Search Documents

Secretary's Apology: Although every effort was made to secure efficient stenographers, the railroad conditions at the time made it impossible to get stenographers from Salt Lake City. Practically all of the discussion was therefore lost, and the Secretary's apologies are offered to those whose names and remarks we are unable to record. 'We are indebted to R. Dawson Hall of Coal Age for what we have been able to print. The question was asked why belt conveyors are not more generally used. BENEDICT SHUBART: Belt conveyors lack the ruggedness of metal conveyors and require more accurate alignment. They are much used in England though comparatively scarce here. The H. C. Frick Company's belt installation at Colonial mine is an unusual installation for unusual purposes. It is hardly main haulage, but is more comparable to railroad transportation. The belts are in long sections,, nine hundred to twenty-three hundred feet, there are no particular grades, only two turns, and the immense tonnage handled justifies a quality of installation that at this day would not prove economical in most mines. EUGENE McAULIFFE, Union Pacific Coal Co., Omaha: Was much impressed on learning at the American Mining Congress that the Hudson Coal Company had mined last year 1,500.000 tons of coal from a 36-inch bed and had transported this coal to the mine cars by scrapers and conveyors. He did not believe that because one or two percent of the men around the mines were opposed to loading machines, that it should be said that the mine workers were inimical to such labor saving means. He believes that when duly explained to them they could see the advantages of the equipment offered and would be friendly to its introduction. The Sheridan-Wyoming Coal Company at Sheridan have eight Goodman Hydraulic loaders in operation in rooms .with Joy loaders driving the headings. It is not possible for the mines which had to pay high wages to compete with those whose wage scales were lower unless by the introduction of loading machines. He received a letter from Dr. L. E. Young of St. Louis, general manager of the Union Collieries Company, that his two Goodman Hydraulic machines were loading an average of three hundred tons each daily. THE SECRETARY: H. N. Taylor, president, Sheridan-Wyoming Coal Company, said Mr. Green of the American Federation of Labor told him he would have no trouble with Union Labor, and, if any local disturbances were created, they would be stopped. The Union nationally is with the introduction of labor saving equipment. J. B. FORRESTER, General Superintendent. United States Fuel Company, Hiawatha. In his opinion metal conveyors are preferred because they can be lengthened and shortened at pleasure, and so can be operated with greater flexibility than belt conveyors. W. C. HOLMAN, Chief Engineer. Phelps Dodge Corp: The Phelps Dodge Corporation have two Jeffrey belt conveyors in tandem which obviates brushing where the coal is low. MR. E. O. WIEDERANDERS, Jeffrey Mfg. Co.: Says he has seen belt conveyors in use in England and is much taken with the idea. MR. WM. MOORHEAD, Phelps Dodge Corp.: Our conveyors are in twenty-foot sections, each with a motor. Three of them tandem make a sixty-foot face. GENERAL: There was discussion regarding the size of the coal produced by conveyors. It was said that when the Gunn-Quealy Company started their operations, the coal was very large, but now there is not so much care taken to produce large coal as the market is now demanding smaller coal. The Secretary said that the use of conveyors at the Kemmerer Coal Company's mine had almost doubled the percentage of lump coal. Mr. McAuliffe questioned

Jan 1, 1925

A. H. Mokken: I am pleased to have been given this opportunity to make a contribution to Dr Muller's paper tonight. The reason for this is that, at one stage in our careers, we were associates in the same undertaking. Dr Muller, then fresh from University, with a degree in pure science, had just stepped onto the first rung of the ladder, which, it was then thought, would lead him to a career in gold extractive metallurgy. However, endowed with an enquiring mind and conscious of a lack of fundamental training in general metallurgy and engineering, he felt a need for further academic study. To meet this need and, more importantly, to meet the necessary finances, he found his opportunity in steel. Armed with a bursary, he bade farewell to gold and proceeded overseas, to the University of Sheffield, to train as a steel metallurgist. The outcome of these academic efforts, which were followed by assignments in the steel industry and a further period at Sheffield, is the man we have listened to tonight-a highly qualified metallurgist who has displayed a sound knowledge of his subject. In choosing Sheffield, Dr Muller became associated with a steelmaking centre of world renown, a centre usually credited with the first systematic production of alloy steels, as far back as the 18th century. Since that time, great advances have been made in the production of alloy steels and this is especially so in the last decade or two, when major developments in civil, mechanical, electrical, aeronautical and nuclear engineering have been made possible by the development of steels with improved properties. In spite of spectacular advances in the technology of non-ferrous alloys, plastics and other materials of construction, steel has maintained its role as a pre-eminent material for engineering use. With the gradual accumulation of data on the properties of steels, and the use of thin film electron microscopy, to study the behaviour and characteristics of such phenomena as dislocations in metals and other microstructural features, the physical metallurgist appears to be approaching the stage of an exact understanding of such phenomena as strength, ductility and brittleness-a knowledge which could lead to close control of such properties and, therefore, to the attainment of the highest goals. An interesting example, illustrating the use of fundamental principles, based on physico-metallurgical research, is the development of the maraging steels developed by Bieber at the International Nickel Company. These steels have met the extreme technological requirements of the space age by providing the material for the cases of large rockets in which qualities, such as high tensile strength, toughness, workability and weldability are most important. Attractive as they might appear to be in considerations of savings of weight, cost of erection, transport of materials and foundations, the use of high strength steels has been accompanied by special problems such as brittle fracture, hydrogen embrittlement, notch-toughness and fatigue. It has been found that high strength steels, which performed acceptably in conventional tension tests, were found to undergo failure, in a brittle manner, in service. Hydrogen embrittlement has caused spectacular failures at a fraction of the normal ultimate tensile strength, and a lack of correlation between fatigue and tensile strengths has diminished the advantages to be obtained from the use of high strength steel in some applications. A new approach to the selection of materials for engineering design has resulted from a consideration of these phenomena in which strength, as such, is no longer as significant as it was previously. Parallel with the development of high strength steel has been the need for suitable techniques for joining component parts and here welding has played an

An on-stream iron ore analyser has been developed in collaboration with Hamersley Iron Pty. Limited for determining the iron content of both lump (- 30 + 6 mm particle size) and fines (- 6 mm particle size) on conveyor belts. The analyser, which is called IRONSCAN, is based on pair production, and is now commercially available from Mineral Con- trol Instrumentation Limited (MCI) in Adelaide. It can be mounted under existing conveyor belts with minimal modifications to the conveyor struc- ture, and the presence of steel cables in the belt does not interfere once the analyser has been correctly calibrated. The analyser has been exten- sively tested on both lump and fines on the shiploading conveyor at Damp- ier, and typically the root mean square (r.m.s.) deviation between single IRONSCAN measurements and conventional chemical analyses is better than 0.5% Fe. It is currently being evaluated on - 150 mm ore from the primary crusher at Mount Tom Price, and initial results are encourag- ing. The principal advantage of IRONSCAN is that it provides rapid infor- mation on ore grades. But perhaps its greatest potential is at the primary crusher where conventional sampling and analysis is very expensive to Implement. at the University of Melbourne, and those of us who were his students had learnt of the application of physical chemistry to pyrometallurgical processing, pioneered by Chipman in the USA, Wagner in Germany, and Richardson in the UK. It was possible, by applying this theoretical insight to the equilibria between metal, speiss or Legierung, matte and slag phases, to find a practical and effective way to recover metal values in some residues which had been accumulating for many years at the NA, but which had defied all attempts to treat them to that date. There was also an opportunity to study the batch lead refining methods still in use at all lead refineries apart from Port Pirie, and to devise optimis- ing techniques which greatly improved the operations and effected considerable savings. Next the writer spent some six years alternating between the BHAS, Port Pirie, and Imperial Smelting at Avonmouth in the UK, concerned with lead or lead-zinc smelting, and the develop- ment of several further continuous lead refining processes, before returning to Australia as Section Leader, Process Development in the CSIRO Division of Chemical Engineering, Fisherman's Bend, Victoria. Metallurgical opportunities which arose during this last period included the problem of tin smelting which had developed over about a decade: the world's tin smelters had been accustomed to treating fairly high grade tin concentrates, con- sisting of almost pure cassiterite, with very little impurity-mostly quartz, limestone, iron oxides, and sundry other silicates. Most such concentrates had been produced from alluvial deposits, where nature had already done some of difficult part of the mineral processor's work-at who knows what recovery-so that he could now produce high grade concentrates at high recovery. The smelters were not really set up for the treatment of lower grade concentrates, such as could be made with reasonably high recoveries from rock mining. Thus they imposed such penalties on impurities and lower than desired tin grades, that whenever a mineral processor improved tin recovery at the expense of lower- ing grade, such an improvement entailed a lower financial return to the miner. There was clearly a need for improved understand- ing of tin smelting, (at that time shrouded in secrecy) and develop- ment of techniques better suited to the treatment of lower grade concentrates. As well as the practical development, a start was made with the computer modelling of the smelting process, with the obiect of optimising the process parameters.

Jan 1, 1988

By B. Pesic, J. E. Wey

Introduction One important class of manganiferrous ores is manganiferrous-silver ores. They occur in the oxidized portions of the silver deposits of the western United States. Silver is often associated with manganese oxides, which in some ore deposits are dispersed through calcite, causing the black color of the host rock, known as black calcite. Black calcites can occur in carbonate rocks (0.3 to 50 kg Ag/t) and in volcanic rocks (less than 30 g Ag/t). Silver mineralization associated with manganese oxides and black calcites can occur in veins (Hewett, 1968) or as disseminations (Graybeal, 1981). In the US, silver-bearing manganese veins are located in a broad arc that extends from southern Colorado to southwest New Mexico, southern Arizona, and southeast Califor¬nia (Hewett, 1964). Areas of disseminated silver-manganese mineralization include the Creede and Silver Cliff districts of Colorado and the Tombstone and Hardshell districts of Arizona (Graybeal, 1981). These deposits are also characterized by significant amounts of silver halides - cerargyrite (AgCl), bromargyrite (AgBr), and iodargyrite (AgI). Black calcites are also common in these deposits. Oxidized silver ores containing the higher oxides of manganese are generally refractory to hydrometallurgical methods of treatment. In the past when these ores could not be smelted, they were treated generally by cyanidation at very low efficiency. The US Bureau of Mines (USBM) studied the problem of treating silver-manganese ores in the early 1920s (Clevenger and Caron, 1925). It was found that the refractory silver in the original ore was insoluble in all the common solvents for metallic silver and its salts. The conclusion was that to obtain the highest recovery of silver, all the manganese had to be dissolved or the higher oxides of manganese reduced to manganous oxide. More recent results from treating refractory silver¬manganese ores were given by USBM (Scheiner et al., 1973). The silver ores from Candeleria District, NV, and Round Mountain District, CO, were investigated. Electrooxidation experiments recovered only 34% silver with minor amounts of manganese dissolved. Sulfurous acid pretreatment followed by cyanidation revealed that silver extracted was proportional to the amount of SO2 used. A similar approach, using sulfurous acid pretreatment followed by cyanidation, was also proposed by Rhoades et al. (1984). Hazen Research Inc. performed extensive testing on silver and manganese dissolutions from Ag-Mn ores obtained from the Candeleria and Round Mountain ore deposits. The methods examined were direct cyanidation, pretreatment with sulfurous acid followed by cyanidation, malonitrile leach, and leaching with ammonium hydroxide-sodium thiosulfate under slight oxygen pressure. The results were not satisfactory. The importance of the vast reserves of Ag-Mn ores and the lack of an efficient method to recover these metals warranted a search for new technologies. One novel method for extraction of these metals is treatment of Ag-Mn ores with acidified thiourea solutions. Preliminary results of the leaching of silver and manganese from Ag-Mn ores were very encouraging (Pesic, 1984a) ; thus, it was decided to examine the new lixiviant in more detail. Experimental Ore from the Round Mountain District was studied. It was crushed, ground, and dry sieved into monosized fractions in the range of 16 to +400 mesh. The ore composition was about 90 g Ag/t and 3% Mn, depending slightly on size. The leaching experiments were performed in apparatus described elsewhere (Pesic, 1982 and 1984b). All experiments were performed at constant temperature conditions. The leaching residues were analyzed for silver and manganese. Atomic adsorption was used to analyze the solution samples and fire assaying to analyze the leaching residues (for silver). The standard experimental conditions are given in

Jan 1, 1987

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work' on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By L. H. Schwartz, S. K. Lahiri, M. E. Fine, D. Chandra

WHILE the yield stress of solution treated Fe-Cu alloys increases rapidly with aging, a precipitate has only been directly observed in overaged samples.'-" This precipitate is essentially pure fcc copper, the E phase. Hornbogen2 suggested that the initial hardening is due to clustering of copper atoms in a bcc iron matrix. Hornbogen was not able to obtain direct confirmation for such bcc clusters by either X-ray diffraction or electron microscopy; however, he did observe analogous clustering in Fe-Au alloys7 where the scattering factor difference between iron and gold is more favorable than that for iron and copper. Fujii, Nemoto, Suto, and Monma4 recently observed diffuse electron diffraction scattering in a 2.5 pct Cu alloy aged at 500°C: for 30 hr. They suggested that part of the diffuse SCattering was due to a modulated structure of 26 to 42 wavelength parallel to the (110) matrix plane. This disappeared with further aging. However, 30 hr at 500°C is well beyond the peak strengthening in this alloy which occurred at less than I hr at 500oc.4 By transmission electron microscopy they could not distinguish between quenched samples and samples aged to maximum strength. The purpose of the present investigation was to try to obtain further confirming evidence for a precipitation stage preceding the formation of the fcc E phase. Change in Young's modulus was selected for study be- EXPERIMENTAL PROCEDURE The Fe-1.67 at. pct Cu alloy was supplied by the U.S. Steel Corporation in the form of a hot forged rectangular bar. The carbon and nitrogen contents of this alloy were 70 ppm and less than 10 ppm, respectively. The samples for Young's modulus measurements were made by cold swaging to & in. diam and cutting to 2 in. lengths. Tensile test samples 1 in. long were prepared by cold rolling to a thickness of 0.012 in. and then machining to gage dimensions of 0.5 by 0.012 in. For Mijssbauer studies, foils 1 mil thick were prepared by cold rolling. During fabrication the alloy was given intermediate anneals at 845OC followed by quenching. The specimens after preparation were solution treated at 1000°C (y field) or 845°C (a field) for 1 to 2 and 5 to 6 hr, respectively, in a dynamic vacuum of about 2 x lom6 torr. The tensile and modulus specimens were drop-quenched into iced brine through an aluminum foil which vacuum-sealed the bottom of the furnace tube. The MOssbauer foils were drop-quenched into helium gas cooled by passing through N2 (liq) in a copper coil. The grain diameter of the modulus and tensile specimens was between 0.025 and 0.035 mm. The samples were aged from 400" to 500°C in a dynamic vacuum of 2 x 10-6 torr and cooled by pulling into a water-cooled portion of the vacuum system. The dynamic Young's modulus was measured at room temperature using electrostatic excitation and detection of longitudinal vibrations.' Neglecting any length change during the aging, (this is expected to be comparatively small), the fractional change of Young's modulus (?Et)/Eav, is equal to twice the fractional change of the resonant frequency (?ft)/fav . ?ft =ft —fo where fo and ft are the resonant frequencies of a specimen before aging and after aging to time t. The measured f's, approximately 51,000 cps, were corrected to 25°C for any variation in the ambient temperature. The tensile tests reported were carried out at room temperature in an Instron with a 1000 lb full scale load cell. The flow stress reported herein corresponds to a strain of 0.002. The Massbauer spectra were taken in a constant acceleration model AM-1 NSEC spectrometer. The

Jan 1, 1970

By Warren D. Stanford

The Alligator Ridge mine is a near-surface gold mine located in a remote area 113 km (70 miles) northwest of Ely, NV. The deposit was discovered in 1976 by a lone prospector working under a grubstake contract for Amselco Minerals Inc. Evaluation of mine potential proceeded quickly. Favorable drilling results led to feasibility and mine design studies by the end of 1978. Mine construction began in early 1980. By September of that year, the process plant was fully operational. The first gold was poured a few months later. Alligator Ridge is designed to produce 1.9 t (60,000 oz) of gold each year. The projected mine life, based on proven reserves, is to mid-1988. However, Amselco is actively conducting exploration nearby for additional reserves to extend the mine's life. Amselco, a subsidiary of the British Petroleum Co., is based in Denver, CO. The company is mine operator and jointly owns the project with Nerco Minerals Inc., a wholly-owned subsidiary of Pacific Power and Light. Alligator Ridge is Amselco's first US mining operation. Geology Alligator Ridge, so named because it appears in outline to be an alligator at rest, contains disseminated micron gold embedded in iron-streaked siltstones. Although definitive conclusions have not been drawn on age and origin, the gold ore bodies are probably young by geological standards. They were formed in a recent volcanic period still evidenced in parts of Nevada by geysers and hot springs. As these superheated solutions rose through the permeable siltstones, they deposited minerals in the rock and formed the present gold ore bodies. During 1977, an extensive soil geochemical sampling program with additional geologic mapping and outcrop sampling were conducted. The results generated several drill targets. Initial drilling was performed in November and December 1977, and ore grade mineralization was encountered in the first drill hole. The Alligator Ridge mine is unusual in relation to other and more recent western US mineral discoveries in that it occupies an area that had no previous mining history. The ore deposits are hosted in upper Paleozoic sedimentary rocks that consist predominantly of a thick carbonate sequence. The main ore host is the Devonian-Mississippian Pilot shale, which occurs locally as a sequence of thin bedded calcareous, carbonaceous siltstones and claystones. The maximum observed thickness of the Pilot section in the mine area is about 140 m (460 ft). Rocks in the Alligator Ridge area have been folded into a series of low amplitude anticlines and synclines that strike north-south and plunge to the south at about 20°, with limbs that dip nearly 20°. The folds have been truncated and deformed by later high-angle faults that generally strike northwest. Although multiple stages of movement are evident on the fault systems, the youngest period of activity is along the major northeast trend. The predominant structural pattern in the area is of the basin- and range-type high angle normal faults. Alligator Ridge is actually a horst block between two basin and range faults. Vantage Ore Deposits There are three principal ore deposits within the Vantage Basin and several smaller satellite mineralized areas. The three Vantage deposits are encompassed in a mineralized zone that covers an area 915 m (3,000 ft) long and 305 m (1,000 ft) wide. All mineralized zones have been outlined by more than 600 rotary drill holes, with an average depth of 150 m (500 ft). Mineralization occurs in both carbonaceous and oxidized rocks. The carbonaceous gold-bearing material is not amenable to current heap leaching practice. Therefore, only oxidized ores are now treated. The carbonaceous gold-bearing material is segregated and stockpiled as it is encountered during mining. The three ore bodies occur along a north-northeast strike, with mineralization becoming progressively deeper from north to south. The ore block dimen-

Jan 6, 1984

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By C. D. Hall

This paper may be divided into two main parts: (1) analysis and data to show that Eq. 6 adequately correlates the authors' experimental data, and (2) the assertion that Eq. 20 "should permit scale-up with data taken from one pipe diameter for Newtonian, inelastic non-Newtonian, and viscoelastic fluids, such as dilute polymer fracturing fluids, which produce considerable pressure reductions." The authors might well recommend that this broad grouping of fluid types could be correlated by using Eq. 6 (requiring data from at least two pipe diameters). On the other hand, Eq. 20 is only shown to be adequate for conditions within the range of the present data set. Specifically, predictions by Eq. 20 for diameter scale-up to casing sizes would give larger deviations than implied in Table 2, and scale-up for some other fluids that give large drag reduction could be grossly in error. The description of a class of fluids "which produce a diameter family of straight parallel lines on a log (d?p/4L) vs log (8 v/d) plot. . ." defines a necessary condition for using Eq. 6; i.e., that s shall be constant for each fluid. The proposal that Eq. 20 is applicable to turbulent flow of such fluids is equivalent to saying that the spacing of these parallel lines, with A being constant, will be found to correspond to m = -1.20 for all such fluids. Table 1 shows the values of m derived from data on 16 non-Newtonian fluids. The key statement of this paper is that the diameter exponents "do not vary significantly from . . . -1.20." In statistical terms, this says that the m value for each fluid, which was obtained from all the measurements made on that fluid. has not been shown to be different from the arithmetic mean of the m values for the 16 fluids tested. This implies that the group mean, -1.20, is a more reliable value to use for an individual fluid than is the m value derived from the data on that fluid alone. No statistical test is described to support the key statement that the diameter exponents do not vary significantly from -1.20. Such a test would have to take into account that each individual m value is shown to correlate the pressure gradients for its fluid, with only about 3 percent standard deviation over the diameter range covered. That is, the m value is not the result of a single independent measurement. Thus, it would not be sufficient, or valid, to compare the deviation of one of the m values with the variance of the 16 values of m about their mean. An alternative interpretation of the key statement is that the diameter exponents do not vary appreciably from -1.20; i.e., that using -1.20 does not cause serious inaccuracy. Table 2 seems to be offered in support of such an assertion. However, such a statistical treatment (1) is unnecessary and (2) cannot lead to any valid scale-up generalization. The amount of error introduced by using a 1"wrong" value of diameter exponent — i.e., -1.20 instead of m — is determined by Eq. 6. The ratio of the pressures predicted by Eqs. 6 and 20 for scale-up from ds in small pipe to d, in casing is The pressure for 30-percent calcium carbonate slurry (m = -1.112) in 10-in. ID pipe would be predicted 30 percent higher by Eq. 6 than by Eq. 20, if based on tests in 0.5-in. ID pipe. The data set tested in Table 2 represents only a limited sample of pipe diameters (ratio of about 4:l) out of the population of diameters that would

Jan 1, 1970

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent investigations1. a data on relative grain boundary energies in silicon iron have been obtained. The present investigation is a continuation of this work along similar lines for the purpose of obtaining additional information on boundary energies. One aim has been to extend the data for a (110) series, which was formerly studied,' to small differences in orientation, since a recent theory3,4 based on a dislocation model of grain boundaries predicts a E. ? (A-ln ? )* form of energy curve for small differences in orientation. Another aim has been to provide data for a (100) series—all grains having (100) planes parallel with the surface of sheet speci-mens—and to compare the results with the predicted form of energy curve. Finally, information on the nature of approach to equilibrium conditions was to be obtained through observations on the movements of grain boundaries. Recently published papers2,3,5 have treated the mathematical problem of expressing equilibrium conditions for grain boundaries for the general case when boundary energy depends upon boundary orientation. The equilibrium equations, which relate equilibrium angles and grain boundary -free energies, contain additional terms that express the variation of energy with boundary rotation. It has been necessary in the present investigation, however, to neglect these additional terms since no data for their evaluation were available. Dropping the additional terms leads to the following approximate equations which were used: E12/sin ?3 = E18/sin?2 =E28/sin?1 or those of the form: E28 + E13 cos ?3 + E12 cos ?2 = 0 Experimental Procedure Except for sample F1, all specimens were made from two lots of silicon iron called C and L respectively. The compositions of these are listed in table I. In the preparation of 12 three-grain specimens for the present investigation, a controlled grain growth technique, which has been described previously,' was used. After preparation, the specimens were notched at the boundaries to shorten them as a means of providing more rapid approach to equilibrium in the anneals. Initial grain boundary angles were determined from micrographs taken at X500. Seven anneals, totaling about two days at 1300°C and two to four days at 1400°C, were run in an atmosphere of pure dry argon as described in a previous paper.' Boundary changes generally could be followed without metallographic surface preparation, because thermal etching occurred during the anneals. These observations indicated angle changes of as much as 35" in some instances, with the major changes occurring during the first anneal. Annealing was discontinued when the angles reached stationary values. Fig. 1 gives a schematic diagram for purposes of defining crystallographic and boundary directions for three grains with common plane parallel with the sheet. Differences in orientations (expressed by A) are the angles between [00l] directions. They can be calculated with the aid of the ?'s. The grain boundary angles can be calculated from the w'S. Results Results are given in table 11. Types of crystal-lographic planes refer to those parallel with the sheet. Orientations are given in terms of [00l] direc-tions as shown in fig. 1. Except for grain 3 of specimen H6, which was unintentionally tilted 7" out of a (100) plane, all grains generally were within 1" or 2" of the plane specified. The directions of boundaries were measured generally to within 1" on both upper and lower surfaces, and the average direc- tions were determined for use in calculating the grain boundary angles. Variations in grain boundary directions refer to deviations from average directions. Boundaries near the junction point for all specimens generally were very close to perpendicu-

Jan 1, 1951

By H. E. Cline, T. H. Alden

A study zvas made of rate-sensitive plastic deformation and superplasticity in alloys of lead and tin. These alloys (lead, PO-19 pct Sn, Sn-38 pct Pb, Sn-2 pct Pb, tin) were extruded, aged at room temperature, or melted and resolidified to produce a variety of ~nicrostrnctures. Flow stress us strain rate data were obtained frorn tension tests for strain rates between 10-6 and 1 min-1. The curve log o .us log £ was S-shaped jor fine-grained materials and approxinzately linear for coarse-grained nzaterials. At constant grain size, the behavior was relatively insensitive to conposition. High rate sensitivity (d log o/d log k) and superplasticity occurred at intermediate strain rates in fine-grained materials and are believed to be associated with a transition with strain rate in the mode of plastic flow. This transition was shifted to higher strain rates with increasing temperataire or decrensing grain size. The high rate rneclzanisrn is presunzed to be slip, while rnetallographic evidence sug-gests that the low rate lnechanism is pain boundary sliding. PEARSON' discovered that extruded eutectic alloys of Pb-Sn and Bi-Sn could be elongated as much as 2000 pct in tension. The ability for stretching decreased with aging time or annealing to increase the grain size. At high strain rates, or if the material was in the cast condition, normal ductility was observed. Following deformation of the extruded Pb-Sn eutectic at low rates, Pearson observed an equiaxed granular structure on an initially flat surface, while rapid straining produced elongated grains. He attributed the large deformation in the extruded alloys to the persistence of extremely small grains to a temperature sufficiently high for inter granular flow. Avery and backofen2 measured the strain rate sensitivity of the flow stress, m = d In old In 6, in the Pb-Sn eutectic and established a correlation between m and the tensile elongation. In the extruded eutectic alloy the strain rate sensitivity was 0.1 to 0.2 at rapid rates and the elongation was small, while at low rates m increased to 0.4 to 0.6 and superplastic elongation was observed. They also noted a grain size effect. In the case of the cast Pb-Sn eutectic the strain rate sensitivity remained at 0.1 over the range of strain rates of their experiment (3 x 10"3 to 2 min-I). These authors suggested that diffusional (Nabarro-Herring) creep was the mechanism by which deformation occurred at low strain rates, while climb-controlled creep occurred at high rates. Two predictions of this model are that, at low strain rates, the strain rate sensitivity approaches 1, i.e., Newtonian viscosity, and that the strain rate at constant stress varies as D/L2, where D is the coefficient of self-diffusion and L the grain size. More recently, a mechanical and microstructural investigation of the dilute superplastic alloy, Sn-5 pct Bi, has been done.3 The results show that the high strain rate sensitivity is associated with a transition with strain rate of the mechanism of plastic flow. At low strain rates, grain boundary sliding and its associated accommodation processes were evident, while at high strain rates quasi-uniform slip was concluded to be the dominant deformation process. The following experiments were performed to extend our knowledge of the phenomena of superplasticity to a larger range of strain rates, compositions, temperatures, and microstructures in the Pb-Sn alloy system. The question of why a cast structure does not exhibit viscous behavior although it appears to have a fine microstructure2 was investigated.

Jan 1, 1968

By T. J. Neil, C. B. Manula, O&apos

This paper describes a simulation model developed to analyze truck haulage problems as they are found in the open pit mining and construction industries. The model, using a computer, cycles trucks between their assigned loading and discharge points over a measured haulage route. Required parameters for model operation include the number and type of operating trucks and loading units, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each origin. Equipment performance characteristics, system profile characteristics, and service time distributions are also included. Records are kept of all waiting times at the loading and discharge points and of any truck interference on the haulroads (moving queues), and a current journal of ore and waste production is maintained. In the pursuit of reduced truck haulage costs, management is confronted with three particular problems in truck and shovel mines. 1) What is the best assignment of trucks to shovels in the system? 2) If new equipment is needed, which new shovels and trucks will operate most effectively in the system? 3) Are any physical changes in the haulage layout warranted to increase productivity? For small open-pit mines the answers to these questions may be obvious. However, for larger operations complex problems are encountered with production and system configuration relationships usually being unknown. The mining simulator discussed here was developed to aid management in evaluating alternative pit-haulage schemes to reduce the risk involved in the selection and assignment of equipment in open-pit truck and shovel mining systems. There are two fundamental differences between this model and other truck haulage simulators: one is a difference of degree, the other a difference of kind. This model can simulate more complex systems than previous models by allowing transportation of material from multiple mine faces to multiple mine destinations and by being readily adaptable to a wide variety of mine layouts. The second difference that characterizes the model is the standard simulation of truck movements. This technique enables each vehicle to perform according to its mechanical capabilities and the physical profile of the haul road. Among the similarities between other truck haulage simulators and this model are the recognition of the probabilistic nature of certain service times in the system and the use of a digital computer to operate the model. The computer inherits the staggering computational and bookkeeping work loads and provides a means for compressing the time scale by allowing several days' operations to be simulated in a matter of minutes. DISTRIBUTION SYSTEM Basic aspects of the system analyzed here may be brought into focus by referring to Fig. 1, a schematic of the typical open pit truck-shovel operation programmed into the simulation model. A single stage materials handling scheme is employed to transport both ore and waste. Loaded trucks are directed to a crusher or stockpile if ore is being mined, while overburden is conveyed to a waste dump. Each shovel has a given number of assigned trucks and has two associated haulage routes, one for waste and one for ore. Up to 5 shovels and as many as 10 trucks per shovel (or a total of 50 trucks) can be operated in the model. Essentially the model, using a computer, cycles trucks between their assigned shovels and the proper discharge points over measured haulage routes. Required input parameters for model operation include the number of shifts to be simulated, operating time per shift, number and type of operating trucks and shovels, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each shovel. Equipment performance characteristics, system profile characteristics, and service time distributions are

Jan 1, 1968

By E. S. Bumps, H. D. Kessler, M. Hansen

The titanium-rich end of the Ti-AI phase diagram has been determined to the compound TiAI3 (62.7 pct Al), thus joining the aluminum-rich portion previously investigated by others and completing the diagram. Micrographic analysis and X-ray diffraction were the chief methods used to determine the phase relationships. THE Ti-Al phase diagram has been investigated as part of a program on titanium phase diagrams for the Wright Air Development Center. Included in the available information concerning the phase relationships in titanium-rich Ti-A1 alloys is a brief statement by Brown' that: "aluminum raises the transformation temperature to 1000°C (183Z°F)." This observation is interesting in that it is the first example of a metallic alloying component raising the transformation temperature of titanium, and consequently widening the field of the a solid solution. Busch and Freyer' presented resistivity data which indicated the formation of titanium-rich solid solutions of 1 and 3 pct A1 alloys prepared by powder metallurgy methods. Duweza found that there is only one other intermediate phase other than the known compound TiA1, (62.7 pct Al). This phase, designated as y, is of variable composition; its crystal structure is of the AuCu type and is therefore based on the composition TiAl (36.02 pct Al). Earlier work on the constitution of the aluminum-rich alloys has been reviewed by Hansen, and need not be discussed here. The tetragonal crystal lattice of TiAl,, as found by Fink, Van Horn, and Budge," was confirmed by Brauer." Recently, Schubert7 has reported that TiA1, is homogeneous within a limited composition range; however, the solubility limits were not given. The Ti-A1 phase diagram as presented in. this paper was determined by micrographic analysis of alloys containing from 1 to 62 pct Al, annealed at and quenched from temperatures between 700" and 1400°C. The phases and phase ranges investigated extend to the compound TiA1, (62.7 pct Al) to join the aluminum-rich end of the system determined by other investigators, thus completing the diagram. Methods of Investigation Preparation of Alloys: Iodide titanium, 99.9+ pct pure, obtained from the New Jersey Zinc Co., and high-purity (99.99+ pct) aluminum sheet from the Aluminum Co. of America were used to make up alloy ingots weighing 10 to 20 g. Detailed descriptions of melting techniques have been presented previously for work on the Ti-Mo and Ti-Cb> nd Ti-Si" phase diagrams. Briefly, the melting practice consisted of arc melting an accurately weighed charge in a copper block crucible insert in a non-consumable tungsten electrode furnace, under helium at atmospheric pressure. All ingots were carefully weighed after melting to detect possible losses. Comparison of weight before and after melting showed no appreciable weight changes. Also, chemical analyses were in close agreement with nominal compositions, Table I. The diagram as presented is, therefore, based on nominal compositions. Alloys were prepared having the following nominal aluminum contents: 1 ... 36 (1 pct increments), 38, 40, 41, 42.5, 44, 45, 46, 47.5, 49 . . . 64 (1 pct increments), 67, 70, 80, and 90. Ingots with up to 14 pct A1 were cold-pressed various amounts in order to increase the rate of attaining equilibrium structures on heat treatment. The amount of cold deformation that could be applied decreased with increasing aluminum content, until alloys containing 12 pct A1 or more cracked after only a few percent deformation. Annealing Treatments: Samples annealed at temperatures of 700" to 1000°C were sealed in

Jan 1, 1953

By W. C. Knopf, I. M. LeBaron

In the Carlsbad area potash is dry-mined and wet-concentrated. Wet concentration involves recircu-lation of saturated brines, with resultant difficulties of brine disposal and inherent losses in recovery through solution of the KCl. A dry beneficiation process for potash minerals would offer many advantages over present methods. International Minerals & Chemical Corp. has been working on development of a dry process for some time. This article is a progress report. Potash ores available in this country are largely mixtures of halite and sylvite contaminated with slimes and often with many sulfate and magnesium minerals. Electrostatic concentration of KCl when the contaminating minerals are in low percentage has been accomplished. Continuous production of better than 60 pct K2O concentrate from high potassium sulfate ores has not been demonstrated at the present time. Laboratory Procedure: Laboratory work on electrostatic beneficiation of potash minerals has been carried out using both pure crystals and mined ore. Electrostatic separation of the two main components of potash ore, sylvite (KCl) and halite (NaCl), is accomplished by first heat-treating the ore to allow for electric charging of the particles. Preferential exchange of' electrical charges between different mineral particles through surface contact is the principal mechanism involved. After proper conditioning of the particle surfaces, the oppositely charged minerals are dropped vertically into a horizontal electric field having a field gradient from about 5000 to 15,000 v per in. The particles are free-falling in the field. A suitable power supply is used to produce the proper total voltage for the electric field. Total required voltage is, of course, a function of electrode spacing. A typical electrode arrangement with power supply is shown in Fig. 1. In general, the total voltage on any system is 75,000 to 90,000 v. Power consumption is negligible, as leakage at insulators and corona discharge are the main losses in the system. Optimum preheat temperatures for pure material components generally are not the same as for mined minerals. Fig. 2 shows clearly that maximum recovery on a 50 pct pure KCl, 50 pct pure NaCl mixture occurs at a preheat temperature of about 600°F. In this test the preheat mixture was allowed to cool to about 225°F before dropping through the electric field. The optimum temperature for sep- aration is practically never the optimum temperature of preheat. Optimum separation for mined Carlsbad potash ores occurs when a preheat temperature closer to 900°F is used, as shown by Fig. 3, which plots percent sylvite (KCl) in the concentrate and tails as a function of preheat temperatures. Here again the ore was allowed to cool to about 225°F before separation. It should be noted that efficiency of separation increases continuously with increasing preheat temperatures until incipient fusion of the ore takes place at about 950°F. The increase in optimum preheat temperature for Carlsbad ores over the pure minerals can be traced to the effect of the clay slimes intimately associated with the mined potash. If the slimes associated with the ore are removed by washing with alcohol or other non-aqueous material, the necessity of preheating to the high temperature is removed. This temperature range has been proved critical within these limits during continuous pilot plant operation. Concentrate and tailings grade and optimum recovery also are functions of the temperature of the potash mineral particles during separation in the electric field. Fig. 4 presents data indicating that feed to the rougher pass should range between 150°F and 275°F for best results. It has been found by subsequent pilot plant work that these temperatures can be maintained in actual operation.

Jan 1, 1959

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.'-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.'' This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12'14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77' and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By J. C. Griffiths, D. W. Bennion

A mathematical model, which does not assume a priori that stratification exists, but was designed to test for the stratification was developed. The model segmented the reservoir horizontally into areas of common variance, then divided it vertically into strata (if strata were present). Next, trend surface techniques were used to determine the lateral extent and variation of each stratum. The model was tested on two reservoirs (sandstone and limestone) using porosity as the reservoir rock property. The sandstone reservoir contained approximately 60,000 samples from 2,000 cored wells, while the limestone reservoir had approximately 24,000 samples from 430 cored wells. Within the areas of common variance tested, the model was able to distinguish four separate lithological units or zones in the sandstone reservoir, four in the Marly section and seven in the Vuggy section of the limestone reservoir. INTRODUCTION To accurately predict the movement and production of fluids from a reservoir rock, it is necessary that the reservoir engineer have a knowledge of the rock properties and their distribution throughout the reservoir. For this study, a reservoir rock is defined as a solid containing interconnecting holes or voids which occur relatively frequently and are dispersed within the rock in a regular or random manner. The fraction of bulk volume that these interconnecting voids occupy is called porosity. The rock must also possess sufficient permeability to allow fluids to move through it and it may be composed of one or more strata or lithological units. A stratum or lithological unit as defined in this study is a body or volume of reservoir rock whose properties are so distributed that its lateral and vertical extent can be traced throughout or through a portion of the reservoir. Operationally, the existence of strata are question- able unless the variance within strata is less than among strata. Within the past few years computers have been widely used as a tool for calculating movement and production of fluids from reservoirs. Most prediction models require some type of a mathematical description of certain reservoir rock properties. In the past, most of these models have been relatively simple. Some have assumed vertical variation but no lateral variation, while others have assumed lateral variation but no vertical variation. In general, most of these models have not used functional relationships to predict reservoir rock properties as functions of position. The object of this study was to develop a model which would predict lateral and vertical variations of reservoir rock properties. Since samples are usually available from only a small portion of the total reservoir rock, it seemed logical that if measurements from these samples were to be used to infer the properties of the actual reservoir, the data should be treated statistically as a sample from the total population (reservoir). Therefore, the model developed in this study to predict reservoir rock properties was a stochastic model. The model was tested using porosity (a macroscopic reservoir rock property) measurements from two reservoirs — the first, a sandstone reservoir from which 60,000 samples were obtained; and the second, a limestone reservoir with 24,000 samples. Several investigators have proposed methods to determine the vertical and areal variation of a reservoir rock property. Stiles: Dykstra and Parsons 2 and Suder and Calhoun3 have all developed waterflooding prediction techniques which assume vertical variation but no lateral variation. Stiles developed a method to segment a reservoir arbitrarily using frequency distribution. Law4 suggested that porosity has a normal frequency distribution and that permeability has a log-normal frequency distribution. Elkins and Skov 5 proposed that when a reservoir is segmented vertically, the

Jan 1, 1967

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil'chenko' found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli' bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil'chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.' The presence of silicon in iron is said to reduce the activation energy for diffusion,' so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen' made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By Richard H. Olson, Lawrence A. Roe

Talc, when it can be isolated as a pure mineral, has a composition of 63.36% Si02, 31.89% MgO, and 4.75% H20. However, as an industrial commodity, talc rarely approaches theoretical purity. Nevertheless, the impure talc products of commerce find a multitude of uses and few substitutes in many industrial applications. Minerals commonly associated with and sold together in talcose mixtures are tremolite, chlorite, dolomite, mica, and magnesite. Steatite was originally a mineralogical name applied to pure talc. In today's commerce steatite generally refers to the massive variety of talc suitable for electrical insulator manufacture. Block steatite ore can be machined into various shapes. Impure varieties of massive or block talc are still commonly referred to as soapstone. Soft massive talc, suitable for crayon manufacture, has been referred to as French chalk. It has been common practice to discuss talc, soapstone, and pyrophyllite under the same general heading. In the case of soapstone and talc, this is a natural thing since many different types of platy, soft minerals exhibiting a high degree of lubricity (commonly referred to as "slip") have been grouped together and called soapstone or talc. Further, there is a mineralogical relationship of pyrophyllite to montmorillonite and talc to hectorite. Thus, talc and pyrophyllite are sometimes referred to as clay minerals. When finely divided talc or pyrophyllite are combined with water in proportions to make a slurry, the end product does have the appearance of a clay-water mixture. Soapstone for utensils and ornaments was mined by prehistoric Indians on Santa Catalina Island, CA. In the mid-1800s, soapstone from deposits along the western foothills of the Sierra Nevada mountains was used by white settlers for building and ornamental stone and in the linings and foundations of furnaces (Anon. 1956). Previous to 1916, the annual recorded production in California did not exceed 2000 tons. In the period 1912 to 1918, output rose sharply when the Talc City, Western, and Silver Lake mines were put into operation. From 1916 to 1935, the state's annual output of talc was in the range of 9,000 to 20,000 tons. In the mid-1930s, the use of talc in wall tile grew rapidly. In California, the production of talc grew to 63,000 stpy in 1943. The post-war building boom helped California production to grow to 120,000 tons in 1951. In 1968, production was 165,000 tons, 1969 was 145,000 tons, 1970 was 185,000 tons, and 1972 was 155,000 tons. Talc mining in New York state dates to about 1878 when a Colonel Palmer and associates opened the first commercial talc mine on the Nelson Freeman farm near Talcville, New York. In 1893, this operation was sold to the International Pulp Co. which changed its name to the International Talc Co. in 1944. The company was acquired by R.T. Vanderbilt Co., Inc. in 1974. A new talc operation, the Gouverneur Talc Co. owned by the R.T. Vanderbilt Co., began operations near Balmat, NY, in 1948. The initial capacity of the processing plant was 200 stpd (Gillingham, 1950). Subsequent expansions have increased capacity to over 600 stpd. The Vermont talc industry began just after the start of the 20th century. Talc was discovered in the area of the present Johnson, VT, talc mine in 1902. The American Minerals Co. initiated plant operations at Johnson in 1904. The Magnesia Talc Co. opened a plant at Waterbury, VT, in 1913 (Burmeister, 1963; Trauffer, 1964) and acquired American Minerals Co. in 1923. The Waterbury mine has a long history as a producer of talc crayons. The Eastern Magnesia Talc Co. was formed in 1924 by a merger of the Eastern Talc, Co.

Jan 1, 1983