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By H. Cecil Spicer

THE results described in this article are based on field work conducted during the periods April-May, 1939, and May-July, 1940. The United States Potash Co. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation was completed under a cooperative arrangement made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an effort was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. EARLIER STUDIES Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedel1 and Messrs. Schlumberger2 reported geophysical work performed in the discovery of the salt domes of Alsace; Carrette and Kelly3described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlumberger5 in a communication. Messrs. Alty6 described studies on salt deposits in which the single-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performed with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 8oo ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,11 through the courtesy of Harry Aurand, of the Midwest Refining Co.

Jan 1, 1941

[EXEOUTIVE OOMWITTEE OF TEE BOARD OF DIREOTORS DONALD H. MCLAUGHLIN, Chairman WILBER JUDSON, Vice-Chairman JOHN L. CHRISTIE CLYE E. WEED FELIX E. WOBYSER]

Jan 1, 1946

By Charles H. Kline

Industrial minerals are the Cinderella of the mining I industry. Often considered as just dirt by traditional hard-rock miners and oil drillers, these products nonetheless comprise the second largest segment of the industry and the fastest-growing one. With annual sales of $5.7 billion, industrial minerals make up 22% of the dollar value of U.S. mineral consumption. By contrast, metals account for only 11%. Fuels, of course, are dominant, representing 67%. The dollar values of production and consumption for the three segments of the industry in 1968 are shown in Table I. The growth rate of industrial minerals is shown in Table II. From 1953-1968, the current-dollar value of all U.S. mineral production increased at the average annual rate of 3.8% while that of the gross national product increased at 5.9%. Industrial minerals are the only segment of the mining industry that approached the growth of the overall economy in this period, with production values increasing 5.1% a year and apparent-consumption values 5.6% These data, expressed in current dollars, include the effects of inflation. The growth in U.S. industrial minerals production is even more striking when expressed in indexes of physical production. As shown in Table III, production of all U.S. industries increased by 4.1% a year from 1953 to 1968. The growth in production of stone and earth minerals just matched this figure. By contrast, the average annual increase for oil and gas was 2.2%: for metals, 1.6% : and for coal, only 0.6 %.

Jan 1, 1970

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By E. V. Potter, H. C. Lukens

In general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation1 the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. Apparatus The apparatus used in these investigations is essentially the same as that used in the manganese work1 and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in gas volume are measured by volume gauge C which is essentially another mercury manometer in which the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 60 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. Method The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient tirne intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1949

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By H. Cecil Spicer

THE results described in this article are based on field work conducted during the periods April-May, 1939, and May-July, 1940. The United States Potash Co. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation was completed under a cooperative arrangement made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an effort was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. EARLIER STUDIES Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friede1 and Messrs. Schlumberger2 reported geophysical work performed in the discovery of the salt domes of Alsace; Carrette and Kelly3 described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlumberger5 in a communication. Messrs. Alty6 described studies on salt deposits in which the single-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performed with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to B00 ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,11 through the courtesy of Harry Aurand, of the Midwest Refining Co.

Jan 1, 1941

The Pinto Valley, Arizona, plant of Cities Service Company is one of the newest copper producers in the United States, having started production in 1975. It is located a few miles west of Miami, Arizona, on the site of the Castle Dome Mine, a World War II operation which was shut down and its mill later moved and renamed the Copper Cities plant. The Pinto Valley concentrator uses six 18 ft (5. 5 m) diameter by 21 ft (6.4 m) long, 4000 hp, single-stage ball mills, taking crushed ore from four 7 ft (2. 13 m) standard and eight 7 ft shorthead crushers. It has a design capacity of 40,000 stpd but has higher tonnage capability for an expanded concentrator. The copper porphyry-ore is mined by two 15 yd and one 20 yd shovels (11.5 and 15.3 cu m) and is transported to the primary crusher by 150-ton trucks. The dump pocket is relatively shallow (14 ft or 4. 27 m deep); and because of the width necessary for the 150-ton trucks, it was designed to use the ore itself instead of manganese steel as an abrasion- resistant lining, although a heavy steel cap protects the dump pocket top edge. The pocket has a capacity of 300 tons of ore. Water sprays under the dumping positions direct a fog toward the truck being dumped for excellent dust control. Breaking of oversize is done by a hydraulic impact breaker mounted on a hydraulically operated articulated arm situated at the side of the dump pocket. Again because of the shallow pocket, no splitter is used to protect the spider of the 60 in. by 89 in. Traylor gyratory crusher, which is equipped with a hydroset mechanism. Crushed ore at 8 in. (203 mm) drops into the 360 st surge chamber lined with AR plate and then is fed directly to the 60 in. (1.52 m) stock- pile conveyor by an 84 in. by 20 ft (2. 13 m by 6.1 m) four-speed apron feeder at a rate of up to 4000 stph. Early in 1977, Cities Service will replace the four -speed electric drive with a hydraulic pump and motor with infinitely variable speed. They are also studying the replacement of the apron feeder with an 8 ft wide (2.44 m) belt feeder similar to those at Similkameen and Palabora. Peak crushing capacity would then be increased to 5000 stph. The AR plate in the crushed ore pocket was installed in large, rectangular sheets which required much less embedded metal to hold it in place than would the more conventional, smaller arid square pieces of cast manganese steel. For duty in the crushed ore pocket, where wear is not severe, the AR plate is a satisfactory material. The new Palabora Figure-8 crusher also uses this design.

Jan 1, 1978

By Henry N. Toler

Development in the Jackson gas field, Hinds and Rankin counties, for 1935 continued at a slow pace, there being only nine wells drilled on the structure, of which five resulted in gas producers and four in dry holes. There were no wells drilled deep enough during 1935 to test any of the horizons below the producing Selma chalk. There are 113 producing gas wells in the Jackson gas field, with three wells on the southeast edge of the field making some oil with a large quantity of salt water; this oil comes from the same horizon as the gas. The combined open flow of the 113 gas wells is about 4,100,000,000 cu. ft. The proven area of the field is approximately 8000 acres. The production of 10,291,000,000 cu. ft. for 1935 represents the largest yearly pull from the field by almost a billion cubic feet. The total production from the field to date is 45,104,000,-000 cu. ft. It is interesting to note that the rock pressure has dropped from 1010 lb. per sq. in. initial to 943 Ib. at the end of 1935, a decline of only 67 lb. in 6 years. There is a difference of opinion as to the age of the deepest formation tested on the Jackson structure; some people holding that it is Tuscaloosa, others, Trinity, and still others that it is Paleozoic, probably Pottsville. The production of the Amory gas field, Monroe County, continued to decline and the capacity was far under the demand. Originally there were four producing wells in the field with a combined open-flow capacity of approximately 15,000,000 cu. ft. and a rock pressure of 680 lb. per sq. in. At the end of 1935 only two wells were producing with a combined open-flow of less than 1 million cu. ft. and the rock pressure down to 100 lb. or less. No attempt has been made to drill new wells in the immediate field but three wells are being drilled in the county in an effort to secure new supplies of gas. The wildcat operations for 1935, with only 11 wells drilled, were the lowest since 1932, just about one-half the number drilled during 1934. None of the wildcat wells drilled in 1935 resulted in producers and, so far as the writer is aware, did not uncover any large structures. The 11 wells drilled were abandoned or junked at comparatively shallow depths, except the well drilled in George County to 6928 ft. by the United Gas

Jan 1, 1936

By Henry N. Toler

Development in the Jackson gas field, Hinds and Rankin counties, for 1935 continued at a slow pace, there being only nine wells drilled on the structure, of which five resulted in gas producers and four in dry holes. There were no wells drilled deep enough during 1935 to test any of the horizons below the producing Selma chalk. There are 113 producing gas wells in the Jackson gas field, with three wells on the southeast edge of the field making some oil with a large quantity of salt water; this oil comes from the same horizon as the gas. The combined open flow of the 113 gas wells is about 4,100,000,000 cu. ft. The proven area of the field is approximately 8000 acres. The production of 10,291,000,000 cu. ft. for 1935 represents the largest yearly pull from the field by almost a billion cubic feet. The total production from the field to date is 45,104,000,-000 cu. ft. It is interesting to note that the rock pressure has dropped from 1010 lb. per sq. in. initial to 943 Ib. at the end of 1935, a decline of only 67 lb. in 6 years. There is a difference of opinion as to the age of the deepest formation tested on the Jackson structure; some people holding that it is Tuscaloosa, others, Trinity, and still others that it is Paleozoic, probably Pottsville. The production of the Amory gas field, Monroe County, continued to decline and the capacity was far under the demand. Originally there were four producing wells in the field with a combined open-flow capacity of approximately 15,000,000 cu. ft. and a rock pressure of 680 lb. per sq. in. At the end of 1935 only two wells were producing with a combined open-flow of less than 1 million cu. ft. and the rock pressure down to 100 lb. or less. No attempt has been made to drill new wells in the immediate field but three wells are being drilled in the county in an effort to secure new supplies of gas. The wildcat operations for 1935, with only 11 wells drilled, were the lowest since 1932, just about one-half the number drilled during 1934. None of the wildcat wells drilled in 1935 resulted in producers and, so far as the writer is aware, did not uncover any large structures. The 11 wells drilled were abandoned or junked at comparatively shallow depths, except the well drilled in George County to 6928 ft. by the United Gas

Jan 1, 1936

By Roy Lindgren

Since the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced1, at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces1. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe¬rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1936

By E. V. Potter, H. C. Lukens

INTRODUCTION IN general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation' the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. APPARATUS The apparatus used in these investigations is essentially the same as that used in the manganese work' and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in ' gas volume are measured by volume gauge C which is essentially another mercury manometer in which . the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 61 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within ± 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. METHOD The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient time intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1948

By Richard L. Gordon, Charles J. Johnson

Electric power demand doubles about every ten years, and because of the associated burgeoning fuel requirements, power stations absorb over half of the coal output in the United States. Throughout the 1960's, demand for coal utilized to generate electricity grew at an average annual rate of 6.5% but coal producers held back greater expansion because they expected nuclear plants to proliferate faster than they actually did. Even so, the growth rate is expected to continue at the 1960's rate until at least 1976. The continuation of the 6.5% growth rate beyond 1976, however, will require additional orders for coal-fired plants during the early 1970's. In fact, plants consuming a total of 130 million tons of coal must be ordered in the next few years. If the requisite plants materialize, total 1980 coal output for electrical power generation will be approximately 600 million tons.

Jan 1, 1971

By Henry Emmett Gross

Two types of decline curves are considered and their applications are discussed. The first is the well-known semilogarithmic decline curve having the rate of production plotted on the logarithmic scale and the time on the horizontal scale. The other curve is the percentage of oil in the fluid versus cumulative production, and it is plotted on Cartesian coordinate paper. These curves are illustrated by carefully and adequately labeled graphs. Where conditions permit application of both types of curves for rationally determining the reserves of a well, both should be applied and the most conservative reserve should be chosen. Formulas are given for determining the economic limits. For a semi-l~~arithmic~decline curve the formula is: A = B X C X D X E X F or B = A/C ? D X E X F A = total monthly operating cost (average of past year), B = economic limit in barrels of oil per day, C = days in an average month = 30.4, D = market price of crude per barrel, E = 1-royalty, F = 1-gross production tax, G = water production in barrels per day at the economic limit, H =per cent oil in fluid at economic limit. The economic limit for a per cent oil in the fluid curve is: H = B/B+G X 100 The semilogarithmic decline curve is treated first. Straight-line extrapolations on semilogarithmic paper follow the compound interest compound discount law, hence the ensuing formulas derived from this law may be used in computing reserves for such extrapolations: [1___1/(1+Y)]

Jan 1, 1939

By Henry Emmett Gross

Two types of decline curves are considered and their applications are discussed. The first is the well-known semilogarithmic decline curve having the rate of production plotted on the logarithmic scale and the time on the horizontal scale. The other curve is the percentage of oil in the fluid versus cumulative production, and it is plotted on Cartesian coordinate paper. These curves are illustrated by carefully and adequately labeled graphs. Where conditions permit application of both types of curves for rationally determining the reserves of a well, both should be applied and the most conservative reserve should be chosen. Formulas are given for determining the economic limits. For a semi-l~~arithmic~decline curve the formula is: A = B X C X D X E X F or B = A/C ? D X E X F A = total monthly operating cost (average of past year), B = economic limit in barrels of oil per day, C = days in an average month = 30.4, D = market price of crude per barrel, E = 1-royalty, F = 1-gross production tax, G = water production in barrels per day at the economic limit, H =per cent oil in fluid at economic limit. The economic limit for a per cent oil in the fluid curve is: H = B/B+G X 100 The semilogarithmic decline curve is treated first. Straight-line extrapolations on semilogarithmic paper follow the compound interest compound discount law, hence the ensuing formulas derived from this law may be used in computing reserves for such extrapolations: [1___1/(1+Y)]

Jan 1, 1939

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By Takahide Wakamatsu, Douglas W. Fuerstenau

Contact angles on alumina are related directly to the adsorption of alkyl sulfonates at the solid-water interface and thus are strongly controlled by the pH of the solution, the concentration of surfactant, and the number of carbon atoms in the alkyl chain. As the pH of the solution is increased above the point of zero charge, sulfonate adsorption ceases and alumina remains hydrophilic. However, in neutral and acidic solutions, contact angles increase markedly in magnitude when the adsorbed sulfonate ions form hemimicelles at the solid-water interface. Under a wide variety of solution conditions, a limiting value of the contact angle is attained at the point of reversal of the zeta potential. Finally, contact angle phenomena are empirically correlated with the sulfonate adsorption density through the work of adhesion.

Jan 1, 1974

Executive Committee Board of Directors L F Reinartz, Chairman, H DeWitt Smith, Vice-Chairman, T B Counselman, M L Haider, Philip Kraft Finance Committee Board of Directors Andrew Fletcher, Chairman, A B Kinzel, D Wilson Endowment Fund "X" G F Moulton, Chairman, Erle V Daveler, '55, Philip Kraft, '56, I Brigden, '57 Honorary Memberships W M Peirce, Chairman, '56, M L Haider, ex officio, Andrew Fletcher, ex officio, John M Lovejoy, '55, D H McLaughlin, '57, Henry Krumb, '58, L F Reinartz, ex officio Investments Erle V Daveler, '57, Chairman, W M Peirce, '55, Henry Krumb, '56, G F Moulton, ex officio as Treasurer, Andrew Fletcher, ex officio as Chairman Finance Committee Local Section Appropriations A B Kinzel, Chairman, M L Haider, W S. Cumings, Fred J Meek

Jan 1, 1954

D. J. DEMOREST,* Washington, D. C. (written discussion ?).-This paper is a real contribution to technical science; it will make it' easier to think accurately about the inner workings of a blast furnace. I was rather surprised to read that the authors regarded as a new discovery the idea that a molten mixture of CaO, A1203, and Si02 is a molten solution of the compounds of these oxides rather than of the oxides in each other. Surely no. chemist with an active respect for the known facts of chemical affinity could believe that these oxides could be melted together without forming compounds, and that these compounds would then dissolve in one another. This work does, however, help to establish what it was supposed must be true. I think it is worth while, in the light of the work of the Geophysics Laboratory, this work of the Bureau of Mines, and that of previous investigators, to visualize what happens as a charge passes down through a blast furnace, thinking especially of the slag-forming materials. These are chiefly kaolin (Al203.2SiO2.2H2O), quartz, and limestone. These substances do not undergo much change until the limestone decomposes at about the middle of the furnace, whereupon the chemical affinities of CaO and SiO2 must begin to he active; especially if there is any amorphous Si02 present. This forms CaSiO3, and the SiO2, CaSi02 and Al2-032SiO2 then come together to form the binary and ternary eutectics so well located by the work of the Geophysics Laboratory. No matter how much lime has been charged into the furnace, the formation of this eutectic will start it about the same height in the furnace and the gangue will start to get pasty at the same height. If the charge is such that the

Jan 4, 1918

By L. C. Brown, J. S. Kirkaldy

AS part of a program to investigate the diffusive properties of dilute ternary austenites, we have made a determination of the effects of cobalt on the activity of carbon in y iron. Samples of pure iron and Fe-Co alloys were equilibrated at 1000°C in controlled CO-C02 atmospheres, following the procedure of R. P. smith.' The 0.010-in.-thick samples were analyzed for carbon by microcombustion analysis2 to give a set of isoactivity curves. The latter were converted to activity-coefficient (standard state at infinite dilution) plots by combination with Smith's data' for the activity of carbon in pure iron measured in a CO-C02 mixture. Table I shows the composition of the base alloys used, while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In the notation of Wagner,' the interaction parameter is the second coefficient on the right, Eq. [I] adequately correlates the experimental points for those alloys which were prepared from electrolytic iron by arc-melting (2,4, and 7 pct Co). The results for the 10 pct Co alloy (supplied by Crucible Steel Co.) do not correlate with the others. In fact, the experimental points for this alloy correspond to an interaction parameter of It is possible that the interaction parameter is a function of concentration for large cobalt additions, but we are inclined to attribute the discrepancy to the presence of a significant amount of aluminum added to this alloy for deoxidation purposes (Table I). Preliminary measurements for the system Fe-C-A1 have indicated an interaction parameter of Which implies that the effect of aluminum in solution on the carbon activity is sixty times greater than the effect of an equal weight percentage of cobalt. These observations cast some doubt on the precision of the results of Chandhok, Hirth, and Dulis who used this same 10 pct alloy for their experiments, obtaining an interaction parameter of E = 2.2. There is considerable doubt as to the activity of a plane Fe-C system. Using a CH4-Ha mixture, Smith obtains cg = 6.1 for the effect of carbon on the activity of carbon in austenite, rather than the value of 8.9 given in Eq. [I]. The use of CHa-Ha mixtures has recently been questioned by Kaufman, Radcliff, and cohens who state that there is some possibility that other hydrocarbons are formed. Fortunately, the determination of the interaction parameter is not sensitive to the coefficient of Nc. For example, using the CHI-H2 results we obtain a value which is almost the same as that obtained using the CO-CO, results. The authors wish to thank Mr. E. J. Dulis of the Crucible Steel Co. of America for supplying us with samples of the 10 pct Co alloy used in their original work. Financial assistance from the American Iron and Steel Institute is gratefully acknowledged.

Jan 1, 1963