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By W. R. Hamilton

THE knowledge of the existence of petroleum in Southern California dates back to the days of the missions. The presence of asphaltum and semisolid bitumen was reported at Santa Barbara in 1792, but no serious attempt was made to develop oil until Professor Silliman's optimistic report in 1865 started California's first oil boom. Wells were drilled in many counties of the State, but the equipment was unsuitable and the drilling difficult and no production was obtained except in Ventura County. Even there the production was of little importance commercially, and not until the early '80s did it become sufficient to again attract attention. In 1888 the production for the State had reached a total of about 700,000 bbl. per year, practically all light oil produced in Ventura County, Pico Canyon, Los Angeles County and in the Puente Hills. The production of petroleum attained the dignity of an industry in 1895 when the Los Angeles City and Coalinga fields were discovered. The subsequent development has been remarkable, and in 20 years the production has increased from 1,000,000 to 100,000,000 bbl. per year. The refining industry has kept pace with the production of oil. The Pacific Coast Oil Co., the predecessor of the Standard Oil Co. of California, was the virtual pioneer refining company of the State, having built a refinery at Alameda about 1880. When purchased by the Standard, about 1902, it was dismantled and the refinery at Point Richmond was built. The Richmond refinery is now one of the largest in the world, having a capacity in excess of 60,000 bbl. per day. A small refinery was built by the Union Oil Co. at Santa Paula in the early days of the industry and later many asphalt refineries were in operation in Southern California. The Pacific Coast Oil Co. was then, as has been its successor, the Standard Oil Co. of California, the principal refiner and marketer of light products, the most valuable of which was kerosene.

Jan 6, 1916

H ORACE VAUGHN WINCHELL was born at Galesburg, Michigan, Nov. 1, 1865, and died at Los Angeles, California, on July 28th of this year, at the age of fifty-seven. Mr. Winchell was one of the conspicuous geologists of his time. It may fairly be said that he was a geologist born and reared. His father, N. H. Winchell, was professor of geology at the University of Minnesota; his uncle, Alexander Winchell, was professor of geology at the University of Michigan. Under both of them Horace studied, graduat-ing at the University of Michigan in 1889. Mr. Winchell at once began that active life in the field which he followed for 34 years and until his death. The first years of his professional life were largely spent in the study of the iron ranges of Min-nesota. In 1898, he re-moved to Butte and became geologist in charge of the geological depart-ment of the Anaconda Copper Mining Co. and allied companies. There he remained for eight years. This period covered the trying days of the mining controversies be-tween the Anaconda and associated companies and the Heinze interests, and it fell to Mr. Winchell to direct the geological studies and development in connec-tion with that litigation. Recognizing the importance of careful geological study in the practical operation of mines, he organized and developed the splendid geological department of the Anaconda Copper Mining Co. This was one of his greatest contributions to the mining industry. Probably no mining company has attached the impor-tance to geological study and continuity of geological mapping in connection with mining operations that the Anaconda company has. It has given broad authority to its geological department and the development of its mines is under the direction of its geologists. The broad vision of Mr. Winchell was responsible for the adoption of this policy, one which is being profitably employed by many other organizations.

Jan 9, 1923

G. SHERBURNE LAGERS (written discussion*).-Mr. Kennedy's discussion1 of Mr. Matteson's paper takes the form of a criticism of my own comments2 on this paper. Mr. Kennedy is a respected authority on matters pertaining to the salt-dome oil fields, and his characterization of my "elaborate figures" as "worthless" is sufficiently candid and comprehensive to warrant a brief reply. My "voluminous figures" consisted simply of a rough estimate of the minimum quantity of salt in the Humble dome, and a calculation of the volume of sea water and of the volume of saturated brine which this salt would represent. Mr. Kennedy apparently interprets my remarks as opposing the idea that so large a volume of salt could have been deposited from sea water, for lie cites the area and thickness of European salt beds; but nothing was further from my intention. Given an arm of the sea, an arid climate, and evaporation under a hot sun, it is easy to conceive the formation: of almost any thickness of bedded salt. I cited the figures in connection with Harris' theory of the origin of salt domes, according to which the plugs were formed by the deposition of salt from ascending brine solutions, owing to the drop in temperature as they neared the surface. I pointed out the well-known fact that the solubility of salt is only slightly affected by temperature, and that a drop of 80° C. would cause the deposition of less than one-tenth of the salt in solution; hence that more than ten times the volume of salt actually forming the plug must have been involved. If ten times the salt actually in sight be computed in terms of brine and multiplied by 50 or 60 to take into account all of the known salt domes, the resulting figure is so enormous that I am not at all as sure as Mr. Kennedy seems to be that the porous stratified rocks of eastern Texas and western Louisiana could contain or furnish so great a volume of migratory brine.

Jan 8, 1918

By C. E. Meissner

THE need for a practical method of deciding upon new alloy steel analyses to widen its markets was the problem facing the Chrome Steel Works at the beginning of 1927. In addition to determining the physical properties of the alloys under consideration, it was necessary to test their value in service. Small melts of steel in a crucible, from which test specimens could be made, were insufficient to determine more than physical properties, therefore actual castings and ingots had to be made before the products could be placed in service. Furthermore, to save further experimental work, it was desirable that these heats should be made on a "pilot" basis; that is, actually duplicating regular open-hearth furnace practice. Therefore a one-ton (2000-lb.) acid open-hearth furnace was built. FURNACE DESIGN There are no special features in the design of this furnace. Standard acid open-hearth practice is followed, with the reproportioning of the dimensions necessitated by its small size; notably, a considerably increased length in proportion to width in order to get proper flame propagation. After the first heat was made it was found that the checkers were insufficient. The checker chambers were increased in size and the checker openings were made much smaller. The furnace was started late in March, 1927, and made 65 heats. Experimental work was then stopped until the data accumulated could be worked up and summarized. The run was resumed in November and the furnace is still operating, having made at this writing 60 additional heats. For the last series of runs, there was some rebuilding of both the furnace itself and the checkers. Slag pockets were added. Fig. 1 shows details of construction; Fig. 2, the, general appearance. All designing was done by the operating and engineering staff. Construction materials were those available around the plant. The reversing valve is a standard butterfly type taken from an old furnace.

Jan 1, 1928

By Daniel M. MacNeil, Raymond L. Presbrey, Carle R. Hayward

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By C. W. A. Newey

I would like to make the following points in connection with the studies of the deformation of NiAl reported in the recent paper by Wasilewski, Butler, and Hanlon. 1) Much of their paper is concerned with demonstrating that slip occurs on either {110)(001) or {100)(001) systems. In their discussion they state "the existence of (001) as the basic slip direction can thus be considered established." This fact was established by the earlier studies of Ball and Smallman.32 Ball and Smallman also concluded that the slip plane was of the type (110) and they showed that cross slip or pencil glide on orthogonal (110) planes could produce macroscopic slip on planes of the (001) zones, e.g., (100). Wasilewski et al. refer to this paper by Ball and Smallman but not in connection with the slip system determinations. 2) Wasilewski et a!. eliminate the possibility of (111) slip in NiAl on dubious grounds. Their statement that ('the very high yield strengths of the (100) oriented crystals", in which (001) slip is constrained, "immediately ruled out the possibility of {110)(111) slip" cannot be accepted unequivocably; it would be reasonable if the crystals were completely brittle but they are not, as Wasilewski et al. and others33734 have shown. Their elimination of the possibility of (111) slip in a crystal compressed along [227] is misleading since there is no obvious reason why (111) slip should occur in a crystal of this orientation. In fact, from an analysis of the macroscopic surface markings on deformed (100) stoichiometric crystals, Pascoe and Newey34 have deduced that slip occurs on systems of the type {211)(111) and {321)(111). 3) Polycrystalline NiAl is known to undergo general deformati~n.Having emphasized that general deformation is impossible if only (100) slip occurs, it is a pity that Wasilewski et al. do not attempt to account for the disagreement between theory and their experimental results. Of course, (111) slip can provide the additional independent systems required for general deformation.

Jan 1, 1969

By Paul D. Merica

One of the most useful, and at the same time least commonly used, methods of thermal analysis for the determination of transformations in metals and alloys consists in the recording of the time intervals required for successive increments of temperature change during heating or cooling, the temperature of the furnace containing the specimen being altered at a uniform rate. The curve obtained by plotting these time intervals as a function of the mean temperature of the specimen durnig the interval is called the inverse-rate curve. It is probably due to the fact that no simple and convenient method has apparently been available for the measurement of the successive time intervals that this method has not been so generally used as, for example, the differential method, for which several types of automatic or semi-automatic apparatus have been designed. Whenever this method has been used, the intervals have usually been measured with the use of a chronograph; its operation as practised at the Bureau of Standards1 is as follows: The temperature of the specimen is measured by a thermocouple and a dial potentiometer. The operator sets the potentiometer at successive values of the electromotive force differing by equal increments, usually 0.02 millivolt, and records the exact instant on the chronograph, by pressing a contact key, at which the galvanometer coil passes through its null position. Two-second intervals are also recorded on the chronograph record, and the number of seconds elapsing between successive signals is afterward counted from the record and plotted as a function of the electromotive force or of the temperature. This is an admirable method and by it most minute thermal arrests may be detected, but it requires a good chronograph, which is generally difficult to obtain, and the time of one operator during the recording and, subsequently, to read the intervals from the record; the latter operation often takes from one to two hours. There is here suggested a simple, convenient, and, it is believed, equally accurate method of recording the successive time intervals, by which the

Jan 1, 1921

By G. W. Healy

G. W. Healy (union Carbide Metals 0.)-The author's paper is a useful contribution to the store of maps of chemical activities of oxides in multi-component slag systems. It is also a good example of the utility of the Gibbs-Schuhmann technique for calculating activities in a system where that of one of the components has been measured. This paper Koh and Caugherty. This plot is reproduced by alor in X-ray Metallography. Because of this nonlinearity, preparation cf suitable standards and/or correction for absorption and enhancement are essential in microanalysis. However, our objection is not the conclusion that Dr. Aaronson has arrived at nor the technique he has used; but only to the foot-note credited to V. Macres. The level of chromium that he was concerned with (less than 3 pet) is so low that the deviation of uncorrected Cr-curve will be negligible. Besides Dr. Aaronson has used chromium intensity from martensite and set it equal the bulk chromium content of the alloy. Using this chromium-intensity as a reference, he has calculated the amount of chromium in the ferrite. This amounts to the same as using an internal standard. Since the chromium content in austenite and ferrite are almost the same, enhancement due to iron in both will be the same and therefore does not need to be corrected. together with the author's recently published one1 on the CaO-FeO-Fe2O3 system will be most helpful to others learning to apply Schuhmann's method, which merits a far wider application than it has received to date and should greatly aid our understanding of equilibria between metal and oxide phases. As shown by okcen" its use may even be extended to sections of systems with any number of oxides. I have some questions as to the selection of equilibrium constants made by Dr. Turkdogan. He has chosen one for the formation of Fez03 from FeO and oxygen which gives Fea3 activities 50 pct higher

Jan 1, 1963

By Alan Morris

THE investigation of the hot-working properties of metals and alloys furnishes a problem which has been attacked in many ways. Tensile, impact and hardness tests on heated specimens have furnished interesting data, but in most cases either the tests are difficult to make or the results hard to translate into terms of practical value. Some investigators have used the drop hammer to advantage. It furnishes a rapid and simple method of comparing the plasticity of metals at elevated temperatures. The indications obtained by its use are of value only in so far as their significance is understood and they can be intelligently used to predict the behavior of a given metal under given hot-working conditions. The work reported here was undertaken not only to add-something to the existing volume of such data but also to contribute to our understanding of the results. Doerinckel and Trockels1 used cylindrical specimens and determined the work required to reduce the specimen to one-half the original height. Ellis2 studied the effect of constitution on the malleability of steel at high temperature. His method and that of Kent3 were similar to the one used in the present work. The tests described by Kent were made on samples of tin, zinc, aluminum, copper, lead, 70:30 and 60:40 brasses, with and without a small quantity of lead. He concluded that the test would "indicate whether a material can be forged at a given temperature without cracking." This interpretation must be used with caution. While it is probably true within limits, one must consider the severity of the forging operation. Again, it will not apply strictly to forms of hot working other than forging. For instance, an alloy running 61.0 per cent. copper, 3.25 per cent. lead, remainder zinc, will crack badly in the test, yet it is extruded commercially. When the possibility of hot-working a new alloy is being considered a study of its drop-hammer test should help

Jan 1, 1931

By R. H. Goodrich

Development in this district during the year 1929 was little different from that of any other year despite the somewhat depressed condition of the oil business in general. The year was marked by: (1) An intensive geophysical campaign in the search of deep-seated salt domes; (2) the rather successful exploration and development of lateral sand production on the flanks of some of the older domes. Geophysical Exploration Geophysical work is confined almost exclusively to the torsion balance and seismograph. At the beginning of the year there were approximately 185 individual instruments of all types engaged in the search of structures in the Gulf Coast of Texas and Louisiana. This total includes 3 magnetometers, 83 torsion balances and 100 seismographs. The number of parties operating the torsion balances was 47; seismographs, 20; magnetometers, 3. It is estimated that 4,800,000 lb. of dynamite or other explosives were used in seismic exploration. During the year the torsion balance and seismograph were credited with having discovered the following salt domes: Texas, Danbury dome, Brazoria County, H. & T. B. R. Co., and Clodine dome, Fort Bend County, John Fredricks and Wm. Stanley, Satowsky Survey; Louisiana, Iowa dome, Calcasieu and Jefferson Davis Parishes, T. 9 S., R. 6 and 7 W., and Cameron-Meadow dome, Cameron Parish, T. 14 S., R. 13 W. Because of the secrecy maintained in these developments, it is somewhat hazardous to venture opinion as to the number of salt domes found during one year. The discovery of gas at Mykawa district and at Genoa district, in Harris County, Texas, is considered of more than passing importance, because there is indication in the performance of these two districts that commercial accumulation of oil and gas may be found in the Gulf Coast on structures other than the wore or less definite salt dome type. While it is generally conceded that the accompanying structure in these instances are deeply buried salt domes, it is a fact that neither the seismograph nor the drill have indicated the presence of salt.

Jan 1, 1930

By Robert Franke

(Butte Meeting, August, 1913.) IN view of the prominence which the conical mill has attained in the fine-crushing field .within the few years since its introduction, the following comparison with its more mature forerunner, the Chilean mill, based on extensive tests, is submitted in the interest of the milling profession. Soon after designing the concentrating plant of the Miami Copper Co. in 1909, the Hardinge conical mill made its appearance in the milling forum. . Its possibility as a suitable crushing device for the plant was well recognized, but in view of the lack of commercial demonstration, at the time, as to capacity, efficiency for desired product, and the still more uncertain factors of cost of maintenance and power consumption, it was deemed that the immediate adoption of this machine throughout the plant would be a hazardous undertaking. For these reasons it was decided to equip the majority of the immediately required units of the plant with Chilean mills, the fine-crushing proficiencies of which were better known, and one section with Hardinge mills, to serve as a test unit for the guidance of future installations and replacements. Thereby, after 1.5 years' operation with both types of mills, a thorough test as to metallurgical efficiency and cost economy has been obtained. The conical mill used in these tests is the 8-ft. Hardinge pebble mill, having a cylinder 22 in. in length. The cylindrical portion of this mill is lined with cast-iron liner plates, and the conical extensions with silex bricks bound together by cement. Each. liner plate carries a projecting lifter, the function of which is to increase the height of drop of the lifted material. Danish No. 5 pebbles, obtained from the coast deposits of Denmark, are used for the grinding charge. The Chilean mill used is a fast-running, 3-roller, 6-ft. Saturn mill, with screens of 0.037-in. opening. The feed to these mills is the oversize of Callow screens having 0.029-in. openings, which. follow rolls crushing to 0.5 in.

Jan 7, 1913

By Robert Mehl

RELATIVELY few data have been collected on the rates of diffusion in ternary solid solution systems. In general it does not seem worth while to gather extensive data for such systems until the factors that determine the rates of diffusion in binary systems are better understood. But the rates of diffusion in a ternary system of limited solid solubility, in which the terminal solid solution is in equilibrium with an intermediate phase and may thus be represented as a quasibinary system, represents a case of special interest. In this case, where by reason of the association of the two solute metals in an intermediate phase a special attraction of the two solute atoms may be safely assumed, some interaction of these atoms during simultaneous diffusion in the solvent lattice might be expected. It has frequently been proposed that molecular solid solutions exist in quasibinary and in other ternary (and binary) solid solutions. There is no direct evidence for such solid solutions; arguments based upon the supposed anomaly in certain physical properties1 are hardly important; unexpected density relationships have proved deceptive ;2 suggestions of molecular solid solutions have been made on the basis of solution laws in their application to certain systems, but without result;3 attempts to find lattice parameters in the solid solution Al-MgZn2, which cannot be calculated from the separate effects of magnesium and zinc and might therefore be taken as evidence for a molecular aggregation, have given negative results.4 Fundamentally, methods for the determination of the state of molecu¬lar aggregation in solution depend upon the kinetic behavior of the par-ticles constituting the system. If it could be shown that the two solutes in a quasibinary ternary system diffuse in molecular proportions, despite a radical difference in the separate rates of diffusion of each solute when diffusing alone in the solvent lattice, some basis for the concept of molecu-lar solid solution would be afforded. Freche5 examined the rates of independent and simultaneous diffusion of magnesium and silicon in

Jan 1, 1939

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

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

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By C. M. Loeb, A. M. Gaudin, J. H. Brown

THE object of most size reduction operations in the mineral industry is to liberate the grains of valuable minerals in the ore from those of the gangue. This is usually accomplished by crushing and grinding the entire mass of ore until there is only a small probability that any single particle contains more than one mineral. During this size reduction only limited control exists over size or composition of the particles exposed to the breaking action, and there is no control over the paths followed by cracks generated during the operation. This lack of control usually results in overgrinding and in production of large quantities of very fine material. The first detriment, overgrinding, is costly in itself, but when combined with the second factor it is doubly so. Not only is the fracture of a free particle unnecessary—the fracture of these particles may also make subsequent separation operations difficult, inefficient, and wasteful. It has been pointed out' that if the object of size reduction is to liberate the valuable mineral component of the ore then, ideally, fracture should follow intergranular paths to the exclusion of trans-granular ones. This would result in liberation of the valuable minerals with as little size reduction as possible. This ideal comminution operation is referred to as intergranular comminution, and it was the object of the investigation to determine the extent to which it could be developed by heat treatments. There are many indications in the literature that heating rocks prior to crushing may be favorable. Reports by Holman,2 Yates3 and Myers' are pertinent. These investigators showed that heating certain rocks prior to crushing them did, in fact, improve their crushing characteristics in that fewer fines were produced, although the fact that intergranular comminution was being effected apparently was overlooked. In addition, Sosman noted that if there is appreciable anisotropism in the thermal coefficients of expansion of even a pure mineral, then considerable permanent separation of the grains of the rock can be expected as a result of heating the rock to a high temperature.' By the same token, if there are ap- preciable differences in the thermal expansion coefficients of the various minerals of a multi-component rock, similar results should be obtained by heating this rock. This has been tested, partially, by Brenner," who obtained patents covering the heat treatment of some pegmatitic rocks in order to facilitate comminution of these materials. It has also been demonstrated that this may occur in taconite." Also, the possibility of causing decomposition of one mineral in a rock as a means of promoting intergranular fracture has been considered. Seigle2 and Schiffman et al. have obtained patents on such processes as applied to calcareous iron ores. These reports all indicate that heat treatments prior to crushing may contribute materially to intergranular comminution, but they also indicate that no organized attempt has been made to determine the controlling factors of the method or to determine its applicability in general. The present article is a report on the initial phase of such an investigation. The authors have reviewed the claims of prior investigators and have attempted, also, to establish the factors that might determine the applicability of heat treatments in the mineral industry. In this work 2000-g samples of various rocks were heated in a small laboratory furnace and crushing and sizing operations were carried out in standard laboratory equipment. All samples of each rock were as nearly identical as possible in particle size, grain size, and composition and contained only lumps coarse enough to contain many grains each. Tests on Granite A number of tests were made on a coarse grained Finnish granite obtained in the form of coarse chips from a local monument yard. This rock exhibited little variation from piece to piece in either composition or grain size. The minerals contained were quartz, orthoclase, small amounts of hornblende, and minute quantities of mica. Grain size ranged from about 1 mm to about 3 mm. Temperature of the Heat Treatment: In some cases the granite was heated to a particular temperature and crushed, hot, immediately upon withdrawal from the furnace—in others the rock was allowed to cool before crushing, but without quenching to room temperature after heating. In most tests on granite the heating period was about 2 hr with the furnace at the highest temperature for about 1 hr. Cases in which these periods were varied greatly will be presented separately.

Jan 1, 1959

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By R. H. Jacoby, V. J. Berry

When dry gas is injected into a reservoir containing a volatile crude oil, a significant amount of the reservoir liquid phase may become vaporized. The resultant rich gas phase, when subsequently produced, con-tributes to tank oil production. This contribution assumes greater importance, the more volatile the oil in-olved. Oil recovery may be sub-stantially greater than that predicted by conventional frontal-drive methods, which do not consider the vaporization equilibrium between the reservoir oil phase and the injected gas. A calculation method has been (developed to account for vaporiza-. tion of the reservoir liquid phase during gas-injectiorz operations, and for the tank oil production which results from this factor. Recovery performance calculations are presented for a reservoir containing a highly volatile oil. Tank oil recovery is calculated to be about twice that predicted by the use of the conven-rional frontal-drive equations. In contrastto usual pressure maintenance performance results, in which the gas-oil ratio rises at an increasing rate after gas breakthrough, the pre-dicated gas-oil ratio rises rapidly to about 12,000 scf/bhl and then rises much less rapidly. During gas inje-tion, most of the reservoir liquid phase contacted is evaporated by the dry injection gar. The gas-oil ratio during this period is dependent upon reservoir pressure. The higher the operating pressure, the lower the gas-oil ratio. The predicted behavior i., in accordance with laboratory PVT tests made to .simulate the vaporization behavior. In addition to recovery performance predictions, results of the calculation procedure include complete wellstrearn composition data of value in the design of gasoline plant facilities often used in con-rrction with gas-injection operations. INTRODUCTION In the cycling of gas-condensate reservoirs, dry gas is injected to maintain reservoir pressure during wet gas production and to thereby eliminate or reduce ultimate loss of liquids due to retrograde condensation within the reservoir. Gas injected into crude oil reservoirs has a dual function. It displaces oil to the producing wells and at the same time serves to partially or fully maintain reservoir pressure. Oil shrinkage which would occur upon pressure reduction is thereby minimized or eliminated. Accepted calculation methods are available'= for predicting recovery performance of either gas-condensate reservoirs or crude oil reservoirs which are being subjected to gas injection. In gas-condensate reservoirs, any retrograde liquid formed does not flow, and it is necessary to account only for the vaporization equilibrium between this liquid and the injected gas. Conversely, in normal crude oil reservoirs, both the oil and gas phases flow, but it has not been considered necessary to account for any vaporization of the reservoir liquid which might occur upon contact with the dry injection gas. Recently, high shrinkage reservoir fluids known as "volatile oils" have been found in increasing amounts. These oils are characterized by tank oil gravities above 4.5" API, solution gas-oil ratios above 1,000 scf/bbl, and reservoir volume factors above two. Special techniques have been devised for predicting depletion performance of reservoirs containing such oils.74.5.1; One of the characteristics of reservoirs producing volatile oils is that the reservoir gas phase carries a significant amount of oil which is recoverable as stock-tank liquid. This unusual vaporization be-havior implies that an appreciable amount of reservoir liquid would be vaporized upon contact of the oil with dry injection gas. In a gas-injection operation, tank oil recovery would he obtained not only through frontal displacement of the reservoir liquid by the injected gas, but also through production of the rich gas phase. This means that not only are improved methods needed to predict recovery of such oils from reservoirs undergoing gas injection, but it would also be expected that high oil recoveries might be obtained by such operations. When relatively dry gas is injected in to a volatile oil reservoir, phase equilibrium between the injected gas and the reservoir oil will tend to bc established. Initially the most volatile components, such as propane, the butanes and the pentanes, will account for most of the material transferred from the oil phase to the gas phase. As the partially stripped oil phase is contacted with additional dry injection gas, the heavier intermediate components, such as the hexanes, the heptanes and the octanes, will gradually transfer to the gas phase in increasing amounts. This is because the supply of lighter components in the oil phase dwindles due to the stripping action of the injected gas. This stripping action will usually continue to be effective down

By W. J. Slatosky

As a means of effecting better control of endpoint temperatirres at the Jones & Laughlin basic oxygen furnace plant, a set of mathematical equations has been developed. The eqlutions are the product of a themlochemical anaysis of the process and aye designed to calculate the required scrap, lime, and hot metal additions in terms of a number of independent variables. Results of test heats have warranted adoption of this technique by the Prodrrction Department. BECAUSE of the autogeneous nature of the basic oxygen steel-making process, bath temperature can be controlled without an external fuel supply by charging the furnace with additions that are thermally balanced. The thermal requirements of the charge materials are such that, during the refining process, they throttle the heat generated by the metallurgical reactions in a manner designed to result in a speci-fied temperature at the completion of the heat. In the past, operating personnel at the basic oxygen furnace plant of Jones & Laughlin's Aliquippa Works relied on their experience and technical knowledge of the process to determine the quantities of charge additions needed to result in a finishing temperature in the range 2880"to 2920" F. (The charge consists primarily of 93 tons of scrap and hot metal plus an amount of lime sufficient to maintain a basicity ratio of 2.8 to 3.2). Estimates of these materials are based on a consideration of the effects on finishing temperature of 1) iron silicon content, having a variation of 0.8 to 1.8 pct; 2) iron temperature, ranging from 2250°to 2600°F; and 3)any excessive cooling of the furnace due to a production delay. The end temperature of the preceding heat also serves as a guide in that, if a heat was within the specified temperature range, the succeeding heat could be charged with materials of nearly the same proportions, provided the hot metal used in each of the two charges was of approximately the same temperature and composition. On the other hand, if a heat was outside the specified tapping range, or if the hot metal used in that heat was of different analysis and temperature from that of the iron to be charged, an adjustment in the proportion of additions is in order for the following heat. Due to the complex thermochemical behavior of the process and to the inexact and subjective nature of the described method of determining charge additions, consistently accurate temperature control was not to be expected. Therefore, those heats out- side the specified tapping range necessitated subsequent adjustments by either reblowing the cold heats for a suitable length of time so as to elevate the bath temperature to the desired level, or cooling hot heats with a proper amount of scrap. Because extra time is required to make these adjustments, production is delayed. In an attempt to devise a method for improving temperature control, an analysis of the thermochemistry of the process was undertaken. This, in turn, led to the development of a set of mathematical equations which enable the calculation of the quantities of scrap, lime, and hot metal needed to result in any specified tapping temperature range. The analysis was not intended to be a repetition of work done by others such as McMulkinl or ~hilbrook.' It was meant to be an extension of their work so that charge additions could be calculated not in terms of silicon alone but, rather, as a function of all independent variables. This paper presents the derivation of these relationships, their effectiveness in controlling bath temperatures, and a method of utilizing them on an operational basis. The Heat Balance—The first step undertaken in the analysis of the problem was the enumeration of the pertinent variables. A list is presented in Table I where it is noticed that these quantities have been separated into the following three categories: important variables, variables considered as constants, and variables to be neglected. The breakdown was an arbitrary one designed to facilitate the analysis; otherwise, the mathematical treatment would have been exceedingly cumbersome and complex. Fortunately, experience has shown that these simplifying assumptions do not seriously impair the accuracy of the calculations. These variables along with the limiting assumptions listed in Table n were then used to write a heat balance of the process by applying the equation of continuity, Rate of Rate of Rate of Increase = Income - Outgo PI ] of Heat of Heat of Heat.

Jan 1, 1962

By R. J. S. Brown, B. W. Ganison

A new logging method has been developed, based on measurement of the nuclear magnetism of formation fluids. The nuclear magnetism log (NML) is the only log that responds solely to formation fluids. It operates equally well in both oil-base and water-base muds and in empty holes, and can be used in all kinds of formations except strongly magnetic ones. Two separate NML measurements can be made, one of which provides a continuous formation fluid curve. This fluid curve is called the free fluid log (FFL) and is believed to indicate a minimum effective porosity in most formations. The FFL not only delineates fluid-containing zones, but provides an excellent correlation curve that can be obtained under conditions where conventional correlation logs are ineffective. Preliminary tests indicate that the second kind of NML measurement may help distinguish oil and water zones and provide information concerning permeability and wettability. (The FFL itself appears to provide some information on permeability.) The second kind of NML measurement requires stopping the logging tool for a short time opposite a zone of interest and taking more extensive NML data that can be displayed as nuclear magnetic relaxation curves. In some instances, oil and water saturations for the region immediately adjacent to the borehole can be read from these relaxation curves. INTRODUCTION In 1946, Bloch, Hansen and Packard and Purcell, Torrey and Pound3 independently announced the successful demonstration of the phenomenon of nuclear magnetic resonance. During the past 13 years, there have been many applications of nuclear magnetic resonance, including applications to the study of chemical structure and to the measurement of magnetic field strengths. Preliminary experiments on the feasibility of using nuclear magnetism measurements in well logging were made independently by California Research Corp. and Varian Assoc., the Varian work being sponsored by the Byron Jackson Tools, Inc. Since then a cooperative research program on nuclear magnetism logging has been carried out by the Byron Jackson Div. and Research Center of Borg-Warner Corp., and California Research Corp., subsidiary of Standard Oil Co. of California. The use of nuclear magnetism in well logging is of special interest because it offers a way of making direct measurements on the hydrogen in the formation fluids and not on the rock matrix. Within the past 1 1/2 years, successful measurements have been made with a research model logging tool in wells in California, Tex as, Utah, Louisiana and Wyoming. NUCLEAR MAGNETISM SIGNALS Polarization, Relaxation and Precession Many atomic nuclei possess magnetic moments and spins; that is, they are similar in some respects to bar-magnet and gyroscope combinations. Molecules and their nuclei are subject to thermal motion, which has a scrambling effect, tending to leave as many nuclear spins oriented in any one direction as in any other. However, if a magnetic field is applied, the magnetic nuclei tend to align in the direction of the field. The scrambling and aligning forces compete with each other, with the result that a few more spins are oriented parallel to the field than in other directions. This gives a net magnetization, or polarization, which is directly proportional to the strength of the applied magnetic field (aligning influence) and inversely proportional to the absolute temperature (scrambling influence). When the magnetic field in, or temperature of, a liquid sample containing protons is changed, the new equilibrium value of proton polarization is not established immediately but requires an amount of time which depends on the nature of the hydrogen-containing materials. The process of approaching the equilibrium value of polarization is called relaxation.'.' Polarization is a vector quantity, and the components parallel to and perpendicular to the magnetic field must be considered separately. Relaxation of the component parallel to the field is called "thermal relaxation", or "longitudinal relaxation", and the corresponding time for this component of non-equilibrium polarization to decay by a factor of e (natural log base) is denoted T. The relaxation of the perpendicular component is called "transverse relaxation", and the corresponding relaxation time is denoted T,. The potential energy of a magnet in a uniform field depends on the angle the magnet makes with the field; therefore, a change of the component of net polarization parallel to the magnetic field involves an exchange of energy between the spin system and the thermal motion of the molecules, leading to the term thermal relaxation for the relaxation of this component. Suppose we subject a sample to a strong magnetic field at right angles to the earth's field for a time greater than TI. A polarization, thus, is established at right an-