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By H. W. Imholz

Active interest in the North Central Texas area centered in the development of the Palo Pinto limestone-producing zone, near the town of Avoca, in the northeast part of Jones County. This producing horizon was discovered in 1937, in the Iron Mountain Oil Company's well No. 1 Olander, in sec. 196, B.B.B. & C. survey, at 3238 to 3250 ft. During the development of this pool, it was generally referred to as the Avoca pool. As a second pool has been discovered in the same producing zone, also near the town of Avoca, the writer has taken the liberty of changing the name of the original Avoca pool to Avoca-Olander pool. Forty producers had been drilled in the Avoca-Olander pool by the end of 1938; their initial ranged from 28 to 300 bbl. per hour. Stimulus was given to the interest in the development of the Palo Pinto limestone when the Ungren-Frazier No. 1 Griffin, in sec. 199, B.B.B. & C. survey, Jones County, found the limestone from 3225 to 3250 ft., with an initial production of 931 bbl. per day. (This new pool has been given the name of Avoca-Griffin pool, by the writer.) The best well to be completed, up to the present time, is the Bert Fields No. 1 Taylor in sec. 199, B.B.B. & C. survey, which had an initial production of 748 bbl. in 3 hours. The Owen-Snebold No. 1 McKeever in sec. 158, B.B.B. & C. survey, in northwest Shackelford County, added to the interest in the Palo Pinto limestone when it extended the Ivy pool with a well in the Palo Pinto limestone from 3145 to 3183 ft., and was estimated good for 6,000,000 cu. ft. of gas and 6000 bbl. of oil per day. During 1938, Stonewall County obtained its first commercial producer when the Stonewall Oil Co. in No. 1 Parriott discovered the Palo Pinto limestone saturated from 5169 to 5176 ft. and tested 371 bbl. per day. Two new producing horizons were discovered about 2 miles east of the old Noddle Creek pool, Jones County; the first, the Humble Oil & Refining Co. No. 1 Irvin, in sec. 48, block 18, T. & P. R. R. Co. survey, which had saturated limestone from 2550 to 2567 ft. and was good for 100 bbl. per day; the second, in the Humble No. 1 Horton, sec. 40, which

Jan 1, 1939

By Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table I), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term "potash" originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first U.S. patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 20.4 million short tons K2O produced in the world in 1970 (Eilertsen, 1971 ) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K,O, a unit of measure which is neither a natural nor synthetic compound of potassium (1 .O% K is equivalent to 1.2046% K,O) . Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and meta- morphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such de- posits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of sea-water or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in [Table 1]. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971).

Jan 1, 1975

By R. I. Jaffee, F. C. Holden, H. R. Ogden

ECENT papers dealing with the properties of unalloyed iodide titanium have been directed primarily at the determination of base-line properties for alloy investigations. Early work was limited to a few tests because of the limited availability of iodide titanium at the time. In the results of papers by Campbell et al.,1 Gonser and Litton,2 Jaffee and Campbell,3 inlay and Snyder,4 and Jaffee, Ogden, and Maykuth, data on mechanical properties are presented for unalloyed iodide titanium in the annealed and cold-worked conditions. Data are presented in this paper which show the effects of heat treatment on the structure and mechanical properties of commercially produced iodide titanium. Correlation is made between microstruc-tural variables and the mechanical properties. Experimental Procedures Melting Stock: The melting stock used was as-deposited iodide titanium, produced by New Jersey Zinc Co. The furnished analysis showed the following range of impurities: N, 0.004 to 0.008 pct; Mn, 0.005 to 0.013; Fe, 0.0035 to 0.025; Al, 0.013 to 0.015; Mo, 0.0015; Pb, 0.0045 to 0.0065; Cu, 0.0015 to 0.002; Sn, 0.001 to 0.01; Mg, 0.0015 to 0.002; and Ni, 0.003. Hydrogen content as determined by vacuum-fusion analysis was 0.0091 wt pct (0.44 atomic pct) after arc melting and fabrication. Nitrogen analysis on the arc-melted and fabricated titanium showed a content of less than 0.002 pct N. The average hardness of the furnished stock was Rf 70, or approximately 85 VHN. Melting Procedure: The as-deposited rods were rolled, sheared, and degreased in preparation for arc melting. The charge was arc-melted with a tungsten electrode in a water-cooled copper crucible under a positive pressure of high purity (99.96 pct) argon. The final ingot was approximately 2 in. in diameter and showed no increase in hardness over that of the initial stock. Fabrication: Heating for fabrication was done in air. It was begun by forging the ingot into a 3/4 in. diam rod, at an initial temperature of 1600°F. Scale was removed by sandblasting. The rod was then swaged to 1/4 in. diam at room temperature through a series of 20 dies, with approximately 10 pct reduction in area between each die. An anneal of 1 hr at 850 °C in air was given after the 1/2 in. die, such that the final cold reduction was 75 pct. Sections cut from this rod were used for test and microstructure specimens. Heat Treatment: Heat treatments were carried out in resistance tube furnaces with stainless-steel linings, under an atmosphere of gettered argon. As further protection against contamination, the specimens were packed in titanium turnings in a titanium sleeve. Control experiments have shown negligible hardness increases with this method, indicating that contamination from oxygen and nitrogen is slight. Three cooling rates were employed in this work; these have been designated as water quenching, argon cooling (to simulate air cooling under a controlled atmosphere), and furnace cooling. The cooling rate for an argon cool is 100°C per min for the first minute, with an average cooling rate of 35°C per min over a 15-min period. A furnace cool requires about 10 hr, with an average cooling rate of 3.6oC per min during the first hour, and an average cooling rate of 1.2°C per min over the 10-hr period. Microimpact Test: The specimen adopted was based on the cylindrical Izod Type Y specimen (ASTM, E23-41T). All dimensions were reduced to half scale, including the notch radius. Specifications are shown in Fig. 1. The specimen is held vertically in an adapter and broken as a cantilever beam. Impact tests were run on a constant-velocity (11.34 ft per sec) Tinius Olsen impact testing machine with a total available energy of 100 in.-lb. Tests were made to determine the correlation between this microimpact and the standard V-notch Charpy impact test. Curves showing impact energy as a function of temperature for both impact tests are plotted in Fig. 2. Transition temperatures, when they occur, are about the same for both impact tests. All three titanium-rich materials have the same conversion factor, 10. Tensile Testing: Tensile tests were conducted on Baldwin-Southwark testing machines using the 600, 2400, or 3000 1b range. Specifications for the test specimen were taken from the 1948 edition of the ASM Metals Handbook, and are shown in Fig. 1. Strain measurements were made using an SR-4 resistance gage (Type A-7) cemented to the reduced section in conjunction with a lever-type extenso-meter. Readings on the SR-4 strain indicator were

Jan 1, 1954

By Theron Wasson

The oil and gas fields of Michigan that have been under development since 1925 are in an area that extends across the middle of the lower peninsula from northeast to southwest, a distance of about 200 miles, and with a width of about 80 miles. In 19 years 70 fields have been discovered. Most of these are relatively small when compared with other oil-producing areas. This is borne out by the fact that since the first wells were drilled these fields have produced a total of only 204,000,000 bbl. However, Michigan is still maintaining its production, for during the past five years the annual production has remained fairly constant at approximately 20,000,000 bbl. Production for 1943, as reported by the Bureau of Mines, was 20,682,000 barrels. Roughly, one third oi Michigan's production in 1943 came from the Reed City field, which was discovered in 1941. During the year, 237 oil wells were completed in Michigan in 1943. The decrease of 56 from the 1942 total is probably due to the continuance of Government regulations requiring a 40-acre spacing pattern over most of the state. Fig. I shows the principal oil and gas fields of Michigan, and the columnar section, Fig. 2, shows the principal producing horizons in relation to the section drilled. The data of Table I and Table 2 have been carefully checked with previous reports to eliminate errors. Six new producing areas were discovered during 1943 and five areas discovered in 1942 were developed during the year. Both the new discoveries and the 1942 discoveries that were developed appear to be small and relatively unimportant. Goodwell Field.—The best discovery of the year is the Goodwell field, T. 14 N., R. 11 W., Goodwell township, Newaygo County. This small structure was located by core testing done by The Pure Oil Co. in 1942 and early 1943. The first producing well, C. R. Harris No. I, was completed on July 5, 1943, ill the Traverse limestone at a total depth of 2742 ft., with ail estimated potential of 1100 bbl. per day. By the end of the year, 18 wells had been completed in this field and approximately 281,000 bbl. of oil produced. The field operated under proration of 262 bbl. per day per well from Oct. I to Dec. I; 150 bbl. per day per well after that date. Woodville Field.—The small Woodville pool, T. 15 N., R. 11 W., 3 miles north of the Goodwell field, was discovered by core testing by the Ohio Oil Co. The discovery well was completed on May 5, 1943, flowing 650 bbl. of fluid, including 18 per cent salt water the first 18 hr., from the Traverse limestone at a depth of 2810 to 2815 ft. Seven wells had been completed by the end of the year and 67,000 bbl. of oil had been produced. Development is now practically at a standstill because further drilling does not aDDear economically iustified.

Jan 1, 1944

By Theron Wasson

The oil and gas fields of Michigan that have been under development since 1925 are in an area that extends across the middle of the lower peninsula from northeast to southwest, a distance of about 200 miles, and with a width of about 80 miles. In 19 years 70 fields have been discovered. Most of these are relatively small when compared with other oil-producing areas. This is borne out by the fact that since the first wells were drilled these fields have produced a total of only 204,000,000 bbl. However, Michigan is still maintaining its production, for during the past five years the annual production has remained fairly constant at approximately 20,000,000 bbl. Production for 1943, as reported by the Bureau of Mines, was 20,682,000 barrels. Roughly, one third oi Michigan's production in 1943 came from the Reed City field, which was discovered in 1941. During the year, 237 oil wells were completed in Michigan in 1943. The decrease of 56 from the 1942 total is probably due to the continuance of Government regulations requiring a 40-acre spacing pattern over most of the state. Fig. I shows the principal oil and gas fields of Michigan, and the columnar section, Fig. 2, shows the principal producing horizons in relation to the section drilled. The data of Table I and Table 2 have been carefully checked with previous reports to eliminate errors. Six new producing areas were discovered during 1943 and five areas discovered in 1942 were developed during the year. Both the new discoveries and the 1942 discoveries that were developed appear to be small and relatively unimportant. Goodwell Field.—The best discovery of the year is the Goodwell field, T. 14 N., R. 11 W., Goodwell township, Newaygo County. This small structure was located by core testing done by The Pure Oil Co. in 1942 and early 1943. The first producing well, C. R. Harris No. I, was completed on July 5, 1943, ill the Traverse limestone at a total depth of 2742 ft., with ail estimated potential of 1100 bbl. per day. By the end of the year, 18 wells had been completed in this field and approximately 281,000 bbl. of oil produced. The field operated under proration of 262 bbl. per day per well from Oct. I to Dec. I; 150 bbl. per day per well after that date. Woodville Field.—The small Woodville pool, T. 15 N., R. 11 W., 3 miles north of the Goodwell field, was discovered by core testing by the Ohio Oil Co. The discovery well was completed on May 5, 1943, flowing 650 bbl. of fluid, including 18 per cent salt water the first 18 hr., from the Traverse limestone at a depth of 2810 to 2815 ft. Seven wells had been completed by the end of the year and 67,000 bbl. of oil had been produced. Development is now practically at a standstill because further drilling does not aDDear economically iustified.

Jan 1, 1944

By Robert Warner

WHEN a new mine is opened, and often when an operating mine must adapt itself to physical or economic changes, a mining system must be selected in complete detail. In the past the plan chosen was usually the product of the local staff alone, however limited the training and experi-ence of that staff might be, which often resulted in the introduction of methods that were familiar to the staff, but not so well suited to the con-ditions as others unknown to the local men. A new management, noting the difficulties with the existing layout, might make modifications or complete changes, so that many mines in their history have seen a whole series of mining systems, each somewhat laboriously grafted on to its predecessor. This should not be interpreted as a condemnation of the older staffs for sticking to the tried systems, such as open square-sets in the early days at the Homestake, because they knew it would work after a fashion, nor does the statement apply to the technically trained, and usually broadly experienced staffs of most present-day properties. The older miners did not have the variety of tools and methods, nor the present freedom of transfer of information as to what the other man is doing, and so did the best they could under the circumstances. Finally, the higher grade of the ores made the choice less vital. The ever-increasing need to mine low-grade orebodies, with a fixed or even lower price for the metal produced, has caused an increasing need for low-cost mining. In most new mines this has simplified the problem of selection by eliminating from consideration all of the high-cost systems, but it has also complicated the choice by the necessity for refinement in detail and a close adjustment of the plan selected to all the conditions at the property. In these low-cost problems any textbook division of mining systems as applied to "beds, veins or masses" avails little as a guide. It should be realized at the outset that to' be successful under modern competitive conditions a system of mining must be worked out with elaborate detail, with careful time scheduling and control of the various elemental operations, and that after it is introduced it must be run with a large amount of technical direction.

Jan 1, 1933

By Norman Ketzlach

Manganese Products, Inc. has developed a chemical process for the recovery of high-grade manganese oxides from low-grade manganese ores. Ammonium sulphate is also produced. Manganese ore is leached with sulphurous-sulphuric acids. The impurities are removed with ammonia, heat, and air. Manganese oxides are produced by addition of more ammonia and air under pressure. Ammonium sulphate is recovered from the remaining solution.

Jan 3, 1950

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th'vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1'2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS' and on GaAs doped with oxygen,5'" manganese,' and copper.' The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By G. Sandoz, D. A. Meyn

The fracture surfaces of specimens of titanium a1loys which exhibited susceptibility to subcritical crack growth in a wide variety of environments, including aqueous solutions, alcohols, hydrocarbon gases, carbm tetrachloride, and dry air, were examined. The dominant and characteristic fracture mode was cleavage. which became mixed with an increasing porportion of ductile fracture modes (dimples. and so forth) as the applied KI was increased. The cleavage plane in all the alloys was oriented at 15 deg from (0001) of the a phase. No indices could be assigned to the 15 deg cleavage Plane because of uncertainty as to which zone it belonged to. SLOW crack growth and delayed fracture take place in certain titanium alloys at stress intensity (KI) lower than the critical values for complete fracture (KIc) found in short-time tests for plane strain fracture toughness.' Such crack growth may take place in very dry air on sustained loading if the alloy contains a sufficient amount of hydrogen and if the stress intensity factor is higher than a threshold value designated KIH.2 Similarly, a number of environments such as water, alcohols, and hydrocarbons may cause slow crack growth provided the stress intensity factor exceeds the threshold value KISCC. In this paper it is intended to examine some fracto-graphic and crystallographic details of this subcritical crack propagation process as related to alloy composition, environment, and stress intensity. It has been previously reported that subcritical crack growth takes place in titanium alloys in aqueous environments by cleavage.2"6 The observations to be described here indicate that in the alloys investigated the mode of subcritical crack propagation is more dependent on the stress intensity during cracking than on the environment. The fracture mode is illustrated with photographs of the fracture surfaces at a wide range of magnifications. The crystallographic character of the cleavage mode is also presented and the results discussed. EXPERIMENTAL APPROACH The studies were made on four titanium alloys— Ti-8A1-1Mo-lV, Ti-5A1-2.5Sn, Ti-7Al-1Mo-lV, and Ti-0.350. Of these four alloys the first two were mill annealed and fine grained. The latter two were noncommercial and coarse grained, having been prepared for other experimental purposes. The crystallographic studies required a large-grain size. Consequently the fine-grained alloys were an- nealed in a vacuum at 1950°F and furnace cooled to produce samples for these studies. This treatment did not alter the microstructure significantly except for grain size. All the aluminum-containing alloys showed primary a with a network of ß-phase particles within the a grains; Figs. 1 and 2 show this microstructure for the specific case of fine-grained Ti-8A1-1Mo-1V. The cracks in the figures will be discussed later. Fractographic studies were made on all the alloys, but the electron fractographs displayed herein are from the Ti-8A1-1Mo-1V alloy in the fine-grained condition. Emphasis was placed on this commercial alloy because considerable information was available on the stress-corrosion cracking characteristics in a variety of environments. Sufficient supplementary studies of the alloy after the anneal to produce large grains were conducted to establish that the stress-corrosion cracking susceptibility and fractographic characteristics were not changed significantly. Thus it could be inferred that the crystallographic data obtained exclusively on large-grained specimens would apply also to fine-grained specimens. Fracture surfaces for study were obtained using precracked cantilever beam specimens loaded as described by Brown. The precracked section of a specimen was immersed in the environment of interest. Values of initial stress intensity factor Kli were chosen slightly higher than KISCC in order to obtain a fairly extensive region of slow crack growth. Fracture surfaces representative of a variety of stress intensity levels could then be examined because in the cantilever beam test KI increases as the crack propagates.

Jan 1, 1970

By F. R. Morral, E. P. Miller

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By E. P. Miller, F. R. Morral

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By AIME AIME

THE 1944 Chairman of the Institute of Metals Division might be classed as metallurgically ambidextrous ; he is teacher of theory and practice of both nonferrous and ferrous metallurgy, and he is consultant on brass and on highspred steel. Arthur Phillips was born in Troy N.Y. and attended the New Haven Connecticut high school. Upon graduation he entered Yale, receiving a degree in metallurgy in 1913. At that time Professor Mathewson was starting his plan of '"co-operation with the metal industries in metallographic work at the Hammond Laboratory of the Sheffield Scientific School, Yale University, and Arthur Phillip, became the first co-operative graduate student, working in the laboratory of the Bridgeport Brass Co., and receiving his Masters of Science degree in 1915. A little later, when the department of metallurgy at Yale was expanded. Me. Phillips was appointed assistant professor. In 1928 he was made associate professor, and in 1934 he was promoted to full professor.

Jan 1, 1944

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

THE following employment items ore made available to AIME members on a nonprofit basis by the Engineering Societies Personnel Service, Inc., operating in cooperation with the Four Founder Societies. Local offices of the Personnel Service ore at 8 W. 40th St., New York 18; 100 Farnsworth Ave., Detroit; 57 Post St., Son Francisco; 84 E. Randolph St., Chicago 1. Applicants should address all mail to the proper key numbers in care of the New York office and include 6c in stamps for forwarding and returning application. The applicant agrees, if. placed in a position by means of the Service, to pay the placement fee listed by the Service. AIME members may secure a weekly bulletin of positions available for $3.50 a quarter, $12 a year. MEN AVAILABLE Graduate Mining Engineer, 31, married. Six years' engineering experience, mining and construction, U. S. A. and Alaska. Underground metal mining, production, development, geology, mine engineering. Engineering on airfield construction, earthwork, location work, mapping, topography, road location; office work. Commercial pilot license. Desires position mining or construction. Available 45 days. Prefer Latin America. M-676-477-E-8-San Francisco. Mining Engineer, 42, married, one child. Fourteen years' mining with much supervisory experience in developing and operating metal mines; also mine safety engineering. Familiar with many large and small mines in the western U. S. and Mexico. Excellent references. M-677.345-E-1¬San Francisco.

Jan 1, 1952

By H. Reinhardt, P. Haglund, J. Rydberg, B. Lunden

As legislation to minimize pollution in effluent streams becomes stricter, it is important to treat used acid pickling baths before discharge. This is usually achieved by neutralization of the acids and precipitation of the dissolved metals in such a way that neither acids nor metals can be re-used. A process has been designed and tested on a pilot plant scale to recover both acids and metals from a stainless steel pickling bath leaving only Na2SOs in the effluent. In this process, H2SOr is added to the spent pickling liquor and the recovery of the pickling acids HN03 and HF is achieved by solvent extraction, using TBP in kerosene as the organic solvent. The extracted acids are stripped with water, giving an acid concentration high enough for direct use in the pickling bath. Molybdenum is also extracted by TBP and is recovered in a separate step. The other metals, Fe, Cr and Ni, are precipitated from the raffinate as hydroxides, dried and recycled to the metal process. In evaluating this process, comparative experiments with mixer-settler and pulsed column have been performed. The process described is being considered for use by a Swedish company pickling 70,000 tons per annum of stainless steel.

Jan 1, 1973

By R. N. Dokken, J. F. Elliott

A high-temperature solution calorimeter was used to measure directly the partial molar heat of mixing of nickel in the Cu-Ni system, 0 to 15 at. pct Ni and 1200°C; of silver in the Cu-Ag system, 0 to 50 at. pct Ag and 1100°C; and of cobalt in the Cu-Co system, 0 to 6 at. pct Co and 1200°C. The heats of fusion of copper and silver were also detervnined directly. The results of these investigations are as follows: Cu-Ni: HM = [2.64 + 0.25Xm JXNiXCy kcal/g-U~OI Cu-Ag: HM =[4.00 + 0.31XAglXAgXCu kcal/g-atom Cu-Co: HF~ = [8- 5X~,]X& kcal/g-atotn Cu, AH, = 3290 * 275 cal/g-atom Ag, AH, = 2890 * 250 cal/g-atom The performance of the calorimeter was enhanced by improving the operational and control procedures, particularly the temperature-wieasuren~ent method and the solute-addition practice. The interpretation of the experimental data was improved by developing machine computational techniques that increased the speed, flexibility, and accuracy of the treatment of the data. THIS paper reports further measurements of the heats of solution of liquid metals with the high-tem- perature solution ca1orimeter.l Measurements were made of the partial molar heats of mixing in the following liquid alloys: Cu-Ni, Cu-Ag, and Cu-Co. In addition the heats of fusion of copper and silver were also determined. The apparatus and the experimental procedure were essentially those of Benz and Elliott.2 Several modifications in the experimental method and the means for interpreting the data were incorporated in this study to improve the results. The operation of the calorimeter and its characteristics will be described only briefly here. The

Jan 1, 1965

By Brian F. Osborne

A continuous on-line particle-size analysis system for solid/liquid suspensions is described. The basic sensor utilizes a centrifugal principle to separate particles according to size, the resultant separation being measured by means of beta-ray attenuation. Results obtained when analyzing a variety of materials at sizes from 65 mesh (210 µ) to 20 w are discussed in detail. Accuracies better than 2% are demonstrated. The effects of particle specific gravity, and mixtures of materials of diverse specific gravities, are discussed from both a practical and a theoretical viewpoint. It is demonstrated that particle specific gravity has a minimal effect on the size reading obtained. This renders the instrument suitable for handling materials where the ratio of light to heavy component may change. The design of the first commercial installation of this instrument is described in detail. This installation will be capable of analyzing three streams in sequence, measurement at three particle sizes being effected on each stream.

Jan 1, 1975

By R. B. Campbell

One of the three power plants that will be in the Curecanti Unit of the Bureau of Reclamation's Colorado River Storage Project is the power plant at Morrow Point Dam. Presently under construction, the Morrow Point Power Plant is between Gunnison and Montrose on the Gunnison River in west-central Colorado. (Fig. 1). Morrow Point Dam will be a thin, double-curvature, concrete-arch dam, 465 ft high and will impound 120,000 acre-ft of water. Two 60,000-kw hydroelectric generators will be housed in an underground power plant in the left abutment just down- stream from the dam. The power-plant chamber will be an unlined opening 205.5 ft long, 57 ft wide and 65 to 134 ft high. The arch-type roof with a rise-to-span ratio of 1 to 4 will be supported with rock bolts and chain link fence. A description and discussion of the design considerations for the power-plant opening and rock bolt design are given by William H. Wolf, Gilbert L. Brown, and Ernest D. Morgan in "Morrow Point Under- ground Powerplant," ASCE Power Division Specialty Conference, Denver Colorado, August 18-20, 1965. The Morrow Point site is in a moderately active region of mild earth- quakes, as evidenced by recent earthquakes in 1960 and 1962. Therefore, the Bureau of Reclamation undertook an investigation of the effects on the underground power-plant chamber when subjected to an earthquake. The art of earthquake engineering has been directed primarily at developing methods of analyzing the nature of ground surface motions and designing surface structures to resist damage from vibrations impressed on the structure by the ground motions. The mechanism of straining an underground cavity by an earthquake

Jan 1, 1968