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By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues' have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.' Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer's value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,' analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By P. B. Bucky

IN previous publications1 it was shown that a scalar model of any weighty structure, where the stresses produced are mainly due to gravita-tional forces, will behave similarly to its prototype if the model and proto-type material are the same arid the model is placed in a centrifugal field of force (substituted for the gravitational field) which has been increased in the same proportion as the linear model scale is decreased. This principle is now being applied to a study of the behavior of mine structures in an attempt to determine the laws that control them. The importance of using models as a means of solving mining problems has been discussed previously, yet it may be well to reiterate here that this method of research and type of solution have been productive of far-reaching results in other engineering fields, notably those of hydraulics and aerodynamics. Model research is a comparatively cheap and time-saving method of checking practical experience. Up to the present time the best guide to what will happen underground has been the judgment of the man who has observed most and been longest acquainted with the local conditions. His experimental work underground is limited by the elements of cost, time and danger, while failure is seldom permissible. In a model, as in a test tube, all elements that affect the solution of a problem are under definite control. Each element may be varied independently at will and its effects noted. Experimental work on a small-scale model may there¬fore be performed at a comparatively small expenditure of time and money, instead of on a full scale in the mine, where the cost, time, and danger elements are necessarily great. The experiments described in this paper are to be considered as part of a progress report and a continuation of Technical Paper 425. One object of the research program is to make each experiment point the way for further research on that particular phase of the general problem. The results and conclusions presented here are therefore not to be considered as final, but are to be interpreted as

Jan 1, 1933

By William B. Potter

It is a time-honored custom in this, as in other kindred bodies, for the retiring President on giving place to his successor, after a year of official duties which have been the means of directing his attention in a more than usual degree to the work and interests of the Association, to report the results of his observations from this outlook, and the thoughts that may be suggested by the view. In looking out over the many fields of activity within the range of this Institute, the attention may be arrested by special features marking recent progress and development, or such as by their meager outline or lack of important detail stand in less pleasing contrast, or. even form unsightly objects in the view. It may be that the special field and particular work in which one is engaged will, when observed from the more distant standpoint, or in the light of the whole outlook of the profession, assume a different aspect or develop features of new interest and importance. In this way some special object may suggest to the observer a, fitting theme for the occasion. To others, again, an outline of the whole view may seem a more useful subject for study and review. All fields are examined and the wide horizon of the whole profession scanned to note and report whatever is new in knowledge and practice—the new permanent bench-marks that appear near the horizon designating ground definitely located; the stakes which mark reconnoissance into new territory, and even the prominent objects that faintly appear through the mist of the distant atmosphere, and which may serve later on as points of attachment for the advancing lines of survey into the unknown. And besides these, there is the progress of the work in older and nearer fields—what has been attempted, what accomplished,

Jan 1, 1889

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

In the January 1956 issue: TP 4137B. Adsorption of Ethyl Xanthate on Pyrite. By A. M. Gaudin, P. L. de Bruyn, and Olav Mellgren. P. 65. Since P. L. de Bruyn is now a member of the AIME, the word "associate" should be removed in describing his status. The address of the third author, Olav Mellgren, should read: 74-2 Chingola, N. Rhodesia. P. 68, second paragraph, last line: the word "300-fold" should be replaced by "3000-fold." Also in the January 1956 issue: TP 4158B. Energy Transfer by Impact. By R. J. Charles and P. L. de Bruyn. The authors wish to express their disapproval of the omission of the abstract from the article, since they believe that an abstract fulfills a very important function in every paper.

Jan 1, 1957

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By Arthur E. Focke

IF a metallurgist employed in an industry producing mechanical parts or assemblies wishes to make the most of his opportunities he will be concerned with every use of metals in that industry. He will not only take part in the testing and treating of the metals used but will assist in their selection and study their behavior in processing and in service. In addition, he will attempt to develop an understanding of the problems involved in the use of the metals in all plant tools and equipment. Metallurgists that follow this course will soon recognize that frequently too little thought is given to the effect of the design of parts on the way the metal in them is expected to behave in service. He will come to realize that changes in the design of a part will often be much more useful than changes in the hardness, strength, composition, or structure of the metals used in them. Does this mean that a metallurgist is out of place in these industries and that he should leave the field to others or be content to fill only a minor role?

Jan 1, 1947

By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

By W. H. Brandt

THERE has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidence. Particularly noteworthy among the empirical work is that of Grossmann,12 who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.1-5 They have shown that formation of pearlite proceeds by a process of nucleation and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to fill in a small part of the gap. A method was presented recently14 for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eutectoid steel was calculated, using linear extrapolations of the ferrite and cementite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and V, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1945

By E. J. Eisenach, W. E. Jones

SAFETY and industrial hygiene have always been recognized as highly important in company policy, and the co-operative support of the company officials and entire plant personnel has contributed largely to the present success of the Company's program in this field. Growth has necessarily been slow, and dependent, at times, on trial and error but the program in its present form combines the regulations, working methods, and equipment that have proved their value under actual operating conditions. Every effort is made to keep the program on a practical basis. Continuous experimental work is carried on in conjunction with the health and safety program, with resultant periodic changes for improvement. As a proof of accomplishment, in 1945 the frequency and severity rates for accidents were the lowest in the history of the operation. A full-time safety engineer was employed in 1933 and an assistant safety engineer in 1936. During the following year a stenographer was employed in the office and a safety inspector was added for the mine. During the gradual expansion of operations that was climaxed by

Jan 1, 1946

By R. J. Wygal

A method is presented by which homogeneous, isotropic, and reproducible aggregates of particles such as glass beads, sand, ground glass, etc., may be prepared simply and quickly by using a "particle distributor". Several applications of the packing method to the construction of model reservoirs are described. The flow characteristics of these packings me given. Some factors which limit the usefulness of unconsolidated packs for simulating reservoir rock are overcome through artificial cementation of the aggregates. INTRODUCTION Many laboratory studies of porous media are based on experiments using test packs of sand, glass beads and other granular materials. More confidence can be had in the results of such studies if the test packs are known to have uniform properties throughout, to be mechanically stable and to be accurately reproducible. This paper presents a method by which such packs of a variety of shapes and sizes may be constructed using a particle distributor. Some factors which limit the usefulness of unconsolidated packs as a means for simulating reservoir rock are described. A method of overcoming these limitations, which involves artificial cementation of the packs, is presented. DEVELOPMENT Particles packed by the tamping or vibrating techniques are usually either non-uniform or mechanically unstable. An invention by Currie and Gregoryl overcomes these difficulties to some extent. The invention is based on the use of a stream of falling particles impinging on and passing through a distributor matrix of several layers of closely spaced spheres. The particles are well dispersed by numerous collisions with the spheres. They become homogeneously distributed at some distance below the distributor matrix and at that position are collected in the sample container. This apparatus, however, was found to be ineffective when small particles were used since small particles accumulate on the top surfaces of the spheres. An improved distributor matrix was made, first in the form of a stack of five sieves, and then in the more adaptable form of spaced layers of wire screen. Fig. 1 shows a longitudinal view through a five-layered distributor of eight-mesh wire screen. This device gives excellent results.* Fine particles pass through the distributor with very little hold up. The fine structure of the wire matrix with its many deflecting surfaces ensures good particle distribution. There are no dead areas immediately below the screen as were sometimes observed to occur below a matrix of spheres. Using such a device, 20-30 mesh sands were packed to a porosity of 32.1 per cent at rates varying from 0.17 to 6 lb/rnin. The lowest porosity achieved by tamping small increments of similar sands into a container was 33 per cent. Motion pictures at 3,000 frarnes/sec of the surface of a growing pack of 2-3/4 mm glass beads have helped to show the mechanism by which packs of low porosity are obtained. The beads, although packed at the rate of 5 lb/min, were observed to hit the pack surface singly, for the most part, and at well spaced points of impact. Part of their energy is transferred to surface beads which are thereby

By F. L. Wolf

THE catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This' means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a, preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of, materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though its importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation.

Jan 1, 1930

By Arthur Taggart

THE major portion of the work described in this paper was performed by R. W. Young,+ a graduate student in the department of Mining and Metallurgy, Sheffield Scientific School, Yale University, working under a cooperative agreement between the Hardinge Conical Mill Co., the Sheffield Scientific School, and himself. Since this cooperative scheme is at present in effect in the case of a considerable number of other students in the department and since it is the hope of the school that the privilege thus extended may be utilized even more freely in the future by mining and manufacturing companies, it may not be amiss at this point to give a summary of the general plan. Briefly it is as follows: A graduate student, whose undergraduate work in this or other universities shows promise of ability to handle research work, is chosen by conference between the company and instructor involved. The aim of the company in the agreement then entered into is to obtain the solution of one or more of the technical problems with which it may be confronted, or, at the end of 1 or 2 years, to obtain as an employee a man especially trained in its work. As. a means to accomplish one or both of these ends, the company furnishes the machine, apparatus, or material to be tested and pays the student during his graduate work a small salary, usually just sufficient to cover his living expenses, tuition and fees. The aim of the student is special training along a line in which he is particularly interested, the attainment of his advanced degree, and the chance to show to his future employer ability to handle such problems as may be presented to him. In return for the financial aid which he receives he agrees to devote at least half of his working time to the special problem submitted by his company. The other half is devoted to study of the collateral subjects required by the department for the granting of the degree which the student seeks. The student further agrees to enter the employ of the company in question at a wage not greater than that paid in like positions to recent graduates not specially trained and to remain with his employer at such wage for at least 1 year. If the student is to obtain a degree, the special work forming the basis of his investigation must be such as will involve real research and not mere routine manipulation. The subject is chosen by conference between the three parties to the agreement. The work is carried on under the direct supervision of the instructor involved. The school furnishes the general laboratory and library equipment essential to the pursuit of any extended investigation, In

Jan 4, 1917

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By Hsun Hu, R. S. Cline

A detailed studj) of texture formation in 2 pet Al-Fe single crystals with initial orientations of approximately (111) [112], (112) [111], and (112) [111] was made by examining the textures developed on the surface and at various interior sections of the crystal after rolling to various amounts. Depending' upon the initial orientation of the crystal, the surface and interior textures may differ only in sharpness, or may differ essentially in orientation. The orientation of the (111) [112] crystal does not change upon rolling up to 70 pet, but after rolling more than 90 pet a distinct component of (001) (110] orientation is developed. The texture formed in the two (112) (1111 type crystals consists of (111) (1121 and (001) (1101 components. The latter, however, is largely confined to the surface layers. The textures formed on both sides of the crystal are identical, and the texture composition profile is approximately symmetrical with respect to the central section of the strip thickness. The formation of these texture components is analyzed. DURING the past seven or eight years, deformation and recrystallization textures in rolled Si-Fe single crystals have been extensively studied by various investigators.1-7 From these studies, much knowledge on texture formation in bee crystals of various initial orientations was obtained. However, these results also raised many questions, regarding particularly the correlation between deformation and recrystallization textures, as well as the deformation texture itself of some particular crystals. To take a (111) [112] type crystal as an example, it was shown by Dunn and Koh2, 3 that this orientation does not change during deformation by rolling. This finding is consistent with the conclusion reached by Barrett and Leven-son8 with respect to iron crystals that (111) [112] is one of the stable end orientations. However, different recrystallization textures were observed by Dunn and Koh3 in (111) [112] type crystals of different initial thickness, which widened differently during rolling even though their deformation textures were identical. Another interesting example, also from the results of Dunn and Koh2'3 is that of texture formation in a (112) [111] crystal. This crystal developed a two-component deformation texture of (111) [112] plus (001) [110]. Its recrystallization texture, however, was found to be predominantly (110) [001], which is related to the (111) [112] component by a simple [110] rotation. This crystal, therefore, behaved as if the other deformation texture component, (001) [110], were not present. There are also discrepancies among the results of different investigators, as well as numerous unexplained fine features of the deformation texture of crystals of various initial orientations. In order to have a better understanding of all of these points, a detailed study of deformation textures is greatly needed. One of the obvious things that has been completely overlooked in previous texture studies is the possible effect of surface texture. All past work on the texture of Si-Fe single crystals was conducted in a rather simple manner, i.e., the rolled crystals were etched to a very thin sheet; then their textures were examined by transmission X-ray techniques. For recrystallization texture studies, unless precautions are taken by etching off a sufficient amount of the surface layer before annealing, the texture developed in the interior may be affected by the surface layer, which may well have a different initial texture and which may have undergone recrystallization earlier than the interior of the specimen. Because of this effect, it is now planned to reexamine the texture of various rolled and annealed single crystals at the surface, and at various sections below the surface by using reflection techniques. In some cases, both surfaces of the rolled crystal will be examined. In one of Dunn's early papers,9 he noted that at an early stage of rolling the crystal seems to divide roughly through the middle to become a sample which in effect consists of two layers having some what different orientations. This effect has never been further explored. The investigation described in the present paper constitutes the beginning of a series of thorough investigations of texture formation in deformed bee single crystals designed to clear up some of the uncertainties which have been discussed. We have chosen a high-purity 2 pet Al-Fe alloy for this investigation. It is known that the allotropic transformation of iron is eliminated by alloying with approximately 1petAl. Such an alloy, being very similar to silicon ferrite, can be heated to the solidus temperature without phase transformation. One reason for choosing A1-Fe instead of Si-Fe for the present investigation is that we have been able to make single crystals of a vacuum-melted high-purity A1-Fe alloy by the strain-anneal method without much difficulty, but were not successful in doing so with a vacuum-melted high-purity Si-Fe alloy. For many research purposes,

Jan 1, 1962

By J. H. Henderson, H. J. Ledbetter, N. B. Gove, J. D. Griffith

INTRODUCTION The results of a series of laboratory flood tests using liquid Iso-butane to displace refined oils from test cores are pre- ented and interpreted on an empirical bask. The study Revealed the similarity of the miscible liquid displacement to that of the immiscible-fluid displacement mechanism. The efficiency of the iso-butane flood decreased markedly as the oil Viscosity increased. but the effect of injection rate on the effectiveness of the primary production stage was negligible over the range investigated. The presence of free-gas saturation prior. to iso-butane breakthrough increased the volume of iso- Butane required to recover a given percentage of the oil present. Injection of liquid i.e.-butane prior to water follicle sculpted in a marked improvement in oil recovery by the water flood. INTRODUCTION The production of petroleum is often enhanced by the injec-1i1)n of extraneous fluids into the reservoir. It has been suggeited that the injection or cycling of a wet gas or a liquefied petroleum gas would he instrumental in increasing the effic.ienr!; of oil recover! to a greater degree than the commonly injected fluids. dry pas and water. Although instances of injection of light liquid hydrocarbons are not unknown, a systrmatic recording of the result is unavailable and superfi- cially, the practice gives the impression of being economicaIIy unsound. For specific types of displacement, analytic: solutions have been advanced which aid in understanding the physical mechanisms involved. However, there is no generalized theoretical concept which permits adequate prediction of displacement efficiency from a knowledge of readily measured reservoir rock and fluid properties. The Buckley-Leverett approach to oil displacement by an immiscible phase is an admirable analysiy of that type of mechanism. Dykstra and Parsons have introduced a useful concept in their evaluation of the role of the mobility ratio and its merit in rationalizing displacement phenomena. Everett, Gooch and Calhoun3 in their report on the effect of viscosity ratio and miscibility have pointed out the lack of a comprehensive theoretical approach and the desirability of investigating the mechanism of miscible-miscible displacement. In lieu of a well-developed theory concerning miscible-111isci1)le displacement and in view of the scarcity of engineering information on actual LPG injection trials, the limited program of laboratory experimentation described below was undertaken. OBJECTIVES The original broad objectives of the program, to study the oil recovery process using LPG as the displacing phase, defined the direction and scope of the laboratory tests. The specific objective. of the experimentation were to evaluate

Jan 1, 1953

By H. L. Stone, A. O. Garder

A numerical method of solving the partial differential equations which describe the one-dimensional displacement of oil by gas has been presented. Possible extension of the method to treat multidimensional flow is discussed, and the limitations of this extension are indicated. Using this method, it is possible to allow for the existence of a gas cap, the presence of any number of gas-injection or oil-production wells and the evolution of dissolved gas from the oil. It is also possible to allow for variation in the cross-sectional area, elevation, porosity and permeability of the reservoir. The influence of relative permeability and the force of gravity in the direction of flow upon the displacement is considered. The influence of capillary pressure upon the flow and the effect of gravity in the direction perpendicular to flow are neglected. The physical properties 01 the fluids are considered to be Junctions of pressure only, and equilibrium between contiguous phases is assumed. The numerical calculations can be readily carried out by the use of a digital computer. Several example analyses have been performed using the IBM 704 computer, and about one-third of an hour of computing time was required per case. Reservoir behavior predicted by use of this numerical method was compared to data obtained by other methods for three cases — complete pressure maintenance, dissolved-gas drive and gas-cap drive. The independent solutions to these problems were obtained by analytical solution, laboratory experiment and field data, respectively. Agreement of the numerical solution with data from these sources was good; this agreement establishes the convergence and accuracy of the numerical method. INTRODUCTION Most petroleum reservoirs can be produced by any one of several alternative programs. When a reservoir is produced by primary methods, production economics can be influenced by controlling the number and location of wells and the flow rate of each well. An even greater influence may be achieved by augmenting the recovery of oil obtainable by primary methods. This can be accomplished by injection of fluids such as water, natural or enriched gas or a bank of light liquid hydrocarbons. Selection of the most desirable operation requires a means of predicting the reservoir behavior which will result from each of the several alternative programs. The purpose of this paper is to present a mathematical method for predicting the behavior of reservoirs produced by gas-cap drive, dissolved-gas drive or pressure maintenance by gas injection. The method described herein takes cognizance of phase changes caused by a decline or an increase (due to gas injection) in reservoir pressure, of the presence of a gas cap and of the effect of gravity on the flow of gas and oil. Relative permeability relationships are used to define the flow properties of the rock. Allowance is made for variation in cross-sectional area, elevation, permeability and porosity of the reservoir. Both the influence of capillary pressure upon the flow and pressure gradients in the gas cap are neglected. Whenever a liquid phase and a gas phase are in contact, they are assumed to be in equilibrium. The physical properties of the fluids are considered to be functions of pressure only. Therefore, if the method is to be used to predict the effects of a gas-injection program, mixtures of the injected gas and formation crude should-have the same physical properties as mixtures of formation gas and crude. The equations to be presented in this paper apply only to a one-dimensional case; therefore, they neglect the influence of gravity in the direction transverse to the flow. As is well known, this gravitational influence may lead to overriding of oil by gas. Consequently, this procedure as presented is most applicable to long, thin reservoirs for which gravity overriding is not important. On the other hand, the equations presented can be generalized to treat multidimensional flow and, hence, to consider gravity overriding, if desired. A word of caution on two points is advisable here, however. First, the authors have not demonstrated the accuracy of the numerical technique for multidimensional flow. Second, and more important, capillary pressure will often be of importance in multidimensional problems. Obviously, in such cases a generalization of the

By John S. Johnson

THE purpose of this article is to describe several types of borehole lining in common use, and especially to offer a relatively new means of reducing the expense of maintaining boreholes where they are subjected to corrosive action of water flowing either inside or outside of their casing. In the Anthracite region of Pennsylvania, boreholes are used for many purposes, the principal ones being: openings between the surface and underground workings through which are passed steam, water and compressed-air lines, ropeways from surface hoists to underground rope haulages, conduits for electric power and signal lines, water-discharge lines from underground pumping stations, and inlets to mine workings for flushing material. LININGS FOR BOREHOLES The inadequacy of steel pipe for use in boreholes has long been recognized. Various substitute materials have been tried, including screw-joint cast-iron pipe (Fig. I). Cast-iron pipe, while very effective as a discharge line for acid water (mine water) being pumped to the surface, is not so effective when serving as a conduit for silt and crushed rock being flushed underground for filling mine voids. Terra cotta pipe (Fig. 2) has been used in boreholes, and lasts a long time if the glazed inner surface of the pipe remains intact. Its installation in a borehole is very difficult and is recommended only where it is certain that there will be no subsidence of the surrounding territory. Accessibility in order properly to join each section of the pipe is essential to a satisfactory job. In large water holes, where it is possible to lower a man into the hole for sealing the joints of the pipe, glazed terra cotta pipe has been used successfully for delivering mine water from pumps in the mines. For large holes used for flushing refuse into mine workings where the surface wash is shallow, standard paving brick have been used to form a tube through the wash to the bedrock. These brick are laid radially, backed by common brick and cobbles laid in cement. It is obvious that the shaft through the wash must be large enough to permit a man to work in it. The flushing material is carried through bare rock from the juncture at bedrock to the openings underground. This plan has been used, particularly where a cast-iron surface line is laid upon the surface to carry the flushing material from the breaker to the hole, and down the hole continuously, with no opening to the air at the top of the hole, thereby eliminating the necessity of an attendant at this point (Fig. 3). Another similar type of borehole lining is constructed of hexagonal pieces of vitrified brick (Fig. 4). This type requires a steel drive pipe through the surface wash large enough to provide a finished tube of the desired size surrounded by a brick wall about 4 in. thick. The special bricks are laid in cement, six to a circle, around a lubricated pipe used as a form, and lowered in sections inside the large drive pipe; the bottom section is seated in a socket drilled in the solid rock, having the same inside

Jan 1, 1941