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By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By J. S. Kennedy, G. L. Simard, A. A. Lefrew, C. M. Judson, R. B. Booth

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By J. S. Kennedy, A. A. Lefrew, C. M. Judson, R. B. Booth, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By Walter E. Duncan

THE ores treated at the concentrating plant largely come from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately intergrown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four concentrates: (I) lead concentrates, (2) zinc concentrates, (3) acid-grade fluorspar concentrates and (4) metallurgical-grade fluorspar concentrates.2,3 Although fluorspar had been floated in Canada in 1921 4 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Mines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; such as, for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1946

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,1 see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in California, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War II. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eightman crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on.2 Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1952

By W. R. Seyfried

THE -problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations, An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper, The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reaent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp, became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant, By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1492°F). (b) The roasted ore would then be leached .with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1948

By Stephen G. Dardaganian

Pore volume compresibilitieu measured in the laborutory on core .samples are reported for typical reservoir .sarrrl.rtorres at reservoir pressure. These cornpressibilities ore different for each reseriloir sample and cannot be correlated to porosity. The compressihilities are a1so functions of presslire. In recent years several authors have pointed out the importance of including pore volume compressibility of the reservoir rock in certain reservoir engineering calculations. Hall' showed that in calculating the hydrocarbon volume of an undersaturated reservoir from the production per unit change in reservoir pressure, the neglect of rock compressibility could, in the extreme case of low porosity rock, lead to results in error by a factor of two. Hawkinsl' and Hobson and Mrosovsky showed that both rock and interstitial water compressibilities must be included to achieve satisfactory accuracy in this calculation. Although rock compressibility is an important reservoir property in these calculations, very few data are available. Hall' made compressibility measurements on a few samples in a small pressure range. No other direct pore volume compressibility measurements have been reported. Geertsma' discussed the elasticity of reservoir rock but did not present any new data. In this paper, rock compressibilities suitable for reservoir calculations are reported for a variety of sandstones typical of U. S. reservoirs. The measurements were made through a range of pressures which is also typical of reservoirs. EXPERIMENTAL PROCEDURE Plugs 1 in. in diameter and 2- to 3-in. long were diamond drilled, 14 from cores from seven oil-bearing or potentially oil-bearing sandstone, one from a quarried sandstone, and another from a shallow, oil-free, pure orthoquartzite. The plugs were extracted in toluene, vacuum dried, and then weighed. The plugs were then saturated with kerosene and reweighed. This gave pore volume. They were then again extracted in toluene. vacuum dried, and jacketed in 0.004-in. thick copper foil. A short length of -in high pressure tubing led from the jacket. The jacketed sample was then saturated with kerosene and placed in the hydraulic pressure cell as shown in Fig. 1. Movement of the mercury slug showed the change in pore volume of the sample under a given pressure change. Temperature was about 72" F for all measurements. Before taking any measurements, the external pressure on the sample was raised to 10,000 psig and kept there for several hours. This formed the thin copper jacket around the plug. 7-he pressure was then removed and the sample left at least overnight, during which time it recovered its original pore volume. An external pressure of 12,000 psig was then applied and held constant. The change in pore volume was noted as the internal pressure was raised in 1,000 psig increments to 10,000 psig. The internal pressure was then reduced to zero, again noting pore volume changes,

By Frederick W. DeVries

Since we first agreed to present this talk we have learned that some of you may have been covering ground we intend to discuss: Bob Schechter, Daryl Tweeton, Don Seidel, Herb Burgman; however, the ideas were original when we began, "novel" as in the title of the talk, and whether our results are news or merely corroborative, we feel they point a direction that could be valuable to all. We worked with many of you in the past on using hydrogen peroxide in in-situ uranium leaching. Our talk today is not directly related to peroxide; it is, I hope, illustrative of Du Pont&apos;s interest in providing service to this industry in any way we can. The scouting work we are presenting was stimulated by field inputs: First, ammonium carbonate leaches cause restoration problems, primarily because ammonium ions exchange on clays with calcium. Second, sodium carbonate solutions, especially in South Texas deposits, can cause intolerable swelling of clays. From discussions with Dr. van Olphen, who wrote the book on clay chemistry, we inferred by comparison of the radii of the hydrated ions of the elements in these clay systems, that since potassium had about the same radius as ammonium, and sodium was much larger, potassium occupied a unique position to solve both problems. We have shown: FIGURE 1 Potassium bicarbonate systems leach uranium without loss of permeability found with sodium Potassium salts are very effective in restoring ammonia-leached sites Before reviewing the details of our work, which was performed by Hazen Research, Inc., I should like to stress its scouting nature. We are trying to assist the in-situ industry by pointing out new, potentially important directions. But, as with our previous work on sodium silicate to restore permeability, we feel the development phases can generally best be carried out in cooperative programs with companies directly involved with operations. DISCUSSION Test Parameters Now for the details: Our leaching tests were designed to note pressure-drop changes across the ore sample as the uranium was leached. Figure 2 shows the apparatus. The [ ] packed length was 20.5 inches (52 cm) with fifteen hundred grams of ore in the two-inch (5 cm)-diameter bed. Pressure drop was measured by manometer and feed rates were maintained constant with a tubing pump. The samples, from a South Texas leach site, were sealed in "Zip Loc" bags, frozen with "dry ice", crushed (still frozen) through six mesh, and blended before placement into the columns. The ores analyzed as shown here: FIGURE 3 Ore Analyses [Sample A Sample B U308 015% 0122% Mo 0004% 0086% Se0012% <0001% Fe3,078%076% Fee- 098% 044%]

Jan 1, 1979

By H. Le Chatelier

An evident connection exists between chemical and calorific phenomena: the most important, of our sources of heat, the combustion of coal, is nothing else than a chemical reaction. Not satisfied with this indefinite statement, investigators have attempted to establish a more precise correlation between these two orders of phenomena, and have questioned whether there be not a necessary connection between the possibility of a chemical reaction and the algebraic sign of the quantity of heat which it would call into play (i.e., liberate or absorb). This question possesses the highest interest for metallurgical chemists. But the study of it by experimental methods only could not completely elucidate it. To arrive at a definite solution, it was necessary to appeal to a science much more general than chemistry,—namely, that of energetics, which embraces all the physical sciences. We can place absolute confidence in its conclusions, because they rest upon a proposition which can scarcely be denied, namely, the impossibility of The main facts in the history of the development o‡ this field of Triassic coals have been already set before the Institute in the papers of Mr. Oswald J. Heinrich, a former member of the Institute and the superintendent of the mines at Midlothian. † From these and other references to the field, it appears that coal was known to exist here as early as 1701; for on the 10th of May that year Colonel Byrd reported to the Colonial Council of Virginia the discovery of coal. Coal was mined from 1770 to 1780; but the amount shipped is unknown. It was much used in Richmond at this early date for gratefires. In 1789 shipments were made to northern ports. During the first half of the century just passed, mining operations attained in this field their greatest development, the number and extent of the collieries and the tonnage of coal raised per annum being greater for that period than for any similar period since. The maximum annual output exceeded 100,000 tons, while in two years only since the Civil War has the amount of coal raised exceeded 50,000 tons. This field covers about 150 sq. in. Its outline and the position of the strata in which the coal-outcrops occur are shown on the accompanying map, reproduced from the latest survey by the U. S. Geological Survey. Mining has been carried on along the margins of the area, often in the primitive manner in vogue at the beginning of operations, by means of shafts and slopes, usually too small in cross-section to permit the proper working of the beds. Most of the output has been won from

Jan 1, 1902

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-&apos; "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~&apos; for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang&apos;s value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- &apos; mole per cal, and a Cdil value of 2.3 x 10&apos; ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-&apos; per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang&apos;s value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-&apos; mole per cal, which is much

Jan 1, 1969

By Joseph E. Worthington

Many thousands of years ago when our earliest ancestor first swung out of a tree, picked up a rock, and threw it at what he hoped might be his lunch, the minerals industry, in a manner of speaking, was born. It was then a very long step indeed to the primitive metal industry of our early civilizations, for we know that precious metals were accumulated and some metal objects were produced several thousand years ago. Prospecting, or "exploration" to use the modern euphemism, consisted of little more than outcrop examination and the use of a gold pan, and it probably did not change much from our earliest civilizations until relatively recent times. In a general sense, all the early explorers of North America were also prospectors, for mineral wealth was certainly one of the goals of the first pioneers and settlers. The earliest pioneers didn&apos;t do too badly either, for they discovered copper and iron in various places in the Appalachians and Michigan, gold in the Southeast Piedmont and many mineralized areas in the Southwest. In most places these were outcropping ores or gossans, and the prospecting was incidental to the arduous task of ekeing out a living in a new land. It was the explosive discovery of rich placer gold deposits at Sutter&apos;s Mill in California that caught the public fancy and precipitated the establishment of prospecting as a full-time occupation. After the end of the Civil War in 1865, full-time prospecting became an important occupation and continued as such for almost three generations. Prospectors equipped with picks, shovels, gold pans and four-footed transportation swarmed all over what are now our Western States, discovering thousands upon thousands of mineral showings-and certainly most of today&apos;s large mining districts. Our vigorous western mining industry is a tribute to the courage and persistence of these men. The techniques of these picturesque prospectors, however, were essentially the same as those of their predecessors-examination of every outcrop and assiduous use of the gold pan. The great increase in discovery at this time was therefore due to increased activity rather than to different techniques. An important result of this in- creased prospecting was the growth of interest in geology. It was during this period that the U.S. Geological Survey began to grow. Many of the major mining districts were mapped, and geological studies and projections began to have an impact on further ore discovery. Ore search and development gradually became more geologically oriented and the geologist became a fixture in most mining camps by the 20th century. The development of mass-mining techniques in the early part of the century also changed exploration concepts.

Jan 1, 1971

By J. K. Stanley

It has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, rema-nence, and coercive force change on cold-working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures—a subject of practical importance in soft magnetic materials—and the other was the feeling that a study of cold-working and strain relief might shed some light onour understandingof what takes place in the deformation of metals. Definition of Terms It is necessary to define the terminology used in this Paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. 1 the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H. (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely demagnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, . Thus u= B/H and if the magnetizing force H (oersteds) is specified as ro or 100 oersteds, the permeability is written as or l00 This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or I00 are chosen as indices for 106

Jan 1, 1945

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported&apos; only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.&apos; Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C&apos;u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon&apos;-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -&apos; and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By G. C. Wallick

Since the appearance of the paper, "Solution of the Equations of Un-steady State Two-Phase Flow in Oil Reservoirs," by W. J. West, W. W. Garvin, and J. W. Sheldon,&apos; a two-fold investigation of this subject has been carried out. One objective of the investigation has been to deter-mine the feasibility of solving such problems 7on a medium-size com-puter such as the Datatron*, and the other objective has been to in-vestigate the application of such cal-culations to experimental and theo-retical petroleum reservoir research. In the first Datatron calculations, the fluid and rock properties published by West, et al, were used, together with the published equations describ-ing the system. Details of the formu-lation not given in the original paper are discussed in the Appendix to this note. Reference should be made to the subject paper for the complete equations and defintion of symbols. An unexpected result of this in-vestigation was the discovery that the linear solution published by West was in error. Thus, in addition to describing the Datatron solutions and to discussing certain numerical diffi-culties which will be encountered if one uses the published method of solution, the purpose of this note is to indicate the nature of this error. LINEAR FLOW Since the linear case requires a minimum amount of scaling, a fixed-decimal point Datatron program was written for the one-dimensional flow problem and an attempt was made to duplicate the solution described by West. In the case described, fluid was produced at a constant rate, Q, until such time as well pressure reached 0.04. Production was then continued at constant pressure. From the constants and curves given by West it was determined that the ini-tial constant production rate could be approximated by Q = 0.007. An ini-tial dimensionless time step ?t = 0.434 X 10 - "as used, and each suc-cessive time step was doubled until a value of = 0.444 was reached. This constant interval was then used for the remainder of the solution. In subsequent solutions, several varia-tions in the time schedule were em-ployed, including smaller time steps and slower rates of increase in the time steps. In all cases, almost identical results were obtained regardless of the time schedule employed. However, as described below, it was noted that the time schedule had some influence on the rate of convergence of the solutions. As a check on the accuracy of the solution, the cumulative production at each time step was calculated using the two methods described in the Appendix. Satisfactory agreement was observed with the differences in these two values of the order of two parts in 50,000. It should be noted that the mass balance check as described is of questionable value, particularly with regard to the well pressure and saturation. This is especially true in the radial solution where pressure and saturation values near the wellbore would make only a negligible contribution to the numer-ical integration. It is believed, how-ever, that such a comparison is ot value in determining the over-all accuracy of a solution. In comparing the Datatron solu-tion with that published by West it was discovered that in the later stages of depletion, the pressures near the well declined more rapidly in our solution than in the West solution, and that the limiting well pressure of 0.04 was reached at an earlier time than that originally reported. It thus became evident that it would be impossible to duplicate the production schedule described by West and a constant rate of production was maintained until the well pressure was equal to 0.0. A representative comparison of the results published by West with those obtained in this investigation is shown in Fig. 1, which is a plot of GOR as a function of cumulative recovery. These two curves should be in agreement until a cumulative recovery is reached which corresponds to a well pressure of 0.04 — for the Datatron solution, a recovery of approximately 5.6 per cent. Actually, a major disagreement is evident. Subsequent correspondence

Jan 1, 1958

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.&apos; The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.&apos; Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900&apos; to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,&apos; when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.&apos; DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature&apos; giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.&apos; If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

Jan 1, 1931