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By J. H. Mallery, J. H. Keeler

THE crystal structure of Zral, the compound richest in zirconium (91.03 pct Zr by weight) in the system Zr-Al, has been found to be ordered face-centered-cubic. This compound is of particular interest, since it is encountered as the precipitated phase in potentially useful zirconium-rich alloys. It forms peritectoidally from body-centered-cubic zirconium and Zr,Al at about 975°C. The Zr-A1 constitution diagram has been reported by McPherson and Hansen.' For the primary determination a 100 g ingot was prepared by arc-melting in a water-cooled copper crucible under purified argon. The raw materials were crystal-bar zirconium (a purity of better than 99.7 pct) and spectroscopically pure aluminum. The ingot was double melted, examined metallographi-cally, and found to be quite uniform as shown in Fig. 1. The hardness of the as-cast button was VHN 390 to 445. A 20 mil diam specimen was prepared from annealed (900°C) filings of Zr,Al. The specimen was mounted in a 5 cm radius powder camera and an 8 hr exposure was taken using copper radiation with a nickel filter. The structure of the compound Zral was found to be ordered face-centered-cubic of the Cuau type, with an a,, value of 4.37220.003A. Its calculated density is 5.976e0.013 g per cu cm. The relative intensities for the lines were calculated using the formula 1+cos2 20 I oc----------------- • p • /F7 sin2 0 cos 0 1 + COS' 20 where----------------is the Lorentz polarization fac- sin2 0 cos 0 tor, p is the multiplicity factor, and F is the structure factor. The X-ray data are given in Table I. The compound has exhibited plasticity when present as particles in a matrix of a zirconium. During hot working at about 900°C, the compound has been found to deform plastically to the extent that some of the particles exhibit a length-to-width ratio greater than 4:1 as shown in Fig. 2. In answer to the discussion of ref. 1, McPherson and Hansen pointed out that the compound may be cold rolled and reduced as much as 33 pct. Zr,Al has also been found2 under certain conditions to precipitate in lamellar form at grain boundaries of the a phase of hexagonal-close-packed zirconium. Acknowledgment This work was carried out under Contract W-31-109-Eng 52 for the United States Atomic Energy Commission.

Jan 1, 1956

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neill1 observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in intergranular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle' in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. [ ] In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1941

By John M. Gallow

Discussion of the paper of JOHN M. CALLOW, presented at the New York meeting, February, 1916, and printed in Bulletin No. 108, December, 1915, pp. 2321 to 2339. R. H. RICHARDS, Boston, Mass.-I think there is one note which would be interesting to have recorded in connection with this paper, and that is another form of flotation machine. The Minerals. Separation machine has a vortex action, with a vertical shaft and a propeller. This new frother has been developed for the Copper Queen Co. at Bisbee, Ariz. It has a horizontal shaft and a paddle wheel for a frother. It has eight cells, I think, all connected underneath in one continuous tank, and the only separation of the cells is in the upper chambers where the froth is. When this paddle wheel goes around it throws out the froth and the sand goes to the bottom and drifts over from the first to the second cell, where it is paddled again, and comes out with its froth; the sand goes to the third cell where it is again beaten. In that way the sand is continually drifting toward the last cell, while each new froth remains in its own cell. You can see in the working of this machine just the same effect that you see in Callow's machine, i.e., the earlier cell has the darker or richer froth, and the latter has the lighter or poorer froth until you get to the farthest one-which has very little froth, and is very light. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-Speaking from the metallurgical standpoint, it is quite desirable, in many cases, that the oil be removed from the concentrate in order to facilitate the metallurgical work, and I think attention should be directed to the desirability of removing from zinc sulphide concentrates the oil which interferes with their subsequent roasting. The value of the oil is not large; in Mr. Callow's plant, for instance, it would be $20 a day, and it may be possible that a process might be developed which, within the limits of the value of the oil, would remove it, and thus facilitate the metallurgical treatment. LEONARD WALDO, New York, ,N. Y.-The question came up about a year ago as to why-Mexican crude was not an admirable oil for flotation. I have never heard any satisfactory answer to the question. The Mexican crude has the peculiar property of comparative freedom from dangers of fire, a very great reluctance to part with its water, and a specific gravity almost identically the same as water.

Jan 5, 1916

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By Paul B. Crawford, Bobby L. Landrum

Electrical model studies have been made of the effect of unsymmetrical vertical fractures on production cnpacity. The study war restricted to the case of two vertical fractures originating at the well and extending out into the reservoir for various distances and orientations. The ratio of the short fracture length to the long fracture length was varied from 0.1 to 1.0 in successive studies. The angle separating the two fractures was varied from 0 to 180 degrees. The most effective fractured patterns were obtained when the fractures were oriented 180 degrees. It was found that when the total fracture length was equal to 0.2 of the drainage radius, the increase in production capacity may vary from approximately 1.55 to 1.95. depending upon the ratio of the short fracture length to the long fracture length and the angle separating the two fractures. If the total fracture length were 0.5 of the drainape- radius. poroduction cavacitv., increases varving 1.95 to 2.65 were observed, depending on the angle between the fractures and the ratio of the .short fracture length to the long fracture length. The fractured well production capacity decreased aPproxin?ately I to 10 per cent as the angle separating the fractures was varied from 180 to 90 degrees. It was dependent on the particular fracture. The commercial application of reservoir fracturing techniques has caused an interest to be expressed in the effect of vertical and horizontal fractures on production capacities. Some data have indicated that substantially vertical fractures may be created in some reservoirs. It is believed that the fractures are possibly unsymmetrical, that is, one fracture may extend due north 100 ft and a second fracture on the opposite side of the well may extend south or southeast only 50 ft. The total fracture length, ratios of the lengths and angles of separation may vary considerably. For this reason variations in these factors were considered. The study was restricted to the case of two vertical fractures originating at the well and extending out into the reservoir. It is not known that such will occur in a reservoir, but the results may be of value in interpreting or studying fracturing applications. PROCEDURE An electrical model was used in this study of the effect of unsymmetrical vertical fractures on production capacity, A wooden tank 30 in. in diameter and approximately 2 in deep was coated with paraffin wax. A copper band was situated at the periphery and a single wire electrode was positioned at the center of the tank. The ratio of the reservoir radius divided by the

Jan 1, 1956

By Horace Pops

Isothermal sections in the copper -rich region of the Cu-Si-Zn a1by system have been determined at 8473 760; 6003 and 482°C by means of microscopic examination with confirmatory X-ray diffraction work. The stability of the bee 0 phase decreases both with decreasing temperature and with increasing copper content. The silicon-n&apos;ch 0 phase decomposes upon quenching from high temperatures either by a martensitic or by a "massive" transformation, depending upon the solute content. A two-phase equilibrium is found to exist in the Cu-Si-Zn system between the hep < phase of the Cu-Si system and the bee ß phase of the Cu-Zn system. It is shown that the isothermal limits of the primary solid solution at 760; 6003 and 482°C are in part affected by the intermediate phases which follow them in the ternary system Possible electron-concentration and size effects upon phase boundaries are discussed. ALTHOUGH the mechanical and physical properties of silicon brasses have been measured in great detail, the factors which influence these properties are not well-understood, partly because the knowledge of the phase relationships in the Cu-Si-Zn system is limited. Gould and Ray1 studied the effects of silicon upon the hardness and structure of Cu-15 pet Zn and Cu-40 pet Zn alloys. They proposed an isothermal section at 800°C which was not based upon experimental data, since the binary phase diagrams had not been completely determined. Using Cu-Si-Zn alloys containing approximately 5 wt pet Si, vaders2 determined the boundary, at 750°C, between the copper-rich solid solution and an unidentified second phase. Masing and wallbaum3 examined a vertical section through the ternary diagram in the region between Cu-20 pet Zn and Cu-10 pet Si alloys, but they emphasized uncertainty about their data. Mima and Hasegawa4 studied the liquidus surface of Cu-Si-Zn alloys, phase transformations in high silicon-bearing (20 to 25 at. pet) alloys,5 and the phase relations in low silicon-bearing Cu-Si-Zn alloys.6 Their experiments were based upon thermal analyses and metallographic observations. The compositions of the phase boundaries were not determined with high precision, and the crystal structures of the phases were not reported. Because of uncertainties in the existing literature, it became of interest to determine more accurately the phase relations in copper-rich Cu-Si-Zn alloys. The crystal structures, stability, and phase boundaries of the primary solid solutions and several intermediate phases were determined, and the data are reported as partial isothermal sections.

Jan 1, 1964

Gentlemen.-The Institute was founded 54 years ago "with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained," At least once a year it is well to take stock of our assets, review our performance and determine how well we are now carrying out the purposes of our Founders. There can be no question as to the work the Institute has done and is doing in promoting the arts and sciences in the fields of mining and metallurgy. One needs only to contrast the methods, the labor and the costs of a half century ago with those now to visualize how far we have gone in the development of accurate technology and sound economics in mineral and metal production. The great mines, mills and smelters of the present, handling individually thousands of tons per day, would&apos; have been impossible except for the accumulation of knowledge, the development of theory, and the improvement in practice that has characterized the period since the foundation of the Institute. The United States has prospered in the last half century greatly, and this has been due not merely to the possession of great natural resources, but to these resources being reduced to possession and put to work. The absence of customs barriers and the freedom of trade across the whole width of this great continent has been an important factor in the growth of our wealth. Unrestricted interchange of goods has permitted each citizen to draw on the resources of the whole country. However, these are but subsidiary causes of prosperity. The free interchange of scientific and technical data, by making the whole body of facts and theory available to each worker, has made this quick and unrivaled development possible. In promoting this free trade in knowledge the Institute may claim a large place without fear of denial. The .72 volumes of TRANSACTIONS, the special volumes, the bulletins and the other publications that have been issued, include a store of knowledge of the arts and sciences related to the production and use of metals and minerals not duplicated elsewhere. The large list of foreign members-1746 in number-few of whom ever have opportunity to attend meetings and all of whom derive their main benefits from membership through the pub-

Jan 1, 1928

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

A simple reproducible method was developed for determining the ignition temperatures of magnesium and magnesium alloys and by this method magnesium and over 100 magnesium alloys were measured. The ignition temperature of magnesium was determined in O2-SO2, O2-N2 mixtures and in O2 from 0.166 to 10 atm pressure. The ignition temperature of magnesium is generally lowered by alloying and increased by an increase in oxygen pressure. WITH the expanded use of magnesium alloys in industry, ignition temperatures are of considerable importance, especially in heat treating and for service at elevated temperatures. Magnesium alloys exhibit a relatively slow linear oxidation rate up to temperatures near the melting point.&apos; At some critical temperature the rate of oxidation becomes extremely rapid. This high rate of oxidation is accompanied by the emission of light and additional characteristics suggesting a flame. The literature concerning the ignition temperatures of magnesium and magnesium alloys is relatively incomplete and the values reported by various authors are not in agreement. The most probable reasons for this are: 1—The absence of a suitable definition of ignition, and 2—the need of a standardized method of determining the ignition temperatures of inflammable metals and alloys. The exact date of the discovery of the fact that magnesium will ignite and burn is unknown. It is likely that H. Davey encountered this property of the metal during its preparation in 1808. The first reference in the literature specifically on ignition of magnesium is by Lenze, Metz, and Rubens.&apos; They investigated the inflammability of certain magnesium alloys. Brown3-&apos; reported that magnesium ribbon will ignite in air at 507 °C by what was called the rising temperature method. Hartman, Nagy, and Brown" reported that magnesium powder ignites from 475" to 560°C depending on particle size. According to Guise, Mars, and Wilson prolonged heating in air at 427°C of common casting magnesium alloy causes it to ignite. Samples of magnesium alloys were placed directly in the flame of a torch by Carapella and Shaw.&apos; These investigators obtained some evidence of melting prior to ignition. For commercial magnesium, they reported an ignition temperature of 650°C. Their values varied from 450" to 800°C for magnesium alloys. Willmore and Peterson" studied the effect of air velocity, humidity, rate of heating, and foreign metal contact on the ignition temperature of magnesium. They conclude that melting is not a prerequisite for ignition and that the conditions which influence ignition are complex and difficult to analyze. The only quantitative theoretical treatment of the ignition temperatures of magnesium and magnesium

Jan 1, 1952

By Max Roseler

THE CHAIRMAN (WILLIAM KELLY, Vulcan, Mich.).-Some 8 or 9 years ago I was at Daiquiri, only a. few miles east of Firmeza, where there are deposits of iron ore of the same general character. There is a great conical hill, perhaps 800 or 1,000 ft. in height and the ore deposit appears to be somewhat in a canoe shape on one side of the hill. The mining has been done by quarrying the ore in benches. These are called levels and to go to the 10th level it was necessary to take mules and ride to the top of the hill, which was to me an upside down arrangement of numbering levels and a novel method of entering and viewing a mine. A little copper ore can be seen in places, and not being a geologist I thought the deposit might possibly be a gossan, but none of the geologists who have written on the subject approve of this hypothesis and the great question seems to be what part, if any, the limestones have played in the origin of ore; whether these deposits are replacements of limestone and whether they are contact ,deposits between the limestone and the other rocks. Examinations have been made by many eminent geologists and the problem has been discussed vigorously on both sides. The deposits are exceedingly interesting from a commercial standpoint and although they have been studied for a number off years the origin of the ore is still a difficult and somewhat controversial question. J. T. SINGEWALD, JR., Baltimore, Md.-I have had the privilege of visiting these deposits and have been very much interested in this paper, of Dr. Roesler&apos;s; having been on the ground, I can easily appreciate the difficulties under which he labored in attempting to work out the geology of that region, and he certainly deserves considerable credit for the way in which he has deciphered the geological relations of the Firmeza district. There are several points in his paper 1 ,would like to discuss; first, in regard to the geological interpretations. His differs from previous interpretations in the relative age of the diorite and the granite, but you will note that Prof. Lindgren suggests the probability. that those two rocks are very closely of the same age, and Prof. Kemp actually suggests, although he does not-accept the idea, that the granite is probably later than the diorite, so that there seems to be no particular reason

Jan 4, 1917

By R. A. Matuszak

This paper discusses the major portion of the hoist (drag or crowd) system and it shows how static control accomplishes its major aims. In 1959, the first truly static control for Ward-Leonard equipped electric excavators was designed, developed and placed in service. The control system, originally intended only as a more modern electronic type of alternate to the proven rotating amplifier control system has since proven to be much more. When they conceived the original system, the designers had much more in mind than simply replacing the rotating amplifier with one that had no moving parts. The long range plan, which started with the initial system consisting of an SCR (silicon controlled rectifier) preamplifier and magnetic amplifier power amplifier, called for eventually, a control system low in cost and maintenance, relatively simple in design and extremely reliable. The plan also included the elimination of as many of the shortcomings of the rotating system as possible. No small accomplishment, when it is considered that the rotating control system had been, with only minor modifications, the standard of the industry for 20 years. The final step in the original design plan called for the eventual development of an amplifier that could be used as one of the basic building blocks of the future. DEVELOPMENT RESULTS Since the successful unveiling of the first static control system, continuous development has resulted in a slow, but sure progression along the path described by the original plan. The first version of the new control corrected one of the shortcomings of the rotating system by removing the necessity of operator anticipation. This was accomplished by making the system faster in response so that the operator noticed virtually no delay between his movement of the master controller and that of the machine. Thus, after the operator became familiar with the operating characteristics of the machine, he was able to become more relaxed while digging. The natural result of this accomplishment was higher production. All of the subsequent versions of this new control were even faster than the initial design. Although it was not distinguishable by the operator, the further increase in response resulted in large gains in the limiting of transient torque peaks applied to the machine while digging. Also, a more effective control of the torque and power peaks was obtained when plugging the motion being controlled to a stop. (Plugging is the use of the Ward-Leonard ability to regenerate power and absorb energy from the load to

Jan 1, 1964

By T. A. Dungan

THE thermal processes for the production of metallic magnesium can be divided into two general classifications, the direct reduction of magnesia with carbon and the indirect reduction of compounds of magnesium by reducing agents that are themselves products of carbon reduction. The latter are so chosen as to cause reduction of magnesium compounds wherein only the magnesium is liberated in the vapor phase. Reducing agents used are: calcium carbide, silicon carbide, silicon, aluminum, various silicides or combinations of calcium, aluminum, silicon in iron. All of these are products of highly endothermic reactions and, with the exception of scrap aluminum, can be produced in an open, submerged arc furnace; that is, the arc is covered only by the charge itself. The more investment in energy required to prepare such a reducing agent, the less is the energy required in the subsequent step to reduce the magnesium compound to the metal. It is impossible, however, to avoid the laws of thermodynamics, no matter how much circumambulation is resorted to in the preparation of successively more powerful reducing agents. Since each such step carries forward its own inefficiencies, it appears evident that the ultimate status of such processes is dependent upon the development of by-products. EARLY EXPERIMENTS IN DIRECT REDUCTION The direct reduction of magnesium oxide by carbon has a decided appeal to both the scientist and the industrialist. The successful production of the carbothermic plant at Permanente is a significant fact in the substantiation of this concept. Like most developments, however, the history of carbon reduction of magnesia is not one of triumph after triumph, or immediate heady success to the investigators. It is understood that one of the early investigators conducted an experiment wherein he placed carbon and magnesia in one end of an evacuated tube and managed to heat this end to a temperature high enough that magnesia and carbon deposited at the other end of the tube. The charge, unreduced, appeared to have been completely transported from the hot to the cold end of the tube. This raised doubt for some time as to whether magnesia could be reduced at all with carbon. It was correctly suspected, however, that the magnesia was in fact reduced and the resultant magnesium vapor and carbon monoxide reacted upon one another upon reduction in temperature to reform the starting ingredients. Attempts were then made to dilute the two vapors by passing a considerable stream of hydrogen through an arc furnace charged with magnesia and carbon. Thus by dilution of the products it was expected to obtain metallic magnesium. The results were positive and metallic magnesium was

Jan 1, 1944

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O&apos;Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By L. R. Blair

Many hydrated silicates have been synthesized and sold for commercial use. However, this paper discusses only hydrated calcium silicates and, to a lesser extent, hydrated magnesium silicates. Synthetic calcium silicates were first formed by man when he found that mixtures of silica or silicates and lime in water set up to form cements. The material which was responsible for the cementing properties was calcium silicate hydrate, although this fact was not recognized until early in this century. In the early 19001s, synthetic calcium silicates, reinforced with fibers and formed simply by reacting calcium hydroxide and silica in water with fiber at atmospheric or under low pressure autoclave conditions, found increased use in thermal insulations and in building products. These insulations were found to have a low thermal conductivity and would withstand temperatures up to 650°C. This, combined with their very low densities (from 8 to 50 Ib per cu ft) and fairly high strength, also made them suitable for use as building products. Following the disastrous Morro Castle fire of the 1930Js, calcium silicate board products were used as partitioning material in all shipboard construction in the U.S. As autoclaving techniques were improved and developed, it was: learned that under hydrothermal conditions new and useful calcium silicates which could be used under more extreme temperatures (up to 980&apos; C) could be prepared. These had high surface areas and other unique properties which suited them for use as fillers, pesticide carriers, low temperature insulating materials, and adsorbents for the removal of fatty acids from various solutions. Hydrated magnesium silicates have not been studied as extensively as the calcium compounds. Their first important use was in the filtration of dry cleaning solutions for the removal of fatty acids. With the introduction of detergents, it was found that these products lost their advantage because of their high affinity for the detergent chemicals. However, in recent years these chemicals are finding increasing use as decolorizing agents for fats and anti-caking agents for resins. Some materials with very high surface are finding new use as adsorbents. CALCIUM SILICATE HYDRATE COMPOUNDS AND THElR CONDITIONS OF FORMATION Within the past ten years much has been done in the field of calcium silicate hydrate chemistry. As a result of this work it has been found that at least 25 different forms of calcium silicate hydrate can either be formed synthetically or found as naturally occurring materials. The stability and composition relationships among these 25 compounds present a very complicated picture, and many of these very closely resemble other forms and are difficult to dis-

Jan 1, 1962

By O. N. Cole, R. E. Davis, T. D. Brotherton

Pvfoperties of rubidium and cesium are compared with those of other alkali metals. Methods for the preparation of rubidium and cesium metal are reviewed briefly, ad hazards and safety precautions required in handling rubidium and cesium metal are described. SimPle methods for handling laboratory quantities of elemental rubidium ad cesium under oil and under argon are illustrated. CESIUM and rubidium were both discovered by Bunsen and Kirchoff in the years 1860 and 1861. Cesium was discovered while Bunsen and Kirchoff were making a spectrographic study of spring water from Durkheim, Germany. It was the first element discovered by this technique. The element was given the Latin name "caesius" for sky blue because of the color it imparted to flames. Elemental cesium was first prepared by Setterberg in 1881 through electrolysis of a molten mixture of cesium and barium cyanides.&apos; In 1861, Bunsen and Mirchoff discovered rubidium while making a spectrographic study of the alkali content of lepidolite ore from Saxony. Two prominent dark red lines appeared in the spectrum and so the element was named "rubidius" or dark red. In 1861 Bunsen and Kirchoff first prepared elemental rubidium through the electrolysis of molten rubidium chl~ride.~ The alkali metals are very similar in their chemical and physical properties. They are the most active metals, and all exhibit a single oxidation state of one. They are so reactive that they are never found in nature in the elemental state. The reactivity of he metals increases with atomic number. Rubidiurn and cesium ignite spontaneously in air and react explosively with water. This extreme reactivity makes necessary special equipment and techniques for the safe preparation and use of the metals. The cation: of Group IA can be separated from the metallic cations of other groups with relative ease, but the separation of the individual alkali cations is much more difficult because of their close chemical similarity. This close chemical and physical similarity of alkali metals can be inferred from the atomic radii, oxidation numbers, and ioni-zation potentials shown in Table I. A difficult but the most practical physical method of separating the elemental alkali metals from one another is by distillation. Only lithium has a boiling point sufficiently far-removed from the boiling points of the other alkali metals to make this method of separation feasible without elaborate and expensive equipment. This method is not used, however, for lithium because it possesses sufficient chemical dissimilarity from the other alkalies for it to be separated relatively easily as lithium hydroxide monohydrate or as lithium carbonate. Francium, the last member of the group, has no known stable isotopes. The naturally occurring

Jan 1, 1962

By H. A. Schwartz, W. Kenneth Bock

In this paper it is shown that when the tensile strength of a given steel in various states of heat-treatment is plotted against its elongation, a straight line results. The equation of this straight line can be computed with considerable accuracy from its chemical composition. The appropriate equations are given. The logarithm of the slope of the tensile-strength locus is shown to be proportional to the cumulative effect of the total alloy addition and the vosition of the line to be directly proportional to the cumulative effect of the alloy content. It is further pointed out that heat-treatment is more effective than composition in determining yield ratio. The latter enters mainly by its effect on hardenability, which is briefly discussed. Reduction of area and Brinell number are given some incidental attention. The data are applicable only to steels that have been normalized and/or quenched. The steels, if normalized, may or may not have been tempered. If quenched they must have been tempered at or above 4oo°C. (75o°F.). Introduction Cast steels vary in composition and frequently are used in various states of heat-treatment. It is obviously important to be able to predict the compositions that might accompany specific engineering properties by suitable selection of heat-treatments. For cast steels, which are of necessity produced heat by heat in accordance with the particular requirements of the castings to be poured, there has been, happily, much less tendency to standardization than for rolled products, whose destination is not necessarily known when particular ingots are made or rolled. It is of distinct advantage to the steel foundry-men to be able to make steel of given properties, using alloys that can be recovered from scrap, or most conveniently or cheaply bought, rather than a particular formula adopted in the interest of standardization. The heat-treatment appropriate to securing a given result in a given steel is well known to be closely related to composition. For example, molybdenum steels are not much softened by tempering except at rather high temperatures. Highly alloyed steels are "air-hardening," and on cooling in air behave like carbon steels that have been quenched. With these matters, we do not concern ourselves in this paper, although we recognize their importance. The entire picture evidently will be very complex and can be brought within accurate understanding only if our knowledge of test results can be coordinated in terms of general principles.

Jan 1, 1944

By F. C. Oliphant, George H. Fancher

Two samples of drilling mud from the Hastings oil field, Texas, were tested, and the solids in each were separated into small fractions of a limited range in particle size. The mineral composition of each fraction by X-ray analysis is reported, and the results are interpreted in relation to other measured quantities, such as the physical properties of the original samples and the density of the various fractions. It was found that only 7 to 8 per cent by weight of the solids was of colloidal dimensions and that neither of the samples contained montmorillonite but did contain illite. Considerable calcite was also found. These data should be useful to the geologist interested in the origin and history of sedimentary strata as well as to the petroleum engineer. Introduction The questions, What is good drilling mud? What constitutes bad drilling mud? are pertinent, because the proper use and control of drilling fluids has been a factor of great importance in the successful drilling and completion of oil wells since the days of Captain Lucas. Adequate control of the characteristics of drilling fluids has assumed greater significance comparatively recently because of the problems introduced by caving formations in deep wells, costly blowouts and impressive mud bills. Much is known about the solution of some of the problems but, despite extensive research directed toward a better understanding of the physical and chemical properties of clay suspensions, it is difficult to define precisely a drilling mud, and much more difficult to say what constitutes a good mud. It is generally believed that the smaller particles of a drilling mud greatly affect its physical properties. In fact, it is customary to blame the colloids in a mud for nearly everything that goes amiss, because colloidal properties have effects out of all usual proportion on viscosity, filtration rate and reaction to electrolytes. It is germane to know whether drilling muds possess colloids and if so, the quantity and kind. Source oF Samples Two drilling muds from the Hastings oil field, Brazoria County, Texas, were selected because it is generally agreed that in this oil field good natural muds made solely from formations penetrated by the drill can be used until the well is nearly ready for completion. Customary drilling procedure in this field is to spud in with water, set a protective string of pipe, drill to 2500 ft. and set the surface casing. Drilling is continued to 5500 ft. with no treatment of the drilling fluid other than addition of water to

Jan 1, 1943

By W. N. Lacey, R. H. Olds, B. H. Sage

The volumetric behavior of five mixtures of black oil and natural gas and of two mixtures of condensate and natural gas from a field in the San Joaquin Valley was experimentally established. This work was carried out at roo°, I9o° and 250°F in the pressure interval between 400 and 5000 psi. The viscosity of the liquid phase of four mixtures of black oil and natural gas was experimentally measured in the above-indicated temperature and pressure intervals. The effect of methane upon the precipitation of bitumen from the black oil was studied at 230°F. Introduction The solution of a number of the economical and technological problems which arise in connection with petroleum production is dependent upon the availability of the necessary quantitative information covering the materials involved. This requires data concerning physical properties of naturally occurring hydrocarbon mixtures at the pressures and temperatures characteristic of underground petroleum reservoirs. The experimental determination of the desired data for each situation encountered is relatively time-consuming. However, it is considered to yield results sufficiently more reliable than those obtained from correlations to justify the effort. For these reasons there was undertaken a laboratory investigation of the viscosity of the liquid phase and the volu- metric and phase behavior of mixtures of oil and gas samples obtained from wells in a field located in the San Joaquin Valley. Terminology The nomenclature of petroleum engineering is not at present entirely standardized. Many commonly used technical terms are not everywhere given the same meanings. For the purposes of this paper the following definitions will be adopted: Black oil refers to the dark-colored, hydrocarbon liquid obtained when the producing horizon of the well lies partly in the condensed hydrocarbon phase of the reservoir. Condensate is the term applied to the relatively volatile, pale yellow or amber-colored hydrocarbon liquid that is often obtained from the surface separator system when the producing horizon of the well lies in the gas cap of the reservoir. The gas obtained from the surface separator system is called natural gas regardless of whether the well is producing black oil or condensate. As might be expected from the multi-component character of naturally occurring hydrocarbon materials, the compositions of black oil, condensate and natural gas are subject to considerable variation depending upon the temperatures and pressures prevailing in the surface separator system as well as upon the overall composition of the material produced from the reservoir. In order to obtain samples capable of reproducing the total hydrocarbon material produced by the well, all oil and gas mixtures used in this investigation were com-

Jan 1, 1949

By B. A. Cheadle, C. E. Ells

The ovienlalion of hexagonal a-zirconium crystals in cold-drawn Zircaloy-2 tubes and in both as-extruded and heat-treated Zr-2.5 wt pcl ND tubes has been rrleasured using the inverse Pole - figure technique. Uniaxial tensile tests hare shown the Zil-caloy-2 lubes to hare highly anisotropic delovmation behavior whereas heat-treated Zr-2.5 wt pet Nb tubes are nearly isotropic. The differences in deformation behavior are esbloilred from the observed textures of the tubes and the deformation systems known to oberate in Zircnloy,-3. Tlze vcsults lead to an explanation of the high effective strain observed fov the Zircaloy-2 tubes as colrzpared to heat-treated Zr-2.5 wt pet Nb tubes in restrained end burst tests at 280° to 300°C. THE Zr-2.5 wt pct Nb alloy. when heat-treated by quenching from temperatures slightly below the (a + p)/P phase boundary and subsequently aged at 500°C, has tensile strengths about 50 pct greater than those of 20 pct cold-worked Zircaloy-2.1 There is. therefore, considerable economic incentive to replace Zircaloy-2 with the heat-treated alloy in some in-reactor applications. notably for pressure tubes, where strength is a prime consideration. However, when tubes of Zr-2.5 wt pct Nb fabricated by extrusion and drawing prior to heat treatment were subjected to restrained end-burst tests at 300 °C. the circumferential expansion at failure1 was only 10 pct that of cold-drawn Zircaloy-2 tubes in similar tests,2 Table I. This result was not predicted from uniaxial tensile tests in which the ductilities of the two materials were quite similar.&apos; The detailed requirement for ductility in pressure vessels has not yet been worked out. and comparison of the relative merits of cold-worked Zircaloy-2 and heat-treated Zr-2.5 wt pct Nb is further complicated by the irradiation-induced loss of ductility and hydrogen pickup each will undergo from reactor operation.1,2 Nevertheless. the lower circumferential expansion of the Zr-2.5 wt pct Nb tubes raised serious doubts on the advisability of their use as pressure vessels. For this reason, an investigation to determine the cause for different ductilities of the two types of tubes was initiated. From a study of uniaxial tensile properties and crystallographic orientation it has been found that the fracture ductilities observed in the burst tests can be related directly to the crystallographic ori-

Jan 1, 1965

By C. S. Matthews, H. M. Girner, C. D. Williams, M. J. Edwardson, H. R. Parkison

Quantitative interpretation of electric logs requires knowledge of formation temperature. In this paper, methods are developed for computing changes in formation temperature caused by circulation of mud during drilling operations. The basis of the method is the mathematical solution of the differential equation of heat conduction. The solution of this equation is presented in a series of graphs. These graphs are used to determine formation temperature disturbance at various radii for arbitrary mud circulation histories. Example comparisons with field results show reasonable agreement. It is concluded that, in general, the temperature disturbances caused by circulating mud are small beyond 10 ft from the wellbore but are quite significant near the wellbore. INTRODUCTION Quantitative interpretation of electric logs requires knowledge of the formation temperature in order to establish the resistivity of the formation water with accuracy. To determine the formation temperature, the temperature disturbances produced by circulating drilling mud must be evaluated. -The objective of this investigation was to develop a method for the numerical determination of these temperature disturbances at any distance from the wellbore as a function of time. The first step was to solve the differential equation describing the temperature behavior in the formation during and after mud circulation. This solution was used to calculate a series of curves relating temperature disturbance to shut-in time for various circulating periods. An "exact" method for computing formation temperatures with the use of these temperature-disturbance plots is described, and the results of an application of this method to a well in Montana are presented. Procedures for approximating formation temperatures are also discussed. BASIC EQUATIONS AND ASSUMPTIONS With the assumptions that (1) cylindrical symmetry exists, with the borehole as the axis, (2) heat flow is 1. The formation can be treated as though it is radially infinite and homogeneous in extent, as regards heat flow. 2. The presence of mud cake can be disregarded. 3. The effect of heat generated by bit action is negligible. 4. After mud circulation ceases, the rate of radial heat flow at the wellbore is negligible and is assumed zero for purposes of calculating temperature change with time. These assumptions are believed to be reasonable because of the agreement achieved between calculated and measured borehole temperature in a well, to be discussed later. Further, the agreement at the wellbore indicates that temperatures in the formation were also approximately correct. since it is the formation temperatures that determine wellbore temperature after ceasing circulations SOLUTION OF THE DIFFERENTIAL EQUATION AND ITS APPLICATION The solution of Eq. 2 for the temperature behavior during and after a single period of mud circulation is

By Alexander Coucoulas

FABRICATION of thin-film circuits deposited on glass substrates requires the formation of permanent electrical contacts. Since thin films are in the order of a few thousand angstroms thick and are deposited on nonconductive surfaces such as glass, new methods of lead attachment are being pursued in the microelectronics industry. Ultrasonic welding is being considered in thin-film technology since joining can be accomplished between a wide variety of dissimilar materials.l,&apos; Ultrasonic welding is accomplished by a transducer-coupling-tip system which converts high-frequency electrical energy into mechanical vibrations and delivers it into the weld region. During the process the tip oscillates in a direction parallel to the surface of the weldments, inducing shear stresses in the work pieces which are clamped between the tip and anvil. Though the basic bonding mechanism is not clearly understood, it has been described as closely akin to friction welding. In the course of an investigation concerned with ultrasonic we!ding of aluminum wires to tantalum thin films (1400A) deposited on glass, low weld strengths were related to glass failure. Upon investigating this condition, an improved method of bonding was developed where the aluminum was held at a temperature where a minimum amount of strain hardening occurred during the introduction of ultrasonic energy. Experimental Procedure. Aluminum wires (0.015 in,) were bonded to tantalum thin films with an optimized set of welding parameters (power, time, clamping force) employing a commercial 100-w 60-kc ultrasonic welder. Forty-five degree shear-peel tests, where the lead is pulled at a 45-deg angle with respect to the substrate at 0.2 in. per min, produced a large variation from zero to the strength of the wire, Table I. Inspection of the weld region generally revealed: glass cracking before and after testing; the removal of glass nuggets from the substrate by the lead during testing, Table I; thin-film penetration. In an effort to improve the shear-peel strength, the aluminum between the tip and substrate was heated above ambient temperature through an argon gas media prior to and during welding with the same parameters employed above. With the addition of heat: wire deformation was increased; shear-peel tests all failed at the weld-wire junction, leaving the bonded portion undisturbed; no evidence of glass cracking or film penetration prior to or after testing was observed. In order to prevent failure at the weld-wire junction due to excessive wire deformation, 0.035-in. aluminum wires were welded to tantalum thin films with an optimized set of welding and heating parameters. As

Jan 1, 1967