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By Henry N. McCarl

[The Construction Materials section contains the following Chapters: Aggregates Cement and Cement Raw Materials Crushed Stone Dimension and Cut Stone Lightweight Aggregates Gypsum and Anhydrite Sand and Gravel Insulating Materials-Thermal and Sound Slag Roofing Granules] Mineral aggregates are those natural and manufactured industrial mineral and rock materials that provide bulk and strength in portland cement concrete, bituminous concrete mixes, and plaster or stucco surfaces. They may also provide special characteristics such as thermal and acoustical insulation, weight, surface textures, abrasion resistance, and impermeability to various concrete products and mixes. Most aggregates are relatively inexpensive materials, but despite their low unit value, the tonnages consumed each year in the United States and throughout the" world make mineral aggregates by far the leading industrial mineral and rock materials both in terms of volume (tonnage) produced and value consumed. The major use of mineral aggregates is in concrete. The low cost, high bulk aggregates tend to keep concrete construction costs at levels competitive with other building materials. Other major uses of aggregates include highway and railroad base or ballast materials, graded fill, and various industrial uses such as metallurgical and chemical fluxes and raw materials-these latter uses are often considered nonaggregate uses of mineral aggregate materials. The per-ton value of mineral aggregate materials at the production plant in 1980 and 1981 varied from $2 to $5 for most sand and gravel and crushed stone, $3 to $6 for air-cooled slag, $7 to $20 for expanded slag and expanded clay or shale aggregate, to as much as $165 to $320 for expanded perlite or vermiculite. The expanded lightweight aggregates have been dramatically affected by increasing fuel costs. It is ironic that the specialized aggregates used as insulating materials to conserve energy cost so much more to produce due to the high proportion of energy consumed in their production. The first four parts of "Construction Materials" deal with the utilization of four major mineral aggregate types: Crushed Stone, Lightweight Aggregates, Sand and Gravel, and Slag. While the focus will be on the use of these industrial minerals and rocks, there will also be some coverage of sources, mining and production, especially in those cases where they are not discussed in the Commodity section of this book.

Jan 1, 1983

By A. B. Kinzel

SILICON, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have devel-oped procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, and the terns "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.1 In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve said further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treat-ment, he does not mention the existence of carbon in the alloy; neverthe-less, lie reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1939

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By R. W. Snyder, W. H. Guilinger, B. S. Gottfried

Two numerical methods are presented JOT solving the equations Jor one-dimensional, multiphase /low in porous media. The case oF variable physical properties is included in the Formulation, although gravity and capillarity are ignored. Both methods are analyzed mathematically, resulting in upper and lower bounds for the ratio of time step to mesh spacing. The methods are applied to two- and three-phase waterflooding problems in laboratory-size cores, and resulting saturation and pressure distributions and production histories are presented graphically. Results oJ the tuo-phase flow problem are in agreement with the predictions of the Buckley-Leuerett theory. Several three-phase flow problems are presented which consider variations in the water injection rate and changes in the initial oil-and ujater-saturation distributions. The results are different physically from the two- phase case; however, it is shown that the Buckley-Lez~erett theory can accurately predict fluid interlace velocities and displacing-fluid frontal snturations for three-phase flow, providing the correct assumptions are made. The above solutions are used as a basis JOT et~aluuting the numerical methods with respect to machine time requirements and allowable time step for a fixed mesh spacing. INTRODUCTION Considerable progress has been made in recent years in obtaining numerical solutions of the equations for two-phase flow in porous media. Douglas, Blair and Wagner2and McEwenll present different methods for solving the one-dimensional case for incompressible fluids with capillarity (the former using finite differences, the latter with an approach based upon characteristics). Fayers and Sheldon4 and Hovanesian and Fayers8 have extended these studies to include the effects of gravity. West, Garvin and Sheldon, l4 in a pioneer paper, treat linear and radial systems with both capillarity and gravity and they also include the effects of compressibility. Douglas, Peaceman and Rachford3 consider two-dimensional, two-phase, in compressible flow with gravity and capillarity and Blair and Peaceman1 have extended this method to allow for compressible fluids. No one, however, has examined the case of three-phase flow, even for the relatively simple case of one-dimensional flow of incompressible fluids in the absence of gravity and capillarity. In obtaining a numerical technique for simulating forward in situ combustion laboratory experiments, Gottfried5 has developed a method for solving the one-dimensional, compressible flow equations with any number of flowing phases. Gravity and capillarity are not included in the formulation. The method has been used successfully, however, for two- and three-phase problems in a variable-temperature field with sources and sinks. This paper examines the algorithm of Gottfried more critically. Two numerical methods are presented for solving the one-dimensional, multi-phase flow equations with variable physical properties. Both methods are analyzed mathematically, and are used to simulate two- and three-phase waterflooding problems. The numerical solutions are then taken as a basis for comparing the utility of the methods.

Jan 1, 1967

By G. H. Gronhovd, W. H. Oppelt

Complete gasification to produce synthesis gas for manufacture of synthetic chemicals and fuels offers possibilities for utilization of the vast lignite fuel deposits in the U.S. The design of a slugging, fixed-bed, pressure gasification pilot Plant is described. Results are presented for initial operation of the plant at moderate pressure and using low-temperature char as fuel. Gasification of solid fuels is becoming increasingly important in the future overall energy picture, both in this country and abroad. Snythesis gas from gasification of coal consists chiefly of carbon monoxide and hydrogen, and after suitable purification and modification this gas can be used in the production of synthetic ammonia, methanol, higher alcohols, and synthetic liquid fuels, or as a reducing gas in the metallurgical field.' Most synthesis gas used in this country is made from natural gas, petroleum oils, and refining tail-gases, but the direct gasification of coal will become more attractive as costs of petroleum oils and natural gas increase.' A gasification process designed for use with brown coal and lignite was developed by the German Lurgi Co. prior to World War 11. In this process a fixed bed of lump-sized fuel is gasified with steam and oxygen at pressures ranging from 370 to 440 psi. Effective heat exchange between the ascending high-temperature gases and the descending solid fuel results in low gas outlet temperatures, high thermal efficiency, and favorable oxygen consumption. Lurgi gasifiers are used commercially for the production of synthesis gas or as a substitute for coal gas in many countries, including Germany, Czechslovakia, Great Britain, South Africa, Australia and Pakistan.3-6 The chief disadvantage of the conventional Lurgi gasifier which operates under nonclinkering conditions is that large quantities of excess steam must be supplied with the oxygen-steam mixture to reduce the temperature in the fuel bed below fusion temperature of the ash. Most of the steam leaves the gasifier undecomposed with the product gas and, after cooling, produces large amounts of dilute liquor. Evaluation of fixed-bed gasification experiments using dry-ash removal indicated that by increasing the oxygen concentration in the oxygen-steam blast the temperature in the combustion zone could be raised high enough to operate under slagging conditions. 7-8 Operation of a fixed-bed pressure gasifier under slagging conditions would reduce the steam requirements and the volume of waste liquor and would increase the steam decomposition, the overall thermal efficiency of the process, and the rate of gas production per unit cross sectional area of the gasifier. Because the Lurgi gasification process, modified for slagging operation, offered possibilities for efficient gasification of American lignite, the Bureau of Mines decided to investigate the process on a pilot-plant scale at the Grand Forks, N. D., Lignite Research Laboratory. DESIGN Description of Pilot Plant: A flowsheet of the Grand Forks slagging gasification pilot plant is presented in Fig. 1. The gasifier unit consits of the coal lock, the gas generator, and the slag lock. The fuel, which is periodically charged to the coal lock, moves by gravity flow into the generator and is continuously gasified by an oxygen-steam mixture introduced at the bottom of the gasifier. Molten slag is formed at the hearth and flows through a central taphole into a water quench bath. The slag-water slurry is periodically discharged from the slag lock. Process steam is generated and superheated in separately-fired, oil-burning units. Oxygen is supplied to the gasifier from a gas storage bank located some distance from the pilot plant. The capacity of the oxygen storage bank is about 130,000 standard cu ft at 2200 psig. Liquid oxygen is delivered by truck and is converted to gas during the filling operation. The superheated steam and oxygen are metered separately, then mixed and fed to the gasifier tuyeres. The gas generator is surrounded by a water jacket. The steam formed is separated in the steam drum and then discharged to the gas offtake, thus equaliz-

Jan 1, 1961

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By G. W. Tracy, R. D. Carter

Numerical calculations were made to determine the behavior of reservoirs with high-pressure drawdown and wide well spacing where the initial productivity is low and the wells are completed by hydraulic fracturing. The two-phase flow equations were solved for the flow into a single well. This well was assumed to be producing from a reservoir with hydraulically created horizontal fractures (four different systems with fractures were studied). For comparison purposes, additional two-phase flow calculations were made assuming a reservoir with uniform rock properties. The two-phase flow results were also compared with the conventional calculation methods, which do not include the effect of saturation gradients resulting from a simultaneous flow of oil and gas which are normal to this type reservoir. It was found that the conventional methods predict (1) a high and too optimistic value of ultimate recovery, (2) a high producing rate and a high reservoir pressure at a given oil recovery and (3) a low trend of gas-oil ratio with oil recovery. Included in the two-phase flow calculations were provisions to control the oil production rate by an allowable rate and, also, by a gas-oil ratio penalty rule. For the systems with hydraulic fractures, the producing rate was controlled by the gas-oil ratio penalty rule for most of the life. This is in contrast to the system with uniform rock properties which went "on decline" almost immediately. An unexpected characteristic of the systems which included fractures was the early rise in producing gas-oil ratio from 730 cu ft/bbl to approximately 1,200 cu ft/bbl, followed by a "leveling off" before the normally expected gas-oil ratio rise began. Additional features which are a result of hydraulic fracturing are (I) greater ultimate recovery, (2) higher average producing rates and (3) a lower average reservoir pressure at a given oil recovery. INTRODUCTION Some oil fields discovered during the past few years are producing from certain volumetric ally controlled reservoirs (often referred to as solution or internal gas- drive reservoirs) which are characterized by high-pressure drawdown at the wells. Since the available pressure drawdown at a well is limited by the static reservoir pressure and the producing rate is controlled by the available drawdown, wells completed in this type of reservoir usually produce at a rate less than the allowable from the time of completion. Because of this, this type of reservoir is referred to as a low productivity reservoir. Economic considerations require the use of wide well spacing and well stimulation by hydraulic fracturing to make commercial wells in this type of reservoir. Performance predictions for volumetrically controlled reservoirs have been made using a combination of two standard equations. 1. The "Schilthuis" or "Muskat" type material balance equation is used to relate the average reservoir pressure and the cumulative oil recovery. 2. The results from the material balance equation and the productivity factor as described by Pirson' are used to relate the cumulative recovery with producing rate and time. The material balance equation assumed uniform pressure and liquid saturation conditions throughout a reservoir. The steady-state radial flow formula allows for a pressure gradient toward a well but assumes uniform liquid saturation. These calculation methods are adequate for application to reservoirs wherein the drawdown at the well to realize satisfactory producing rates is small compared to the total pressure. In low productivity, volumetrically controlled reservoirs, the pressure drawdown at the well is large cornpared to the total pressure. Although a precise number cannot be given for the magnitude of a large pressure drawdown, values in excess of 1,000 psi would definitely be included. For practical considerations, this usually occurs when the formation flow capacity is less than about 100 md-ft. However, this limit of formation flow capacity will vary with the well producing rate. The low pressure in the neighborhood of the well which results from a high drawdown causes evolution of large volumes of gas. This causes the gas saturation to be higher near the well than at a greater distance—-hence, a non-uniform gas saturation. Also, the relationship between the relative permeability to oil (K/K) and gas saturation is nonlinear but decreases approximately in an exponential way with increases in gas saturation. Because of this, the following chain reaction is established.

When the writer first began his search for the early history of coal he was amazed at the paucity of information in literature about it, and while after six years many of the reasons for such a scarcity are understood, there are still many cases, even within the last two centuries, when one who can appreciate the tremendous part coal has played in the development of modern times, finds it hard to realize how little attention was paid to this material in those early clays. Occasionally a traveller or observer is found who foresaw how valuable coal was to be when industries were developed, but these were few and to most of those recording its occurrence it was just another mineral. George Washington was farsighted in his view of the development of this country and the need for means of transportation across the mountain barrier, but it was at least sixteen years after he must first have known of coal before he made any reference to it in his journals. He did, however, knowingly or not, select some valuable coal properties in the lands lie obtained in the West. This was then almost entirely an agricultural country, and what industries there were found a great abundance of wood fuel within easy access, there were no steam plants, and all iron was made with charcoal; in fact, the "captive mines" of the iron industry then were large timber "plantations," and when these were exhausted the furnace usually was abandoned and another one built elsewhere, as transportation of charcoal was quite expensive. Along the seaboard the cities and industries began to import coal from England and Nova Scotia early in the eighteenth century, but until the war of the Revolution began the total quantity of coal used yearly in this continent did not exceed nine thousand tons. In 1800 only two places, Pittsburgh and Richmond, Virginia, were using coal to any extent for domestic purposes and it was much later. than this that the amount of coal used in Philadelphia, New fork, and Boston exceeded that of wood. Practically all of the early travellers and writers mentioning coal are noted in the following pages. Several Englishmen who were evidently familiar with its use and value at home, mention its presence as being of great future promise to the young nation, but to nearly all it was more or less of a curiosity and the smoke caused by its use an abomination, and it

Jan 1, 1942

By W. A. Klikoff, I. Fatt

The concept of fractional wet wattability is examined. Fractional water wettability of a reservoir rock is defined as the fraction of the internal surface urea that is in contact with water. Capillary pressure and relalive permeability of unconsolidated sand are shown to be functions of fractional wettability. INTRODUCTION The petroleum industry has long recognized that wettability of reservoir rock has an important effect on multiphase flow of oil, water and gas through reservoirs. As early as 1928 the American Petroleum Institute sponsored a study of wettability as part of API Project 27 at the U. of Michigan.' Despite 30 years of research, there is still little exact knowledge of the wettability of reservoir rocks. There are two parts to the wettability problem. After agreeing to a uniform nomenclature in regard to wettability,' the first question to be answered is, "What is the in situ wettability of a given reservoir rock?" If this can he answered the next question is, "What part does wettability play in determining the characteristics of multiphase fluid flow through the rock?" This paper represents an oblique attack on the problem of wettability. No attempt is made here to answer the basic question of wettability in situ. instead the consequences of the concept of fractional wettability are examined. Multiphase flow in sandpacks is shown to he highly influenced by fractional wettability. Jennings' has given 3 definition of wettability and the other terms used in discussing wettability. These terms must be applied to the physical situation existing In reservoir rock. A survey of the pertinent literature from 1928 to 1956 indicates that the concept of a contact angle was applied to reservoir rock in the same way it would be applied to a flat, homogeneous surface. Attempts were made to state quantitatively the wettability of a reservoir rock in terms of a contact angle which was presumably constant at all points on the very rough and heterogeneous interior surface of a porous rock. Calhoun, et al,3-6 prepared synthetic consolidated and un-consolidated porous media in which they claimed there was a known uniform contact angle. They then showed the effects on the capillary pressure and relative permeability characteristics of varying this angle. The API Project 47 at the U. of Texas' and others' have made extensive studies of an indirect approach to the contact angle through the use of heat of wetting data. Even if successful. however, this approach also states the wettability of porous rock in terms of a contact angle which is uniform over the entirc surface. If the angle varies from one part to another on the internal surface, there is no way of determining from the measurements the area distribution of contact angles. In 1956 Brown and Fatt5 suggested that the concept of a contact angle, as applied to reservoir rock, be abandoned. This suggestion was made because it is known that the internal surface of most reservoir rocks is composed of many different minerals, cach with a different surface chemistry and a different capacity to adsorh surface active materials from reservoir fluids. Furthermore, the operation of a contact angle in determining the form of a fluid-fluid interface is difficult to picture in the very complex geometry of a pore. Brown and Fatt proposed that the wettability of reservoir rock be stated in terms of the fractional internal surface area that is in contact with water or oil. All surfaces on which there is water are called water-wet; surfaces on which there is oil are called oil-wet. The fractional water wettability is then stated as a number which represents the fraction of the internal surface that is in contact with water. A symmetrical statement can be made for the fractional oil wettability. The concept of a fractional wettability as previously stated has in its favor the recognition of the heterogeneous mineral composition of most reservoir rocks. Another point in its favor is that fractional wettability can be measured quantitatively with relative ease. Hol-brook and Bernard10 se a simple dye adsorption test to obtain fractional wettability of reservoir rocks. Amott11 uses a combination of imbibition and displacement to arrive at a wettability index of reservoir rocks which seems related to fractional wettability in the range 0.25 to 0.75 fractional water wettability. Jennings" has shown the changes in relative permeability that take place when a porous material is changed from unity to zero fractional water wettability. He also shows that reservoir rocks in their natural state, but at room temperature and atmospheric pressure, have relative permeability characteristics which would indi-

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By Ivor Jenkins

PROCESSES employing controlled atmospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been associated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and difficult problems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases Controlled atmospheres such as dissociated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties: especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,1 but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1947

COMMITTEE IN CHARGE SPENCER PENROSE, Chairman A. E. CARLTON, Chairman Finance Committee GEORGE M. -TAYLOR, Vice-chairman. J. DAMSON HAWKINS, Secretary DENVER COLORADO SPRINGS Finance Finance T. B. STEARNS A. E. CARLTON RICHARD A. PARKER SPENCER PENROSE T. B. BURBRIDGE GEORGE M. TAYLOR A. L. BLOOMFIELD, Treasurer Arrangement Registration DAVE G. MILLER LOREN C. LENNOX FRANK BULKLEY HORACE F. LUNT GEO. E. COLLINS J. M. TIPPETT Entertainment Arrangement and Entertainment F. H. BOSTWICK GEORGE M. TAYLOR F. E. SHEPARD J. D. HAWKINS HOWLAND BANCROFT A. E. CARLTON B. P. MORSE A. L. BLOOMFIELD J. G. PERRY THOMAS B. CRONE E. P. ARTHUR ETIENNE A. RITTER CRIPPLE CREEK PUEBLO THOMAS B. CRONE J. F. WELBORN E. B. ARTHUR H. B. CARPENTER N. S. GREENSFELDER L. B. EAMES A. E. CARLTON F. ROBINSON B. F. HILL J. G. WILLIS

Jan 8, 1918

By H. E. Brauer

PART I INTRODUCTION Among the zinc base alloys used for casting in metal moulds, particularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortness which facilitate casting. Objection to the use of these alloys may bee raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intercrystalline corrosion. In all cases which have come to our knowledge where the conditions of service were known, failure has occurred upon exposure to moisture and heat varying from a hot moist atmosphere to high pressure steam. Moreover, the alloys described in all such cases contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intercrystalline oxidation in zinc-aluminum alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Bauer2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the most part, and Rawdon's3 examinations were made on an alloy containing 0.4 per cent. lead also exposed to the Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to determine the exact nature of this phenomenon and the effect of other metals present as impurities or intentional additions in accelerating or-retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation.

Jan 8, 1922

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By Nathaniel Arbiter, Norman L. Weiss

Factors now accelerating the trend to larger concentrators and larger equipment units are reviewed. After almost 40 years of stability with unit sizes less than 100 cu ft, 200 and 300-cu-ft flotation-cell units are now operating and a 500-cu-ft machine is being built. The design of these cells is considered, as is the design and operation of flotation circuits against the background of the need to achieve greater process efficiency while holding down operating and investment costs. Particular attention is paid to the scale-up problem. With the newer cells having five to ten times higher unit capacities, the advantages resulting from this in sampling, mill operation nnd control, testing and plant layout are indicated, as well as the broad direction for changes in the overall design of 50,000 to 100,000-tpd concentrators. A comparison is given of the available larger cells of U.S. manufacture with analysis of differences and similarities. After almost 60 years of application in this country, froth flotation is still by far the most important process for concentrating metallic ores as well as a number of nonmetallic ores including fluorspar, phosphate rock, and potash. Its use on iron ores and coal is increasing. In the metals groups, the largest plants and the greatest progress are found in copper and molybdenum mills, and the section of this paper that deals with applications will be found most pertinent to that field. During its long reign, the flotation process has passed through several phases of evolution and has achieved progress in economy, efficiency. and simplicity of operation. Much of today's success in the flotation of low-grade ores can be attributed to that progress. Even more important to us than our ability to cope with today's conditions are tomorrow's problems, which we can contemplate with some prescience and confidence. Our annual production of copper, lead, zinc, and molybdenum—to mention only the most important metals occurring in the U.S. as sulfides- must be held at a high level in the face of a declining grade of ore. It is probable that the tonnage of such ores mined and processed will double in this country before the turn of the century. Not only will many of the existing flotation mills be enlarged again and again, but larger mills will be built here and abroad to meet our needs. At this moment, in fact, there are at least three proposed new foreign mills or expansions that envision 100,000-tpd milling rate on copper ores. Table 1' shows the trend in copper ore grades in U.S. in recent years. Table 2' shows the projected annual growth rate of consumption 1966-1985. A study by one of the authors 25 years ago showed that of 32 copper mills in North America with more than 100-tpd capacity, only eight had capacities exceeding 10,000 tpd. The average for these eight was 25,000 tpd. These included the three giants of that day, Magna, Arthur, and Morenci; the other five averaged a little over 10,000 tpd. Today instead of the eight mills with capacities exceeding 10,000-tpd capacity we have 25, and the mill with less than 1000-tpd capacity is fast becoming extinct. Much less range is found in lead and zinc mills, which are still generally small except for the few with over 1000-tpd capacity in Missouri, Utah, and Idaho, and a few zinc ore mills in the same size category. Molybdenum and potash operations are the fastest growers in North America today, but when one considers the projected increase in consumption of copper together with the projected decrease in grade of ore (3% annually), he can foresee that copper ore milling will soon lead the list. Technological improvements to meet the challenge of lower-grade ores have taken the wholly predictable path toward bigger equipment. In mining, shovels, draglines, scrapers, and trucks have led the way; in ore processing, we have seen a rapid increase in size of grinding mills, flotation cells, and pumps. Twenty-five years ago, for example, the 10-ft-diam ball mills treating 2000 tpd at Morenci were considered the giants, but today some grinding mills in similar service have five times that capacity. The specific matters to be dealt with in this paper are 1) the underlying principles that affect flotation-machine design, and the conditions required to produce

Jan 1, 1971

By Richard I. Petritz

A brief review of today's processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting' to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967

By W. A. Hutchins

Water laws important to the mining industry are those which govern or affect the right to use water, to dispose of water after using it in mining or milling, and to discharge waste material into watercourses. They include statutes and court decisions having general applicability, as well as others that pertain specifically to mining. THE INDUSTRY'S CONTRIBUTION TO WESTERN WATER LAW Despite sharp differences of opinion, the water law the Spaniards brought to the Southwest appears to have included some form of appropriation of water. The Mormons, who settled in Utah in the mid-nineteenth century, also developed a system of appro-priative water titles. But by far the most profound impact on western water law was made by the gold-seekers who flocked to the Sierra Nevada foothills of California after the discovery of gold in 1848. Much of the gold was extracted from the ground by hydraulic or placer mining, and so the miners' rights to the use of water became fundamentally important. Since there was no organized government in the foothills and no laws other than those made by the miners, they helped themselves to the land, the gold, and the water needed to work their claims.1 They established and enforced regulations governing the acquirement and holding of mining claims and their rights to the water they needed.' In 1879 Justice Field, former Chief Justice of the California Supreme Court, spoke for the U. S. Supreme Court in saying that the miners were "emphatically the law-makers, as respects mining, upon the public lands in the State."" Rules of the California mining camps were based on two essential principles: 1) priority in discovering claims and appropriating water by diverting it from streams and putting it to use, and 2) diligence in working claims and applying water in mining. The customs so developed, which were copied in mining areas of other states and territories, were enacted into law in one western jurisdiction after another. They form the basis of what is called the arid-region doctrine of prior appropriation of water, which received the attention of Congress in legislation recognizing and protecting appropriations of water for mining, agriculture, and other purposes on the public domain.' In several western states a great number of water cases decided in the early years involved relative rights to the use of water for mining purposes or for milling connected with mining." The miner's inch, the customary unit for measuring water in the mining camps, is still used in various western communities, although its relation to the cubic foot per second varies from one area to another. Undoubtedly, the miners of a century ago made the major contribution to the appropriation doctrine as it is now recognized and applied throughout the West. What inspired the California gold-seekers to develop these principles? Thoughtful writers have pointed out that their regulations and customs were strikingly characteristic of much earlier mining enterprises in the Old World.D It is said that the right of free mining and free use of flowing water therefor —so similar to the California conditions and practices—-was a part of the customs of Germanic miners in the Middle Ages, that it spread from middle Europe to other countries and colonies, and that the doctrine of prior appropriation was widespread in the important mining regions of the world. Certainly the Forty-niners came to California from many countries. It does not tax the imagination to consider that they may have brought with them some knowledge of the old Germanic customs and applied this knowledge in their new environment. RIGHTS TO USE OF WATER IN GENERAL In the West, rights to the use of water of watercourses fall into two categories—appropriative and riparian. The doctrine of prior appropriation is recognized in each of the 17 western states. The riparian doctrine is recognized concurrently with the appropriation doctrine in some of these states but has been abrogated in the others. The riparian doctrine prevails generally throughout the East, although there is now considerable interest in developing something else. Generally speaking, the appropriation doctrine has been highly developed in the West, whereas the principles of riparian doctrine have been comprehensively established in only a few states throughout the country. The subject of water rights is a big one. Space permits no more than a brief discussion of aspects that bear upon the title of this article. RIGHTS OF PRIOR APPROPRIATION Fundamental to the doctrine of prior appropriation is the principle first in time, first in right. Although in some states there are statutory exceptions. the original and still generally prevailing rule is that the first one who initiates a right to divert and use water of a stream, and who completes his undertaking with reasonable diligence, acquires thereby the first right of appropriation of the specific quantity of water involved. Each succeeding right in point of time is junior to all earlier rights but senior to all later ones. The practical effect of this priority system is that when the water supply is not enough for all, the earliest rights must be fully satisfied before any water may be taken by those later in time. Acquirement of Appropriative Rights: Each of the 17 western states has a statute under which water may be appropriated pursuant to a prescribed procedure. Generally, the first step to be taken by the intending appropriator is to file application in the office of the State Engineer for a permit to make the appropriation. In most but not a11 states, valid ap-

Jan 1, 1961

By J. K. Buehler

With the rapid acceleration of the cost of shovel dippers and major standard shovel clipper rebuild components, maintenance management at Kennecott Copper Corp.'s Bingham Canyon mine initiated a dipper maintenance and rebuild program. The program focused on extending the service life of the shovel dipper, reducing field labor in maintaining dippers, and lowering shovel dipper rebuild costs. While comprehensive evaluation of the program is still underway, preliminary benefits of the program indicate: •Reduced field ,gelding for shovel dipper field maintenance, •Fewer dipper rebuild units entering the shop, and •Reduced dipper rebuild costs per unit.

Jan 1, 1979

By B. S. Butler

The principal ore deposits of Arizona are in the southern, cen-tral, and western portions of the state, which physiographically are part of the Basin and Range province, southwest of the Colo-rado Plateau (Pl. I). The Basin and Range province is characterized by numerous subparallel mountain ranges separated by plains or valleys. Most of these ranges trend northwest to north, parallel to the margin of the Colorado Plateau; but in southeastern Arizona, southern New Mexico, and northeastern Sonora, they trend northward, transverse too the edge of the Plateau. The mountains rise abruptly from plains or valleys, the margins of which in many places are pediments cut on hard rock. Some of the plains form closed basins (bolsons, playas), but most of them are drained. The Basin and Range province in Arizona is divisible into the Mountain Region and the Desert Region4 (Pls. I and II). The Mountain Region forms a belt 60 to 100 miles wide that contains most of the large ore deposits. Its longest range measures about 55 miles, the widest 20 miles, and the highest peak more than 10,000 feet above sea level or 7,000 feet above adjacent valleys or plains. Broad plain-forming valleys are exceptional, but several with maximum widths of 20 to more than 30 miles appear in the southeastern portion. In the Desert Region the mountains are relatively low, narrow, serrated, and steep, with sharply angular profiles. There are a few exceptionally large ranges of which the longest measures nearly 100 miles and the widest 18 miles. The highest peak is some 7,000 feet above sea level, and the maximum local relief amounts to about 5,400 feet. Broad and comparatively low desert plains form 50 to 75 per cent of the area.

Jan 1, 1939

By Howard N. Eavenson

FROM the Pittsburgh coal bed in the four states of Pennsylvania, Ohio, Maryland and West Virginia has been produced an output that, at mine prices, represents a greater value than any other single mineral deposit in the world has yielded.12 While this distinction may in a few years pass to the gold reef of the Witwatersrand, it is possible that eventually, owing to the tremendous reserves still remaining, the ultimate yield of the Pittsburgh bed will be greater than that of any other known single deposit. Considering its importance, not a great deal has been written of its early history and development as a whole; most of the accounts have been of limited localities, or, at the most, of the area within a single state. In "Coal through the Ages" the writer mentioned some references to its early history, but this study will deal not only with its history but with the character of the bed, where and why it was first developed, and its effect upon the states in which it is found. It has not been the intention to write a detailed history of the development of the seam in each locality, as neither time nor inclination were available for doing such work, but only to show the influences that tended to hasten or retard such development. In general the historical matter ends about 1830, when geological surveys began to be made. Some of the maps show data available only since that time, and the sections about coal preparation and coking have been extended to the present time to show the changing conditions. It is believed that the early history includes all published records, and many more sources than those shown in the bibliography were consulted. It is quite likely that some references to coal in this area may be found in the unpublished papers of some of our early soldiers and colonizers, which exist in several libraries, and it is hoped that some future

Jan 1, 1938