Search Documents

The One Hundred Eighteenth Meeting of the. Institute was held at the Milwaukee Auditorium, on Tuesday,. Oct. 8, to Thursday, Oct. 10, inclusive, 1918, under the joint auspices of the Committee on Iron and Steel (Chairman, Prof. J. W. Richards), and the Institute of Metals Division (Chairman, William M. Corse), and simultaneously with sessions of the American Foundrymen's Association and of the. American Malleable Castings Association. It was preeminently a war meeting. It was attended by 104 members of the Institute. The social features, so far as the members of this Institute were concerned, were slight, but generous and appropriate entertainment was offered to the ladies, consisting of automobile sight-seeing trips, reception, concert and dance on Tuesday evening, a theatre party Wednesday evening, and -a banquet in-the Auditorium Thursday evening, at which the speakers were Charles M. Schwab, Director General of the United States Shipping Board Emergency Fleet Corporation, Major A. Radclyffe Dugmore, and W. H. Blood, Jr., Assistant to the President of the American International Shipbuilding Corporation. A joint session was held on Tuesday morning, at which an address of welcome was delivered by Hon. Emanuel L. Phillipp, Governor of Wisconsin, with a response by Benjamin D. Fuller, President of the American Foundrymen's Association, and the following addresses: Activities of the Army Ordnance Department, Especially as Applied to Foundry Matters. By C. S. Koch, Cannon Section, Production Division, Ordnance Department. Washington. D. C.

Jan 11, 1918

By H. H. Vogel

THIS paper describes the milling practice and operating results of the recently installed heavy-media separation plant of Barton Mines Corporation, the world's largest producer of garnet. This pioneer application of heavy-media separation (sink-float) processes for the beneficiation of a nonmetallic ore is unique in many respects, the details of which will be apparent from the following presentation. CHARACTERISTICS OF THE ORE The property is on Gore Mountain, 5 miles west of the village of North Creek, New York, and 11 miles by road. The altitude of the mine is approximately 2800 feet. The valuable mineral, garnet, occurs in a surface deposit, the ore body being about ¾ mile long and varying in width from 50 to 300 ft. The garnet, principally almandite, Fe3A12 (Si04)3, occurs in a metamorphic rock of uncertain origin. The gangue mineral is principally hornblende, which constitutes from 40 to 80 per cent of the rock. The remainder of the gangue is divided between plagioclase feldspars and hypersthene, with smaller amounts of biotite, apatite and pyrite. The garnet content of the ore body varies from 5 to 20 per cent of the mass and averages about 10 to 12 per cent. The garnet occurs as crystals, mostly imperfectly developed, known locally as "pockets." These crystals vary in size from a fraction of an inch to a foot or more in diameter. Occasionally crystals have been found up to 30 and 36 in. in diameter but they average 4 to 6 inches. Nearly every crystal of garnet is surrounded by a rim of coarsely crystalline hornblende. The quarry faces are striking in appearance, showing crimson-red garnet crystals with their coal black rims scattered over a grayish black background. The specific gravity of the garnet is 3.8 to 4.1 while that of the hornblende ordinarily is 3.07 to 3.24. Some specimens of very dense hornblende have been found with a specific gravity as high as 3.40. The garnet crystals are laminated in structure, and readily cleave into flat, tabular pieces with sharp, chisel-like edges. Even when crushed to a very fine size, the garnet retains this flat, sharp, slivery grain shape. This characteristic, together with its hardness and toughness, gives it its value as an abrasive. FORMER OPERATIONS Mining operations have been carried on for 60 years. Until 1023, only the oxidized (soft rock) section of the ore body was mined. The oxidation, which affected the garnet only slightly, made possible the removal of the garnet from the rock by hand after it was blasted down, using small hand picks. In 1923 a mill was erected on the property, and was rebuilt and redesigned in 1928. Before the adoption of heavy-media separation, concentration was effected by

Jan 1, 1943

By W. T. Bishop

FOR many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. HISTORY The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and coat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree-rosin and turpentine-but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country's rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is, supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores" industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.1 In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1946

[ ]

Jan 1, 1938

By A. U. Seybolt

The solubility of oxygen in a iron has been determined in the range between 700° and 900°C. The solubility is a function of temperature and varies from about 0.008 pct oxygen at 700°C to atureandabout 0.03 pct at 900°C. The heat of solution is approximately +15,500 cal per mol. AS pointed out in a recent paper by Kitchener et al.,1 there has been a lack of agreement among many investigators even as to the order of magnitude of the solid solubility of oxygen in the various forms of iron. This lack of agreement is attributable in large part to the difficulties in the determination of a small oxygen solubility; but because the problem has remained so long unsettled, it also indicates a lack of interest which is rather surprising when the demonstrated importance of small amounts of soluble nonmetallic impurities in iron is considered. The work of Kitchener et al. apparently leaves the solubility of oxygen in iron in a satisfactory state, but no attempt was made to investigate the solubility in a iron. The solubility of oxygen in a iron is actually of greater interest, since it is in this form that iron and mild steels are employed ordinarily. That the effect of oxygen in iron is of more than theoretical interest has been well established by Fast,' and more recently by Rees and Hopkins," who demonstrated that oxygen in the range between 0.0008 and 0.27 wt pct has a pronounced effect upon the mechanical properties. Previous Work and Methods Used To report in detail the literature relating to the solubility of oxygen in a iron would require an inordinate amount of space. For those interested in reviewing this work, a bibliography4-13 of the more significant papers is appended. In general, two methods of studying this problem have been used. One is the gas-metal equilibrium method where the H2O-H2-Fe or the CO2-CO-Fe equilibria have been used. The other is the more direct approach of the oxidation of thin strips of pure iron by packing in mill scale or by air or gaseous oxygen at some desired temperature. In this method oxygen is allowed to oxidize the surface and then to diffuse inward until saturation is obtained. In the gas-metal equilibrium method the oxygen dissolved in solid iron at a given temperature is proportional to the ratio of the water vapor-hydrogen pressures or the CO2-CO pressures over the sample for small ratio values. If the ratio becomes higher than a critical value, then an oxide phase makes its appearance (the solution becomes supersaturated). In principle, it is possible to use a series of H2O/H2 or CO2/CO ratios and to find by analysis the corresponding amounts of oxygen in solid solution at constant temperature. At the point where a very small increase in the gas ratio (increase in oxidizing powder) produces a large increase in oxygen content, the solid solubility limit is reached. Alternately, if the critical ratio is known, it is possible to use the procedure of Kitchener et al.1 and to use a ratio which is near but below the critical one. The solubility corresponding to this lower ratio will not be the saturation solubility at the temperature employed, but the saturation solubility can be calculated by multiplying the measured solubility by the critical ratio over the ratio used. However, in the case where oxygen gas is the oxidizing medium, the saturation solubility is not a function of pressure, providing the pressure exceeds the dissociation pressure of FeO in equilibrium with iron. This is 1.2x10-16 mm at 800 °C, according to Dushman." As pointed out by Darken17 in discussing the FeO phase diagram, most of the possible errors tend to yield high values of oxygen solubility. For example, one circumstance which evidently caused the reporting of many high values was the use of finely divided or powdered iron in the gas equilibrium method. Because of the large surface area of such a sample, and the likelihood of some surface contamination if only by exposure to air, the results tended to be high. The direct oxidation method which was used in this work has the advantage in that it is simple and direct, but it suffers from one disadvantage: equilibrium can only be approached from the low oxygen side. The important factors to be kept under control are the following: 1—use of high purity iron to avoid internal oxidation (oxidation of readily

Jan 1, 1955

By Maxwell Adams

OLIVER C. RALSTON, Salt Lake City, Utah.-We are indebted to these two gentlemen for the work which they have done with the oils derived from sage brush. Their work should not be confused, however, as the work of Mr. Adams deals with steam-distilled oils and that of Mr. Clevenger with destructively distilled oil, largely. In other words, Mr. Adams' oil is probably the original essential oil that existed' in the brush before distillation while Mr. Clevenger's oil not only contained this essential oil but also some products of destructive distillation of the wood constituents. I had noticed the work of Mr. Adams on attempting to separate the various constituents in the oils of some of the Western conifers and had sent to him to ask if he could send me small samples of some of. these pure products. This he very kindly did, and with them included some samples of oil from the common sage brush, whose characteristics he has here described, as well as a sample of oil from the common "rabbit brush." Only the sage brush oil proved of much value for flotation, but it, was very powerful, and I so informed Mr. Adams. Even in amounts as small or smaller than 1/10 lb. per ton of ore, it gave very quick and positive flotation of many ores, with high-grade concentrates and good extractions. It proved to be especially desirable for the flotation of carbonates of lead and of copper which had received an artificial coating of sulphide by treatment with a solution of a soluble sulphide. I also received a sample of crude pyroligneous acid from sage brush prepared by Dr. W. C. Ebaugh, of Salt Lake City. It did not do very good work in flotation, but it is possible that by concentration of this product to obtain the residual tar a good flotation oil might result. This has not been done as yet and I am sorry to see that Mr. Clevenger has not done this. It might be that the dissolved tar, added to the settled tar, would make a total yield of flotation oil higher than the 4 per cent. which Mr. Clevenger feels is a safe estimate. The importance of this point will be seen in the following discussion of the possible costs of sage brush oils for flotation.

Jan 10, 1916

By R. R. Webster, H. T. Clark

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951

By J. Winlock

To have been chosen by you to give the Howe Memorial Lecture is the greatest honor I have ever had and I should like to have you know that I appreciate it deeply. Many years ago I had the privilege and the pleasure of working with Professor Howe in the private laboratory which he had established in his home at Bedford Hills, New York. Without doubt he was one of the world's greatest metallurgists and so you can imagine what a difficult task it has been for me to live up to his teachings. Every morning Professor Howe would outline the work he wanted done and the recollections of those conferences are clear to me to this day. Sometimes he would ask me to ride in his automobile and the chauffeur had full instructions to go no more than fifteen miles an hour. If he did so, Professor Howe was sure to rap upon the man's shoulder with his cane. I assure you, however, Professor Howe's thinking was not at that rate. His homely advice, his patience and his perfect control of the English language still impress me. Many times I heard him dictate a complicated paper on metallurgy and never find it necessary to change a single word. There are no better words to describe the character of Professor Howe, in my opinion, than those used by Professor Sauveur when he presented the John Fritz Medal to him in 1917: "Lover of justice and humanity Public servant and public benefactor, Master of the English Language, Loyal and devoted friend, Untiring and unselfish worker in an important field of science." I hope you will bear with me with the same patience and understanding which he used to give to me. The peculiar behavior of steel at the yield point has long been known and has been the subject of much research, both in this country and abroad.',' Many theories, including some of mine and my colleagues, have been suggested, but none of them, in our opinion, fully explains to our satisfaction why the phenomena occur. Of particular importance has been the work of Nadai,3 Siebel and Pomp,' Sachs and Fiek,5 Rawdon,0 Kenyon and Burns,' Gensamer," Gensamer and Meh1,0 Davenport and Bain,'" Fell," Deutler,12 Brinkman,13 MacGregor,14 Hollomon,15 Cot-trell,16 and Palm." The question of what is occurring during this singular behavior is not only of interest from an academic point of view, but is of great practical importance for at least two reasons: 1—The highly localized plastic flow which occurs during the deep drawing of light-gage steel gives rise to surface markings which seriously mar its appearance, Fig. 1. If the forces causing the deformation are primarily tensile forces, these surface markings occur as depressions in the surface. Whereas, if the forces causing the deformation are primarily compressive, irregular lines of elevations occur. These surface markings are known as Luder's lines, Hartmann lines, the Piobert affect, and, in the shop, as "stretcher strains." 2—The steel is in the most suitable condition for deep drawing after the yield point phenomena have been removed. When this is done, the steel may be deep drawn more easily and to a greater extent.' It should be mentioned that steel is not the only metal which shows this peculiar behavior at the yield point. Stretcher strains occur, also, during the deformation of some copper-nickel-zinc alloys." The purpose of this paper is not an attempt to describe what causes the steel to behave in this peculiar manner, but an attempt: l—to describe what is taking place at the yield point; and 2—to show the influence of the rate of deformation on the tensile properties of some plain carbon steels. As is well-known, there are two methods of deforming a metal in tension: 1—by actually hanging an increasing amount of dead weight on the metal; or 2—by deforming the metal at some given rate or rates by means of oil pressure cylinders, screws, etc. With the first method, the load is always present and, clearly, no drop in load can ever occur while the steel is deforming. With the second method, the registered load is the resistance of the steel to the deformation being imposed upon it. The second method is the one most widely used, and is the one referred to throughout this paper. In order to describe clearly what is occurring at the yield point in steel, it will help, I believe, if a description is first given of what occurs when alumi-

Jan 1, 1954

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones' studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.' Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:'-' the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis' developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By T. Cantwell, N. C. Rasmussen, H. E. Hawkes

Beryl is a mineral that may be difficult to distinguish from quartz by casual field inspection. The easily recognized green color and hexagonal crystal form of coarse-grained beryl are by no means universal, even in beryl from pegmatitic deposits. If it occurred as a fine-grained accessory mineral in an igneous rock, it would almost certainly escape detection unless samples were submitted for petrographic or chemical analysis. There may be substantial deposits of some beryllium mineral, other than beryl, that has been overlooked because that mineral also closely resembles the common rock-forming minerals. A reliable and simple method of identifying beryllium minerals and determining the beryllium content of a rock would be helpful in exploration. This article describes preliminary experiments in applying nuclear reaction to the qualitative identification of beryl and to the semiquantitative determination of the beryllium content of rock samples. Gaudin,1,2 the first to apply a nuclear reaction in detecting beryllium minerals, developed a method that irradiates the sample with gamma rays, which react with beryllium nuclei to produce neutrons. The neutrons are then measured with standard equipment. The cross section for this reaction is about 1 millibarn. The cross section is a measure of the probability that a reaction will take place, for example, between a beryllium nucleus and an incident gamma ray or alpha particles.3-5 At 1-millibarn cross section for the reaction, satisfactory performance required a source strength of the order of 1 curie (3.7 x 10"' disintegrations per sec, where each disintegration releases one or more gamma rays). The reactions will not take place if the gamma radiation is below a minimum energy, in this case 1.63 mev. The size of the source and the energy of the radiation made heavy shielding necessary for these experiments, both to reduce the background count of the neutron counter and to safeguard personnel. The original discovery of the neutron by Chad-wick in 1932 resulted from experiments with another nuclear reaction, induced by bombarding beryllium with alpha particles in which the products are carbon-12 and neutrons. The equation for this reaction is as follows:' " ,Be" + ,He'? 6C12 + 8,n' [1] re-particle neutron In the above nuclear equation (Eq. 1), the sub- script number indicates the number of protons in the nucleus (the atomic number) and the superscript the total number of neutrons and protons (approximately the atomic mass). For the alpha-neutron reaction the cross section is about 250 milli-barns, or 250 times that of the gamma-neutron reaction used by Gaudin. The positively charged alpha particle is repelled by the positive charge of the beryllium nucleus; it must, therefore, have a certain minimum energy in order to approach close enough to the beryllium nucleus to react. For reaction with the beryllium nucleus, the lower limit of the alpha-particle energy is 3.7 mev. The alpha-neutron reaction, with polonium-210 as an alpha source, was selected for the present experiments. Alpha particles are emitted by polonium-210 at 5.30 mev, which is adequate for the reaction with beryllium. Furthermore, this isotope of polonium emits alpha particles with negligible associated gamma radiation, thus eliminating the necessity of shielding. The half-life of polonium-210 is 138 days. Inasmuch as alpha particles carry a possible charge and are large compared with most nuclear particles, their energy is rapidly dissipated in passing through matter. Their range in standard air is 3.66 cm,3 and they penetrate only a few tens of microns into a mineral sample. The short range in air can be minimized by preparation of a flat sample surface that can be brought very close to the alpha source during analysis. On the other hand, short range of alpha particles in air lessens the radiological health hazard and makes it possible to use this method without shielding. It must be emphasized, however, that the alpha emitters are potentially very dangerous if they enter the human body. Polonium must be handled with extreme caution. The literature has reported experiments on the yield of neutrons from reaction of alpha particles with beryllium nuclei. Feld" reports that in intimate mixtures of polonium and beryllium, 3 x 106 eutrons per sec are produced per curie of polonium. Elsewhere in the same reference it is stated that a sandwich-type source yields about one third as many neutrons as an intimate mixture. A table of neutron yields for full energy polonium alpha-particles on thick targets as reported by Anderson7 is the basis of Table I. From Table I it can be deduced that the elements most likely to interfere, i.e., those that also produce neutrons when bombarded by alpha particles, are boron and fluorine. These data also show that it will probably not be possible to determine very small quantities of beryllium in rocks because of the masking effects of the major elements, sodium, magnesium, and aluminum. The neutrons emitted in the alpha reaction are detected by another nuclear reaction. Either of the

Jan 1, 1960

By George W. Crawford, W. P. Aycock, E. W. Hough

Forty oilfield brines have been examined so far by a polarographic technique new in petroleum engineering called the "tensatnmetric method" by the team of biochemists who perfected its use in their field. Samples of brine were obtained from various oil fields in which the wells were known to be producing fluid from oil productive zones in well-known geologic formations. Most of the reservoirs from which the samples were obtained are believed to have an active water drive under the prevailing conditions of operation. The 40 samples represent brines produced front 16 different formations of various geologic ages. Graphs have been prepared of the data obtained in the testing of each sample, and the distinctive waife-like curves so obtained are characterized by reproducible profiles, called "response curves." Careful comparison of the response curves of salt water coming from different fields producing from the same geologic formation reveals that the curves are similar. The response curves of salt water coming from productive zones of different geologic formations are characteristically different. Preliminary work offers the further hope that response curves of an oilfield brine indigenous to a particular oil-bearing formation and hence representative of a particular geologic environment, such as deposit-ional and all subsequent morphological conditions, may be of value in reservoir engineering in the interpretation of surface and interfacial phenomena. For example, the wettability of the rock matrix and more specifically, the classification of productive oil-bearing strata as hydrophyllic or hydrophobic may be determinable. However, many more brines must be examined and the resulting response curves analyzed in comparison to known causal phenornena before this objective is achieved. INTRODUCTION One of the perennial moot questions in the literature of petroleum engineering is whether the reservoir rock is oil- or water-wet. Possibly an answer to this question could come from a careful examination of oilfield brines. None of the conventional methods of examining brines (chemical analysis, pH and electrical conductivity measurements, and the like) answer the question. Careful analysis of reservoir behavior observed in the exploitation of oil fields, particularly in the application of fluid injection, has been fruitful to the extent that a few reservoirs are believed to be properly classified. Physical chemistry suggests the behavior of reservoir brine and rock may be due to something in the brine in small amount. The ever increasing development and modification of theory in the general field of surface and interfacial chemistry has, and is, contributing to a better understanding of the problem, particularly as theory is verified by data. The work herein reported was begun in 1953 by Hough and Roebuck 1,2 who employed a new form of alternating current polarography, i.e., tensammetry, developed by Breyer, et a13,4 and who studied eight oilfield brines in adapting tensammetry to petroleum engineering needs. THEORY AND DEFINITIONS Tensammetry is a new technique of inquiry into surface phenomena. Specifically, a weak alternating current voltage is superimposed upon the direct current voltage applied to a dropping mercury electrode in contact with an electrolyte containing a small amount of a surfactant. The resultant alternating current can be measured and provides the experimental data for this new area of research. Under the influence of the direct current voltage, polar molecules arrange themselves in a double layer at the electrode. This double layer may be compared to a variable condenser, the capacitance of which is a function of the imposed direct current voltage. The direct current voltage determines the degree of adsorption of the surface active molecule on the electrode. Whenever the molecules are strongly adsorbed on the electrode, the capacitance of the double layer is low and the alternating current through the cell is low. Desorption occurs at some values of the direct current voltage, and at these voltages the capacitance of the double layer is high, resulting in an increase in the alternating current through the cell. The direct current

Jan 1, 1958

By Henry G. Petrow, Edward S. Porter

MAJOR occurrences of lignite with significant uranium concentrations have been reported in western parts of the Dakotas, especially in Harding County, S.D., and Billings and Slope counties, N.D. Samples containing as much as 2 pct U3O8 were received at the Winchester Laboratory, but those deposits reportedly of major significance have generally contained 2 to 4 lb of uranium per ton of lignite. Most of the uranium appears to be associated with the carbon in the lignite as a urano-organic complex, although in most instances analysis of inorganic material has shown uranium values. Molybdenum is similarly associated with the carbon, and its concentrations generally parallel the uranium. The noncarboniferous material is mainly composed of gypsum, jarosite, bentonite, sandstone, and miscellaneous carbonates and silicates. The heating value of these lignites has been determined as about 3500 Btu on a dry lignite basis. The ash content of lignite has varied widely, the important samples containing 30 to 60 pct ash on a dry lignite basis. Because of the significant upgrading of uranium values obtained by ashing the lignite, and because recovery of uranium from raw lignite presented formidable processing problems, major emphasis at Winchester has been placed on devising methods to recover uranium from lignite calcines. Proper roasting removes the problem of organic fouling of solutions, reduces the size of the leaching plant for an equivalent uranium throughout, and generally provides equal or better acid leaching efficiency with less acid than can be obtained from the raw lignite.

Jan 9, 1957

By Benny J. Nelson

AS a part of the fundamental research program of Aluminum Research Laboratories, some data were obtained on the ternary system Mg-Al-Mn. As very little information on the magnesium corner of this diagram has heretofore been published, it seems desirable to make available the values found for the liquidus and solidus surfaces of this system. Procedure The settling procedure was used for the determination of the liquidus compositions. Metallo-graphic examination of quenched samples, and stress-rupture upon incipient melting, were used for the solidus determinations. The settling procedure has been described in a previous paper.' Briefly, this method involved saturating the alloy with manganese at a temperature substantially above that at which the sohbility was to be determined, then cooling the melt to the latter temperature, and holding it at that temperature for a substantial period of time. Samples for analysis .were carefully ladled from the upper portion of the melt at hourly intervals during the holding period. After the ladling of each sample, the melt was stirred to redistribute some of the manganese that had already settled, because it appeared that when the latter particles of manganese again settled, they aided in carrying down more of the manganese and thus hastened the attainment of equilibrium. The melts were prepared and held in a No. 8 Tercod crucible holding approximately 4 lb of metal. The manganese was added either in the form of a prealloyed ingot (Dow M) containing about 1.5 pct Mn or by the use of a flux (Dow 250) containing manganese chloride. In calculating the flux additions, it was assumed that the manganese introduced would be equal to 22 pct of the total weight of the flux. Temperatures were measured with an iron-constantan thermocouple enclosed in a seamless steel tube, the lower end of which was welded shut. This protection tube also served as a stirring rod. The samples ladled from the upper portions of the melts at the various intervals were analyzed for aluminum, manganese, and iron. When making the alloys which were to be used for the determination of the solidus, 2½ in. diam tilt mold ingots were cast, scalped to 2.0 in. in diam, and extruded into ? in. diam wire. The principal impurities in the melts for this investigation were iron and silicon; their total not exceeding 0.03 pct. Portions of the wire, approximately 2 in. in length, were enclosed in stainless steel capsules for protection from the atmosphere. Bundles of these capsules, with a dummy capsule containing an iron-constantan thermocouple, were heated inside a large steel block (acting as a heat reservoir) in a closed circulating-air type electric furnace. At ap- propriate times, the capsules were removed and quenched in water. The wires were examined metallographically to determine the temperature of initial melting. Short times at temperature were used at the beginning for wire specimens of all alloys to obtain quickly the approximate temperatures at which melting could be first observed. When approximate solidus temperatures had thus been determined, equilibrium heating was attempted. This equilibrium heating consisted of an 8 or 16 hr period at a temperature, about 50 °F below the lowest temperature at which melting occurred when short heating cycles were used, followed by further heating for 1 hr periods at consecutive 10" higher temperatures. The theory for the method of stress-rupture at incipient melting has been well covereda and its limitations are recognized. Thus, if the interfacial tensions are such that the first minute quantity of liquid is "bunched up" at the grain boundary junctions instead of spreading out along the grain boundaries,³ temperatures higher than the solidus are required before melting will be manifested by rupture of the specimen. This point will be elaborated later. Specimens of the wires with a reduced section (approximately 1/16 in. diam) were suspended vertically in a tubular furnace. The setup used is shown in Fig. 1. The clamp holding the specimen was made from alumel thermocouple wire and the thermocouple was thus completed across the specimen by attaching a chrome1 wire to its lower end. Temperatures were read from a Speedomax recorder used in conjunction with a calibrated thermocouple. The small weight attached to the specimen and a vibrator attached to the furnace tube, to aid in distributing the molten constituent along the grain boundaries, were used to bring about rupture at a temperature closely approximating the solidus. The specimens were heated at a rate of about 5°C per min. The rupture of the specimens was indicated both by sound and by the action of the recorder. An argon atmosphere containing a small amount of SO² was used for protection of the specimen. The assembly was taken out of the furnace immediately following rupture and the specimen removed. Some of the broken specimens were examined metallographically and will be referred to later. Results and Discussion Fig. 2 shows a set of typical time-composition curves for liquid samples of the Mg-Al-Mn alloys used for the settling tests. The data as presented

Jan 1, 1952

By Charles H. Morgan

THE process of wire drawing depends upon the property which certain metals possess, termed ductility, 'which is defined in Brande's Dictionary of Science as a property in consequence of which metals may be drawn out at length without interrupting the continuity of their constituent parts. As defined by M. Tresca, it is the property of flowing when subjected to pressure, and is termed by him the "flow of solids," in his paper, read before the Academy of Sciences in Paris, November, 1865 * In the simple language of the wire shop, it is that quality in certain metals that permit, them to be drawn (or stretched) out through a tapering, hole in a metal block or die, the die being more dense and harder than the metal to be reduced. It is a fact well known to those skilled in the art, that to succeed in drawing iron or steel wire, it is of the utmost importance to have thorough lubrication, as a lack of it would caws abrasion of the wire, or of the walls of the tapering hole in the die or plate, and quickly put an end to the operation. In drawing coarse or large sizes of wire, say 2/10 inch diameter, the pressure upon the sides of the tapering hole, where the wire comes in contact with the die, is so great that an ordinary lubricant is squeezed out when the usual reductions in size are made, and abrasion takes place. In order to meet this difficulty, and secure proper lubrication, it has been' a common practice for years to apply a paste made of rye or wheaten flour, or lime, to the surface of the wire to be drawn, and when the paste is dry, to smear the wire with tallow or grease; the wire is then ready to be drawn, the dried paste serving to prevent the lubricant from being pressed out in the. process. Some years since, when Bessemer metal came largely into use as material for wire, "the writer found that its drawing required so much more power than iron wire, that he was led to institute a series of trials to ascertain the difference in power required. It was found that Bessemer wire required from 100 to 200 per cent. more power to make the same reduction in sizes than soft iron wire, the difference depending upon the amount of carbon and other chemical constitu- * Interesting experiments in the flow of metals have been made, by Messrs. Hoopes Townsend, of Philadelphia, in cold-punching iron, published and illustrated in the Journal of the Franklin Institute, of March, 1878, by Mr. David Townsend.

Jan 1, 1881

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

RICHARD A. CONKLING (communication to the Secretary*).-Mr. Hager says that his results on the correlation of well logs in the north Cushing field are the opposite to those of the author. Can he, then, explain why the structural dip of the formations increases with depth, as Dr. Ohern, in his criticism, sets forth that it does, and as all who have worked in these fields will admit, if the shales thicken on the crest of the anticline, as he says they do? We are willing to agree with Dr. Ohern that there is some evidence of a slight unconformity below the Bartlesville sand and think that we can prove, from a specimen in our office, that .this unconformity comes at the base of the Bartlesville sand in the south Cushing pool. On the Ingalls dome, in the southeast corner of Township 19 North, Range 4 East, however, we get results the same as those given by the author on Cushing. The Ballard well in the center of the Northeast Quarter of Section 33 is just 10 ft. higher, structurally, according to tile, surface contour, than the Ringold well -in the center of the Southwest Quarter of Section 34. The dip in the Bartlesville sand, between these wells, is 40 ft. and the dip on the top of the Mississippi lime is 75 ft. This also might be accounted for, partly by the unconformity, but the author used the interval between the top of the Oswego lime, which is about 420 ft. above the Bartlesville sand, and the oil horizon found in the lime in the Ballard well-just mentioned above-to find the depth at which the same oil should be found in a well in Section 5, Township 22 North, Range 3 East, 25 miles North. Using this interval below the Oswego in the former well, we predicted within 2 ft. where they would find the oil in the latter well. Of course, we know that it was accidental that we missed it only by 2 ft., but if there were much of an unconformity in this interval it would be more of an accident if we came within 100 ft. of the depth. Since it can be proven from most of the structures in this section that the clip continues to increase downward, below the Bartlesville at least, to the Mississippi lime, it does not seem necessary to the author to try to prove otherwise that the depth at which the shales will tend to thicken on top of a fold, has not been reached above the

Jan 6, 1917

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.' Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.' The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm'3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.' The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

By H. Foster Bain

THE "miracle of production." which was such an essential element in winning the European war, was nowhere more in evidence than in our Western States. In shipbuilding alone the Pacific Coast States -et a mark never before equaled, and in production of war goods of many kinds, both Rocky Mountain and Coast States accomplished more than their proportionate share if measured by population standards. This was only possible because of the building of immense new plants of many types, largely financed with Government money. Their operation has built up payrolls in the West and brought a measure of prosperity which Westerners are naturally anxious to have made permanent. A widespread doubt obtains, however, throughout the nation and even in the Western States themselves, as to whether, and if so to what extent, this may prove possible. The question has been raised as to whether the national treasury has not been raided to stock the Western ranges with a voracious breed of white elephant .

Jan 1, 1945

By Howard I. Smith

The mineral trona was discovered on Government land in 1938, about 18 miles west of the town of Green River, Wyo., in the core of the John Hay, Jr., well, a test well drilled for oil by the Mountain Fuel Supply Co. in sec. 2, T. 18 N., R. IIO W., sixth principal meridian. Although no oil or gas was reported, the drilling led to a discovery of great potential economic importance and exceptional scientific interest. Trona is a relatively rare mineral found at various places in playa deposits but not previously found at any great depth. It is composed of hydrous sodium carbonate and sodium bicarbonate (Na2CO3 NaHCo3.2H2O). Pure trona con-tains the equivalent of 70.35 per cent of sodium carbonate. Total sodium computed to carbonate times 1.42 equals the percentage of trona in the absence of other sodium carbonate minerals in the sample. Analyses Two short pieces of core sent to the author a few days after the completion of the Hay well were analyzed by R. C. Wells† and found to be exceptionally Pure trona. A brief article on this discovery has already been published.1 Arrangements were then made through W. T. Nighten-gale‡ for the author to inspect and sample the core. The company log of the well included notations of sodium salt crystals from a depth of 1190 to 1820 ft. Not being able to identify all the minerals present, the author selected several specimens of the core for petrographic examinations and sampled the sections of trona for analysis. J. J. Fahey, of the Geological Survey, examined the specimens and reported most of the crystals to be a new anhydrous sodium carbonate and calcium carbonate mineral (Na2CO 3.2 CaCO3), which he named shortite,² after Maxwell N. Short." He analyzed the samples of trona, with the results shown in Table I. In addition to the 10 ft. 1 in. of trona in the first section, it is reasonable to assume that the 9 ft. 8 in. for which no core was available for sampling is either i mostly trona or some other soluble salt, but it should not be included in calculating | reserves. In the part of the core between i 1590 ft. 3 in. and 1600 ft. 4 in. the material insoluble in cold water, amounting to about 5 per cent, was estimated petrographically I to contain 70 per cent clay, 25 per cent shortite, and 5 per cent pyrite. Accompanying Minerals Fahey later secured about 600 ft, of the core for a detailed examination and study

Jan 1, 1942