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By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By C. W. Stratford

[During the last few years, the necessity for development work has been generally recognized by executives throughout the oil industry, resulting in greatly accelerated progress and the adoption of many noteworthy improvements in refining methods and equipment. Several years ago, the Associated Oil Co. decided to improve distillation methods with the object of reducing refining costs. This extremely interesting work was entrusted to the writer, and W. S. James, now Chief of Research for Studebaker Corpn. of America, was selected as the principal collaborator. The latter contributed much during his two years with the Associated Oil Co., to the development work that has followed. The writer extends to the Associated Oil Co. his appreciation for permission to disclose the details of distilling equipment. In petroleum refining the principal requisites of good economics are the separation of high-priced distillates from those of lower price; maxi-mum yield of any desired distillate; lowest capital investment in refining equipment; lowest cost of operation and maintenance, and the best adaptability and flexibility of the same refinery equipment for handling crudes of widely varying characteristics. The first two items mentioned, separation and yields of distillates are determined by efficiency of fractionating equipment,. Discussion in this paper is chiefly concerned with oil-heating equipment, combustion and furl economy. It has long been well known that velocity plays a very important part in all heat transfer systems. Any betterment in specific transfer. rates in such systems must. always involve velocity. Realizing this fact, IV decided to adopt as a basic principle, the employment of energy to impart velocity required for high transfer rates through a heating diaphragm, and our method of modernizing obsolete shell stills is founded on this principle. Mechanical energy is usually cheap and its rational rspcntliture is returned in the form of greatly increased heat transfer rates, on both oil and gas sides of the sheet. Certainly there is nothing new in this principle, the only novelty being that of our peculiar method of application On the oil side (Fig. I) use is made of a centrifugal pump to jet the oil against the heated sheet thereby creating a high velocity sheet flow over the entire fired area. Such a pump is one of the most efficient machines, so far developed, for moving fluids. 'I'he oil, under pressure impinging

Jan 1, 1928

By J. T. Berling, J. B. Conway

MANY studies have been devoted to the correlation of low-cycle fatigue behavior. Several of these have also been concerned with the identification of an effective approach to the prediction of low-cycle fatigue behavior from short-term tensile data. Perhaps the first such approach was that reported by coffin1 in the form: where is the plastic strain range, Nf is the number of cycles to failure, and c is a constant characteristic of a material. In this analysis by Coffin it was reasoned that in a short-term tensile test the value of Nf could be considered as equal to a , in which case the value of c is interpreted as the tensile ductility, f, measured in such a test. If, therefore, the Coffin equation is assumed to be applicable to a given material, it is a simple matter to predict the low-cycle fatigue behavior. Once the tensile ductility is known, this point is located at Nf = 1/4 on a log-log plot of vs Nf and a line is drawn through this point with a slope of to yield a prediction for the fatigue life. Actually, while this equation is quite useful it is not generally applicable, for experiment has shown that the value of —$ does not reflect the relationship between and Nf for all materials or even for a given material over all temperature ranges. An equation similar to the Coffin equation was prepared almost simultaneously by Manson.2 This expression had the form: In this case the exponent on Nf was not assigned any particular numerical value in accord with the various values of this exponent which had been observed for different materials and at different test conditions. Because of this characteristic it will be recognized that little use can be made of this expression in predicting low-cycle fatigue results. A fairly effective expression for use in predicting fatigue behavior was proposed by Manson3 based on a study of numerous sets of experimental results. This relation (Method of Universal Slopes) makes use of modulus of elasticity, ultimate strength, and tensile ductility, and assumes an exponent on Nf equal to 0.6 in representing the plastic strain range contribution to total strain range. While this equation of Man-Son does not yield completely accurate results it must be recognized as being the best means available at

Jan 1, 1970

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel'' and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel's and Arafa's studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969

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 T. E. Kihlgren

SYSTEMATIC data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541. INTRODUCTION The demand for an alloy essentially white in color, which could be cast and worked by simple methods and which possessed strength and corrosion-resisting properties superior to the usual brasses, led to the discovery and early use of cupronickel alloys containing zinc, and some-times tin, lead and other metals. This type of alloy was generally known as German silver until the war, when the term "Nickel Silver" became generally accepted. The element principally responsible for the white color of the alloy and for its strength and corrosion resistance is nickel, which may constitute from 8 to 30 per cent of the alloy. The functions of the other elements will be described later. The manifold uses of nickel silver are largely due to its color, corrosion resistance, ease of casting, fabrication, joining and rather moderate cost. In many instances the alloy is finished by grinding and polishing while in others it may be finished with a silver or nickel plus chromium plate. Electroplates

Jan 1, 1935

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

The binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-A~ili~r~ony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Ti11 These three systerrls are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

By R. E. Somers

1. INTRODUCTION 1. Location, Topography, and Climate The Burro Mountains are located in the southwestern part of New Mexico, in Grant County. The group is made up of two distinct moun-tain masses, known as the Little Burros and the Big Burros, the former lying about 6 miles southwest of Silver City-, and the latter about 9 miles farther in the same direction. They are separated by the valley of the Mangas River, a tributary of the Gila, and a stream only in name, except after a heavy down-pour of rain. . The Little Burros attain an elevation of 6,625 ft. above sea level, and the Big Burros 8,054 ft., with the surrounding country averaging about 6,000 ft. To the south of these mountains stretches the desert plain, while to the north are the more frequent elevations of the mountainous country.

Jan 5, 1915

By E. E. Schumacher, G. S. Phipps, H. M. Bouton

The seriousness of the present tin scarcity has stimulated large consumers of this vital metal to develop drastic conservation measures in order to extend the available supplies to cover the emergency period. By devising new soldering methods and alloys the Bell System has contributed a substantial share in the tin conservation effort. Fortunately, the changes, as far as can be determined now, have not introduced weakness into the soldered joints. Some of the new procedurcs were already in the process of development at the onset of the emergency, while others were devised under its stress. In some instances, the newly developed solders were found to be more difficult to use than the alloys previously available, and would not have been introduced under normal conditions. One major change made that previously had been under consideration will result in large savings of tin. Unless service difficulties are encountered, this modification gives promise of remaining after the emergency has passed. The change involves a reduction in the amount of solder placed on a wiped joint between the cable sheath and the sleeve. Instead of the customary full sized wiped joint, a wipe of fillet proportions is formed. Through this change, a solder saving of more than 60 per cent per joint can be realized. Plumbers and cable splicers for many years have joined lead pipes and cable sheath by a soldering process called " wiping." The name is an apt description of the operation. For a wiped joint, the sections to be united are heated by molten solder poured over their surfaces, and the resulting semiliquid mass is manipulated by wiping with cloth pads to a well rounded symmetrical form like the one shown in Fig. I. The operation requires considerable skill on the part of the splicer and close control of the composition of the solder. At first consideration, the problem of tightness in such joints seems simple but experience shows that even under the best conditions the fissures frequently found in the solder occasionally link and form a path that allows leakage to occur. In telephone cables not maintained under gas pressure, such leaks permit the entrance of water, which wets the paper-covered conductors and thereby impairs the insulation value and causes service interruptions. Ry going to an extreme and wiping off all the solder in excess of a fillet, it has been found that many causes of porosity are eliminated. Figs. 2 and 3 show cross sections of joints wiped in the old and the new ways. The saving in solder, and consequently in strategic tin, is evident. The field splicing forces find that joints are easier to make by the new method and are less likely to be porous. The metallurgical considerations that are responsible for the success of the fillet wipe are of interest. Much has been written about the wiping process of soldering cable joints and the many requirements of a good wiping solder have frequently been listed. The success of the procedure described

Jan 1, 1943

By G. S. Phipps, E. E. Schumacher, G. M. Bouton

THE seriousness of the present tin scarcity has stimulated large consumers of this vital metal to develop drastic conservation measures in order to extend the available supplies to cover the emergency period. By devising new soldering methods and alloys the Bell System has contributed a substantial share in the tin conservation effort, Fortunately, the changes, as far as can be determined now, have not introduced weakness into the soldered joints. Some of the new procedures were already in the process of development at the onset of the emergency, while others were devised under its stress. In some instances, the newly developed solders were found to be more difficult to use than the alloys previously available, and would not have been introduced under normal conditions. One major change made that previously had been under consideration will result in large savings of tin. Unless service difficulties are encountered, this modification gives promise of remaining after the emergency has passed. The change involves a reduction in the amount of solder placed on a wiped joint between the cable sheath and the sleeve. Instead of the customary full sized wiped joint, a wipe of fillet proportions is formed. Through this change, a solder saving of more than 60 per cent per joint can be realized. Plumbers and cable splicers for many years have joined lead pipes and cable sheath by a soldering process called "wiping." The name is an apt description of the operation. For a wiped joint, the sections to be united' are heated by molten solder poured over their surfaces, and the resulting semiliquid mass is manipulated by wiping with cloth pads to a well rounded symmetrical form like the one shown in Fig. I, The operation requires considerable skill on the part of the splicer and close control of the composition of the solder. At first consideration, the problem of tightness in such joints seems simple but experience shows that even under the best conditions the fissures frequently found in the solder occasionally link and form a path that allows leakage to occur. In telephone cables not maintained under gas pressure, such leaks permit the entrance of water, which wets the paper-covered conductors and thereby impairs the insulation value and causes service interruptions. By going to an extreme and wiping off all the solder in excess. of a fillet, it has been found that many causes of porosity are eliminated. Figs. 2 and 3 show cross sections of joints wiped in the old and the new ways. The saving in solder, and consequently in strategic tin, is evident. The field splicing forces find that joints are easier to make by the new method and are less likely to be porous. The metallurgical considerations that are responsible for the success of the fillet wipe are of interest. Much has been written about the wiping process of soldering cable joints and the many requirements of a good wiping solder have frequently been listed. The success of the procedure described

Jan 1, 1943

By H. M. Bouton, G. S. Phipps, E. E. Schumacher

The seriousness of the present tin scarcity has stimulated large consumers of this vital metal to develop drastic conservation measures in order to extend the available supplies to cover the emergency period. By devising new soldering methods and alloys the Bell System has contributed a substantial share in the tin conservation effort. Fortunately, the changes, as far as can be determined now, have not introduced weakness into the soldered joints. Some of the new procedurcs were already in the process of development at the onset of the emergency, while others were devised under its stress. In some instances, the newly developed solders were found to be more difficult to use than the alloys previously available, and would not have been introduced under normal conditions. One major change made that previously had been under consideration will result in large savings of tin. Unless service difficulties are encountered, this modification gives promise of remaining after the emergency has passed. The change involves a reduction in the amount of solder placed on a wiped joint between the cable sheath and the sleeve. Instead of the customary full sized wiped joint, a wipe of fillet proportions is formed. Through this change, a solder saving of more than 60 per cent per joint can be realized. Plumbers and cable splicers for many years have joined lead pipes and cable sheath by a soldering process called " wiping." The name is an apt description of the operation. For a wiped joint, the sections to be united are heated by molten solder poured over their surfaces, and the resulting semiliquid mass is manipulated by wiping with cloth pads to a well rounded symmetrical form like the one shown in Fig. I. The operation requires considerable skill on the part of the splicer and close control of the composition of the solder. At first consideration, the problem of tightness in such joints seems simple but experience shows that even under the best conditions the fissures frequently found in the solder occasionally link and form a path that allows leakage to occur. In telephone cables not maintained under gas pressure, such leaks permit the entrance of water, which wets the paper-covered conductors and thereby impairs the insulation value and causes service interruptions. Ry going to an extreme and wiping off all the solder in excess of a fillet, it has been found that many causes of porosity are eliminated. Figs. 2 and 3 show cross sections of joints wiped in the old and the new ways. The saving in solder, and consequently in strategic tin, is evident. The field splicing forces find that joints are easier to make by the new method and are less likely to be porous. The metallurgical considerations that are responsible for the success of the fillet wipe are of interest. Much has been written about the wiping process of soldering cable joints and the many requirements of a good wiping solder have frequently been listed. The success of the procedure described

Jan 1, 1943

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 R. B. Woodworth

In the sinking of bore holes, there are but two fundamental operations —drilling and hoisting—which determine in the main the character of drilling mechanism and structures. There are endless ramifications, however, in the execution of these fundamental operations, according to the purposes for which the bore holes are drilled, their maintenance after completion, the protection and convenience of workmen, etc. The three main lines of use for bore holes are in mineral exploration, the sinking of water and salt wells, and the exploitation of pqtroleum and natural gas. This paper has to do more especially with the last. Here again there are many divergences. Wells may be drilled by either the percussive, the hydraulic, or the abrasive method. Finally, each of these methods, as applied by drillers of diverse nationalities, has followed somewhat different lines of development. The American system of cable-tool drilling has perhaps had the widest application; the hydraulic rotary is also in extensive use; but the Canadian system, the Galician system, and the Russian free-fall system all have their points of recognized merit and are preferred by operators accustomed to their use. These differences in drilling procedure, which rest ultimately on essential variations in geological conditions, are reflected in the drilling structures as well as in the drilling mechanism. The purpose of the present paper is to record those stages in the development of the application of steel to the construction of drilling mechanism and structures with which the writer has been intimately associated, and to contribute to the history of the art of drilling other data acquired in the course of his personal investigations. It is necessarily limited by reason of space to American practice, with especial reference, therefore, to the cable-tool system and the hydraulic rotary method of drilling wells for oil and gas.

Jan 1, 1916

By Morris Cohen, Robert C. Ruhl

The phases in Fe-C alloys over a wide composition range have been studied after splal quenching from the liquid state. Binary alloys containing 0 to 5.1 wt pel C as /cell as a large number of ternary Fe-C-Si alloys with 2.5 to 5.0 wt pct C and 0.3 to 5.1 wt pct Si were attlong those sludied. Olher Fe-C-X alloys, zcilh X being Co, Cr, ,Wn, Ni, and Ru , were also inrestigated after splat quenching. At high carbon contents, a new hcp phase (designaled 6 phase, but different from e carbide) is retained upon splat quenching. The .fraction of this phase varies up lo 97 pcl for a Fe-4.K-1.9% alloy. The composition of the E phase ranges from about 3.8 10 4.8 wt pet C, and the corresponding laltice parameters increase linearly ulith carbon content, while the c/a ratio remains essentially conslc~nl. The E phrtse appears to he a solulion of carbon in E iron, the latler being nornially found only at high pressures. It is deduced that the unit cell of the E phase corresponds to the formula Fe12C3, and llzal il is relaled to tlie ordered slruclures 0.f 6 iron carbide and c iron nilride. The E phase is compared and contrasted to the olher known carbides and nitrides of iron and nickel. An exlrapolaTion of the atomic volume 1,s carhon conlent of /he E pllase lzcts giz.en a neu7 estitnale jor /he alomic volume of E iron, 11.30 cu A, a1 atmospheric pressure and temperature. Other alomic volume relalionships lead to /he co~zpositioti Fe2.iC tor E iron carbide, /he unit cell fortr~ula being -Fe2rClo The E phase undergoes a lulo-slage decomposition upon healing, .forrning firsl rnarlensile plus E carhide, a/ler 1 hr at 140" lo 200°C, slid then ferr ite Plus cementile, after 1 lir a1 330" to 460°C. A1 carbo,l contents between 1.5 and 3.0 LC/ pcl, (he predo.wirzar/t plzase alley quenching is fcc austenite. The retained carbon content of this phase increases with itlcreasing silicon in certain concentration ranges, reaching a maximum of 2.37 wt pct C itz a Fe-2.6C-4.OSi alloy. This is the highest carbon conten1 reLaitled in austenite to date. These high-carbon aus-tenites can be partially tm?zsforttled lo tnartensile hy severe deformation in the temperature range of — 190 to -50°C. TECHNIQUES for splat quenching from the liquid state have been utilized in numerous recent investigations to produce metastable phases in a variety of alloy systems. Among the several ways of splat quenching, the shock-tube method appears to yield the highest cooling rates1-3, 7, 8 and was adopted here. Estimated cooling rates attained in the present experiments ranged from 10' to 10 80Cper sec.' As a part of a research program on interstitial al- loy phases, the Fe-C system was selected for splat-quenching studies. It was hoped that splat quenching would allow high metastable supersaturations of carbon to be retained in solution. Also of considerable interest were the conditions governing the occurrence of the various intermediate phases upon solidification. The alloys investigated included both binary Fe-C compositions as well as six ternary Fe-C-X alloy systems. The known phases in the Fe-C system are summarized in Table I.* Only the ferrite and graphite are ent investigation.14 and is described in detail herein Table II summarizes corresponding data on Fe-N phases, which are also of interest here because of their similarity to the Fe-C phases. EXPERIMENTAL PROCEDURES Alloys were prepared by melting the elements. 99.9 pct purity, in an inert gas nonconsumable electrode arc furnace. The buttons. weighing about 5 g. were remelted twice. were then fragmented. and their interior surfaces were examined for uniformity: if any doubt existed. they were remelted again. Chemical analyses were performed on all the alloys. the accuracy being about k0.05 wt pct. At high temperatures, carbon-containing alloys react with alumina crucibles as follows: If the atmosphere in the splat-quenching furnace does not contain sufficient carbon monoxide the alloy can be depleted of carbon and contaminated with aluminum. Calculations and experimental observations showed that 50 to 100 torr CO partial pressure effectively blocked the above reaction in all the alloys investigated. The splat-quenching equipment in Figs. 1 and 2 provides for evacuation and back-filling with CO-Ar mixtures. The furnace is capable of operation up to 1650°C. and the gettering action of the graphite heating element reduces the oxygen partial pressure in the furnace atmosphere to below 10-5 torr, thus preventing oxidation of the specimens.

Jan 1, 1970

By J. J. Gilvarry, B. H. Bergstorm

The first part of this paper describes a new approach to the problem of energy relationships in fracture and comminution. The basic theoretical method used (as contrasted to previous empirical or semi-empirical approaches) is an attempt to verify or disprove the hypothesis of von Rittinger, In the second part of the paper, theoretical conclusions for the three headings of single fracture, plural fracture, and comminution are tested. Agreement between theory and experimental results is demonstrated. The classical hypotheses on the energy relationship in brittle fracture are those of von Rittinger-that the energy required is proportional to the new surface formed— and the alternative one of Kick.' Over the years, repeated attempts have been made to discriminate experimentally between the two assumptions, or to replace both of them, as has been done by Bond? However, no semblance of agreement seems to exist among different investigators. This paper is the first in a series essaying a new approach to the entire problem of energy relationships in fracture and comminution. The purpose of this program of research is to verify (or disprove) the hypothesis of von Rittinger. In contrast to previous empirical or semi-empirical approaches to the problem, the basic method adopted is theoretical. The prime aim is to determine the distribution function for fragment size theoretically and to verify the predicted distribution experimentally. This approach should make possible determination of the total surface of the particles by integration over the corresponding distribution function; one may hope that this direct procedure will yield more definitive results than use of gas adsorption or other methods. The surface area so obtained can then be compared with experimental energies, as obtained by Bergstrom, Sollenberger, and Mitchell,4 for example. It is convenient to distinguish between single fratture, plural fracture, and comminution. Single fracture of a brittle solid is defined as fracture by an external stress system which is removed instantly and permanently when fracture is initiated. Plural fracture consists of single fracture of the original specimen, followed by a sequence of only a few secondary fractures; comminution differs in that the sequence of secondary fractures consists of a large number of repetitive steps. For single fracture, Gilvarrys has given a rigorous derivation of the proper distribution function for fragment size, based on a closely defined physical model and deduced strictly by the laws of probability. Gilvarry and Bergstrome have compared the predictions of the theory with experiment, and have found excellent agreement. The prior work of Gilvarry and of Gilvarry and Bergstrom considers only single and plural fracture. The purpose of the present paper is to extend the discussion to the case of comminution. For prefatory purposes, the theory of Gilvarry for single fracture will be outlined. The considerations will then be applied to the cases of plural fracture and comminution. SINGLE FRACTURE The derivation is based on the Poisson law.7 For Points distributed with mean density y over a domain, this law states that the probability p(t)dt of one point lying in the range t to t + dt with none in the interval 0 to Ms p(t)dt = ye-yt dt. For this distribution to be valid, it is necessary and sufficient that the points be distributed at random, individually and collectively in the sense of ~~~.7 The former qualification requires that the position of One Point be independent of another, and the latter implies that the probability of a region containing a

Jan 1, 1961

George W. Maynard, New York, N. Y.:—It is well known that there are many magnetite-mines of which the ore is too low-grade for direct use in the blast-furnace. For carrying out the sintering process, the preliminary step, in the case of magnetites, is the separation of the ore from the gangue by magnetic concentration. The resulting fine-grain product is very objectionable in the blast-furnace, and when used must be a very small percentage of the charge. The sintering process has saved the situation by furnishing a product which is absolutely ideal on account of its cellular structure. (In reply to questions by W. J. Tudor, and Joseph W. Richards, the following additional information was given by Dr. Maynard.) The percentage of iron in the product is determined entirely by the degree of concentration of the raw material and is practically not increased by the sintering operation. The magnetic concentrates at Port Henry and at the Benson and one or two other mines contain from 65 to 67 per cent. of metallic iron. The cost of sintering is from 39 to 41 cents per ton of product, including superintendence, depreciation, and repairs. The itemized figures are about as follows : Mixing (including labor), 24; power, 9; ignition, 5; repairs, 3; total, 41 cents. Prof. J. W. Richards, South Bethlehem, Pa.:—From a metallurgical standpoint I question the accuracy of the statement on p. 374: " C.—An increased reducibility of the iron so treated. (This has been conservatively estimated as 5 per cent. better than the best available ore.)" It seems to me that when a material is' sintered in this way, the constituents present, as lime, silica, and alumina, have a chance to form a compound with the iron oxide; that such a compound, if formed before the material goes into the blast-

Jan 1, 1913

My predecessor in the office of President of the Institute started a custom of visiting the various local sections, thus obtaining their points . of view and their ideas as to how the Institute can best serve the interests of its members. Exceedingly valuable- exchange of ideas was thus brought about. I am following this custom as far as the limited amount of free time at my disposal will allow me, and I trust that my successor in office will appreciate the benefit to be derived from following the custom thus initiated and will continue the swing around the circle of the local sections. The activities of the Institute are increased by the prestige gained from large numbers and I trust that every member of this local section will consider himself a member of the committee on increase of membership and will see if he is not able during the coming year to gain at least one new member for the Institute. This is a perfectly possible proposition for, although the membership of the Institute is at present approximately seven thousand, I feel sure there are at least seven thousand more men in the United States who are interested in mining, metallurgy or geology from the metal-mining point of view who would make admirable members or associate members of the Institute. The first consideration of the Institute as a body, and of each member as an individual, is to win the war and defeat the Huns. In order to accomplish this, the Institute, as a body, has cooperated with the other national engineering societies and the great bureaus of the Department of the Interior, the United States Geological Survey and the Bureau of Mines in forming committees to study and advise the Government on pressing problems of vital importance.

Jan 5, 1918

By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By Rollin A. Slater

This paper presents a composite of ideas on materials handling systems by describing the design of an over-all system for a hypothetical steel pellet plant located on the Great Lakes. The bulk materials handling industry has served for years as the skeleton and the central system of nerves and nourishment for the body of basic industries. During the past two decades, this body has undergone substantial growth and mutation to meet the surging demands of our national economy for more and better products. The steel industry has kept pace with spiralling demand by innovation which has resulted in new processes and improved designs which generally yield greater production from fewer units. Materials handling technology has likewise improved its techniques and currently has a new, stronger generation of equipment to perform its necessary supporting function. Drawing upon excerpts from several recent plant designs, this paper describes a basic approach to the selection and application of modern bulk materials handling systems to an entirely new steel plant. Specific details are not available for publication, and therefore the plant described herein is a composite of ideas. This imaginary plant will be located on the United States side of the Great Lakes and its owner will be called the Hypothetical Steel Corp. for purposes of discussion. TYPES OF EQUIPMENT The basic bulk materials handling systems and components required in a plant so situated are: lake boat unloaders; railroad train unloading systems; storage pile stackers and reclaimers; large bins and regulating feeders; and the conveyor systems — with their attendant controls— which connect the foregoing. PROGRAM OF DEVELOPMENT The initial work on the plant must be that of the process engineers who develop and refine the basic data, i.e., the logistics of all raw materials, waste materials and products within the plant. During this phase of study, the materials handling engineer may advance his planning only in basic areas such as movements at the dock and movements at the railroad. This initial planning work is concerned only with defining logical plant locations in the light of channels, currents, existing traffic, governmental regulations, locations of existing railroads and available rights-of-way. These systems alone have their own individual criteria which must be respected and accommodated in the final layout. All other elements, such as the arrangement of the blast furnaces, power house, coke plant, by-product plant, scrap preparation plant, BOF shop, and facilities for continuous casting, degassing, calcining, etc., are dictated by their own specific needs and their relation to each other. In the arrangement of these latter facilities, the materials handling system is secondary and must be designed to accommodate. BASIC LOGISTICS The result of the process engineer's work can be expressed in terms similar to those shown in Table I. Plants are customarily rated in terms of annual tons of ingots. Therefore, the basic size of this plant can be determined by referring to the BOF Shop wherein it is sized at 5 million tpy. From the base, the required hot metal can be traced to the blast furnace, which in turn indicates the amount of required flux, iron bearing materials and coke —which in turn establishes the demand for coal. Likewise, the total demand for flux can be determined by the combined demand of the lime plant and blast furnace. The generation of fines and waste products, which have significant value but are not usable as such, create the need for a sintering plant. From projections such as the foregoing, the complete flow of materials can be established and accommodated. The basic premise upon which this typical materials balance is predicted is that the plant will be a producer of high tonnages of non-SpecialtV- products. All basic raw materials (flux bearing, iron bearing, coal) will be prime quality. For example, the basic iron charge will be pellets, and the iron ore fraction will be sized lump, all of which

Jan 1, 1970