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By Wm. Hamilton Merritt

IN this paper, which I have the honor to submit to the Institute, it is my intention to treat especially of that part of the North Staffordshire field which converges to a long tongue in the neighborhood of Congleton, and which includes the villages of New Chapel, Ford Green, Norton, Biddulph, Bradley Green, Gillow Heath, and the immediate vicinity. My object is not so much to give a minute description of the geology or systems of mining and smelting, as by a general review, some idea of the extraordinary facilities for the production of excellent iron, which have enabled this district to maintain its position more successfully than any of its rivals against the late depression in trade. The North Staffordshire coal field has the Cheshire and Lancashire fields some thirty-five miles to the north, those of Derbyshire and Nottinghamshire forty miles to the east, those of South Staffordshire and Shropshire, about thirty miles to the south, and the Denbighshire and Flintshire fields some forty miles to the west. It is highly probable that the coal continues under the new red sandstone to the Western and Southern fields as the dips on both sides, and absence of large faults, make it impossible to come to any other conclusion. In a section of this coal field, from Chatterly to Whitfield, thirty-two workable seams of coal are shown, of an aggregate thickness of 130 feet, varying from 2 feet 6 inches to 7 feet, and thirteen seams of ironstone, 24 feet, averaging from 2 to 4 feet. All of these seams have been minutely described in a paper by Mr. Charles J. Homer, read in 1875 before the British Iron and Steel Institute. In the northern part, to which I especially wish to direct your attention, the beds lie in a V-shaped basin, the underlying millstone grit and Yoredale rocks rising and forming escarpments on either side of the valley containing the coal. Throughout this district, at the outcrop of the coal, there are indications of old workings. A shaft 4 to 5 feet in diameter reaches the coal at about 14 yards from the surface, and from it the coal has

Jan 1, 1880

By William Hamilton Merritt

In this paper, which I have the honor to submit to the Institute, it is my intention to treat especially of that part of the North Staffordshire field which converges to a long tongue in the neighborhood of Congleton, and which includes the villages of New Chapel, Ford Green, Norton, Biddulph, Bradley Green, Gillow Heath, and the immediate vicinity. My object-is not so much to give a minute description of the geology or systems of mining and smelting, as by a general review, some idea of the extraordinary facilities for the production of excellent iron, which have enabled this district to maintain its position more successfully than any of its rivals against the late depression in trade. The North Staffordshire coal field has the Cheshire and Laucashire fields some thirty-five miles to the north, those of Derbyshire and Nottinghamshire forty miles to the east, those of South Staffordshire and Shropshire, about thirty miles to the south, and the Denbighshire and Flintshire fields some forty miles to the west. It is highly probable that the coal continues under the new red sandstone to the Western and Southern fields as the dips on both sides, and absence of large faults, make it impossible to come to any other conclusion. In a section of this coal field, from Chatterly to Whitfield, thirtytwo workable seams of coal are shown, of an aggregate thickness of 130 feet, varying from 2 feet 6 inches to 7 feet, and thirteen seams of ironstone, 24 feet, averaging from 2 to 4 feet. All of these seams have been minutely described in a paper by Mr. Charles J. Homer, read in 1875 before the British Iron and Steel Institute. In the northern part, to which I especially wish to direct your attention, the beds lie in a V-shaped basin, the underlying millstone grit and Yoredale rocks rising and forming escarpments on either side of the valley containing the coal. Throughout this district, at the outcrop of the coal, there are indications of old workings. A shaft 4 to 5 feet in diameter reaches the coal at about 14 yards from the surface, and from it the coal has

Jan 1, 1880

By Theodore R. Butkovich, Jesse L. Yow

Geological storage of spent-fuel assemblies from an operating nuclear reactor has been underway since the Spring of 1980 at the U.S. Department of Energy's Nevada Test Site. The primary objective of this generic test is to evaluate granite as a medium for deep geological storage of high level reactor waste and to provide data on thermal and thermomechanical behavior of granite from imposed heat loads.(l) The underground installation in the Climax stock granite was sited at about 420 m below the surface and 145 m above the existing water table. As shown in Figure 1, three parallel drifts were excavated spaced on approximately 10 m centers. Seventeen storage holes were drilled at the central drift on 3 m centers in which eleven spent fuel canisters and six thermally identical electrical simulators were emplaced. Electrical resistance heaters were emplaced in vertical holes in the floor of the side drifts on 6 m centers. The thermal output of these heaters is being periodically adjusted to simulate the thermal response of a large storage array. Rock and ventilation air temperatures are being measured continuously in the drifts and throughout the rock surrounding the excavations. Measurements of drift deformation have been made routinely since the emplacement of the spent fuel. Both vertical and horizontal measurements are being taken at five locations along the heater drifts and at six locations along the central canister drift (Fig. 1). Two types of instrumentaton are being used: convergence wire extensometers which are monitored automatically, and a manually operated tape extensometer with which measurements are taken periodically. The tape extensometer measurements were initiated about 6 weeks following fuel emplacement. The lack of a temperature correcting capability for the convergence wire extensometers make that data unavailable for analysis at this time.

Jan 1, 1982

By P. E. Demmler

PHOSPHORUS combines with copper in various proportions, forming true alloys, some of which are of commercial importance. These materials find wide application as deoxidizers and as a means of introducing phosphorus into other alloys, as in phosphor-bronze. Phosphor-coppers containing 10 and 15 per cent. of phosphorus are the commercial grades that are most generally offered. Each has certain advantages when used in making other alloys. The 10 per cent. grade of phosphor-copper has an advantage over the 15 per cent. in that it has a much lower melting point and can be prepared by certain methods with a much lower loss in phosphorus. The 15 per cent. grade has the advantage of lower freight rates per unit of phosphorus and, by the method to be described, a uniform product can be prepared with practically no loss of phosphorus. Alloys of copper and phosphorus containing any desired percentage of phosphorus lower than 15 per cent. can be prepared by melting together the requisite amounts of copper and 15 per cent. phosphor-copper. Processes for making phosphor-copper may be divided into two classes as follows: (1) Those depending on the smelting of phosphate rock or superphosphate of calcium with copper or copper-bearing materials, and coal or other carbonaceous material; (2) those depending on the direct combination of metallic copper and elemental phosphorus. A number of formulas for preparing phosphor-copper according to the first method have been published. The Metal, Industry' gives-the following: Superphosphate of calcium, 60 lb.; granulated copper, 301b.; finely powdered coal, 10 lb. Similar formulas are given by Brannt2 and others, and detail 'variations are covered by patents, such as those of L A Jeffs3 and H A Webster.4

Jan 8, 1920

By Edward Judd

CONSTRUCTION of the long projected Moffat tunnel, on the Denver & Salt Lake R. R., between Tolland and Irving, Colorado, is now actually and actively progressing. This 6.1-mile bore through the Rocky Mountains, at an elevation of about 9200 ft., will eliminate 33 1/3 miles of probably the most tortuous standard-gage track in the world, and at the same time will avoid the necessity for crawling over the snow-bound continental divide at an elevation of 11,660 ft Completion of the tunnel within the stipu-lated four years, is expected to nave an immediate effect on the develop-ment of the known coal fields in north-western Colorado, already penetrated at Craig, the present terminus of the road, while it will also enable the railroad to carry out the original designs of its founder, David H. Moffat, for through traffic from farther west. The intention now is to accomplish the latter object by an extension from McCoy following the canon of the Grand River down to a connection with the Denver & Rio Grande at Dotsero. Legal impediments to the financ-ing of the tunnel having been removed by action of the Colorado legislature in April, 1922, the Moffat Tunnel Improvement District issued bonds to the amount of $6,720,000 which have been widely and quickly distrib-uted through a New York banking house. Responsi-bility for the execution of the project has been vested in the Moffat Tunnel Commission, to which a board of consulting engineers has been appointed for carrying out the details of administration. This board includes D. W. Brunton and L. D. Blauvelt, of Colorado, and J. Vipond Davies and J. Waldo Smith, of New York; R. H. Keays, who has managed large tunnel projects in New York, is chief engineer for the Commission.

Jan 11, 1923

By Donald B. Gillies

THE great source of iron ore for the furnaces of this country has been the Lake Superior district. Ore was first discovered there in 1844, and the first shipments made via the Great Lakes in 1852 to a furnace at New Castle, Pa. The stream of ore from that region increased slowly to exceed a million tons in 1873, and did not reach 10 million tons until 1895. By 1901 it exceeded 20 million tons, and in 1907 over 40 million tons. Total Lake Superior output through 1948 was about 2500 million long tons. Outside the Lake Superior district are the Southern district, including mainly Alabama, Georgia, Missouri, and Texas; the Eastern district of New York, New Jersey, and Pennsylvania; the Western district embracing Wyoming, Utah, and California.

Jan 1, 1949

By M. W. Lightner

IN 1947 the steel industry rebounded from its wartime effort and produced a record-breaking peacetime tonnage of steel ingots. During the first six months of the year the industry produced 42,000,000 tons of ingots and expected to produce 85,000,000 tons for the year. With a rated capacity of some 91,000,000 tons, production was at a rate of about 93 per cent of capacity. Credit must be extended to the steel producers who have maintained this steady state of operations while faced with many problems, not the least of which was a continued shortage of satisfactory scrap. Furthermore, the steel industry started a record-breaking peacetime expansion program at a total cost of more than $1,000,000,000. This program will increase the ingot-making capacity of the country by 2,500,000 tons and should be completed in 1948.

Jan 1, 1948

By E. A. Devuyst, M. A. Mosoiu, V. A. Ettel

Nickelic hydroxide is an important metallurgical reagent used for precipitating cobalt from nickel sulfate solutions. Existing methods of preparation of nickelic hydroxide involve electrolytic oxidation of Ni(OH)2 or the use of strong oxidizing agents such as chlorine, ozone and persulfate. Although the oxidizing properties of the SO2 + O2 system have been known for some time, e.g., detection of SO2 and oxidation on iron in acidic solution, the application of this system for the preparation of nickelic hydroxide as a process was not considered in the past. The present paper describes a new method for chemical preparation of nickelic hydroxide which has been developed in INCO laboratories. The technique consists of reacting nickelous hydroxide suspensions with a slurry of calcium sulfite in the presence of air or oxygen. The main advantage of the process is the cost of reagents and an absence of soluble by-products (e.g., C1-). The chemistry of this process is unusual since the redox potential obtained during the reaction exceeds that of the oxygen electrode. Therefore, the effect of CaS03 is not just a catalytic acceleration of the reaction NI(OH)~ + 02. The so3= must be involved in the stoichiometry of the overall reaction producing in the initla1 phase some strongly oxidizing intermediate species.

Jan 1, 1981

By E. G. Banks

This paper is presented in the belief that metallurgists and chemists will be interested in the practice of grinding in tube-mills in connection with stamps, especially since the records of working here given extend over a lengthy period of time (since May, 1905). The ore from the Waihi mine—more especially that produced in the upper levels—contains a large proportion of hard, chalce-donic quartz, and the gold exists in an exceedingly fine state, conditions which necessitate very fine crushing in order to obtain a high extraction of the precious metal. Before the introduction of tube-mills at the 90-stamp Waihi mill, it was found necessary to stamp through 40-mesh (1,600 holes per sq. in.) woven wire-screens, having a fairly high discharge. The pulp then graded : Per Cent. Per Cent. On 50-mes11, .- 0.1 On l20-mesh ..8.77 On 60-mesh, . 8-74 On 150-mesh,.... 7.48 On 80-mesh,... 16.06 Passed 150-mesh,... 55.19 On 100-mesh,.... 3.66 The stamp-dnty was 2.89 short tons per stamp per day, or a total of 260 tons daily. Although the extraction on this pulp was: gold, from 88 to 90 per cent., and silver, from 74 to 78 per cent., it was recognized that finer grinding of the sands would prove beneficial, provided a machine could be found to do this work economically. Various grinding-mills and pans were tried, but without satisfactory results, the particles of sand being so hard that the capacity of any of the machines was too small to be economical. The results of grinding in tube-mills in other countries were so satisfactory that three tube-mills mere erected at the Waihi

Jan 1, 1908

By Dorsey Hager

The possibilities of finding new oil pools in Oklahoma and Kansas are far from promising. In 1916, the only new pools of importance were the Franchot pool near Bixby, the Garber, and the Billings pools in Oklahoma, and the Virgil and Utopia fields in Greenwood County, Kansas. In the first 8 months of 1917, a small pool of unknown extent was opened south of the Stone Bluff pool in Oklahoma, and a pool near Casey, Paunee County, Oklahoma. In Eastern Kansas, interest has been caused by the sinking of new wells near the old Iola pool, but nothing of magnitude has yet been found. The outlook for new pools is far from encouraging, especially as geological surveys have covered all of Oklahoma and Kansas. There are a few areas where geological surveys throw little or no light on the subject, as exposures are poor, but the chances of finding new pools in such areas are slight indeed, if one can judge from the past history of such areas. So far the geologists have based their opinions largely upon the presence or the absence of geologic structure, such as anticlines, domes, and terraces, but some pools will most certainly be found where no surface structure exists, but where local changes in the sand body favor oil accumulations. However, the possibilities of new pools off structure are small, as fully 90 per cent. of the oil pools are on definite structure. In the past, it is estimated that one test in 150 "wild cats" or new tests has brought in a new field. The writer feels safe in asserting that the proportion will decrease still further, so that but one out of 500 new tests may bring in a pay well in a new area. Prom now on the principal field of work in Oklahoma and in Kansas will consist in developing the present pools. The years 1915, 1916 and 1917 saw the high peak of Oklahoma and Kansas oil production. The Eldorado and the Augusta oil fields present the largest possibilities for continued production in Kansas. These two pools have been scarcely more than one-third developed, and have greater potentialities than any of the present Oklahoma pools. In Oklahoma, pools of magnitude should

Jan 1, 1918

By A. Patton, F. N. Speller

The use of roll scale in the Bessemer process dates back, to the best of our knowledge, at least 20 years. It was first used by the Ohio Steel Go., Youngstown, Ohio (now the Ohio Works of the Carnegie Steel Co.) under the direction of Sam McDonald, Superintendent of the Bessemer Department at these works. Two 10-ton vessels and one blowing engine capable of blowing one heat at a time were employed. The object of using the scale was to shorten the length of the blow, or in other words, to increase the production with the same equipment. Various means were tried out for introducing the roll scale into the bath of molten iron: It was shoveled into the vessel before the heat was charged, so that the metal would flow over the scale; it was shoveled into the bath after the vessel was turned up; it was dumped into the empty iron ladle by the wheelbarrow-load, and at times was dumped on top of the molten metal in the iron ladle. But the practice of introducing the scale into the iron ladle had to be abandoned on account of danger from explosions and of skulling the ladles. It was soon learned that the proper place to charge the scale was in the empty vessel, so that when the molten iron was poured into the vessel it flowed over the scale, causing a considerabIe reaction to take place before the heat was turned up. Eventually, cylindrical chutes similar to those now in use were installed. Into these chutes the scale is dumped and carried into the empty vessel. Before this convenient means of introducing the scale was adopted, the Ohio Works had satisfactorily demonstrated that roll scale would increase production, by blowing 107 heats in one 12-hr. turn (1,087 tons) with one blowing engine, blowing one heat at a time; whereas, prior to the use of scale, the best practice at these works was about 80 heats under the same conditions. In using roll scale and other oxides of iron to facilitate and control the refining of pig iron in the converter, the Bessemer plant has borrowed one of the most active agencies used in the open-hearth process with, as would be expected, much the same results. The effect of such additions to the Bessemer charge may be discussed as to the influence of this practice on quality, production and cost.

Jan 1, 1917

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By R. G. Ward, John Henderson. R. G. Hudson, G. Derge

Densities of melts of the iron oxide-silica system in contact with solid iron have been measured by the maximum hubble pressure method in the composition range O to 37 wt pct SiOz and the temperature range 1255 to 1410C. The constitution of the melts is discussed and it is postulated that the structure changes from a dislribution of iron ions in an oxygen ion network at pure "FeO" to a distribution. of iron ions in a network of silicate tetrahedra at the orthosilicate composition. JOHN HENDERSON, Junior Member AIME, was formerly with the Metals Research Loborotory, Carnegie Institute of Technology, Pittsburgh, Pa., on leave from Broken Hill Proprietary Co., Ltd., Research Division, Shortland, Australia. R. G. HUDSON, formerly with Metals Research Laboratory, is now with the John Jay Hopkins Loborotory for Pure and Applied Science, General Atomic Division, General Dynamics Corp., LaJolla, Calif. R. G. WARD, was formerly with the Department of Metal lurgical Engineering, Carnegie lnstitute of Technology, while on leave from the Department of Metallurgy, University of Sheffield, England. G. DERGE, Member AIME, is Jones and Laughlin Professor of Metallurgical Engineering, Carnegie lnstitute of Technology. Manuscript submitted January 19, 1961. ISD The system iron oxide-silica is an important one metallurgically because it forms the basis of several complex slag systems in use for industrial smelting and refining processes. In recent years considerable work has been done on liquids of this system but there are still many points of difference among workers using different experimental techniques and theoretical approaches. Phase equilibria/"3 activity,4-6 electrical conductivity,' current efficiency,' transference number,8 viscosity,9 surface tension,'' and density" measurements have all contributed to an understanding of the problem. Measurement of density is one procedure which is directly indicative of liquid structure since any deviation from ideality must be a result of structural interactions. Liquids of the iron oxide-silica system are of special interest because this is one of the few metal oxide-silica systems on which measurements can be carried out conveniently over the entire composition range from pure oxide to silica saturation. This includes the range of high basicity which has received relatively little attention in other systems. Although one investigation of density in this system has previously been undertaken," the results seem of sufficient importance to warrant the independent redeter-mination reported here.

Jan 1, 1962

By M. J. Spendlove, H. W. St. Clair

An automatic surface-follower mechanism was used to measure the surface temperature and the rate of evaporation of molten zinc while undergoing distillation at low pressure. At pressures of 50 to 100 microns Hg, the rate of evaporation may be 60 to 80 pct of the theoretical maximum corresponding to the measured temperature. The rate decreases rapidly at pressures above 100 microns Hg, to only 7 pct of the theoretical maximum at 2000 microns Hg. Measured temperature gradients at the surface are in agreement with theoretical gradients calculated from the heat of vaporization, rate of evaporation, and thermal conductivity of molten zinc. THIS paper covers a series of careful measurements of the rate of evaporation of molten zinc at low pressures, undertaken as a part of a general investigation on the separation of metals by distillation.' Preliminary results on the rate of evaporation of zinc were described in a previous publication.' The results of the preliminary study are as follows: 1—The observed rates of evaporation of zinc were as high as 0.60 g per sq cm per min, corresponding to 75 pct of the maximum rate as determined by the temperature of the metal. 2—The evaporation rate was decreased from 0.30 g per sq cm per min at a pressure of 25 microns to only 0.09 g per sq cm per min when the pressure was increased to 5 mm. 3—The temperature of the surface during rapid evaporation may be 35" to 100°C less than the main mass of metal. Observed temperature gradients at the surface are consistent with those calculated from the heat of vaporization and the thermal conductivity of liquid zinc. In the preliminary experiments, the rate of evaporation was determined from the loss in weight of the metal in the crucible during the test. This was compared with the weight of the condensate. Obviously, this method was subject to error because of some uncertainty as to the period of evaporation that should correspond to the loss in weight. Furthermore, this method did not permit taking into account probable variations in the rate of evaporation during the test. A more serious shortcoming was that the temperature at the evaporating surface was not known, so the maximum theoretical rate of evaporation could not be calculated accurately. To improve the precision of rate measurements and to allow accurate measurements of the surface temperature, a refined experimental technique was developed whereby the temperature and position of the surface could be measured accurately. This was done by an automatic surface-follower mechanism that gave a continuous record of the surface temperature and the amount of zinc evaporated. These data permitted an instantaneous determination of the actual rate of evaporation and the surface temperature throughout the test. Pure zinc (99.99 pct Zn) was used in all experiments. Description of Distillation Furnace The details of construction of the distillation furnace are shown in Fig. l. The furnace is enclosed in a large quartz tube open at one end. The open end of the quartz tube is sealed by means of a water-cooled head. The entire enclosure is vacuum tight. The connection between the water-cooled head and the quartz tube is sealed by means of a rubber gasket which fits tightly against the smooth end of the tube. The metal is heated by induced current set up in the molten zinc and the walls of the graphite crucible by means of a water-cooled induction coil outside the quartz tube. High frequency current is passed through the induction coil from a 6 kw mer-

Jan 1, 1952

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By M. A. Selim, W. H. Somerton

Thermal expansions and heats of reaction of three typical sandstones were measured in the temperature range of 25°to 1,000°C. The significance of these data in subsurface heat-transfer calculations is discussed. Linear thermal expansions were measured both parallel and perpendicular to the bedding planes. Volume expansions are reported as the perpendicular expansion plus two times the parallel expansion. Expansion behavior of the sandstones was found to be controlled by the expansion characteristics of the quartz content. Differential expansion of the quartz grains and other minerals included in the sandstones caused permanent deformation of the heated samples after they were cooled to room temperature. Structural damage resulting from heating is probably an important cause of the reduction of thermal conductivity of heated samples. Measurements of heats of reaction were based on the known heat required for a- quartz inversion. Thermal reactions, which probably include deby-droxylation of clay minerals and decomposition of carbonate minerals contained within the samples, were found to require more than one-fourth of the amount of heat necessary to raise the temperature of the rock alone. In shales and limestones, the reaction heat could be substantially greater than that required from specific heat considerations alone. INTRODUCTION In earlier work, l-3 methods of measuring thermal properties were developed and thermal data for several sedimentary-rock types were reported. Data included thermal conductivity, specific heat and thermal diffusivity. In addition, calculations of heat transfer in subsurface formations may require data on the thermal-expansion characteristics of rock and the heats of reaction of mineral constituents. Thermal expansion of rocks is relatively small in magnitucle and, from the standpoint of change in bulk density, has only minor effects on heat-transfer cliaracteristics. Thermal-expansion behavior, however, may have significant effects on the structure of rocks. Differential expansion of different minerals and along different crystal-lographic axes may result in structural damage which could effectively reduce the thermal conductivity of the rock. Many mineral constituents of sedimentary rocks undergo phase or related changes when heated to sufficiently high temperatures. Although some of these reactions (such as the a-ß quartz inversion) are reversible and the heat absorbed is returned to the system upon cooling, many of the major reactions are irreversible. Through certain temperature ranges, the additional heat energy required to complete the reactions may be nearly as great as that necessary to raise the temperature of the rock in the absence of thermal reactions. If the heat requirements for these reactions are not considered, serious errors in heat-transfer calculations may result. Thermal-tzxpansion and thermal-reaction data have been obtained for three typical sandstones. Methods of measurement and results obtained are reported and discussed in the following. THERMAL EXPANSION OF SANDSTONES The linear expansions of three outcrop sandstones (Bandera, Berea and Boise) have been measured in the temptbratue range of 25° to 1,000° C. Expansion measurements were made in the directions parallel and perpendicular to the bedding. The differential expansion apparatus used is that described by Mitoff and Pask.4 The test sample is heated in an electric furnace with a temperature rise of 6°C/minute. The lengthening of the samples upon heating is compared with the small and known expansion of a fused silica rod. The change in length is transmitted to an X-Y recorder by means of a Statham transducer. A maximum error of ± 1.5 per cent has been obtained with this apparatus

By T. J. Hudson, P. B. Queneau, J. D. Prater

The process parameters for effective utilization of nitric acid as an oxidant for copper-iron sulfides have been developed. Leaching variables found to be important were acid concentration, temperature, time, atmosphere, pressure, mineral type, particle size, and percent solids. Particular attention was devoted to analysis and control of fumes evolving during the oxidation. Data were recorded on metal extraction, elemental sulfur formation and oxidation, product gas composition and evolution rate, reagent consumption, and residue flotation response. The study was concluded by laboratory testing a flowsheet based on the foregoing observations. Ninety-eight percent of the copper contained in a chalcopyrite-bornite concentrate was recovered, requiring 1.6 lb of nitric acid to be regenerated externally per pound of copper extracted. Iron remained in the leach residue as hydrogen jarosite and was ultimately rejected from the system by froth flotation. Sixty percent of the sulfur contained in the copper concentrate reported in the elemental form; the remainder was oxidized to sulfate and eliminated with the hydrogen jarosite in the flotation tails or by neutralization of the solvent extraction raffinate with lime. Nitrogen was evolved primarily as NO and NOD; up to 3% N2O also was present. Gases containing sulfur were absent except when pyrrhotite was solubilized in the absence of soluble copper. In this case, HAS was evolved.

Jan 1, 1974

WHEN Georgius Agricola, in 155o, dedicated his now famous De re Metallica to the rulers of Saxony, Thuringia, Meissen, and other, smaller principalities, he included in his review of previous works on similar subjects reference to two books written in German: one, an "anonymous, rather disorganized account of assaying for metallic content and of metals," which must be the Probierbüchlein, the other, "dealing - with veins, written by Calbus of Freiberg, a well-known physician."* Calbus is mentioned a second time-and cited-at the end of the Third Book of De re Metallica. Comparison of the citation with the Bergbüchlein leaves no doubt that Agricola considered Calbus of Freiberg the author of the latter work, although all the editions of the Bergbüchlein known now were published anonymously. It is generally accepted by those who have dealt with the bibliography of the Bergbüchleint that Calbus was Ulrich Rülein von Kalbe, who served the City of Freiberg, in Meissen, as health officer in 1497, as member of the City Council in 1509, and as mayor in 1514 and 1519. He died at Leipzig in 1523. In connection with the very garbled description of the mining compass toward the end of Chapter 3 of the Bergbüchlein it is of interest that von Kalbe is supposed to have been not only a physician of repute but a mathematician, astronomer, mine sur-

Jan 1, 1949

By C. F. Weinaug

In recent years, several methods have been proposed for correlation of physical properties and behavior of hydrocarbon systems. These correlations were found to be unsatis. factory for predicting differential gas liberation and shrinkage data now obtained experimentally. To achieve the desired accuracy, methods were developed to adjust the correlations with two experimental pieces of data. The required data are the saturation pressure at reservoir temperature and the specific volume or density at these conditions. The saturation pressure is used to adjust the vapor-liquid equilibrium-ratio correlations. The density measurement is used to determine the apparent density of liquid methane. With these adjustments, differential gas liberation and shrinkage are predicted within the experimental error. EQUILIBRIUM RATIOS Equilibrium ratios published by the National Gas Assn. of America' were used as a basis for the calculation. The convergence pressure for the sample was determined by using a hypothetical binary system, with methane as one component and the remainder of the system lumped together to form the other component. For the critical temperature of the heavy constituent, the weight average of the critical temperatures of the ethane and heavier components was used. The correlation of pseudo-critical temperature, density and molecular weight of Matthews, Roland and Katzl was used in this calculation for the hexane and heavier fractions. Points for the critical properties of methane and the hypothetical heavy constituent were placed on a chart of the critical loci of hydrocarbon systems. A critical loci for the hypothetical binary system was drawn, and the critical pressure of this system was determined at the reservoir temperature. This critical pressure became the convergence pressure for which equilibrium ratios were read from the NGAA4 charts. The NGAA equilibrium constants for C, through C, were used for the C,; through C, fractions since they were separated on the bases of normal paraffin boiling points. The correlation of Hoffman, Crump and Hocott5 as used to estimate the equilibrium constant for the C fraction. The NGAA eauilibrium-ratio charts are based primarily on paraffin systems and have to be corrected for the presence of naphthenes and aromatics. The correlations in the literature proved too unsatisfactory for determining these corrections. EXperimental data, the saturation pressure, is used with the correlation of Soloman2 to make this adjustment. The correction factors of Soloman were cross-plotted so that the factors for ethane and heavier components were made a function of the factor for methane. a2 = 0.7927 at + 0.1646 .........(1) where a, = correction coefficient for for methane NGAA equilibrium ratio, and a2t = correction coefficient for ethane and heavier NGAA equilibrium ratios. This equation and the equation for the bubble point are solved simultaneously for the correction coefficients. The bubble-point equation is anKnXn = 1.0 . . . . (2) The equilibrium constant for the saturation pressure at reservoir temperature is used. This procedure not only corrects for the relative volatility between components, but also assures that the results will be directly related to the experimental saturation pressure. METHANE DENSITY After determining a set of equilibrium ratios, the apparent density of condensed methane at 60°F and 14.7 psia was estimated. This was found to be necessary because the correlations of Standing3 ere found to be unsatisfactory. The law of additive volumes was employed to make this calculation.