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By H. B. Pulsifer

One of the most common basic open-hearth furnace products is a simple carbon steel with a carbon range from 0.05 to 0.15 per cent. The material is widely used for sheets, tubes, bars, wire and the innumerable special objects of secondary fabrication. The properties of the material vary over wide ranges, depending on the more exact composition and details of manufacture or treatment that affect its structure. The present paper is a review of those properties and structures that have been found by studying this steel as used in the cap screw industry. At first glance this might be thought a narrow application of the steel, but, since the industry uses the material in the cold-worked, annealed and heat-treated conditions, the title of the paper may be excused for its comprehensiveness. Yet, in studying the wide ranges of properties and structures that preclude a more specific title, there can be no suggestion of completeness or finality. Even a summary of a few years' work is no more than a preliminary survey of a field that will be fertile in scientific data and industrial products for many years to come. An outline of the structures will be given first, then a list of the previous contributions that are at hand and finally some details of the work and related problems, especially concerning this low-carbon steel in the surface-hardened condition. Wire Used in Manufacture of Cap Screws The wire that is used for making cold-upset and roll-threaded cap screws has been cold-drawn from hot-rolled rods that were pickled and limed. The common sizes used in the industry range from 0.185 to 0.750 in. dia., the exact diameters depending on the plant practice and having the usual tolerances of 0.002 in. for the smaller sizes and 0.003 in. for the larger sizes. The carbon range, by pit analysis, is usually between 0.07 and 0.12 per cent. Manganese should be within the usual 0.30 to 0.50 per cent. range. Sulfur rarely exceeds 0.045 per cent. and phosphorus seldom exceeds 0.030 per cent. Silicon is usually below 0.03 per cent. but in the silicon-killed steels may be in the customary 0.10 to 0.25 per cent. range. Rimmed steel is not considered most suitable for cap screws that are cold-headed or for parts that are to be surface-hardened.

Jan 1, 1931

By D. M. Milne, R. F. Stoner, W. Bakiewicz

The Lower Indus Basin deposits form a substantial unconfined alluvial aquifer of excellent quality. This aquifer contains basically highly saline groundwater, overlain in places by considerable amounts of fresh water whose origin can be traced to the present and historical courses of the River Indus. In the past, the main source of groundwater recharge has been direct river seepage and water tables were generally deep. Since the establishment of a perennial irrigation regime however, deep percolation from the increased irrigation supplies has predominated and the water table has risen to within a few feet of the surface. The river system itself is being progressively devel-oped for irrigation and very shortly a situation will arise where the entire low winter flow will be utilized. Fresh groundwater will then be exploited to supplement the surface supplies, and at the same time a drainage system, mainly based on wells will be used to stabilize the water table at safe depths. This paper discusses some of the methods used to ensure optimum economic development of the fresh groundwater and describes the general design philosophy evolved by the authors' firms for both irrigation and drainage wells, with respect to both well configuration and operation. Water quality standards are discussed insofar as they affect subsequent use of the groundwater. A few particular aspects are considered, including the values of the relevant aquifer constants, the construction of wells, and the determination of screen losses. A major problem solved during the Lower Indus Project investigations has been the design of wells to produce fresh water from layers overlying saline water. This solution is also discussed. The recent interest in the groundwater of the Lower Indus Plains of West Pakistan has two main aspects. Firstly, soil waterlogging and the associated salinity hazards caused by rising water tables are a serious problem in agriculture, and the ease with which drainage requirements can be met by aquifer pumping makes this an obvious solution. The second interest stems from the rapid intensification of irrigation agriculture and the growing shortage of water supplies. In the areas where the groundwater is of suitable quality it can be used immediately for irrigation at relatively small cost and with large financial returns. In addition, the aquifer forms a potential storage reservoir which could be recharged from high river flows and depleted by pumping at times of scarcity. SOURCE OF GROUNDWATER The Lower Indus plain is a relatively long and narrow alluvial basin on a north-south axis, some 23,000 sq miles in area, bounded by higher land to the east and west. One hypothesis to explain the distribution and quality of groundwater in the region1 presupposes a river system considerably larger than, but very similar to the present river. This is characterized by a single mainstream, with subsidiary overspill channels in times of flood, running along the crest of a self-deposited ridge and with an extensive advancing delta. Sea water is contained in the alluvial pores of the advancing delta, forming the native groundwater. This has been partially displaced from two sources, namely direct seepage of fresh water from the river channel in meander flood plain areas and percolation from flood spillage in cover flood plain areas. Percolation has been subject to much re-evaporation and is thus slightly saline even as it reaches the groundwater. The whole complex has been further affected by two main influences: evapotranspiration from the land surface that tends to salinize the groundwater and down-valley flow that tends to bring fresher water

Jan 1, 1970

By Warren E. Wilson

PRESENT-DAY design of launders is essentially an art depending to a marked degree upon the experience of the designer, whose problem is that of determining the dimensions of a conduit that will transport the pulp within the physical limitations of the plant and in the most economical manner. This paper has been prepared in an effort to place launder design upon a more scientific basis. A method is developed from elementary principles and presented in a form that may be used directly by the designer in determining launder dimensions.. The equations that are developed are believed to represent an advance over older ones, in that they give due consideration to all the pertinent variables, either including them in the analysis or showing that they may be neglected within the limits of applicability of the equations. Experimental data from several sources are used in evaluating the coefficients that are not determined in the mathematical analysis. On the basis of the material presented, it is concluded that launders may be designed with a much greater degree of accuracy than previously believed possible, when due consideration is given to all the factors involved in the problem. However, a great deal of work still remains to be done in the laboratory before a complete answer to all the questions in launder design can be made available. HISTORY OF LAUNDER DESIGN Among the references1-11 are cited accounts of many experiments that have been conducted in an effort to advance the knowledge of the flow of liquid-solid mixtures in flumes and pipes. With three notable exceptions, this work was carried on in such a manner that the results have limited value in solving the general problem, since not all the pertinent variables were measured and controlled. The exceptions are found in the works of Blue,6 Gilbert,7 and Blatch,11 who exercised great care in controlling and measuring all the significant quantities involved in the experimentation. It is notable that much of the work done by men directly connected with the mineral industries1-4 lacks somewhat in completeness, owing apparently to preconceived notions concerning the factors that determine the flow. For example, many measurements on flow in pipes and flumes carrying liquid-solid mixtures determined only the slope and percentage of solids, with no mention of size of particles, depth of flow, roughness of channel or specific gravity of solids. Material in current handbooks8,9 and textbooks is based largely on the experimental work cited above. Although most discussions of the topic-include statements that the results to be obtained by using the data presented are limited by the fact that all variables have not been considered, it is

Jan 1, 1943

By S. Nakajima, H. Okazaki

Quantitatiue studies of the deformation texture in drawn tungsten wives were made by the X-vay dif-fractottletetr. Experimental results show that the diffraction Intensities are equal to tilose pvedicted from the (1 10). fiber lexlure but the angxla), spreads of. diffraction peaks in the pole distribution curres are different for different diffraction planes and directions. For this reason a modified (110) fiber lextuve model, in which a kind of anisotropy is assumed, is proposed to explain the results. According to this model the poles lying on a line directing front the (110) to the (110) poles in the (1 10) standard stereograpllic projection should show spreads which are different from those lyitlg on a line directing from the (001) to the (001) poles, which is confirmed by the experiments. The anisolvopy and the spveads of the pole positions are large at the outer part of the wires and decrease gradually lowards the inside of the wire. The possibilily of occurrence of such anisolropy in irrelals with fcc stvuctures is discltssed. THE deformation texture of drawn tungsten wires has been assumed by different investigators to be the simple ( 110) fiber texture.' Recently, however, Leber2,3 has shown that a swaged tungsten rod has a cylindrical texture. It changes gradually to the (110) fiber texture by drawing through dies. However, even after drawing to 0.25 mm in diam, the cylindrical texture can still be found in wires together with the (110) fiber texture. This was deduced from the pole figures obtained from the longitudinal section of these wires. Use was made also of quantitative measurements of the pole distribution curves. Leber stated that the angular spread of the pole distribution curves (henceforward called dispersions) are quite different for (400) 45 deg and (400) 90 deg: the former is always larger than the latter. This inequality is accompanied by deviations of the diffraction intensities from the theoretical values for the ( 110) fiber texture. Bhandary and cullity4 have reported similar results on iron wire and explained them by assuming a cylindrical texture. Both Leber3 and Bhandary4 used only the results of the (400) reflection for the determination of the dispersion. The pole figures found by Leber3 and by Rieck5 are largely different. The model given by Leber to explain the effects is in the authors' opinion in some respects unsatisfactory, especially if one looks at other than the (400) reflections. Intensities and dispersions of diffraction peaks are conclusive factors for the determination of the fine structure in wire textures. For this reason we studied them extensively to come to a model which is more suitable to fit the facts. In the following, after giving the experimental set-up, we report about measurements of X-ray diffraction on drawn tungsten wires. Different models to describe the experimental results will be discussed. EXPERIMENTAL GO-SiO2-A12O3 doped tungsten wires drawn to 0.18 mm in diam were used for the measurements. The wires were chemically etched to various diameters down to 0.03 mm. Measurements were carried out for the different wires in order to determine the dependence of the texture on the radius. The wires were cut to pieces of 10 mm length and fixed with paste closely against each other on a flat, polished glass plate. Parallelism of the wires with the surface of the glass plate should be adequate. For the diffraction studies three different X-ray sources were applied, respectively, giving the CuK,, FeK,, and FeKp emission. The measurements were carried out with a diffrac-tometer with a GM counter. The latter was fixed to a certain diffraction angle 20hkl and the diffraction intensity was recorded as a function of the angle of rotation of the specimen around the axis, lying in the specimen surface and perpendicular to the wire axis, as shown in Fig. 1. Measurements were also done with the detector at angles slightly deviating from the diffraction maxima The measured intensities in this case were taken to be equal to the background level. The deviations were chosen as small as possible but large enough to eliminate the influence of the diffraction maxima. The useful range of the rotation angle x of the specimen is generally limited by the wavelength of the X-rays. We have: where and cp is the angle between the wire axis and the normal of the diffraction plane. Intensity measurements were made to find the necessary corrections for counting loss of the GM counter and for distortion resulting from such effects as absorption of X-rays and from inclination of the reflection plane under study with respect to the surface of the specimen. The counting loss was esti-

Jan 1, 1968

By Donald R. Reichmuth

Most brittle solids are relatively weak in tension and this weakness can be very significant in determining their performance in structures and excavations. Consequently, accurate knowledge of the tensile strength of brittle materials has long been recognized as important. In the past, measurements of the tensile strength of materials such as concrete, ceramics, and particularly rock have been hindered by problems encountered in fabricating test specimens and in accurately loading them. These difficulties have resulted in a scarcity of published tensile strength data. This can be readily seen in tabulations such as Wuerker's "Annotated Tables of Strength and Elastic Properties of Rocks."1 There are now three distinct approaches being used to determine the tensile strength of brittle materials. These are shown schematically in Fig. 1. The first method consists of simply pulling the specimen apart by applying an axial load. Although this procedure is the easiest to understand, the technical problems encountered during testing are numerous. Specimens cannot be readily fabricated into dumbbell-shaped specimen* like those customarily used for testing inetals. Cylindrical specimens cannot be loaded in jaw-clamps because adverse stress conditions arise at the clamping points, which causes unreliable results. An innovation developed by Niles Grosvenor at the Colorado School of Mines, in which the load is applied through steel-end caps glued to the ends of the specimens, has considerable merit, hut the samples are costly to prepare.2 All tests using a direct pull are further handicapped by the possibility of small amounts of bending being present, the specimen's surface condition, and

Jan 1, 1968

By Fred C. Bond

SIZE of grinding media is one of the principal factors affecting efficiency and capacity of tumbling-type grinding mills. It is best determined for any particular installation by lengthy plant tests with carefully kept records. However, a method of calculating the proper sizes, based on correct theoretical principles and tested by experience, can be very helpful, both for new installations and for guiding existing operations. As a general principle, the proper size of the make-up grinding balls added to an operating mill is the size that will just break the largest feed particles. If the balls are too large the number of breaking contacts will be reduced and grinding capacity will suffer. Moreover, the amount of extreme fines produced by each contact will be increased, and size distribution of the ground product may be adversely affected.

Jan 5, 1958

By N. S. Greensfelder

The firing of explosive charges by electricity dates back to 1745 when a Doctor Watson is said to have used an electric spark for igniting gunpowder. His method failed in practical application because, to ignite blasting powder, heat must be applied for a period longer than the duration of an electrostatic spark; Wheatstone found that this does not exceed 1/24000 sec. The usual result, therefore, of an electrical discharge in gunpowder is to scatter the grains, without igniting them. Benjamin Franklin partly overcame this difficulty by confining the powder and crushing grains that lay in the line of discharge. In 1822, after the primary cell had been discovered by Volta, Robert Hare, professor of chemistry at the University of Philadelphia, noticed the heating of a short piece of wire placed in the circuit of a voltaic battery. Later work by Oersted, Faraday, Wheatstone, and Henley resulted in the developmcnt of the magneto blasting machines. Fulminates of gold and silver are thought to have been discovcrcd by Cornelius Drebbel, about 1600. Pepys, in his diary for November 11, 1663, recounts a conversation with Doctor Allen, who told him about aurium fulminans "of which a grain ... put in a silver spoon and fired, will give a blow like a musquett and strike a hole through the silvel spoon downward, without the least force upward.'ll This fallacious belief that explosives act downwards only is still held by many who should know better. Fulminate of mercury was discovered by Howard in 1799. J. Shaw of Philadelphia is said to have invented a fulminate-of-mercury cap in 1814; his idea was later adopted by gunmakers in England and France. The principal advantages of mercury fulminate for use in detonators are the simplicity of exploding it and the great shock developed by its explosion.

Jan 1, 1923

By N. S. Greensfelder

The firing of explosive charges by electricity dates back to 1745 when a Doctor Watson is said to have used an electric spark for igniting gunpowder. His method failed in practical application because, to ignite blasting powder, heat must be applied for a period longer than the duration of an electrostatic spark; Wheatstone found that this does not exceed 1/24000 sec. The usual result, therefore, of an electrical discharge in gunpowder is to scatter the grains, without igniting them. Benjamin Franklin partly overcame this difficulty by confining the powder and crushing grains that lay in the line of discharge. In 1822, after the primary cell had been discovered by Volta, Robert Hare, professor of chemistry at the University of Philadelphia, noticed the heating of a short piece of wire placed in the circuit of a voltaic battery. Later work by Oersted, Faraday, Wheatstone, and Henley resulted in the developmcnt of the magneto blasting machines. Fulminates of gold and silver are thought to have been discovcrcd by Cornelius Drebbel, about 1600. Pepys, in his diary for November 11, 1663, recounts a conversation with Doctor Allen, who told him about aurium fulminans "of which a grain ... put in a silver spoon and fired, will give a blow like a musquett and strike a hole through the silvel spoon downward, without the least force upward.'ll This fallacious belief that explosives act downwards only is still held by many who should know better. Fulminate of mercury was discovered by Howard in 1799. J. Shaw of Philadelphia is said to have invented a fulminate-of-mercury cap in 1814; his idea was later adopted by gunmakers in England and France. The principal advantages of mercury fulminate for use in detonators are the simplicity of exploding it and the great shock developed by its explosion.

Jan 1, 1923

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By William Newnam

WHEN Hugh Lee Pattinson discovered, in 1829, that the crystals formed during the slow cooling of molten lead were poorer, and the remaining liquid richer in silver, than the original lead, an important step was made in the metallurgy of this metal. Being the first process applicable to the desilverization of low-grade lead bullion, it soon found its way into all European countries having such a product to treat, thereby effecting the saving of many ounces of silver annually which previously had been thrown away. The old hand process was expensive, as viewed from the standpoint of more modern methods; the labor was great anti the tonnage was small, but on the other hand the results were fairly, satisfactory. This process flourished for some time after the introduction of the cheaper Parkes process in 1852 and it is still in use in a few European smelteries. Only one notable improvement was made on the original process, that of Luce and Roan at Marseilles, France. It consisted in the application of steam for stirring and the tapping of one-third of the liquid lead, through perforated plates covering the tap holes flush with the bottom of the kettle, thus leaving two-thirds in the form of crystals in the original kettle. This modification considerably lowered the operating costs as it permitted of much larger kettles, an increased tonnage and eliminated much of the slow, hard labor of the hand process.. The Luce and Rozan process has persisted in its original form to the present clay. Stephen Tredinnick, English born, spent most of his years around the Luce and Rozan plants at Marseilles and elsewhere in Europe, coming later to Eureka, Nev., in 1878, to operate the Luce and Rozan plant at that point. Mr. Tredinnick was a competent Luce and Rozan operator and being devoted to the process he firmly believed that with modifications the costs could be so lowered as eventually to supplant the Parkes process.

Jan 5, 1917

By P. A. Young

The historical background of on-strand cooling is given, together with a resume of recent practical developments. Laboratory test procedures are then considered in detail, for both productivity and quality parameters, with particular reference to the design of the Ravenscraig No 3 machine (Scotland). A heat transfer model is presented for a porous sinter with propagating cracks. The influence of cooling/sintering area ratio, sinter strength, granulometry, return fines, coke consumption and FeO levels are examined in relation to economics. A detailed comparison of capital and running costs for two different strands, designed for identical duties, but with off or on-strand cooling, is then given.

Jan 1, 1977

By R. H. Jacoby, V. J. Berry, R. C. Koeller

The experimental phase behavior of several field gas-condensate systems, one field volatile oil system, and a series of synthetic systems having gas-oil ratios from 2,000 to 20,000 scf/bbl stock tank oil was measured. The data were used to calculate the depletion performance of the field systems at their respective reservoir temperatures and of the synthetic systems at various temperatures. The results of the performance calculations were used to prepare correlations of total stock tank oil and separator gas in-place, and the amount of each recovered by primary depletion. Data needed to use the correlations are initial gas-oil ratio, initial tank oil gravity, reservoir temperature and reservoir pressure. The correlations presented should be useful for estiinating recovery from reservoirs producing volatile oils or rich gas condensates having gas-oil ratios from about 2,000 to 30,000 scf/bbl of stock tank oil. INTRODUCTION Prediction of depletion performance for gas-condensate reservoirs usually requires extensive laboratory work or lengthy phase-behavior calculations. For many small gas-condensate bearing zones the expense of such work is often not justified. Furthermore, where large holdings are involved, it is useful to have estimates of future oil and gas production in advance of the results of a laboratory analysis, even if such work is ultimately planned. For these reasons, it would be of value to have a method for rapidly estimating the depletion performance of gas-condensate reservoirs from the type of field data usually available. Few data on the reservoir depletion performance are available for the purpose of developing correlations. The increasing number of gas-condensate discoveries and the advent of high-speed computers have stimulated the development of methods for predicting performance. Such calculated performance data have been shown to be reliable and are becoming accepted as a basis for reserve estimates and for engineering studies. It therefore seems satisfactory to use results of performance predictions themselves for the purpose of developing the desired correlations. Such an approach is described in this paper. Several rich natural gas-condensate systems (gas-oil ratios of from about 3,600 to 60,000 scf/bbl) and one natural volatile oil system were studied (2,363 scf/bbl). In addition, to provide a more systematic basis for correlating purposes, a series of related, synthetic reservoir fluid mixtures was also studied (GOR's from about 2,000 to 25,000 scf/bbl). The purpose of this paper is to show how the recovery of oil and gas by primary depletion may be estimated from surface gas-oil ratio, reservoir temperature and pressure, and tank oil gravity. procedure Experiments Companion samples of gas and oil were collected from the high pressure separators in nine different fields at the time of their discovery. These samples were each recombined in accordance with the respective producing GOR to reproduce the reservoir fluids. Eight of these fluids, designated F-2 through F-9, were rich gas-condensate systems at the respective reser-

By Eduardo Martinez Baca

Although Mexico has always been justly considered by the whole world essentially a mining country, this reputation is due principally to the richness of the deposits which have been worked. In reality, the majority of the States have been little

Jan 1, 1902

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

By G. R. Purdy, J. A. Malcolm

The isothermal dendritic precipitation of y in p CuZnSn is compared with the isothermal formation of Widmanstatten a plates in p CuZn. Although both precipitates are evidently bounded by semicoherent interfaces, the dendritic shape of y evolves through smooth "sinuoidal" shape perturbations, while a-p interfaces tend to be strictly planar, or rnicroscopically faceted. An estimate of the average inter-facial free energy of cube-oriented y in p through the Mullins-Sekerka analysis indicates that it is low (of the order of 50 ergs per sq cm). Interface mication is apparently controlled by volunle dij'usion, and the observed anisotropy in growth probably results from anisotropy of inter facial free energy. Studies of the grain boundary precipitation of y in p indicate that the precipitate can grow in both $ grains, but becomes unstable with respect to the grain with which it shares a mobile semicoherent interface. Facets observed at the tips of Kurdjumov-Sacks-oriented Wid-manstatten a plates correspond to variants of an irrational hahit, near (231)0. Comparison with Hu and Smith's determination of relative interfacial free energies of a-(3 boundaries suggests that this system possesses an extremely deep o cup, which results in an ej'ective low-o zone. The possible effects of such a cup on the stability of a-p interfaces are discussed, a needles, grown during rapid continuous cooling, possess microscopically smooth interfaces, and are characterized by a high degree of' damage in the region of the boundaries. These boundaries, induced to move on tempering at 200"C, become faceted as equilibrium is approached, which seems to indicate that boundary structure and mobility in this system are dependent on the local degvee of departure from equilibrium MULLINS and sekerkal have elucidated the phase boundary stabilizing effect of surface tension. a factor not taken into account in previous treatments of morphological development. Their analysis applies to the isothermal growth of a pure spherical precipitate (planar in the limit of infinite radius) in a slightly supersaturated solution, under conditions of inter-facial local equilibrium and isotropy of interfacial free energy. More recently, several other factors which might tend to stabilize planar interfaces have received attention. These are: i) interface diffusion;4"8 and ii) slow interfacial reaction. cahn7 included a slight anisotropy in interfacial free energy, and showed that it has no stabilizing effect, but forces shape perturbations to reflect the anisotropy. shewmon4 noted that dendritic morphologies are rarely observed in solid-solid systems, and, in particular, postulated that slow interfacial reaction occurs at all boundaries between proeutectoid ferrite and austenite, except those which propagate parallel to {11 l)y planes (for Kurdjumov-Sachs [K-S] related phases). Previously, Aaronson~ had proposed interfacial reaction at the broad faces of Widmanstatten plates, and expected that the lateral motion of high-mobility incoherent ledge edges would produce planar precipitates bounded by law-mobility semi-coherent interfaces. The problem of interfacial reaction during the dif-fusional formation of precipitates has often been ignored, although it is apparent that a small component of chemical reaction must exist at any moving interface." Further, all solutions of the diffusion equations for boundary conditions corresponding to isothermal growth predict infinite growth rate at time zero, so that elements of interfacial reaction would be most easily detected at early times. However, reported deviations from diffusion control are comparatively rare," and the local-equilibrium diffusion-control model appears adequate for the description of many isothermal growth systems.'2"9 Cahn14 has treated the problem of migration of an interface which is able to reach positional energy minima, and concluded that such an interface, if subjected to a high local ther-modynamic "driving force", may migrate normal to itself without the benefit of ledges. As local equi-

Jan 1, 1968

By David B. Reger

The substantial expansion of previously discovered gas pools was the principal feature of petroleum activity in West Virginia during 1940. At least one new gas pool was discovered and various other successful wildcat completions may prove to be gas-pool openers. Some slight extensions of oil pools were also made. The new productive territory, principally gas, added by these extensions was approximately 33,800 acres. ' In general, oil activity was slight because of unfavorable crude prices. Gas activity, on the contrary, increased considerably, although the price of gas did not materially change. The account of operations, as gathered from trade journals and other reporting services, shows that 709 new wells were drilled, resulting in 102 new oil wells with I055 bbl. of daily new produc-tion; 468 new gas wells with 633>g47,000 cu. it. of daily open flow; and 139 dry holes. Also, 91 old wells were drilled to deeper sands, with 143 bbl. and 44,833,000 cu. ft. of added production. On the new wells the oil average was 10.34 bbl, per well per day; and the gas average was 1,354,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 19.61 per cent. On deeper drilling to other sands the ratio of failures was 12.I per cent. From an exploratory standpoint, one strictly new gas pool (Lorentz) was opened in Upshur County. Little forecast of its extent or reserve can now be made. The new extensions of various other previously discovered pools, however, give assurance of a new gas reserve that will equal approximately a year of gas demand. In addition to these definite supplies two widely separated Oriskany sand (L. Dev.) wildcats in Jackson County, one of which was completed late in 1940 and the other early in 194.1, may indicate two separate pools or may greatly extend known pools. In south-ern Kanawha County, also, an old Oris-kany-sand well deepened to the White Clinton sand (Sil.) showed a volume of 733,000 cu. ft. and rock pressure of 1800 Ib., giving rather clear assurance that this deep sand, in which only slight quantities of gas had previously been found, should eventually supply much new gas. On the other hand, various deep tests to the Oriskany sand in Harrison, Putnam, Randolph and Wood Counties were totally dry or gave only small volumes of gas, The principal oil wells completed, by counties, were: Calhoun, 15; Clay, Ir; Pleasants, 14; Ritchie, 15; and Roane, 7. Production for the year was estimated by the U. S. Bureau of Mines as 3,444,000 bbl., as compared to 3,684,000 bbl. in 1939. The leading counties in gas-well completions were: Boone, 36; Braxton, 17; Cabell, 25; Calhoun, 16; Clay, 22; Gilm.er, 47; Jackson, 38; Kanatvha, 77; Lincoln, 18; Putnam, 32; IGtchie, 40; and Wayne, 31, Production for the year is estimated by me as I70,000,000,000 cu. ft. as compared to I59,226,000,000 cu. ft.* in 1939. No long pipe lines were built but various gas-line extensions and cross connections,

Jan 1, 1941

By David B. Reger

The substantial expansion of previously discovered gas pools was the principal feature of petroleum activity in West Virginia during 1940. At least one new gas pool was discovered and various other successful wildcat completions may prove to be gas-pool openers. Some slight extensions of oil pools were also made. The new productive territory, principally gas, added by these extensions was approximately 33,800 acres. ' In general, oil activity was slight because of unfavorable crude prices. Gas activity, on the contrary, increased considerably, although the price of gas did not materially change. The account of operations, as gathered from trade journals and other reporting services, shows that 709 new wells were drilled, resulting in 102 new oil wells with I055 bbl. of daily new produc-tion; 468 new gas wells with 633>g47,000 cu. it. of daily open flow; and 139 dry holes. Also, 91 old wells were drilled to deeper sands, with 143 bbl. and 44,833,000 cu. ft. of added production. On the new wells the oil average was 10.34 bbl, per well per day; and the gas average was 1,354,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 19.61 per cent. On deeper drilling to other sands the ratio of failures was 12.I per cent. From an exploratory standpoint, one strictly new gas pool (Lorentz) was opened in Upshur County. Little forecast of its extent or reserve can now be made. The new extensions of various other previously discovered pools, however, give assurance of a new gas reserve that will equal approximately a year of gas demand. In addition to these definite supplies two widely separated Oriskany sand (L. Dev.) wildcats in Jackson County, one of which was completed late in 1940 and the other early in 194.1, may indicate two separate pools or may greatly extend known pools. In south-ern Kanawha County, also, an old Oris-kany-sand well deepened to the White Clinton sand (Sil.) showed a volume of 733,000 cu. ft. and rock pressure of 1800 Ib., giving rather clear assurance that this deep sand, in which only slight quantities of gas had previously been found, should eventually supply much new gas. On the other hand, various deep tests to the Oriskany sand in Harrison, Putnam, Randolph and Wood Counties were totally dry or gave only small volumes of gas, The principal oil wells completed, by counties, were: Calhoun, 15; Clay, Ir; Pleasants, 14; Ritchie, 15; and Roane, 7. Production for the year was estimated by the U. S. Bureau of Mines as 3,444,000 bbl., as compared to 3,684,000 bbl. in 1939. The leading counties in gas-well completions were: Boone, 36; Braxton, 17; Cabell, 25; Calhoun, 16; Clay, 22; Gilm.er, 47; Jackson, 38; Kanatvha, 77; Lincoln, 18; Putnam, 32; IGtchie, 40; and Wayne, 31, Production for the year is estimated by me as I70,000,000,000 cu. ft. as compared to I59,226,000,000 cu. ft.* in 1939. No long pipe lines were built but various gas-line extensions and cross connections,

Jan 1, 1941

By H. R. Page, A. E. Jr Lee

From the inception of zinc retorting on a commercial scale in the United States in 1890,' the retort employed has undergone wide variations in its composition and manufacture, facilitating in part equally remarkable improvements in furnace capacities. The early day hand made clay retort was charged with carbonates or silicates or with coarse dead roasted concentrates mixed with a large proportion of charge fuel resulting in a relatively low zinc burden and fired 24 hr in direct coal fired furnaces. Its modern counterpart is fabricated in hydraulic presses from clay mixtures containing sizeable amounts of either silicon carbide or silica flour, charged with sintered flotation concentrates to more than three times the early day zinc burden and fired 24 to 48 hr in gas fired furnaces. This paper does not attempt to describe in detail the early day clay retort practice as it is well outlined in treatises by Ingalls,2 Lodin,3 Liehig,4 Hofman5 and others. A brief review of clay retort practice is presented together with a description of the major developments since 1912. Clay Retorts The Belgian type retort, both in the circular and elliptical forms, has been used almost exclusively. Typical dimensions of press made clay retorts around 1910 are shown in Table 1. Variations in these dimensions were used at different plants according to local conditions to a maximum inside diameter of 9 in. and inside length of 54 in. However, the effective heat penetration in a 24 hr firing cycle and the tendency of the retort to bend limited the retort size. Use of the elliptical vessel was an attempt to present a stronger cross-section resisting the tendency to bend and to increase the burden without increasing the depth of heat penetration. One exception to the 48-54 in. length was the 60 in. retort used as early as 1905 at Palmerton by means of supporting the last 12 in. at the butt end with a specially designed furnace back-wall. This backwall construction with the 60 in. retort had been developed and used at Bethlehem by G. G. Con-vers and A. B. DeSaulles. An attempt was made at Blende, Colo. to use even larger retorts of the Rhenish type based on European practice and requiring much higher furnace temperatures. Satisfactory plastic clays capable of withstanding these temperatures were not available, and the plant never operated successfully. PREPARATION OF BATCH Composition of the clay retort by weight was 40 to 50 pct raw clay and the balance "grog." Generally speaking the mix consisted of 7 parts plastic clay to 9 parts grog by volume. Principal source of the clay used was the Cheltenham vein—sometimes referred to as "St. Louis city clay." A typical analysis was A12O3-31.0 pct, SiO2-50.0 pct, Fe2O3-2.5 pct, MgO-0.3 pct, CaO-1.5 pct and loss on ignition 14.0 pct. At the smelter the clay was weathered whenever possible and then crushed to 0.08 in. or finer. Grog consisted of calcined adobies, cleaned retort scrap and cleaned refuse fire brick such as old furnace brick, blast furnace linings, and others. Saggers from ceramic plants and calcined flint clay were later used. The grog materials were ground to 0.12 m. or finer. Occasionally coke dust up to 10 pct of the mix was substituted for a part of the grog following European practice.² Particle size of the grog has a major influence on the retort properties—the larger the grain, the better can the retort withstand thermal shocks, resist bending at furnace temperatures and resist corrosion from slag; the smaller the grain, the lower the loss of zinc vapor through the retort walls. Grog forms the skeleton of the retort, and the clay shrinks around its grains to act as a binder. In the drying process, the grog has a stabilizing effect on the drying rate, decreasing shrinkage and giving up previously absorbed water to the surrounding clay to minimize the danger of cracking or checking.² Grog and clay were mixed through a horizontal pug mill with 10 to 20 pct water added, depending on whether the retort was to be formed by hand or mechanically, more water being required for the hand process. The batch or "mud" extruded from the pug mill was cut in convenient lengths for handling, stacked in piles or in special rooms, covered with wet burlap and allowed to "rot" or age from 1 to 8 weeks to increase plasticity. HAND MOLDING If the retort was to be molded by hand, the mud was repugged after the rotting period and given to the molders. Their molds consisted of 3 sheet iron or wood cylinders, each one third the retort length and defining the outer shape of the retort. Beginning with the bottom section, mud was placed in the form and tamped with a rammer

Jan 1, 1950

By W. R. Hicks, J. E. Pollock, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935

By J. E. Pollock, W. R. Hicks, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935