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By R. G. Weavind, R. S. Young, I. Wolf

ONE of the most important fields of investigation at the Diamond Research Laboratory in Johannesburg is concerned with improvements in metallurgical practices for the diamond mining companies, with particular reference to increased recoveries of the smaller industrial stones. Considerable work has been done on the possible application of flotation processes to the diamond industry. From the viewpoint of recovery processes, diamonds in their natural state may be grouped into two classes, the water-repellent diamonds, which adhere to a grease surface, and the water-avid diamonds, which, because of their wettability, will not adhere to a grease surface and must be recovered by means other than the grease tables used for water-repellent diamonds. Experiments in the flotation of small diamonds from both kimberlite and alluvial deposits indicate the following conclusions: Water-repellent diamonds: Satisfactory flotation of —16 mesh diamonds, which are naturally water-repellent, may be accomplished using either Aero-float 25 together with cresylic acid, or Du Pont B23 as frother together with kerosine as auxiliary oily conditioner or froth stiffener. The quantities of reagents required are of the order of 0.15 lb per ton Aerofloat and 0.18 lb per ton cresylic acid. The use of acid circuits is detrimental, and for best results a pH between 7 and 9 should be maintained. R. G. WEAVIND and I. WOLF are with the Diamond Research Laboratory, Johannesburg, South Africa, and R. S. YOUNG, Member AIME, is Director of Research, Diamond Research Laboratory. TN 76B. Manuscript, March 23, 1951. A flotation period of 5 to 10 min is necessary to insure that all floatable diamonds are removed. Diamonds larger than 16 mesh cannot be recovered satisfactorily by flotation. Xanthates do not act as collectors for diamonds, and this is probably associated with their inability to impart a water-repellent surface to this mineral. Water-repellent diamonds smaller than 28 mesh can be floated quite well by the addition of a frother alone, such as pine oil or Du Pont B23. Water-avid diamonds: Partial flotation of the smaller sizes of wettable diamonds can be achieved by preconditioning with fatty acid soaps, cationic amines, and similar reagents, which will impart a water-repellent film to diamonds. Washing to remove excess reagent, followed by flotation, will result in a fair recovery, but the latter is much lower than for water-repellent diamonds. Crushed boart: Recovery of crushed boart from the waste products of industrial uses is best accomplished by first conditioning the diamonds present in the mixture with fatty acids, cationic amines, etc., removing the conditioning agent by washing, and floating in a cell of the pneumatic type. Flotation reagents found to be most suitable are Du Pont B23, and Aerofloat 25 together with cresylic acid. The optimum quantities are 1.2 g Du Pont B23, and 0.55 g Aerofloat plus 1.4 g cresylic acid, per liter of pulp in the cell. A solids-to-water ratio of 1 to 4 is found to be the most suitable, and alkaline circuits are necessary for best results. Diamonds larger than 28 mesh are not recovered satisfactorily by this procedure, but for finer sizes flotation offers an excellent procedure for the reclamation of this strategic industrial material.

Jan 1, 1952

• "This country eventually may have to rely on foreign sources for some metals, not because it does not have them here but because it may have difficulty getting the labor to mine them. Few people realize the extent to which the 'old timers' are still the backlog of the important districts." --Fred Searls, Jr. • A new filter has been developed by Arthur D. Little, Inc., for the ABC which will remove all dust from the air. Submicroscopic asbestos fibers are used as filter media and are claimed to stop all dust and pollen while passing suitable quantities of air. •Out in front public relationswise is the Peabody Coal Co. which has launched a 15-min television news program on WNBQ at 10:30 C.S.T., Tuesday and Thursday nights. Clifton Utley, news commentator, will tell how coal is mined today and indicate, with pictures, the improvement in efficiency and safety which has resulted from today's mechanized operations. •Two hundred coal mining companies are using roof bolts as a means of supporting about 14 million sq ft of roof surface, Edward Thomas of the Bureau of Mines reported. Various types of metal and wooden pins can be used. The method was first used by the St. Joseph Lead Co. over 20 years ago, but is now being studied and adopted widely in metal, nonmetallic, and coal mines. * The first ten technical graduates have reported at Hanford Works in the state of Washington, to begin the newly installed General Electric rotational training program, believed to be the first of its kind at any U.S. atomic energy plant. The program is to provide suitably trained personnel for the nation's atomic energy program. •The need for top-notch scientists and engineers to stimulate mining programs in British colonies is acute. About 60 American experts are being sought for the ECA sponsored program. Positions for mining engineers, geologists, assayers, topographers, and petrologists are open. •Production of primary aluminum for the first quarter of 1950 was 322,4250008 lb which is 6 1/2 million lb more than was produced in the first quarter of 1949. Shipments of aluminum sheet, plate, and strip amounted to 259.772,1571b for the first quarter. •Policy on manganese procurement for the stockpile is being studied by a House Armed Services Subcommittee with the possibility of lowering specifications. The U. S. Bureau of Mines is drafting a bill to encourage domestic production for stockpiling through producer subsidies. 'It will have to be cleared by the Bureau of the Budget and other agencies before going to Congress. •Oil men consider dry holes a necessary evil in their search for oil. Last year 34 out of every 100 wells drilled were dry holes. Yet Texas Technological College is attempting to drill a dry hole on its campus at Lubbock, taking every precaution to make sure it is a "duster" so its petroleum engineering students can play around with experiments without being bothered by any messy crude oil. --Natural Resources Notes. •A portable alertness indicator which signals lethargy in persons doing monotonous jobs has been developed for the Navy's Special Devices Center. A possible application to hoistmen is indicated but broaching the matter to them would be tricky.

Jan 6, 1950

By M. H. Caron

D. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron's papers today is a matter of some disappointment. Adaptations, modifications and improvements have been made by several organizations or individuals and to complete the record I want to document a number of them. The Nicaro Nickel Co. operated a Government owned plant at Nicaro, Oriente, Cuba, during the past war. A report on the project was written for Reconstruction Finance Corp. and is in the document file collected by the Office of Technical Services, Commerce Department and filed with the Library of Congress, where it can be consulted or bibliofilm or photostat copies obtained by asking for copies of PB 97271. Nicaro Nickel Co. has obtained a series of U.S. Patents, my list (probably incomplete) of which bears the following numbers: 2,400,098; 2,400,114; 2,400,115; 2,400,461; 2,400,612; 2,458,902 and 2,473,795. International Nickel Co. has also studied the problem and U.S. Patent 2,478,942 shows that some of the complications involving occasional low extractions have been unraveled. Forward, Samis, and Kudryk, of the University of British Columbia, have also published a study of copper-nickel sulphide concentrate.' Others are interested and it is evident that this type of hydrometallurgy is likely to find a happy application in the not-too-far distant future. Caron's two papers practically amount to a summation of his life's work on the important subject of nickeliferous iron ores and the American Institute of Mining and Metallurgical Engineers is fortunate to have been chosen the medium of publication. M. Rey—The ammonia leaching process has been the subject of certain studies in New Caledonia, but at the present time, the conditions are not very favorable to its adoption. The process is a combination of a thermal and a hydrometallurgical process. As a result, the first costs and the operative costs are rather high. To counteract this unfavorable situation, it would be necessary to make a very high extraction. But unfortunately, the process is delicate and in spite of all of Caron's valuable work, there are still many unknown factors. It is difficult to obtain regularly a high extraction, exceeding 75 to 80 pct. It would be interesting to have the opinion of Inter-national Nickel on the process and to know what the Dutch are doing in Celebes. M. H. Caron (author's reply)—I am quite familiar with the different types of nickel and cobalt ores as found on New Caledonia, and it may be pointed out that the Celebes ores are quite the same in their properties. Their behavior when treating the ores by the ammonia-leaching process is also alike and in my opinion, there is no reason why a high extraction of the New Caledonian ores could not be obtained if the process is properly applied. For the sake of completeness I may add that one of my patents has not been discussed in the papers. This patent deals particularly with the treatment of serpentine nickel ores. (Netherlands No. 62693 40a, French No. 965.786 April 21. 1948. and Cuban No. 13.625 Jan. 1950.) O F. A. Forward, C. S. Samis, and V. Kudryk: Trans. Canadian Institute of Mining and Metallurgy. (1948) 151 (Bull. 434) 350-355.

Jan 1, 1951

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By Alfred Siegel

Mineral pigments give color, opacity, or body to paint, stucco, plaster, mortar, cement, linoleum, rubber, and similar materials. They must be finely divided, substantially insoluble, and generally inert for such uses. Inorganic pigments may be grouped somewhat arbitrarily as follows: A. Natural mineral pigments dug from the earth. 1. Those consisting mostly of iron oxides, such as hematite and limonite. 2. Those containing large amounts of clay or noncoloring matter, such as ocher, sienna, umber, and colored shales. 3. Those whose color is not due to iron oxide, such as Vandyke brown (including sap brown, an alkali extract of Vandyke brown), graphite, and terre verte. B. Synthetic pigments. 1. Those containing iron oxide as the essential coloring matter, such as "pure" reds, yellows, and blacks, and Venetian reds. 2. Those not containing iron oxide, but rather such compounds as lithopone, zinc white, titanium white, ultramarine, Prussian blue, and the like. Only groups A and B-1 are discussed here. All the pigments in those two categories, except Vandyke brown, sap brown, and some of the carbonaceous slates, contain, as their essential color constituents, one or more compounds of iron; namely, an oxide-limonite (2Fe2O3.H2O to Fe2O3.4H20), hematite (Fe2O3), or magnetite (Fe2O3.FeO). Man's first permanent coloring materials were earth pigments-the ochers, iron oxides, and various iron-stained clays. The caves occupied by prehistoric man and the arts of the ancient Chaldean, Egyptian, and Cretan civilizations bear mute witness to this and also testify to the beauty and permanence of earth colors. As the Roman era developed, earth pigments were pushed from their pre-eminent position by white lead and red lead and in the Middle Ages by zinc oxide. Today, of course, the number of acceptable pigments is very large and on a value basis the group of natural and synthetic earth pigments stands forth with $16,000,000 per year; it is surpassed by titanium, lead and zinc pigments. Of this sum,21 natural pigments supplied 31 pct of the tonnage and 16 pct of the value of the total finished pigment in 1957, the remainder representing the tonnage and value of sales of the synthetic iron oxide colors. The average value of finished natural pigments in 1958 was $80.62 per ton. The average value of manufactured pigments in the same year was $202 per ton. Of the 60,000 tons of manufactured colored pigments sold in 1958, the reds comprised 76 pct of the market and the yellows 20 pct. The reds furnished 68 pct of the value and the yellows 24 pct. Of the finished iron oxide pigments (natural and manufactured) sold in 1958, the reds dominated the market with 66 pct of the quantity and 63 pct of the value; yellows supplied 17 pct of the quantity and 20 pct of the value, and browns furnished 11 pct of the quantity and 10 pct of the value. The average value of the reds was approximately $152, and the average value of the yellows $190 per ton. The highest valued pigment in 1958, with almost 12 pct of the total tonnage and 21 pct of the value of the iron oxide pigment market, was manufactured red from calcined copperas valued at $286 per ton.

Jan 1, 1960

By A. M. Rowe

A considerable quantity of experimental hydrocarbon K-factor data has been correlated as a function of component identity, temperature, pressure and convergence pressure. To utilize these correlations effectively, convergence pressure must be determined accurately, particularly for volatile mixtures near their critical states. This paper presents phase diagrams that illustrate physically the meaning of convergence pressure. A new method, referred to hereafter as the "critical composition method", will be outlined for calculating convergence pressure. An example calculation has been included to illustrate how to use this new technique. INTRODUCTION The principle of hydrocarbon phase composition calculations as applied to such diverse problems as optimizing separator performance or predicting fluid compositions at various stages of reservoir depletion is the same. Usually, temperature, pressure and the numbers of moles of the various components of the fluid contained in a given volume are known. Questions answered by the phase calculation are what fraction of the total mass of fluid exists in each of the equilibrium phases, and what are the mole fractions of the various components in the two phases? To answer these questions the Natural Gasoline Supplymen's Assoc. (NGSMA) has correlated a considerable quantity of K-factor data as a function of temperature, pressure, component identity and convergence pressure.l To use these correlations to obtain the best answers possible, one must be able to calculate the convergence pressure. This is particularly true for over-all fluid compositions in the neighborhood of the critical state. STATEMENT OF THEORY Use of convergence pressure as a correlating parameter is based on a postulate similar to the law of corresponding states used in correlating PVT data of hydrocarbon gases. This postulate, which proposes convergence pressure as a correlating parameter, has been stated as follows: "The equilibrium vaporization constant for one component in a complex system is the same as the equilibrium constant at the same temperature and pressure for the same number or kind of components, providing only that the convergence pressures of the two systems are exactly the same at the same temperature and that the components are of the same homologous series".2 This law, as with all laws of physics, cannot be proven theoretically. It can only be justified by experimental data supporting its premises. Arguments have been made that this law violates Gibb's phase rule. For example, consider a four-component system. By Gibb's phase rule, which is thermodynamically rigorous, f = c — P + 2 =4, for a four-component, two-phase system. Thus, four independent intensive variables must be specified to establish completely all the intensive variables of the equilibrium phases. On the other hand, according to convergence pressure theory, only three variables need be specified for any mixture containing four different components. These variables are temperature, pressure and convergence pressure. Thus, the two laws appear to be in conflict. However, the convergence pressure postulate is more restrictive than Gibb's phase rule. It applies only to mixtures of the same homologous series. Hence, these two concepts are not in disagreement. PHASE DIAGRAMS DESCRIBING CONVERGENCE PRESSURE This paper presents phase diagrams grading from the simple two-component system to the more complex four-component system to illustrate convergence pressure. A less abstract definition of convergence pressure will be stated that is

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc.* When Mr. Carnegie made his gift which made possible a home for the engineering societies, a separate corporation was organized to act as a holding company and to manage the common property. This was long known as the United Engineering Society but the name has now been changed to one which more nearly reflects the real function of the corporation. It holds title to the Engineering societies Building and to various funds placed in its charge and is managed by a Board of Trustees of which three are chosen by each of the four societies, American Institute of Mining and Metallurgical Engineers, American Society of Mechanical Engineers, American Institute of Electrical Engineers and American Society of Civil Engineers, which own equal and undivided interests in the property. The land and building cost two million dollars. The interest of each of the Founders societies, aside from especial trust funds, is now valued at $493,352. The A. I. M. E. trustees are Arthur S. Dwight, J. V. N. Dorr and H. A. Guess. George D. Barron will succeed Mr. Guess as trustee at the end of this year. The President of the Board is Francis Lee Stuart and the Secretary, Alfred D. Flinn. The Engineering Foundation The Engnieering Foundation was established in 1814 as a result of a gift of $200,000 made by Ambrose Swasey. It is intended not only "for the Furtherance of research" along broad lines but also "for the advancement of" a wide variety of other activities of benefit to engineering as need arises. The endowment fund, which now amounts to $630,000, is administered by the United Engineering Trustees, Inc. Through The Engineering Foundation board, on which the Institute is now represented by J. V. N. Dorr, John M. Callow and Galen H. Clevenger, the income of the endowment, approximately $28,000 a year, and funds contributed for special projects are appropriated for the purposes intended. H. C. Bellinger will succeed Mr. Callow on the board at the end of this year. Alfred D. Flinn is Secretary- and Director. Researches of wide interest in many lines have been aided by Engineering Foundation. . A grant from it to the Mining Methods Committee assisted in the preparation of Volume 72 of the Transactions. For several years the Foundation has aided in support of the study of Blast-furnacc Slags by R. 8. McCaffery at the University of Wisconsin, sponsored by the Institute. The Foundation has raised over $230,000 to support the Alloys of Iron Research endorsed by the Institute and George B. Water-house is serving as Chairman and Director of the Iron Alloys Committee which has been brought together to direct this work. The Foundation has also on recommendation of the Institute made a grant in aid of the studies of Mining and Strata being conducted at Columbia University by P. B. Bucky, which promise information of great usefulness relative to mine subsidence and support of ground. John Fritz Medal Board of Award The medal was established in 1902 and lias since, been awarded not oftener than annually by a hoard of sixteen members, four representatives each from the American Societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers.

Jan 1, 1930

By Harold Margalin, Elmars Ence

M. H. Mueller, M. V. Nevitt, and H. W. Knott (Argonne National Laboratory)—We have reported1 the crystal structure of Ti2CU as body centered tetragonal with a. = 2.944A and co = 10.786A, six atoms per unit cell, and space groupl4/mmm(MoSi2 type). This cell is larger but definitely related to the unit cell reported by the authors. It permits definite positions for the titanium and copper atoms in the cell located as follows: 2 Cu (a) 0 0 0; 1/2 1/2 1/2 4 Ti (e) 0 0 z; 1/2 1/2 1/2 + z; 0 0z; 1/2 1/2 1/2- z where z = 0.341 The face centered tetragonal cell reported by the authors can be transformed to a small body centered tetragonal cell with flo (small bet) = ao(fct)v2 Both unit cells have the same CO. Neither the face centered tetragonal cell with four atoms per unit cell nor the small body centered tetragonal cell with its two atoms per unit cell lend themselves conveniently to an orderly arrangment of the 2 to 1 ratio of titanium to copper atoms. When the co of this small body centered cell is tripled, however, a large body centered tetragonal cell results with six atoms per unit cell as described above. We had also noted that the X-ray patterns of Ti2Cu indicated that the structure could be approximately described by the face centered tetragonal cell as reported by the authors; how- ever, there was evidence for a few additional very weak lines whose positions indicated a larger unit cell. Since the X-ray scattering amplitudes of titanium and copper are nearly equal, it is evident that it is difficult to distinguish their positions especially from X-ray powder patterns. It was therefore decided to look at a powder pattern obtained by neutron diffraction since the scattering amplitudes of the two elements are considerably different in magnitude and opposite in sign. The sample used for neutron diffraction was selected from a group of three alloys prepared by arc melting using crystal bar titanium of 99.92 pet nominal purity and 99.999 pet pure Cu. The alloys designated as A, B, and C had the following respective compositions: Ti-32.8 at. pet Cu, Ti-33.3 at. pet Cu, and Ti-33.8 at. pet Cu. On the basis of the melting losses incurred, it was established that the actual concentration of either component in any of the alloys probably did not deviate from the intended value by as much as 0.1 at. pet. The alloys were annealed for 5 days at 700°C in evacuated Vycor capsules and quenched in tap water. The metallographic structures of these alloys are shown in Fig. 1. None of the alloys contained sufficient second phase to permit its positive identification. Since alloy B contained the least amount of second phase and since its composition placed it closest to the ideal stoichiometry, it was chosen for the neutron diffraction study. The oxygen content of alloy B was found by chemical analysis to be 0.06 at. pet. This particular intermetallic compound is especially suitable for investigation with neutron diffraction since if the titanium and copper atoms have a random statistical distribution, a near null-matrix would result in which there would be practically no coherent scattering of neutrons, and hence no Bragg diffraction peaks. Such a condition could come

Jan 1, 1962

By J. E. Gruzleski, O. Knacke, M. J. Meixner

The evolution of CO from small specimens of solidifying steel was investigated using a thermobalance technique. Gas evolution begins in the temperature range between 1400" to .1450°C. This behavior is independent of the initial carbon content and the cooling rate. At a constant temperature above 1220°C, the rate of gas evolution is temperature independent. Out-gassing of the specimen is thought to proceed through small channels formed by the coalescence of bubbles between dendrites. LIQUID metals have a higher solubility for gas than the solid. During freezing, these gases form bubbles which may either escape or remain trapped in the solid. Recent work1 on the evolution of oxygen from solidifying silver showed that the gas is not liberated until a large fraction of the melt has solidified, and that the gas is evolved in an almost explosive manner. Because of the commercial importance of CO evolution in solidifying steel, a similar investigation was undertaken to study the mechanism of gas liberation in steel. EXPERIMENTAL The thermogravimetric method of Knacke and eixner1 to follow gas evolution by weight changes was employed. Weight differences of 0.1 mg could be reproducibly measured on specimens weighing 2.5 g. These specimens were taken from alloys with varying carbon contents from <0.01 to 0.11 wt pct and <0.01 wt pct of each of silicon, manganese, and aluminum. Specimens contained in 8 mm ID magnesium alumi-nate crucibles were heated to 1550°C under 1 atm of very pure (99.995 pct) CO with a tungsten resistance furnace. The specimen temperature was measured with a Pt-Pt/Rh thermocouple located directly beside the crucible. It is felt that the temperature thus measured was within 5" to 10°C of the specimen temperature since on fusion the weight of the specimen increased due to uptake of CO, and this weight increase was always observed to begin within the temperature range of 1530" to 1540°C. Even after 3 hr there was a small weight increase with time indicating that the molten specimen was not completely saturated with CO. Therefore, complete saturation was not attempted, and all specimens were simply held for 3 hr at 1550°C before cooling. Two types of cooling experiments were performed. One consisted of continuous cooling at linear rates from 5°C to 20°C per min down to 1020°C. The second type of experiment involved continuous cooling at 10°C per min to a predetermined temperature, and then holding the specimen at this temperature for a certain time. During all of these experiments, the sample weight was recorded as a function of time and temperature. OBSERVATIONS Continuous Cooling Experiments. No gas evolution was detected above 1450°C. The initial weight decrease always occurred between 1400" and 1450°C with the average at 1430°C. With further cooling, gas evolution continued to about 1150°C. Between this temperature and 1020°C no further outgassing was observed. This behavior did not seem to depend on the initial carbon content nor on the cooling rate in the range investigated. Typical patterns of gas evolution are shown in Figs. 1 and 2 for different initial carbon levels and cooling rates. The total amount of gas liberated during solidification varied with the rate of cooling. The total weight change on continuous cooling at a rate of 10°C per min

Jan 1, 1970

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;&apos; the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By H. R. Brannon, R. J. Robinson, G. W. Kattawar

Accurate prediction of storm wave characteristics are needed for design of offshore structures. Statistical methods of random noise analysis provide techniques for predicting required wave properties. These techniques have been used to analyze and characterize storm wave profiles from Gulf of Mexico recording installations in 34, 65 and .98 ft of water. Correlations based on the results can be used to predict wave crest probabilities and wave shapes for a range of Gulf water depths and storm conditions. Example predictions of wave crest probability as a function of water depth for a particular set of storm conditions are given. INTRODUCTION Accurate predictions of wave crests and wave shapes are needed for design of offshore structures. With predictions of wave crests, platform deck elevations giving adequate protection from exposure to storm waves can be selected. Use of hydro-dynamic wave theories with the wave crest and wave shape predictions permits an estimate of the wave forces an offshore structure must withstand. Observation of ocean waves suggests use of statistical analysis for studying wave characteristics for water depths beyond the breaking wave zone; recent wave generation theories lend support to this approach. l-3 One of the most powerful methods of statistically analyzing wave profiles was introduced by Cartwright and Longuet-Higgins; most of the basic relations used were developed by Rice5.6 in studies of random noise theory. This method predicts wave crest elevation probabilities from two parameters characterizing a wave profile. The statistical approach also provides a means for predicting wave shapes. In the random noise model of a wave profile, surface elevation is represented as an infinite sum of sine waves with closely spaced frequencies and random phase angles. Power density is proportional to the sum of the squares of the amplitudes of sine waves having frequencies within a narrow band, and the distribution of power density as a function of frequency is called the power density spectrum, or power spectrum. The power spectrum characterizes an irregular sea, and hence finds use in motion studies of ships, barges and semisubmersible drilling platforms. From the power spectrum, a wave profile of any duration of time can, in principle, be calculated; this long wave profile depicts the many wave shapes to which a structure may be exposed. Thus, the statistical methods of wave analysis provide an approach to selecting wave shapes as well as wave crest elevations needed for design of offshore structures. For practical application of these techniques, power spectra and related quantities must be predicted from storm properties. Barber and Tucker 7 have reviewed correlations of wave properties and storm conditions. Their review summarizes work of Darbyshire,8 among others, in which a correlation of power spectra with wind intensity of the North Atlantic was developed. These results, plus more recent work by Pierson and Moskowitz and Kitaigorodskii,10 establish feasibility of correlation, but there is no theoretical basis for modifications extending the relations to other areas as remote as the Gulf of Mexico. Hence, to predict characteristics of Gulf of Mexico waves, a study of local observations is needed. This paper presents (1) a practical approach to computing wave profiles hat depict shapes of waves for use in force calculations, (2) a summary of relations for predicting probabilities of wave crest elevations, (3) correlations of parameters needed to apply these methods in the Gulf of Mexico and (4) examples of application of the techniques. THEORETICAL BACKGROUND The following sections summarize relations needed to calculate wave profiles and to estimate wave crest probabilities. These relations also identify quantities that must be related to storm

By A. Berghezan, E. Bull Simonsen

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

Jan 1, 1962

By C. W. Phillips, D. N. Frey

A commercial Ti-Fe-Cr alloy, Ti-150, exhibits a martensitic transformation on cooling and two nucleation and growth reactions, one above and one below the Mg-Mf region, on isothermal holding below the single-phase ß temperature range. The reactions were followed by metallographic, X-ray diffraction, and microhardness methods. THE rapidly expanding engineering application of titanium and its alloys makes increasingly urgent an adequate knowledge of the effect of heat treatment on this material. The work herein reported is an attempt to determine certain aspects of the behavior of a commercially available alloy, Ti-150, during heat treatment. The alloy, with a nominal composition of 2.7 pct Cr, 1.3 pct Fe, 0.25 pct 0, 0.02 pct N, and 0.02 pct C, was received in the as-rolled condition as a 3/4 in. round. Slugs 0.11 to 0.12 in. thick were cut under a coolant using a silicon carbide wheel. Preliminary work established that the alloy consists of two phases, a (hexagonal close-packed) and /3 (body-centered cubic), at temperatures below 1750" to 1775"F, and of only /3 phase at higher temperatures. The slugs were heated for 1 hr in air at 1800°F to form a single-phase /3 matrix, then transferred to molten tin (1250° to 1650°F) or lead (1150°F and below) for isothermal holding. Holding temperatures ranged from 700° to 1650°F, times from 0.001 to 23 hr. The treated slugs were then sectioned, one part for metallographic examination and diamond pyramid hardness, the other, after deep etching to remove the high oxygen surface,&apos; for comparative lattice parameter determination and X-ray phase identification. Hardness measurements were taken on the lightly etched surfaces of the metallographic specimens; a 1000 g load on a 136° diamond pyramid was used. Five impressions on each sample were made and the average of the hardness calculated. The use of microhardness measurements to follow the course of an isothermal transformation reaction is undesirable because of the possibility of wide differences in microconstituent hardness.&apos; They were used in this case, however, because of the small amount of material available. At the higher transformation temperatures, where the above-mentioned objection was apparent, the readings were proportioned to correspond to the estimated ratio of transformed and untransformed constituents present. At lower temperatures, resulting in much finer microconstituents, the microhardness measurements were more uniform. The standard deviation of the mean of five impressions calculated from these latter values was 4.2 DPH. Employing 2a limits (probability 0.95) the experimental error of the hardness measurements averages was 8.4 DPH. The etchant used was composed of one part glyc-erol and one part 48 pct hydrofluoric acid." Of a number of etches tried, this one appeared most satisfactory. All micrographs were taken at 500X magnification and with oblique lighting to permit easier identification of the acicular structure resulting from rapid cooling. No advantage was gained by using polarized light for metallographic examination. Phase identification and lattice parameter measurements were made with a North American Philips high angle spectrometer in conjunction with a recording potentiometer. Considerable difficulty was encountered with some of the lattice parameter measurements because of the extreme broadness of the few diffraction lines obtained from samples consisting mainly of strained, untempered, quenched structures.

Jan 1, 1953

By G. H. Pardue, L. H. Gollwitzer, J. H. Moran, R. L. Morris

Experimental and theoretical studies of casing-borne signals have provided data on the attenuation efect, compressive strength and shear modulus for different types of cement. These data resulted in the establishment of a definite relationship between the cement compressive strength and the Cement Bond log reading. The relationship is influenced by the casing dimensions, but is independent of the type of cement and the curing conditions. The theoretical analysis provides a mathematical statement of the phenomenon and shows that the attenuation rate is basically a function of the shear modulus of the cement and the thickness of the casing. The lab tests provided a connection between the shear modulus and the compressive strength, and permitted a comparison of the experimental and theoretical work. The results of the experimental and theoretical study have provided means of quantitative interpretation of the Cement Bond log. This interpretation is made more convenient with the use of a nomograph. INTRODUCTION Past interpretation of Cement Bond logs has been essenlially based upon a qualitative comparison between the log response in the zone of interest and the responses in the "fully cemented" and the "uncemented" intervals. Most of the variables influencing the magnitude of the signals were recognized in an earlier paper&apos;; however, insufficient laboratory data were available at that time for quantitative evaluation of these variables. Early attempts to use the numerical amplitudes of the signals without full knowledge of their significance resulted in erroneous comparisons between various types of cement. An extensive program was undertaken to evaluate, both experimentally and theoretically, the attenuation phenomenon and to study the effects of the more common variables. A major objective of the experimental program was to obtain data on the relationship between cement-bond-tool response and physical property standards used by the industry so that practical interpretation methods could be devised. The studies included a comparison of attenuation rate with these properties as a function of time, temperature and pressure, using common sizes of casing. The main result was that a definite relationship was established between the compressive strength of the cement in inti- mate contact with the casing and the response of the cement bond tool. For a given casing thickness, regardless of the type of cement or the curing conditions used, the attenuation rate is a function of the compressive strength. A theoretical analysis showed that the attenuation rate for casing-borne signals should be a function of (among other things) the shear modulus of the cement and the thickness of the casing. The relationship between the compressive strength and shear modulus for curing times similar to those encountered in the field was determined from laboratory tests. Using this relationship, the computed attenuation rates showed reasonable agreement with the measured attenuation rates. The purpose of this paper is to report the results of the experimental and theoretical investigations and to present the first practical method for a quantitative interpretation of Cement Bond logs based on known variables. This method is applicable where the casing-borne signal is not affected by high-velocity formation arrivals. DESCRIPTION OF LOGGING TOOL The Cement Bond logging tool shown schematically in Fig. 1 has been described previously.&apos; The tool consists of two sections: acoustic and electronic. The acoustic section contains a transmitter and a receiver, usually spaced 3-ft apart. Sonic energy emittted by the transmitter travels through the casing and is detected at the receiver. The electronic section measures the amplitude of the

By William E. Galloway, Gary E. Smith, Christopher D. Henry

INTRODUCTION Studies relating to the Oakville aquifer as presented in this report and by Henry et al. (this volume), are part of a larger , comprehensive examination of regional and local stratigraphic, hydro- geologic, and geochemical parameters within the Oakville Formation recently completed by the Bureau of Economic Geology. The Oakville serves both as a major Gulf Coast aquifer and an important uranium host (Fig. 1). Regional and local controls on hydrodynamics and hydrochemistry have important implications for hydrochemical exploration, the establishment of premining baseline parameters, and the design of post mining restoration procedures. Investigations of the Oakville Formation were de- signed for the purpose of determining the response of the aquifer to uranium extraction and were funded by the U.S. Environmental Protection Agency under grant numbers R-805357-01 and R-805357-02. Physical Stratigraphy Physical stratigraphic analysis shows that the Oakville Sandstone, a lithostratigraphic unit deposited by a major coastal-plain f luvial system, consists of five mappable, component depositional elements (Figs. 2 and 3). Each major component element is the product of one or more rivers traversing the Miocene coastal plain. In turn, each river possessed a unique sediment load, discharge characteristics, and source terrane. Consequently, each element exhibits distinguishing geometric and compositional parameters that potentially influence the flux and hydrochemical evolution of contained ground waters (Galloway, Henry, and Smith, in preparation). The Oakvil le Sandstone, as mapped and interpreted as a lithostratigraphic unit in the study area, corresponds closely to the Jasper aquifer system, an equally well-defined Gulf Coastal Plain hydrogeologic unit (Baker, 1978). Principal surrounding hydrogeologic units include the underlying Catahoula confining system, the Jasper aquifer system itself, and the overlying Burkeville confining system (lower Fleming mudstones). The Evangeline aquifer system includes much of the Fleming Formation. The Jasper aquifer system is bounded above and below by relatively less transmissive, finer grained confining systems, although absolute transmissivity varies greatly within both the Jasper and confining units. Lithostratigraphic and hydrogeologic boundaries coincide almost exactly within the Hebbronville flu- vial axis (Fig. 3). Correspondence of geologic and hydrostratigraphic boundaries is good within the George West axis; farther to the northeast the correlation of the Jasper aquifer with units mapped as Oakville Formation diverges to varying degrees. A complete analysis of these trends and a study of the depositional facies comprising the Oakvillle are included in Galloway, Henry, and Smith (in preparation). REGIONAL HYDROGEOLOGY The stratigraphic, compositional, and structural framework of the Oakville Formation and the mosaic of interrelated depositional facies that are combined in this framework play a key role in defining the hydrogeology of the Oakville. Furthermore, a combination of climate and hydrogeology, as well as past and present socioeconomic conditions, has determined water and land use patterns within the region of Oakville outcrop. Utilization of Oakville Ground Water Stratigraphic control for determining which wells produce ground water from the Oakville aquifer was established by preparing structural and isopach maps of the Oakville Formation using regional electric log cross sections. Surface elevation and screened interval data (or total well depth, if open-hole completion techniques were used) from each water well, combined with the stratigraphic data, allowed accurate assessment of the producing aquifer for individual wells. Information on well and screen depths, water levels, and usage of water from

Jan 1, 1980

By Oliver Bowles

Dimension stone is a term applied to stone sold in blocks or slabs of specified shapes and usually of specified sizes, contrasted with crushed, broken and pulverized stone covered in another chapter. Dimension stone includes cut stone, rough building stone, ashlar,* rubble, monumental stone, paving blocks, curbing, flagging, and many types of ornaments and novelties carved from stone. Riprap-large, irregular blocks used for shore protection-is classed with crushed and broken stone. Composition, Varieties, and Properties Dimension stones are of many kinds. The principal varieties are granites, trap rock (diabase, basalt, and gabbro), sandstone, limestone, and marble. Slate is covered in a separate chapter. Granite is a visibly granular crystalline rock consisting essentially of feldspar, quartz, and mica or hornblende. The basaltic rocks are darker in color than the granites. They contain little or no quartz and consist largely of plagioclase feldspar, augite, pyroxene, and hornblende. They are classed commercially as black granites. Limestone consists essentially of calcium carbonate. Dolomites and magnesian limestones used as dimension stone are classed with the high-calcium limestones. Marble is a crystalline form of limestone, but in the trade, any carbonate rock which will take a polish is called a marble. Many limestones which are fossiliferous but which will take a polish are sold as a decorative stone for lobbies of hotels and office buildings. Sandstone consists essentially of silica in the form of sand grains cemented into a coherent mass. Although rock occurrences are numerous and widespread, the exacting requirements of use condemn all but a small fraction of them for commercial use as dimension stone. No deposit that has closely spaced joints or planes of weakness can be used because sound blocks of moderate to large size are demanded. Uniform texture and grain size, constant and attractive colors or color pattern, and freedom from impurities that may cause stains or deterioration usually are demanded. Hardness is a variable property. Granites and diabases are as hard as or harder than steel, while limestones and marbles may be scratched with a knife. The hardness of sandstone depends upon the degree of cohesion of the grains. Workability depends to a considerable extent on hardness, but the degree of hardness has little influence on use except where stones are subjected to abrasion as on steps or floors. "Texture" as applied to stone relates to the arrangement, uniformity, and size of the constituent grains. Stones are of many colors and thus can satisfy a variety of tastes. For monumental stone, a marked contrast between polished and tooled surfaces is preferred in order that inscriptions may be read easily. Strength requirements usually may be disregarded because any sound structural stone suitable in other respects is almost invariably many times as strong as would be required for any ordinary use. The pressure on the base course of the Washington Monument, Washington, D. C., is less than 700 psi, and highgrade granites, limestones, sandstones, and marbles will sustain a crushing load of 10,000 to 25,000 psi. A structure made of stone with a crushing strength of 15,000 psi would have to be nearly 21h miles high before crushing of the lower courses would occur. However, stone disintegrates more readily under severe

Jan 1, 1960

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953