of coals for use in residential stokers is not available. For the past several years a joint committee, appointed from the membership of the Residential Stoker Committee of Bitulninous Coal Research, Inc., and from the Engineer- ing and Research Committee of The Stoker Manufacturers Association, has been working to develop a standard procedure for testing and evaluating bituminous stoker coals. This procedure has been completed to the extent that it has been drawn up in tentative form. It is now planned to install the equipment in several laboratories and to run check tests, using portions of identical lots of coal, to determine the degree of reproducibility offered by the method. Completion of this standard test procedure should greatly facilitate the evaluation of coals for use in residential stokers. Acknowledgments The cooperation of coal operators sponsoring the coal evaluation tests, in granting permission to use data and results from their tests, is gratefully acknowledged. Acknowledgment is also made to Carroll F. Hardy, Chief Engineer, Appalachian Coals, Inc., for his interest and timely suggestions on the preparation of this paper. Special thanks are due to Ralph Sherman, Assistant Director, Battelle Memorial Institute, who was largely responsible for development of the evaluation procedure, for helpful suggestions and advice. References I. H. A. Sherman: The Evaluation of Coal for Use in Domestic Stokers. Univ. of Ill., Eng. Experiment Station, Circular No. 39 (1939). 2. . Q. Shotts: The Relation of Free- swelling Indexes to Other Characteristics of Some Alabama Domestic Stoker Coals. TP 2314, Coal Tech., (Feb. 1948); Trans. AIME (1948) 177, 502. 3. . J. Helfinstine and C. C. Boley: Correlation of Domestic Stoker Combustion with Laboratory Tests and Types of Fuels 11. Combustion Tests and Preparation Studies of Representative Illinois Coals. Ill. State Geol. Survey, Re1. of Zntlestigations No. 120 (19467 ) p. 35. DISCUSSION E. R. Kaiser*—AS a former fuel engineer assigned to residential stokers at Battelle, the writer has read with considerable interest the paper by Messrs. I'urdy and Nelson. It is gratifying to note that earlier test techniques have been developed and that criteria found important in the years 1935 to 1938 are still important in judging the performance of stoker coals for residential heating. The authors have plotted a number of the primary coal data singly against performance data of the stoker in an effort to establish relationships. Unfortunately, wide scattering of points usually resulted, which did not illustrate what experience generally indicates to be the case. For example, Fig 3 indicates almost no trend in the percentage of released ash converted to clinker with change in ash-softening temperature. Other factors, such as fuel bed temperatures and zones of heat release must have influenced the results. In the present state of our knowledge, we cannot explain all of the reasons why suitable stoker coals perform satisfactorily, nor why one satisfactory coal may be better than another. It would therefore

Jan 1, 1950

By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953

By A. Romero-Juarez

This paper is concerned with the effect of propping-agent concentration on flow capacity of a fracture in the case in which there is embedment of the propping agent. Previous published studies have shown definitely that there is a relationship between fracture flow capacity and prop ping-agent concentration, and it has been shown that the theoretical results are confirmed by laboratory experiments. The problem of directly finding sand concentration for maximum flow capacity of a sand-propped fracture is solved, and formulas and charts are given to obtain this concentration under various conditions of effective overburden pressure, medium sand-grain diameter and rock properties. It is shown that, for the same effective overburden pressure and the same rock characteristics, optimum sand concentration in pounds per gallon does not depend on medium sand diameter. For conditions met in bydraulic fracturing operations, it is found that sand concentration in grains per square inch for maximum flow capacity varies within a wide range of values; this indicates the convenience of using data of fracturing pressure and rock characteristics for calculating sand concentration in order to achieve the best results in fracture treatments. INTRODUCTION It has been pointed out in the published literature1 that one important factor controls the success of a hydraulic fracturing operation — the propping of the fracture. The main effect of the propping agent is to hold the fracture open by means of the reaction forces that oppose the pressure due to the overburden. It is assumed in this paper that the propping agent is sand, that the grains are spherical and uniform in size, and that this sand is distributed in a monolayer in the fracture. The existence of a sand concentration value for maximum fracture flow capacity has been recognized since the publication of one of the first studies on the subject.2 In the reference cited, flow capacity was assumed to be proportional to the cube of the fracture volume per square inch not filled by sand. The obtained experimental curves relating to flow capacity and sand concentration had the same appearance as the curves obtained with the afore-mentioned assumption. Recent work3 has shown that fracture permeability, in the case of a monolayer, can be calculated accurately by means of a modified Kozeny-Cacman equation; thus, it can be shown that fracture pqmeability is a function of free volume in the fracture and of the rock and sand wet surfaces. The flow capacity of a fracture is dependent on the permeability of the fracture and on the fracture width. If all excessive quantity of sand is present in the fracture, its width may be large but its permeability i:; low due to the greater flow resistance; too few grains of sand per square inch are present in the fracture, sand embedment in the rock is greater and the width becomes small enough to appreciably decrease the rate of flow. To determine optimum conditions of flow, therefore, it is necessary to know the dependence of fracture width on density or concentration of propping agent. This relation is given in a study4 in which the approach to embedment is similar to the one made in a penetration hardness test of metal. With the equacions presented by Darin and Huitt,3 the number of sand grains per square inch that results in maxirnum fracture capacity can be determined graphically by plotting fracture capacity vs sand concentration. Since the relationship between fracture capacity and sand concentration may be considered known, one is led to formulate the analytical problem of directly determining sand concentration for maximum fracture flow capacity, in order to study the effect of the various quantities that come into the process. The solution of this problem appears to be interesting both from the viewpoint of fluid mechanics and from the practical viewpoint of oil production in hydraulic fracturing treatments. EQUATION FOR FRACTURE FLOW CAPACITY It can be shown3 that the fracture flow capacity of a monolayer is given by the following expression,

By L. D. Jaffe

From the limited experimental data in the literature, preliminary values were derived for the thermal diffusivity of titanium alloys and for the quenching severity of various mediums used in heat treating them. The thermal diffusivity, under quenching conditions, was found to be approximately 0.006 sq in. per sec. The quenching severity H for brine is approximately 8, for water 4, for oil 0.9, for air 0.08, and for argon 0.02 in. -' The quenching severity of the Jominy-Boegehold end quench water jet against titanium alloys appeared effectively infinite. Using these results, graphs were prepared showing ideal round sizes and Jominy positions having cooled conditions equivalent to those at the center and surface of titanium alloy rounds, plates, and sheets quenched in various media. THE importance of proper quenching of steel parts has long been recognized, and much quantitative work has been done on the subject. Recently, it has become evident that for titanium alloys, too, the rate of cooling from high temperature is important in obtaining high strength and hardness. Maximum hardness and strength may not be attained in the as-quenched condition but rather after a subsequent tempering or aging treatment. Nevertheless, if cooling from temperatures near the ß transus is too slow, for the hardenability of the alloy used, a soft a-ß structure will be produced which will not harden on subsequent aging.'-" The quenching of parts of practical interest can usually be approximated by simple shapes, such as cylinders (rounds) and plates (or sheets) of various thickness and combinations of these. A standard that has been used extensively for comparison purposes is the center of an ideal round: a cylinder quenched in a medium that instantly cools its surface to room temperature." For steel, considerable practical use has been made of the Jominy-Boegehold end quench hardenability specimen,".' and its value for titanium alloys is becoming evident. It therefore appeared worthwhile to attempt comparison of cooling conditions in titanium alloy rounds and plates of various sizes quenched in various media with cooling conditions in ideal round and Jominy quenches. These comparisons are based upon measurements reported in the literature. Quenching Severity of Jominy Water Jet and of Brine As one starting point, there were available the data of Phillips and Tobin8 for positions on a Jominy specimen having the same hardness as the centers of round bars of various size quenched in 5 pct NaOH brine, shown in Table I. The Jominy speci- men is a round bar, normally 1 in. diam and 4 in. long, quenched by a water jet at one end and air cooled on the other surfaces.' After quenching, hardness is measured vs distance from the quenched end on longitudinal flats ground 0.015 to 0.10 in. deep. The data of Table I were based on a subsized specimen of 3/4 in. diam. Since the positions tested are close to the jet quenched end, cooling there may be taken as due solely to the jet, and air cooling can be neglected. These positions are then equivalent to various locations near one surface of an 8 in. plate jet quenched on both sides. Assuming that the thermal diffusivity is constant and that Newton's law of cooling holds, temperature vs time curves at corresponding positions in Jominy specimen and round bar then may be calculated for various assumed quenching severities of the water jet and of the brine. Cooling curves are generally taken to be metallurgically equivalent when they show the same time to reach a temperature halfway between the initial (heat treating) temperature and the final (quenching medium) temperature.5 On this basis, using Russell's tables,9 upplemented by heat flow tables derived in similar fashion by the author for positions near the surface of severely quenched plates, it was found that the experimentally observed equivalence, Table I, was best matched if the quenching severity H of the Jominy water jet was taken as infinite (H = co). This means that the jet quenched surface should be considered as instantly cooled to the temperature of the water

Jan 1, 1956

By J. B. Cheatham, J. G. Yarbrough

Although adequate removal of cuttings from beneath a drill bit is important for efficient drilling operations, very little basic data are available relative to the fundamentals of chip removal by hydraulic jets. A discussion is presented in this paper of an experimental investigation of the jetting action of hydraulic jets in removing loose particles from the bottom of a cylindrical hole. Conditions for which the jet is no longer capable of removing chips from the bottom of the hole are determined. This situation represents equilibrium between the chip removal force and chip Bolddown forces such as gravity and pressure. In most of the tests loose particles were jetted with water or a water-glycerine mixture to determine the dependence of chip removal on hole size, jet size, height of jet off bottom of hole, flow rate, particle density and fluid viscosity. ,A test with a pressurized mud system indicated that relatively low pressures can completely overcome the removal action of a hydraulic jet. Although the system studied herein is not directly applicable to a rotary drill bit, the work with such simplified systems can provide a better understanding of the chip removal action of jets, and with logical extensions it may provide a reasonable basis for the best use of fluid jets in drilling. INTRODUCTION The primary deterrent to maximum drilling rates is the inability of the drilling system to remove rock cuttings efficiently enough to prevent interference with the drilling action.1-2 The objective of chip removal studies is to permit predicting and controlling removal forces under downhole drilling conditions. Conditions at the bottom of a hole during rotary drilling are exceedingly complex and are not likely to be described in a quantitative way by investigations in terms of the total drilling action until a better understanding is developed of the simplified components of the problem.3 The present study is concerned with the elementary condition of removal of chips by a single central jet. Even this relatively simple model provides mathematical difficulties because of the turbulent nature of the flow from the jet and because of the shape of the bottom of the hole beneath the jet. Theoretical and experimental studies have been made of turbulent jets impinging normally on an infinite body and deductions based on analytical solutions to simplified problems can give some insight into the problem of cutting removal by a jet. However, because of the present lack of understanding of the behavior of the interaction between the fluid jet and the chips being removed, an experimental approach was chosen for the present study. Methods have been developed for maximizing hydraulic horsepower, impact force and jet velocity; but whether maximizing these parameters maximizes chip removal with present drilling bits has not been demonstrated. Simplifying the problem of chip removal may make it possible to develop some understanding of the manner in which the jet velocity is dissipated. Better understanding of a simple case should materially assist in extending analysis to more complicated cases. Thus, we are not concerned in the present study with the rock fracturing process itself but only with the removal of the debris from the bottom of the hole. A problem which is quite similar to the chip removal problem is the suspension of solids in stirred vessels. This problem has been studied by the chemical industry and correlations have been obtained by dimensional analysis which permit the design of mixing vats7 An approach similar to that used in the mixing vat problem is used in the analysis of the jetting data in the present paper. EXPERIMENTAL PROCEDURE The test equipment arrangement shown sche-matically in Fig. 1 allows the jetting action to remove particles until an equilibrium height is attained for each combination of hole size, jet size and flow rate.*** Equilibrium conditions require that the removal force is unable to remove additional particles. This balance between holddown and removal forces implies a relationship between the two forces which is constant for the particular system. When the holddown forces are constant,

Jan 1, 1965

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl' who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By W. A. Alexander, L. M. Pidgeon

Metallic magnesium and similar meta!s near the top of the electromotive series have been commercially produced by the electrolysis of a suitable molten salt. Despite the success of electrolysis, sufficient inherent objections exist to justify the search for a direct reduction method. Such a method would widen the choice of raw materials, relax the rigid electrolytic requirements of raw-material purity, and, by obviating direct current, over simplicity of plant equipment. This paper describes the pilot-plant development of one such method, which has subsequently formed the basis of operation of six commercial plants-—one in Canada and five in the United States. Unlike aluminum, magnesium is volatile at relatively low temperatures. This physical property, which produces its greater inflammability, also offers possibilities of direct reduction that are not available with aluminum. In the basic reaction MgO + X = XO + Mg if X is nonvolatile, the reaction may be forced to the right at high temperatures by the evolution of magnesium vapor, despite the large negative value of the heat of reaction which is almost bound to follow the use of any available commercial reducing agent. The cheapest X, of course, is carbon, but this notable advantage is modified by the production of a volatile oxide CO, so that both Mg and CO are evolved simultaneously. Elaborate devices are required to shock-cool the equilibrium mixture in order to prevent back reaction. At best, a pyrophoric powder is produced, requiring redistillation to provide marketable metal. The practical development of this process, is due to F. Hansgirg, and his methods have recently been given a trial on a grand scale in the plant at Permanente, California, and smaller plants were previously built in Austria, England and Japan. A second class of reducing agents is available, those which produce nonvolatile oxides. When XO and X are relatively nonvolatile, magnesium is the only volatile member of the system. It may be evolved in a simple distillation step and condensed without the formation of powder. Two basic requirements must bc fulfilled in order that such a reaction may proceed: I. The reducing agent when heated to a reasonable temperature in presence of MgO must cause the production of an appreciable equilibrium vapor pressure of magnesium. This magnesium must be removed continuously. z. A supply of heat must be maintained. In order to fulfill the first requirement, operations must be conducted in vacuo or in a stream of Hz. Owing to its greater efficacy and relative safety, vacuum has been employed in the work to be described. The choice of a suitable reducing agent formed the subject of an extensive series

Jan 1, 1944

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By G. W. Thomas

A simplified mathematical model of underground conduction heating in a system of limited permeability is presented. The model applies to underground retorting of oil shale, or to reservoirs containing extremely heavy oils. We assume that heat is introduced at a constant rate into a horizontal fracture which communicates between wells. The radial temperature distribution along the fractured surface is approximated by a step-function. Heat transfer away from the fracture is assumed to be by vertical conduction, and all convection effects are neglected. The model also takes into account the possible temperature dependence of thermal conductivity. A general expression for calculating the growth of the step-function temperature distribution with time is derived. The use of this expression and solutions to the one-dimensional heat equation make it possible to construct isotherms. Expressions for calculating .oil recovery, well spacing and heat efficiency are also given. An example calculation is presented for the conduction heating process in oil shale. Finally, the effect of the heat transfer coefficient between the gas and the fracture boundaries is investigated. INTRODUCTION Thermal recovery processes of oil recovery fall into the four general areas of hot fluid injection, forward combustion, reverse combustion and conduction heating. The first three of* these processes have been rather extensively studied in the past decade from both the experimental and theoretical points of view. As a result, it is possible to make reasonable engineering predictions and analyses of these processes. Little attention has been devoted, however, to the conduction heating process other than to note its possible utility.I To a certain extent, conduction heating cannot be divorced from the other regimes cited above, insofar as these provide the source of heat energy. In the conduction heating process, heat is introduced (either by combustion in the forward or reverse mode or by hot fluid injection) into a small fraction of the total reservoir thickness. This fraction may be either a streak of high permeability or an interwell fracture. Heat penetrates by conduction into the adjacent, less permeable regions of the oil-bearing rock, where the direction of conduction is essentially perpendicular to the streak or fracture. The heated product then drains by gravity or is gas driven to production wells. Conduction heating is probably most applicable to systems containing immobile bitumens such as tar sands and oil shale deposits and perhaps to low-permeability reservoirs containing highly viscous crudes. The mechanism also acts in combination with other thermal processes where fingering or overriding of a bed occurs. It seems probable that in at least one field test, conduction heating of this type was very influential.2 In this presentation we give a first approximation to some of the quantitative aspects of conduction heating. Marx and Langenheim3 treated a similar problem where they focused attention upon the injection interval, which spanned the total reservoir thickness. In their model, conduction heat losses to the bounding media imposed a practical limit on the calculated heated area. In the present study, however, we shall confine the injection interval to a small fraction of the reservoir thickness and assume it has no heat capacity. We therefore direct our attention to regions outside the injection interval into which the conduction of heat is beneficial. In particular, we will endeavor to locate specific isotherms in the media bounding the injection interval. Furthermore, we will construct our model to allow the thermal conductivity to vary arbitrarily with temperature. Thus the model will be applicable to underground retorting of shale where variations in thermal conductivity may be important. THEORY We consider the rock matrix to have no or, at best, a very limited permeability; consequently a

Jan 1, 1965

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.' Later, De Boer et al.' determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.' It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators'-' have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By Fernando A. Buttazzoni, Jorge C. Munita

INTRODUCTION To provide a background for discussing long-range financial and operational planning in the mining industry, we would like to begin by describing the role of planning in Codelco. Having taken part in Codelco's planning process since its inception in 1976, we believe that useful conclusions may be drawn for the experience we shall relate. Although Codelco is a state-owned copper producer with an important role in the Chilean economy, and is consequently very much at the core of national economic planning, the following discussion is not related to government planning but to planning in an operationally and commercially autonomous business concern with all the characteristics of a private enterprise. The only way in which Codelco differs from private business is that its financial successes or failures have a more direct impact on the countryls ability to participate in international trade, to meet its international financial commitments and to achieve economic and social growth. Thus, what follows is a presentation of the conceptual features of the planning process at Codelco and a description of the current state of planning in the company. It is understood that certain conceptual components are basic to any formal strategic planning process, and that the components of Codelco's planning process are therefore generally applicable in similar companies. First, the mission and scope of operation of the company must be defined, and goals must be set to achieve leadership in the business activities in which it engages. Having set this framework, the company must constantly scrutinize those internal elements and conditions that are essential to fulfill its mission and achieve leadership. In Codelco this means considering the actions which can best serve to define future capacities, taking into account declining ore grades and determining optimal production levels; watching over the productivity and skills of its labor force, and; keeping abreast of technological developments in non-ferrous mining and processing. If the company is proficient in these three areas, it will be cost efficient and there- fore competitive. Codelco must also watch over the business environment in which it operates. The company sells concentrate, blister and fire-refined copper, wirebar, cathodes and wire rod and must study the behavior of the market to attune its product mix to the demand existing for these various commodities in the international market and the copper consuming industries in general. By examining the internal and external environment in which the company conducts its production and commercial operations, it is able to diagnose its strengths and weaknesses, to identify the hazards it must overcome to stay ahead in the copper trade, and to take full advantage of business opportunities as they arise. CHARACTERISTICS OF CODELCO-CHILE Although our subject is Codelco, readers should keep in mind that there are many other copper producing operations in Chile, all in the private sector, and many valuable deposits that may be exploited in the future. Codelco is the only public sector copper producer, although there is one other state enterprise that operates smelting and refining facilities principally to serve a large number of very small producers of copper concentrate. In the mid-19801s, Codelco is the largest copper mining company of the world and the largest producer and exporter of copper with yearly sales totalling close to US$ 1.8 billion in 1983. Moreover, it is a highly profitable copper company at a time when the world copper industry as a whole has reported losses for several years. Codelco-Chile is a fairly new organization. The history of the four mining operations it manages is much longer: El Teniente was opened in 1912, Chuquicamata in 1915, Salavador in 1959 -- with installations of the old Potrerillos mine dating from 1927 -- and Andina in 1970. Having had separate owners, the management systems of the

Jan 1, 1985

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 Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By K. D. Jacob, W. L. Hill

Fluorine recovery in the United States has been restricted chiefly to manufacture of ordinary superphosphate and wet-process phosphoric acid. However, there is an expanding use of fluorine by industry in the form of hydrofluoric acid. Improved methods for recovering fluorine from phosphate rock would yield an adequate supply of fluosilicates and a substantial contribution to the hydrofluoric acid requirement. THE bulk of natural phosphates is comprised of calcium phosphates, which are usually apatites;' calcium aluminum phosphates such as pseudowavel-1ite; and aluminum phosphates, which occur in extensive deposits, notably on Grand Connetable Island." Nearly all deposits of current commercial value are apatite, often with admixed material of other classes. In the trade coarsely crystalline material, mainly fluorapatite of igneous origin, moves as apatite, whereas the fine-grained material of sedimentary origin is marketed as phosphate rock. The latter classification includes the phosphate shales in western North America. Although several genetic varieties of phosphate rock are recognized, most known reserves are of marine origin. Calcium phosphate is concentrated from Florida land pebble and Florida hard rock deposits and from Tennessee brown rock deposits. Phosphate Rock as a Fluorine Carrier: More than two decades ago Reynolds and Jacob surveyed the fluorine content of commercial phosphate rock from various parts of the world. Later these samples were re-analyzed by a new and more reliable method of determining flourine. The revised results with interim additions of new samples, published a few years ago in a brief summary," are shown in Figs. 1-3. Through the points representing the respective varieties of rock medial straight lines are drawn. In some instances the lines are well defined by the points; in others, where scattering renders the position of the best line uncertain, the greater weight is given points near the end of the covered range. Wherever distinct varieties are not recognized among regional deposits the custom is to identify the sample with the geographical location of the deposit. Although all rock varieties cannot be classified with certainty, the plotted results exhibit three distinct types of rock in which the F to P2O5 ratio diminishes, remains sensibly constant, and increases, respectively, as the grade of rock increases. Existence of two types of Florida land pebble, Fig. 1, is supported by additional results recently supplied by a producer." Generally speaking, phosphate rock from continental deposits carries considerably more fluorine, and apatite and insular phosphates less, in proportion to the phosphorus content than is required by the formula for fluorapatite. Exceptions to this are apatite from Canada and certain samples of Florida waste-pond phosphate. The manner in which excess fluorine is held and the nature of the carbonate in carbonate apatite are discussed in recent articles. High-grade calcium phosphates with F to P2O5 ratios less than 0.05 have been found in Curacao, Christmas Island," Mexic,13 and elsewhere. The calcium aluminum phosphates and aluminum phosphates aften carry notable amounts of fluorine. The F to P2O, ratio for one sample of pseudowavel-lite concentrate was 0.05." Aluminum phosphate from Grand Connetable Island is very low in fluorine, whereas some aluminum phosphate minerals" carry as much fluorine as highly fluorinated phosphate rock. Fluorine in Domestic Phosphate: The curves shown in the figures permit interpolation of the F to P2O5 ratio corresponding to the midpoint of selected ranges in grade of any one of the several varieties of phosphate. Multiplication of the interpolated ratio by the mid-range grade (P2O5) yields a figure for the percentage of fluorine in this grade. Then, with the use of the mid-range grade, the amount of fluorine held in phosphate reserves can be estimated, see Table I. Accordingly, on Jan. 1, 1950, the fluorine complement of known domestic reserves exceeded 420,000,000 long tons of the element. A previous figure," deduced in 1940 by a simpler procedure

Jan 1, 1955

By Frank T. Weems

The basic operating properties of the DorrClone are discussed and certain metallurgical applications which exploit these properties are presented. An effective method of controlling the consistency of the DorrClone underflow is described. THIS paper presents in a general manner some of the applications of the DorrClone (Dutch States Mines cyclone) in the metallurgical and heavy chemical fields. Technical or mathematical analyses of the design factors and of the mechanism whereby the cyclone effects its separation have been capably treated in a series of previous papers.'-' Engineering and operational aspects of a few installations and laboratory tests have been chosen to emphasize the unique classification characteristics of the DorrClone and to illustrate its utility in certain difficult situations. Its use in coal washing and heavy-media operations are not considered. Some 25 or more industrial installations and applications of the DorrClone in the metallurgical fields are operating at present, ranging from single trial units to complete batteries composed of a multiplicity of units. The data were obtained in part from some of these, and in part from operations of units at the Westport Mill, the laboratories and testing plant of the Dorr Co. at Westport, Conn. The DorrClone was developed, in principle, by the research dept. of the State Mines, Limburg, Holland, during World War 11. Its first use was to dewater a —50 micron sand used as a dense medium in coal washing. The metallurgical wet cyclone was first publicized by Driessen and Yancey and Geer.6 ince then the cyclone has been studied as a means of de-watering, heavy media concentration, and fine size classification. The DorrClone is shown in Figs. 1 and 2. pulp to be treated is pumped through the feed nozzle, A, into the feed cylinder, B. The feed nozzle is of rectangular cross-section, the outermost edge being tangent to the feed cylinder walls. Feed shims, C, may be attached to the innermost walls to adjust the open area of the feed nozzle available to entering pulp. The tangential injection of feed under pressure supports the vortex action of the pulp that has been detained in the cyclone; the centrifugal forces of this vortex throw the coarse particles to the walls of the cone, D, where they collect and pass downward and out through the adjustable apex opening, E. The fine particles contained in most of the water that entered with the feed pulp move to the inner spiral of the vortex and flow out through the vortex finder, F, contained in the orifice plate, G, which forms the top of cyclone chamber. The overflow pulp may then spray freely into a spray chamber, H, surmounting the cyclone or pass directly into a 90' elbow, I, of somewhat larger diameter than the vortex finder. Installation Where more than one cyclone is to be installed, best overall efficiency and ease of control are obtained with equal distribution of both pulp volume and weight of solids among the cyclones, and with the same pressure being maintained at each cyclone feed nozzle. Fig. 3 is a suggested arrangement for feeding two or more cyclones in parallel. Feed pressure control: Under normal operating conditions it is not unusual for some surge to exist in the feed that is to be sent to the cyclone. As will be discussed later, surges in the solids content of the pulp are usually not of great operational consequence, but surges in feed volume are a problem. Several systems have been devised for absorbing surges in feed volume, each involving a surge tank. If the surges are small and fairly rhythmical, a tank of sufficient size might be installed to dampen out

Jan 1, 1952