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By Wallace Thorneycroft

FOREWORD This paper by Mr. Thorneycroft, Past President of the Institution of Mining Engineers (Great Britain), and chairman of its Subsidence Committee, is a valuable contribution to the assemblage of data on ground movement and subsidence from coal mining. It deals with the effects of advancing longwall, a method almost universal in Europe but as vet little used in the United States outside of Northern Illinois and in a few scattered places elsewhere, in thin coal beds, as in the Lexington field, Missouri, Canon City field, Colorado, and the Birmingham field, Alabama. Although by advancing- longwall, a maximum recovery of coal is obtained and it has to be employed where there are weak shale roofs, especially in deep mines, it is a more expensive method of operation unless the mining conditions are favorable, which is unusual in the United States. On the other hand, there is a growing use in this country of what is essentially retreating long wall, with an approximately straight break-line as described by Rayburn.1 With this method, in which the pillars are substantial, it was shown that the ground movement effect is practically identical with that of advancing longwall, hence the value to mining engineers of the precise data given by Mr. Thorneycroft. His study is unusual in several respects; it deals with conditions connected with ,the mining of a coal bed 20 in. thick, about 490 ft. below the surface, over a mined-out area in a 5-ft. bed about 90 ft. below, which had been mined about 12 years earlier. Both mines passed under Plean House, a building of massive cut stone construction built over a century ago, in which Mr: Thorneycroft resided throughout the under-mining period. Slight cracks opened in the walls as the longwall face approached the house in mining the upper seam, and closed after the face passed and subsidence took place. In the northwest wall, the last wall the face passed under, some stone blocks were broken, which was attributed to a strike period when the advance of face came nearly to a standstill. Other than this there was no perceptible permanent damage, as indicated by the photographs taken by the undersigned in 1923 (Figs. 1 and 2). Mr. Thorneycroft used a novel means of studying the successive positions of the corners of the building: he hung plumb bobs from the eaves and traced the paths of the respective plumb bob points on level surfaces. The angles made by the house walls with the plumb bob lines gave measures of the slope of the subsidence wave at the respective points. A slight upward wave was indicated by the surveys ahead of the subsidence, which would appear to be due to a tilting over of the massive sandstone stratum in the roof measures near the surface, the edge of the subsidence area acting as the fulcrum.

Jan 1, 1931

By R. Al-Hussainy, H. J. Ramey

Previous gas well test analyses have been based mainly upon linearizations of ideal gas flow results, although a method for drawdown analysis based upon real gas flow results has been proposed. Linearizations based upon ideal gas flow require estimation of gas physical properties at Tome sort of average pressure, and implicitly involve the assumption that pressure gradients are small everywhere in the reservoir. A new real gas flow equation has been developed by means of a substitution which couples presTure, viscosity and gas law deviation factor. This sub-stitution has been called the real gas pseudo-pressure. Use of the real gas pseudo-pressure leads to simple equations describing real gas flow which do not contain pressure-dependent gas properties, and which do not require the assumption of small pressure gradients everywhere in the flow system. Equations required to determine flow capacity, well condition and static formation pressure from pressure drawdown and build-up tests with the real gas pseudo-pressure concept are presented. Also shown are applications of the real gas pseudo-pressure to back-pressure testing, the gas materials balance and rigorous determination of average gas properties for previous gas flow equations. Included are sample calculations for well test analyses. INTRODUCTION A recent study' of the flow of the transient flow of real gases in ideal radial systems showed that it is possible to consider gas physical property dependence upon pressure by means of a substitution called the real gas pseudo-pressure. The substitution has the advantage that it enables engineering solutions for steady and transient flow of real gases that are more accurate and general than those previously available. The solutions are particularly important for the case of gas flow in tight, high-pressure formations under large drawdowns. Even for more ideal flow conditions, the real gas pseudo-pressure concept leads to important rules for finding average gas physical properties pertinent for older well test analyses. Ref. I provides a detailed study of the theory behind the real gas flow correlations to be used in this paper. The purpose of this paper is to provide necessary engineering forms for use of the real gas flow results, and to illustrate applications. The following considers flow of real gases in an ideal radial flow system. It is assumed that: (1) formation thickness, porosity, water saturation, absolute permeability, temperature and gas composition are constant; (2) gas compressibility and density are functions of pressure as described by the gas law pv = znRT; (3) gas viscosrty is a function of pressure; (4) effective permeability to gas may be a function of pressure to account for liquid condensation; (5) condensate is immobile; and (6) the formation has no dip.

Jan 1, 1967

By M. H. Cullender

The performance characteristics 01 gas wells producing from formations which fail to stabilize within a relatively short period of time are obscured by the interrelation of the coefficient (C) and the slope "n" of the conventional back-pressure curve q = C(P2 f- p2s)n An empirical method is presented whereby the characteristic or true slope (11) of the back-pressure curve may be determined for a particular gas well. For those gas wells which do not stabilize within a relatively short period of time, the coefficient (C) is considered as a variable with respect to time and as a constant only with respect to a specific time. Thus, the back-presrure performance of such a well is presented as a series of parallel curve5, each curve representing the performance of the well at the end of a given time interval. Through use of the method presented, a simple presture gradient is developed and maintained within the drainage area around a producing gas well during the test period in order that the variation of the coefficient (C) with respect to time does not obscure the true value of the lope. INTRODUCTION The back-pressure method of testing gas wells as set forth by Schellhardt and Rawlins1 is dependent upon the requirement that a series of flow rates and corresponding pressure data be obtained under stabilized conditions. These data arc then plotted on logarithmic coordinates of flow rate (Q) vs difference in squared pressures (P2f — P2s) in order to determine the constants (C) and (n) for Equation 1. With respect to this method of presenting the performance characteristics of a gas well, it should be pointed out that although Equation 1 is an empirical relationship, the form of the equation was justified to a considerable extent by an independent development by Muskat and Botset.2 This development was theoretical in nature; however, certain assumptions with respect to the type of flow existing (viscous vs non-viscous) were madc which may or may not be correct. As the use of the method presented by Schellhardt and Rawlins spread through the industry, it became evident that the method of testing was applicable for those wells which approached stabilized prbducing conditions within a relatively short period of time. Performance characteristics could not be determined by this method, however, for wells which approached stabilized protlucing conditions slowly over a considerable period of time. This characteristic of "slow stabilization" has generally been associated with gas wells producing frorn reservoirs of low permeability. As the demand for natural gas continued to grow through the years, a great number of wells were completed in reservoirs of low permeability which exhibited "slow stabiliz:~tion" characteristics. Consequently, the problem of determining the true performancc characteristics of these wells became more apparent. It is with this problem in mind that the isochronal performance method of determining the flow characteristics of gas wells is presented.

Jan 1, 1956

By A. J. Phillips, A. A. Smith, J. S. Smart

THE preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in properties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. PREPARATION OF HIGH-PURITY COPPER The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuS04-H2SO4 electrolyte using bagged anodes, low current .density (5 amp. per sq. ft.) and low temperature (25°C. max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe 2(S04)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then refiltered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2S04 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 434 by 43a by I-in anodes cast from high-quality electrolytic wire bar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars-which would result in fouling of the contacts and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By J. Murray Riddell, George A. Morrison

This paper is a companion to the one by George A. Morrison on Mining a Deep Limestone Mine in Ohio.‡ Barberton is 8 miles west of Akron, Ohio, and 23 miles south of Cleveland. The underground mining of limestone at Bar-berton constitutes the world's deepest limestone mine. The stratigraphy is as follows: 0-20 ft. Loam, clay, sand and gravel. Water bearing. 2-40 ft. Fractured sandstone. Water bearing. 40-110 ft. Sandstone with interbedded shale, slightly fractured. Water bearing. 110-314 ft. Sandstone with interbedded shale, slightly fractured. Water carrying. 314-2197 ft. Shale with occasional seams of sandstone, which varies in thickness from a few inches to 4 feet. Dry. 2197-2247 ft. Limestone. Dry. 2247-2742 ft. Dolomitic limestone. Dry. 2742-2767 ft. Salt. Dry. 2767- Dolomitic limestone. Dry. All of the strata dip to the southeast, about 0.5 per cent from the horizontal. The top 110 ft. of the crust is water-bearing. The rock strata are naturally fractured to a depth of 314 ft., sufficient to allow the passage of water. In the shaft-sinking operations, a stra- turn of oil-bearing sandstone one foot thick was encountered at a depth of 520 ft., and flows of methane gas were pierced at depths of 1350 and 1952 feet. Specifications for the mine plant called for, in part, the sinking of two vertical shafts and a hoisting plant capable of producing at the rate of 300 tons per hour. No. I shaft is 550 ft. west of No. 2 shaft. Each shaft measures 8 by 17 ft. outside of steel. General features of the design (Fig. I) are: Principal set members, 6-in. H-section; connecting angles (studdles), ? by 4 by 4-in. angle irons; spacing of sets. 8 ft. centers; spacing of bearer sets, generally, 160 ft.; bearers, of 12-in. I-beams. Each bearing set featured a concrete ring about the periphery of the shaft, steel to rock, and 8 ft. in height; permanent guides, 6 by 10-in. long-leaf yellow pine, 85 per cent heart. The Shaft-sinking Operation The preliminary shaft-sinking work consisted of driving interlocked steel piling about the exterior of the shafts to depths of 35 and 32 ft., respectively, and of such horizontal dimensions as to ultimately permit the pouring of a concrete collar 2 ft. in horizontal thickness. Following the pouring of a shaft collar, a temporary wooden headframe for shaft-sinking purposes was erected. The head-frame, while ordinary, featured: (1) a storage pocket of 300 cu. ft, capacity with truck servicing facilities, and (2) pneu matically operated dump doors, which mere actuated by the hoistman, thus caring

Jan 1, 1946

By H. Furman Byars

INTRODUCTION of bottom dump hauling units into the Ray, Ariz., stripping operation of the Isbell Construction Co., was motivated by several reasons, with what appears to be debatable results. The accepted theory of truck design for use in open-pit holds that end dump vehicles are the most adaptable for the work. But, because operations of the bottom dump, under certain construction and haulage conditions, proved economically feasible, the unit was put to work in the Ray copper pit. The decision to try bottom dump was reached after considerable observation of the unit in action on construction of earth filled dams, levees, airport construction and several other similar tasks. Basic tire design also motivated the choice. All things being equal, a vehicle running on low pressure single tires will outperform another operating on dual high pressure tires, providing load carrying capacities are the same. The investment required to equip a vehicle with four single tires to handle the same load as one with dual tires mounted on two axles and single front axles is about 60 pct greater. Thus, in order to reach the break even point on tire costs, single tires must operate 60 pct longer. Comparison is made with a truck outfitted with 10 16:00x25 tires. Two other factors were considered in selecting bottom dump trucks. It was felt the bottom dump principle would work well in dumping ore into a hopper where gate design fits this particular method. Also, with the absence of hydraulic dumping, ore pollution with oil is reduced. The mechanical simplicity of the unit also lent weight to its choice. Ordinary reasoning indicated maintenance costs would be low compared with other units carrying similar loads. The bottom dumping principle is not new. It dates back to the days when horses were used to haul the same kind of rig. The unit employed at Ray holds 25 cu yd struck measure, or approximately 42 short tons. Dumping is accomplished by releasing an air cylinder opening a dog holding the doors. Doors are closed by a cable system operating off a wheel wind deriving power by friction with the trailer tire. The unit is mounted on four 27.00x33 and two 14.00x24 tires on the front axle. The power unit is a 300 hp Cummins engine. Hydraulic power boosts the steering. A straight mechanical drive and friction clutch with 10 speeds is used. Conditions Not Ideal Top performance of the truck can be expected only under the conditions for which it was designed, in particular grades under 5 pct, handling fine material, and dumping where one thin layer can be placed on top of another. The machine will handle 42 tons per haul, operating at high speed, with only seconds used for dumping. On a 2 or 3 pct grade over a one mile haul,

Jan 1, 1952

By N. Tiner

In an article on magnesium and its alloys, Gann and Winston! stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 675°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I). This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of, these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing 0.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C. and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. Experimental Method The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By G. R. Rubly, H. J. Steele

The San Manuel property is in town&ips 8S and 9S, range 16E, Gila and salt River Base and Meridan, State of Arizona. This area is in the Old Hat mining district, southern pinal county, and is about 31/25 miles southwest of the town of Mammoth on the San Pedro River And one mile south of the Mammoth mine at Tiger, Arizona, The property consists of over 150 contiguous lode claims. The old Hat district was prospected prior to the civil war, but there was little or no production until 1881.1 The chief producers have been the Mammoth and Mohawk mines, now consolidated and operating as the st. Anthony Mining and Development Co., Ltd. Production to 1936 was $5,200,000, of which 83 pet was gold.2 Since 1940 the production has been chiefly lead and zinc, and some molybdenum and vanadium. There are a few small properties in the vicinity that have produced very minor tonnages of copper ore. In the San Manuel group there are claims which have been held continuously from 1906 to the present time, and at least two churn-drill holes were put down on or near the outcrop in 1917. No logs for these holes are available, but it is assumed that the grade of copper encountered was not sufficient to encourage further exploration. A small amount of ore has been shipped from open cuts on the San Manuel outcrop area, but there is no record of the tonnage Or grade. It is estimated that not more than 50 tons were mined. These cuts, plus a few shallow shafts and some short adits indicate limited and unenthusiastic prospecting at San Manuel. In 1942, through the efforts of James M. Douglas, R. B. Giffin, Victor Erickson, and Henry W. Nichols, owners of the Sari Manuel group, the Reconstruction Finance Corporation and War Production Board authorized the United States Geological Survey to investigate the property, and by their recommendation, the United States Bureau of Mines was authorized to put down a limited number of churn-drill holes. The Bureau of Mines carried On drilling from November 1943 to February 1945 Seventeen holes were drilled, varying from 305 to 1990 ft in depth. The property was brought to the attention of Magma Copper Co. in June 1944, and an option agreement was made with the Owners. Subsequently, a group of claims lying north of the original group and held by the Apex Lead Vanadium Mining Corp, and a group to the east held by the Quarelli family, were optioned. A drilling program was laid out to conform to the Bureau of Mines pattern, and drilling started in December 1944 Sari Manue1 Copper Corp. was incorporated September 1945, and has carried on the exploration program to the present time. Geology General The mineralized outcrop, chief copper mineral of which is chrysocolla, is a tri-

Jan 1, 1949

By G. R. Rubly, H. J. Steele

The San Manuel property is in town&ips 8S and 9S, range 16E, Gila and salt River Base and Meridan, State of Arizona. This area is in the Old Hat mining district, southern pinal county, and is about 31/25 miles southwest of the town of Mammoth on the San Pedro River And one mile south of the Mammoth mine at Tiger, Arizona, The property consists of over 150 contiguous lode claims. The old Hat district was prospected prior to the civil war, but there was little or no production until 1881.1 The chief producers have been the Mammoth and Mohawk mines, now consolidated and operating as the st. Anthony Mining and Development Co., Ltd. Production to 1936 was $5,200,000, of which 83 pet was gold.2 Since 1940 the production has been chiefly lead and zinc, and some molybdenum and vanadium. There are a few small properties in the vicinity that have produced very minor tonnages of copper ore. In the San Manuel group there are claims which have been held continuously from 1906 to the present time, and at least two churn-drill holes were put down on or near the outcrop in 1917. No logs for these holes are available, but it is assumed that the grade of copper encountered was not sufficient to encourage further exploration. A small amount of ore has been shipped from open cuts on the San Manuel outcrop area, but there is no record of the tonnage Or grade. It is estimated that not more than 50 tons were mined. These cuts, plus a few shallow shafts and some short adits indicate limited and unenthusiastic prospecting at San Manuel. In 1942, through the efforts of James M. Douglas, R. B. Giffin, Victor Erickson, and Henry W. Nichols, owners of the Sari Manuel group, the Reconstruction Finance Corporation and War Production Board authorized the United States Geological Survey to investigate the property, and by their recommendation, the United States Bureau of Mines was authorized to put down a limited number of churn-drill holes. The Bureau of Mines carried On drilling from November 1943 to February 1945 Seventeen holes were drilled, varying from 305 to 1990 ft in depth. The property was brought to the attention of Magma Copper Co. in June 1944, and an option agreement was made with the Owners. Subsequently, a group of claims lying north of the original group and held by the Apex Lead Vanadium Mining Corp, and a group to the east held by the Quarelli family, were optioned. A drilling program was laid out to conform to the Bureau of Mines pattern, and drilling started in December 1944 Sari Manue1 Copper Corp. was incorporated September 1945, and has carried on the exploration program to the present time. Geology General The mineralized outcrop, chief copper mineral of which is chrysocolla, is a tri-

Jan 1, 1949

By R. A. Nadler and

Specimens of Ti-155A (Ti-5Al-1.3Fe-1.3Cr-1.2Mo), Ti-6Al-4V and Ti-4Al-3Mo-1V were hydrogenated, aged to high strength levels, and subjected to notched stress-rupture tests and tensile tests at two strain rates. Both Ti-6Al-4V and Ti-155A were relatively unaffected by hydrogen in amounts exceeding those found in commercially -produced material. Inconsistencies in the data and a relatively low initial level of ductility prevented an accurate determination of the hydrogen tolerance for aged Ti-4Al-3Mo-1V, but there was no evidence that this alloy was any more susceptible to hydrogen embrittlement than Ti-155A and Ti-6A1-4V. THE metallurgical literature has been considerably enriched in the past five years by the publication of the results of many investigations which were concerned with the effects of hydrogen on titanium and its alloys. Although it is not the authors' intention to provide a complete literature survey of this vast field, it is worthwhile to summarize briefly some of the important factors which influence the embrittling phenomenon in a - B alloys. Some of the influencing factors are those of strain rate, temperature, and composition. Hydrogen embrittlement in a - B titanium alloys is now believed to be a strain-induced phenomenon, and whether or not embrittlement occurs at high hydrogen levels depends largely upon whether sufficient time is available for hydride precipitation. This condition is fulfilled by tensile testing at very slow strain rates or by rupture testing smooth or, preferably, notched specimens over relatively long periods. Conveniently, maximum embrittlement occurs at or near room temperature. The presence B - stabilizing elements, in amounts sufficiently small to prevent an all -B or nearly all -P condition, promotes hydrogen embrittlement and this tendency is believed to be related to the amount of a - B interfacial area present. Aluminum, by increasing the solubility of hydrogen in A titanium, greatly reduces the danger of hydrogen embrittlement, while oxygen has been shown to have detrimental effects.' The preceding discussion is based on experimental work performed on annealed a - P alloys. This early work has shown that annealed Ti-6A1-4V and Ti-155A are relatively insensitive to the embrittling effects of hydrogen.' Although no work has been reported on annealed Ti-4A1-3Mo-lV, the alloy would be expected to exhibit somewhat the same insensitiv-ity as Ti-155A. In sharp contrast to the voluminous literature on annealed titanium alloys is the paucity of reported investigations on materials receiving commercial heat-treatment cycles. To date, the most notable contributions in this field have arisen from two separate investigations on Ti-3Mn-1Fe-1Cr-1V-lMo, the so-called 3Mn comple~. These investigations

Jan 1, 1961

By Y. L. Yao

THE NaT1-type compound may be considered as the penetration of two diamond lattices in such a way that a superstructure of the bcc lattice is formed. Examples of the NaT1-type compound of lithium are LiZn, LiCd, LiA1, LiIn, and LiGa. Except for LiZn and LiCd, each molecule of these equiatomic compounds contains a total of four valence electrons. In LiZn and LiCd it was suspected (for example, see Ref. 1) that the fourth electron was withdrawn from the 18-shell of zinc or cadmium. An incomplete 18-shell would have to show strong paramagnetism. In 1955 Klemm and Fricke2 determined the magnetic susceptibility of LiZn, LiCd, LiA1, and LiIn (also NaTl and NaIn). The molar susceptibility of the outer electrons of LiZn and LiCd was found to be not strongly but weakly positive; that of LiAl and LiIn not negative but weakly positive. Thus they questioned the hypothesis about LiZn and LiCd in particular and the description of the NaT1-type structure in general. However, they did not determine the magnetic susceptibility of LiGa. This note is to report results for all five compounds of lithium. The starting materials are 99.9 pct pure lithium sticks containing less than 0.005 pct Na. 99.9 pct Zn, 99.9 pct Cd, 99.99 pct Al, 99.999 pct In, and 99.999 pct Ga. Weighed amounts of two components were wrapped in tantalum foil and placed in a graphite crucible. It was found that the tantalum sheath minimized the vaporization losses of lithium during melting. The sheath was easily stripped from the alloy rod and the tantalum in the alloy was barely detectable (less than 0.01 wt pct). The melting was performed in a resistance furnace under an argon atmosphere. Alloy specimens were annealed for 1 hr at 400°C in vacuum. The magnetic susceptibility at room temperature was determined by the Faraday Method, using the procedures previously described.' The results are shown in Table I. The interpolated values at 50 at. pct of Li and the average values at 48 to 52 at. pct of Li at 20°C determined by Klemm and Fricke2 are also shown. It is seen that the present value for LiZn and LiCd is slightly more positive but the present value for LiAl and LiIn is slightly less positive than their corresponding values. Also, it is noted there is an abrupt decrease of susceptibility of LiAl from 51.2 to 52.5 at. pct of Li. Klemm and Fricke2 found that the total susceptibility of LiZn, LiCd, LiA1, and LiIn is almost independent of temperature. slater4 gave a working expression for the diamagnetism of the atomic core as follows:

Jan 1, 1964

By J. Murray Riddell, George A. Morrison

THIS paper is a companion to the one by George A. Morrison on Mining a Deep Limestone Mine in Ohio.[+] Barberton is 8 miles west of Akron, Ohio, and 23 miles south of Cleveland. The underground mining of limestone at Barberton constitutes the world's deepest limestone mine. The stratigraphy is as follows: 0-20 ft. Loam, clay, sand and gravel. Water bearing. 20-40 ft. Fractured. sandstone. Water bearing. 40-110 ft. Sandstone with interbedded shale, slightly fractured. Water bearing. 110-314 ft. Sandstone with interbedded shale, slightly fractured. Water carrying. 314-2197 ft. Shale with occasional seams of sandstone, which varies in thickness from a few inches to 4 feet. Dry. 2197-2247 ft. Limestone. Dry. 2247-2742 ft. Dolomitic limestone. Dry. 2742-2767 ft. Salt. Dry. 2767- Dolomitic limestone. Dry. All of the strata dip to the southeast, about 0.5 per cent from the horizontal. The top 110 ft. of the crust is water-bearing. The rock strata are naturally fractured to a depth of 314 ft., sufficient to allow the passage of water. In the shaft-sinking operations, a stra was encountered at a depth of 520 ft., and flows of methane gas were pierced at depths of 1350 and 1952 feet. Specifications for the mine plant called for, in part, the sinking of two vertical shafts and a hoisting plant capable of producing at the rate of 300 tons per hour. No. I shaft is 550 ft. west of No. 2 shaft. Each shaft measures 8 by 17 ft. outside of steel. General features of the design (Fig. I) are: Principal set members, 6-in. H-section; connecting angles (studdles), 3/8 by 4 by 4-in. angle irons; spacing of sets, 8 ft. centers; spacing of bearer sets, generally, 160 ft.; bearers, of 12-in. I-beams. Each bearing set featured a concrete ring about the periphery of the shaft, steel to rock, and 8 ft. in height; permanent guides, 6 by 10-in. long-leaf yellow pine, 85 per cent heart. THE SHAFT-SINKING OPERATION The preliminary shaft-sinking work consisted of driving interlocked steel piling about the exterior of the shafts to depths of 35 and 32 ft., respectively, and of such horizontal dimensions as to ultimately permit the pouring of a concrete collar 2 ft. in horizontal thickness. Following the pouring of a shaft collar, a temporary wooden headframe for shaft-sinking purposes was erected. The head-frame, while ordinary, featured: (I) a storage pocket of 300 cu. ft. capacity with truck servicing facilities, and (2) pneumatically operated dump doors, which were actuated by the hoistman, thus caring for the dumping of the "ball-and-chain"

Jan 1, 1944

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By Arthur F. Taggart, A. W. Thomas, T.C. Fitt

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By P. W. Bakarian

PREVIOUS determinations1,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc-also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {102}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. EXPERIMENTAL METHOD Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 32 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. 2. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in, and evenly etched in dilute hydrochloric acid to a diameter of 0.038 ± 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1941

By N. Tiner

IN an article on magnesium and its alloys, Gann and Winston1 stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 695°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I): This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing o.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. EXPERIMENTAL METHOD The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By O. L. Culberson, J. J. McKetta

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

By J. J. McKetta, O. L. Culberson

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951