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By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By D. E. Marks, Arnold, C. W, R. J. Robinson, A. E. Hoffmann

The efficiency of operation of a fixed-bed adsorption unit is infEuenced both by the absolute adsorption capacity of the bed and by the rate of adsorption. This paper describer studies of adsorption rate which were conducted in an experimental unit designed such that conditions existing in the treatment of high-pressure natural-gas mixtures could be duplicated. Variables investigated included pressure, temperature, gas composition, adsorbent particle size, depth of packed bed and gas velocity. The adequacy of a simplified mathematical model for predicting the observed phenomena was tested. A correlation is preserited which relates adsorption rate to the process variables stlldied. This correlation is useful in combination with the matheinatical model. INTRODUCTION Of the techniques available for contacting adsorbent particles with fluid streams to be treated, fixed-bed adsorption columns offer definite advantages in simplicity and ease of operation. As a result, they are often used in preference to others for such petroleum industry applications as dehydration and purification of natural gas and hydrocarbon recovery. Fixed-bed adsorption units usually consist of two or more towers filled with a desired adsorbent and operated in a cyclic manner. While one is being used to process the main flow stream, the others are undergoing regeneration to remove the adsorbed phase. When the tower on stream becomes saturated with the preferentially adsorbed material, the roles of the towers are switched, and the freshly regenerated tower is placed on stream. Cacle duration is determined by the bed capacity under the process conditions and by the flow rate through the bed. The sharpness of separation which can be effected is a function of both the absolute capacity of the bed and the rate of adsorption in the bed. The effect of rate for a particular set of conditions is evidenced by the sharpness or diffuse-ness of the adsorption front as it advances through the bed. Since data needed for design of adsorption units to treat high-pressure natural-gas systems were not available, an experimental program was designed to investigate the effects of different variables upon adsorption rate in fixed beds. In the present paper, effects of gas composition, column length, temperature, pressure, adsorbent particle size and flow rate (actual linear flow rate of the gas) are shown, and utility of a simplified mathematical model for describing the process is discussed. As gas enters the top of a cool, clean bed of adsorbent, preferentially adsorbed materials are stripped from the main flow stream by the uppermost particle layers. As these layers become saturated with a particular component, new supplies of this component are carried further down the column until fresh adsorbent is encountered. An adsorption wave thus moves through the column as material is supplied to saturate succeeding elements of the bed. Adsorption from a Multicomponent gas stream occurs as a succession of such moving waves corresponding to the different components in the gas. The leading edge of an adsorption wave for a component of a natural-gas stream moving through a bed of a common commercial adsorbent such as silica gel would be sharp but for the influence of certain broadening fac tors. These factors include a nonuniform velocity profile in the bed, longitudinal dispersion or mixing in the main gas stream, and the time required for a molecule to migrate from the main gas stream and be adsorbed at a site within the body of an adsorbent particle. If packing is uniform and the ratio of column to particle diameter is greater than approximately 15:1, the first factor is relatively unimportant' Longitudinal mixing is of importance only for the case of moderately high mass transfer with extremely slow flow rates.' The sharpness of an adsorption front, therefore, is, primarily a function of the rate of adsorption or the time required to saturate a particle of zdsorbent. Two methods for defining adsorption rate are used in this work. The first is a normalized or relative rate which describes the rate of saturation of a differential element of the packed bed. This can be measured by observing the time required for the concentration of the preferentially adsorbed material in the effluent gas from the bed to rise from zero to a value equal to that in the inlet gas stream. The second definition describes the absolute rate of mass transfer from the gaseous to the adsorbed phase. This definition is used in a mathematical description of the adsorption process. If the concentration of a component in the gas strcam leaving an adsorption column is measured and plotted as a function of time, a curve such as that shown in Fig. I results. It is seen that for a period of time the effluent gas is devoid of the component under consideration. As the bed approaches saturation, a small percentage of this material will appear in the effluent gas. The concentration will then rise with time, or increasing cumulative gas flow, until it is equal to that in the inlet gas stream. If adsorp-

By R. C. Thompson

The lead-zinc mill of Phelps Dodge Corporation, Copper Queen Branch, Mines Division, Bisbee, Arizona, is about 3 miles from the main hoisting shafts of the Junction and Campbell mines at Lowell. All the ore treated in the mill is obtained from these two mines. The mill was designed for an all-flotation treatment of 450 tons of lead-zinc ore per day, and has been operated at that capacity since the start of milling operations on Nov. 17, 1945. An expansion program is underway whereby the mill capacity will be doubled, but this article describes only the original program and presents results of the 450-ton operation. General Description The milling plant consists of an ore-receiving bin and three steel-constructed buildings housing, respectively, the primary crushing equipment, the secondary crushing equipment, and the ore-storage bins, grinding, flotation, and filtering equipment. The mill site is the one that was used for a previous copper-concentrating plant, which was operated over a period of years and then dismantled. There remained from this operation some milling equipment, a reservoir for mill-water supply, railroad tracks, tailings-disposal ponds, and a steel-constructed building, all of which were incorporated in the design of the present lead-zinc mill. The location plan of the plant layout is shown in Fig I. The flowsheet of the mill is based on the conventional scheme for lead-zinc treatment, however, several innovations were made necessary in order to utilize the existing building. Placing of equipment also was governed by the design of the building; thus making the mill unique in many respects. The following brief description of the mill building as adapted to the flowsheet points out the compactness of the installation and some of its unusual features. The first floor (Fig 2) houses the grinding equipment, with connecting conveyors for ore feeding, also an air compressor, two vacuum pumps, bins for lead and zinc concentrate storage with individual conveying systems for loading the two kinds of concentrates. Filtering of concentrates is done on the second floor, the concentrates discharging directly into the concentrate-storage bins. On this floor are the lead and zinc filters, two diaphragm pumps, sample-filtering equipment, sample-preparation room and a change room for the mill employees. The flotation machines are on the third floor, at elevations allowing a gravity flow of the lead and zinc concentrates to the thickeners. The annex to the building contains a freight elevator and provides space for all reagent mixing and feeding, also storage of reagents and grinding balls. All the water used for milling purposes is pumped from the Junction mine and

Jan 1, 1949

For many years the occurrence of gold in the Coeur d'A1ène region had been rumored among the pioneers of the Northwest. It is stated that as early as 1853 gold was discovered in this district by Donelson, of the Stevens expedition, but the hostility of the Indians prevented prospecting. In 1858, when Lieutenant John Mullan surveyed the military road across the Bitter hot mountains, the members of his expedition, most of whom had mined in California, noticed sundry outcrops of good-looking quartz, and some of them actually found gold, as is recorded in a letter that Mullan wrote, from Washington, in 1884. The first successful prospector in the Coeur d' Alène was Tom Irwin, who worked a quartz vein on the Mullan road in the spring of 1879. Two years later he met A. J. Prichard, who was engaged in the lumber business; he told him what he thought of the chances of placer mining in the upper reaches of the Coeur d7AlBne river. This was in 1881. Prichard became keenly interested, and himself found gold on several creeks, one of which is now known by his name, at a place close to the site of the town of Murray.* In 1883 Prichard located a number of claims, and shortly afterward he wrote a letter to the members of a Liberal League to which he belonged, inviting them to "secure the lion's share" of the mineral wealth he had uncovered. His letters caused a stampede from Montana and Colorado, and from South Dakota also, to the Coeur d'Alène gold belt in the summer of 1883. A town, named Eagle City, was surveyed; in 1884 lots sold at prices ranging from $200 to $2000. The buildings were made of logs and shingles. Shoveling of the snow in' front left s

Jan 1, 1932

By V. C. Williams

Some of the physical, chemical, and electrical processes for conversion of saline water to potable or industrial water are economically surveyed from an engineering viewpoint. Since all these processes require energy for drive and equipment for containment, the correlative economic factors are developed which indicate directive influences in the choice of particular regional processes. The supply of natural waters and its distance also affect decision. Any one process will probably not prove dominant in the field because auxiliary considerations such as the saline water source; types and continuing availability of fuel; electric power use or recovery; area economic status and advancement; and the political pressures of population, group demands, and land use tend equivocally to obscure capital and operation cost decisions. Basic engineering considerations, data, and economic factors are presented to assist in the direction of these decisions. An exploding world population, increasing industrialization, advancing standards of living, and the desire of less-privileged nations for betterment focus attention sharply on a major problem: water. *19 Up to now, in retrospect, people have had it relatively easy in the handling of this problem. All the better dams in the most advantageous sites, the better aquifers, the shortest aqueducts have been built. In another phase of the problem, concern is evident that wastes cannot indefinitely be disposed of merely by keeping them dilute and discharging them promiscuously. 7-9 And, perhaps, as past civilizations have done,l5 water, watersheds, streams, and irrigation may have been mismanaged or, at the least, not adequately studied.3,5,36,37 In this last is perhaps the core of the problem. As Gross states, "Ignorance and too often, indifference are contributing factors. Archaeology and theology both furnish ample testimony to the existence of rich lands where deserts now stand; it was man who ravaged his land. Unless education is a companion to water development, development might as well be forgotten. But without water, there is no beginning."13 The U.S. is showing increasing concern about its water for predictions are that by 1980 the daily withdrawals will be 494 billion gal, a figure nearly equal to the dependable supply.Is This is based on a conservative projected population of 230 million. The major categories of withdrawals are: To make available this per capita average of 2150 gal per day will require an expenditure of $219 billion over the next 20 years. The U.S. is not alone in this concern. The United Nations shows as arid zones of the world: all of Africa north of the equator and south of the 20's parallel; all of the Arabian peninsula; all of the middle east and Iran, Iraq, Pakistan, Afghanistan, northern and central India; a great band about 1000 miles wide along the 40'~ parallel from the Caspian Sea east across Russia through China to the Pacific Ocean; all of Australia except the coastal plain; the Caribbean Islands; the western nations of South America; and the western third of the United States and of Mexico. With one quarter of the earth's 57,500,000 sq miles of land thus suffering from lack of good water, increasing attention goes to the treatment of brackish and sea waters. The U.S. has been a leader in this field4,12, 16123,24 through its Office of Saline Water in the Dept. of Interior because even now some of its cities and regions are short of potable water. 11j'7,M Industrial water is also of vital concern as a result of ever higher industrialization1,14122 Other nations, among them JaPan, Israel,13188 Germany, Union of South Africa, Australia, Netherlands, France, Yugoslavia, Russia, and groups such as the Organization for European Economic Cooperation (OEEC)' are also diligent. The objective is low cost water, which means that both technology and economics have prominent roles in saline water conversion processes. TECHNOLOGY: SALINE WATER CONVERSION A number of reviews of methods have been made, principally by staff members of the Office of Saline Water (U.S. Dept. of Interior). Jenkins,31'32 Gillam,34p

Jan 1, 1962

By H. Cecil Spicer

THE results described in this article are based on field work conducted during the periods April-May, 1939, and May-July, 1940. The United States Potash Co. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation was completed under a cooperative arrangement made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an effort was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. EARLIER STUDIES Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedel1 and Messrs. Schlumberger2 reported geophysical work performed in the discovery of the salt domes of Alsace; Carrette and Kelly3described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlumberger5 in a communication. Messrs. Alty6 described studies on salt deposits in which the single-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performed with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 8oo ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,11 through the courtesy of Harry Aurand, of the Midwest Refining Co.

Jan 1, 1941

By E. De Golyer

The only known direct method of discovering oil deposits is by the drilling of test wells. Such exploration is always hazardous and generally very costly. The problem of the prospector, therefore, is one of selecting test sites that are favorably located and so to reduce the odds against his venture. Early in the history of the oil industry, it was realized that oil and gas deposits, other conditions being favor- able, were usually found in anticlinal types of structure. This very understandable and rational habit of occurrence furnished the first substantial clue to the prospector. Oil occurs in sedimentary rocks, and beds of such rocks are deposited originally in parallel planes. An anticline at the surface, therefore, could be accepted as an indication of an anticline in lower beds. Structural geology became the tool of the prospector, and by its use in the past two decades, the majority of the known important oil deposits of the world have been discovered. This is but an incomplete, and the simplest, statement of the problem. Nine-tenths and more of the important oil pools of the world belong to the great class of accumulations controlled by structural traps- anticlines, faulted structures, salt domes, etc.-but by

Jan 1, 1932

By J. B. Stubbins, R. A. Blais

Extensive geological work was initiated — and continues — when operations of the Iron Ore Co. of Canada commenced in the Labrador-New Quebec area. Such geological operations include: mapping, test pitting, drilling, underground workings, volume factor and structure tests, and the calculation of ore grades and tonnages. Details of such work are given. Development is carried sufficiently ahead of mining to provide reliable tonnage and grade estimates and allow final mine planning. In order to make full use of geology in mining operations, the pit engineer combines the duties of geologist and mining engineer. The iron deposits of the Knob Lake range are located in the central part of the Labrador peninsula, a territory nearly twice the size of Texas, which is bounded by Hudson Bay on the west, Hudson Strait on the north, the Atlantic Ocean on the east and the Gulf of St. Lawrence on the south. The mining district proper is about 1000 miles northeast of Toronto. A 360-mile railroad links this mining area to the port of Sept-Iles on the Gulf of St. Lawrence. Schef-ferville, which is only a few miles from the open-pit mines, is the center of operations of the Iron Ore Co. of Canada. It has a population of nearly 5000. The nearest settlement is Labrador City, some 120 miles to the south, where this company is erecting a large plant for beneficiating its huge reserves of local low-grade iron ores. HISTORY The mineral possibilities of the area were recognized as early as the end of the last century, when A.P. LOW' of the Geological Survey of Canada made his famous trek across the Labrador Peninsula. After mapping several belts of iron formation, Lovr recommended that the area be thoroughly prospected for iron. In 1929, two well known Canadian geologists, J.E. Gill and U'.F. James, led a private expedition in central Labrador and discovered the first deposit of high-grade iron ore near what is now the Ruth Lake Mine. In 1936 the Labrador Mining and Exploration Co. was formed to 11ake over a prospecting concession of over 20,000 sq miles in central Labrador. An adjoining concession of 3900 sq miles in New Quebec was obtained in 1942 by Hollinger Consolidated Gold Mines, which had just Purchased the Labrador Co. The same year the M.A. Hanna Co. Purchased an interest in both exploration companies. From 1942 to 1950 extensive exploration was conducted by the Hollinger-Hanna technical staff to systematically appraise these vast concessions. More than 40 deposits of high grade ore were found and, by the end of 1950, the total ore reserves reached 418 million tons. In 1949 five American steel companies joined the Hollinger-Hanna interests and formed the Iron Ore Co. of Canada. Financing and full-scale construction were decided upon in 1950. This included the construction of a 360-mile railroad through very difficult terrain, the erection of two hydroelectric plants, the installation of terminal port facilities at Sept-IIes, the building of a modern town-site at Schefferville, the construction of crushing and screening plants, and the preparation of deposits for mining. Ore was first shipped in July 1954. Total open-pit mine production to date is 66 million long tons of direct-shipping ore. GEOLOGICAL ENGINEERING The above achievements would not have been possible without irtegrated teamwork of people of diverse skills and extensive use of geology. In their paper on the role of geologists in the development of this iron ore field, (Gustafson and Moss1 rightly emphasized the difficulties facing the early workers in the area. In an uninhabited land with no roads or railroads and no navigable rivers leading to the interior, everything had to be flown in. It was not until 1948 that aerial photographs and adequate base maps became available. In spite of these and other difficulties, an impressive amount of field work has been done since 1942. Nearly all this work has been directed by geological engineers and geologists. About 15,000 :sq miles have been geologically

Jan 1, 1962

By Kennedy, Joseph E.

MANY things must be considered in coming to a decision as to what type of crushing and grinding equipment is to be used for preparing run-of-mine ore for concentration, amalgamation, flotation, or cyanidation. This paper is intended in no sense as a thorough discussion of these various factors, but rather contains a few observations based on a wide experience in the manufacture and application of milling machinery. One important governing factor is the tonnage to be dealt with. In large plants treating several thousands of tons in eight hours, a large jaw or gyratory crusher of substantial construction is standard equipment for reducing ore to 8 or 10 in. or finer. In open-pit work, using power shovels with 4- or 5-yd. dippers, a jaw crusher should have a receiving opening of 48 by 60 in., or 60 by 84 in., so that dynamite or hand sledging will not be required for breaking to a finer size before primary crushing. The coarsely broken ore is then conveyed by a belt to vibrating screens, the oversize from which is again conveyed by belts to secondary crushers having openings of 12 or 14 in., the product from which is conveyed to storage. From storage, the material goes to a finishing gyratory for reduction to 1/4 in. or finer.

Jan 1, 1936

By Leslie G. McMillion

A field project to develop and demonstrate a method for alleviating problems of highly mineralized ground water where they occur as isolated zones or pockets in fresh-water aquifers is being conducted in the Ogallala aquifer of eastern New Mexico by the Robert S. Kerr Water Research Center. Removal of contaminated water is by a large-capacity well and the pumped poor-quality water is used locally for secondary recovery of oil. Benefits of the operation are threefold in that the aquifer is being reclaimed for future fresh-water production, contaminated water is being used beneficially, and fresh water which otherwise would have been used for waterflooding is available for other purposes. Ground-water quality in the site has improved markedly after two years of operation. Use of water in the arid and semiarid Southwest has grown so rapidly that demands in many localities far exceed available supplies. In the High Plains region of New Mexico, Oklahoma, and Texas, the only large sources of water are underground reservoirs, being depleted at an alarming rate. In some parts of this region, the aquifers contain pockets of highly mineralized waters; and the mineralized waters in some of them have started spreading in response to the drawdown effects of pumping wells. The aquifers of this region are primarily composed of sand and gravel beds; any cleanup by natural processes will require many tens or even hundreds of years. Most of these pockets of highly mineralized water were caused by oil-field brines seeping downward from earthen disposal pits. Thousands of these pits were in use in the region until only a few years ago when they were prohibited by the oil regulatory agencies of the respective states. The resulting areas of poor quality water are serious enough to warrant much corrective attention. Correction will involve one or more of three approaches: 1) Restrict the pumping of fresh water in the zones where the drawdown of the pumping well will significantly influence the movement of the contaminant. 2) Remove the highly mineralized water entirely from the affected area. 3) Develop and pump the poor-quality water in such a manner that its movement is held in check, even though only a part of the contaminant is actually removed. The principal hurdle to overcome in applying methods 2 or 3 is financing of the operations, since there are very

Jan 1, 1972

By E. S. Anolick, Joseph Singer

The magnetic after-effect, in the form of time decay of permeability (l/µ), has been used to obtain independent data on the solubility of' carbon in pure iron. The results differ slightly from the solubilities obtained through internal -friction experiments. The mechanism of the time decay being the magnetic analogue of internal friction, it appears necessary to explain the observed discrepancies, and some suggestions are made. THE purpose of this work was to establish the reliability of the time decay of permeability as a measure of dissolved interstitial in the body-centered-cubic lattice, and further, to establish techniques suitable for such measurements with samples of a form convenient for various other measurements. This particular sample form was the "epstein" strip, i.e., 25 cm by 3 cm by 0.035 cms. While the general conclusions are not limited by this geometry, there are two aspects of the samples that may be relevant: a) texture, and b) grain size, which ranged generally from 1 to 10 mm. Effects due to these two possible parameters were thought to be small and were not investigated. Calibrating the time decay technique and the other experimental procedures by measuring the solubility of carbon in pure iron suggested itself because of the accumulation of data on this subject through the related technique of the internal friction'; The essentials of this report have been published in a somewhat condensed form.5 Since then some additional data have been taken. It is the purpose of this paper to add these data and to provide more complete description of the experimental techniques than was possible then. The time decay of permeability is a form of the magnetic after-effect.6,7 Permeability is measured immediately after demagnetization (µº) and also long after (µ8). The time decay, ?(l/µ), is the difference 1/µ8 - 1/µ0 and has been considered to be proportional to the concentration of a dissolved interstitial6,8,9,12 The relaxation time! 7, is characteristic of a particular diffusion, and affects the permeability as follows: where he being the activation energy for diffusion of the interstitial. Reference is made to the works of snoek6 and Neel7 for a complete discussion. A brief exposition of the principal ideas may be in order here, as follows. On the basis of the simplest model, resistance against domain wall motion increases with time after demagnetization due to the diffusion of interstitials to preferred sites created by the magnetostrictive tetragonolization under the strong magnetic field. Thus permeability, measured with a small field after the abrupt removal of the large field, will continuously fall with the process of diffusion of the interstitials, and the total "time decay" (or "time decrease") should be proportional to the amount of interstitial in solid solution. In the present report, use is made only of the total time decay rather than of the nature of the progress of the decay; the only problem involved in this approach is the need for assurance that only one interstitial is contributing to the effect as used. It is felt that the special use made here of the total time decay warrants the conclusions. Other work has been going on elsewhere on the detailed study of the nature of the time decay.8'9 EXPERIMENTAL A) Materials—12-lb ingots were made in a vacuum furnace from high-purity iron and by a series of hot and warm reductions were brought down to 14-mil strip. This was cut into 25-cm epsteins. The pure iron was decarburized at 750 °C by hydrogen. The time decay measurement for the decarburized iron (see below) indicated a satisfactorily low starting level of interstitials. Grain growth to grain sizes of 1 to 10 mm was produced in the pure iron by a 700" anneal in hydrogen after a critical reduction of about 7 pct as suggested by previous trials. No measurement of texture in the pure iron was made. The grain size was taken to be large enough to be beyond any sharply critical size regarding solubility. B) Infusion of Carbon—Since the permeability measurement required about two dozen epsteins, a special method of carbon infusion had to be developed to ensure homogeneity of infused carbon. This was accomplished by setting the samples edgewise in a

Jan 1, 1961

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,' and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By W. T. Thom

Many able men have contributed to the subject of coal classification, and recent publications on the subject have indicated a crystallization of opinion in that connection which promises the development in the near future of a scheme of coal classification which will be of real and increasing value to coal producers and users, as well as to those interested in coal on more exclusively scientific grounds. It is obvious that such a classification must be simple; must be based upon readily ascertainable factors; and if properly developed will apply to the whole range of coals between peat and anthracite and not merely to certain types of coal. Many of the numerous schemes of classification proposed in the past have given quite satisfactory results when applied to the higher rank coals, but have broken down when applied to the younger coals of higher moisture, and, as previously pointed out by the writer,' this breakdown has been due to the practice of ruling out "moisture" as an essential component of the volatile matter reported in the customary proximate analysis of coal, whereas a review of the mode of formation and natural history of coal satisfies us that moisture is a normal and natural ingredient among its volatile constituents; and a knowledge of analytical practice shows that the "moisture" and "volatile matter" reported are both mixtures of moisture and volatile matter, rather than sharply differentiated distillation fractions. After an extended consideration of the subject the writer regards the conventional proximate analyses of coals as affording the information essential for a both practically and scientifically satisfactory c1assification—assuming that the coal samples compared have been collected and analyzed according to standard methods. Two variables are required for a workable classification, and these appear to be afforded by the calorific value and proportion of volatile constituents (including moisture) credited to the coal on an ash-free basis. The writer originally proposed that the figures used for classification purposes be those given for the "air-dried" and "ash-free" form of the proximate analysis,

Jan 1, 1930

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By John C. Shyne, Eric R. Morgan

BORON as a hardenability agent of commercial importance has been the subject of extensive study in recent years. It has been suggested in the past that boron increases hardenability by combining with nitrogen, thus rendering it innocuous.&apos; More recently it has been proposed that boron increases hardenability by reducing the free energy of sites of ferrite and pearlite nucleation.&apos; The segregation of boron to grain boundaries, the primary site of nucleation, would account for the large hardenability effect of minute additions of boron in steel. This grain boundary theory has found general acceptance while the concept of boron as a nitrogen scavenger has been disregarded. However, the interaction of boron and nitrogen in steel is considered to be important to hardenability because boron may be made ineffective by combination with nitrogen.". * The present work was undertaken to examine some of the effects of boron and nitrogen arid their interaction in steel. A base composition of moderate hardenability was chosen. This was a 0.35 pct C steel containing 2.50 pct Ni and 0.30 Mo. This composition was used because it contained no strong carbide, nitride, or Table I. Composition of Steels by Analysis, Wt Pct Steel C Ni Mo 0&apos; B N* Base 0.35 2.50 0.30 0.0012 nil <0.0001 Boron 0.35 2.50 0.32 0.0012 0.0022 <0.0001 Nitrogen 0.33 2.60 0.35 0.0015 nll 0.0052 Boron plus nitrogen 0.35 2.48 0.30 0.0006 0.0020 0.0040 * Obtained by vacuum fusion technique. boride-forming elements. The other alloys examined were modifications of the base composition and contained nitrogen, boron, or nitrogen plus boron. The compositions of the four alloys used are listed in Table I. The alloys were vacuum melted from electrolytic iron, electrolytic nickel, ferromolybdenum, and fer-roboron. When required, nitrogen was added by admitting a partial pressure of nitrogen over the melt after vacuum melting. The alloys were cast into 21h-in. diam ingots and hot rolled to %-in. sq bars. No ingot pattern was discernible on the polished and etched cross sections of the hot-rolled bars. The alloys were normalized at 1650°F, then machined into standard %-in. diam end-quench hardenability test bars. Four different austenitizing treatments were used: 60 rnin at 1550°F, 45 rnin at 1800°F, 30 rnin at 2000°F, and 20 rnin at 2000°F followed immediately by 30 rnin at 1550°F. The 1550" and 2000°F treatments were carried out in duplicate for each of the four steels. In order to prevent surface oxidation the bars were austenitized while buried under charcoal in an atmosphere of argon. After quenching the bars in a conventional end-quench fixture, the hardness surveys were made in the usual fashion on parallel flats ground along opposite sides of each bar. These were ground 0.050 in. deep rather than the conventional 0.015 in., to avoid decarburized or deboronized regions.5 The austenite grain sizes which resulted from each heat treatment were observed metallographically using Vilella&apos;s etch for martensite. The criterion used as a measure of hardenability was the distance from the quenched ends of the bars at which a hardness of RC 35 was observed. This hardness represented the inflection point on the hardness vs distance plot. Fig. 1 shows the hardenability of each steel after the several heat treatments. The duplicate tests demonstrated excellent reproducibility; the distance to Rc 35 was reproduced within 1/16 in. for duplicate test bars. All four alloys had the same grain-coarsening characteristics. Neither boron nor nitrogen had any observable effect on grain size. The grain sizes resulting from the various austenitizing treatments were ASTM 7 at 1550°F, ASTM 4 at 1800°F, and ASTM 2 at 2000°F. The small amount of boron in the boron steel greatly enhanced hardenability when the samples were austenitized at 1550°F. The low hardenability of the boron plus nitrogen steel showed that nitrogen eliminated the boron contribution to hardenability. Both steels containing nitrogen, with and without boron, exhibited lower hardenability than the base composition when quenched from 1550°F.

Jan 1, 1958

By John J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these .melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. In the early days, the process was thought of as a simple one. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. Using cryoscopic data, Rolin has determined the following composition for molten cryolite. Na2,AlF 3Na + 3F + AlF [1] He postulates the following equation for the ioniza-tion of alumina at low concentrations Al2O3 Al + AlO2 +O. [2] At concentrations above 0.025M he supposes the ionization of alumina to proceed as follows Al2O3 AlO + AlO2. [3] Rolin&apos;s mechanism of electrolysis for the more concentrated solution in Eq. 3 is as follows. The AlO&apos; ion migrates to the cathode. where it is dis- charged, giving metallic aluminum and 0&apos; ions which migrate to the anode. The AlO2- ion migrates to the anode, where it is discharged, giving Al ions and oxygen which reacts with carbon to form CO2 In the case of the extremely dilute solution in Eq. 2 the Al ion migrates to the cathode and the AlO2-and 0 migrate to the anode as before. Another possible mechanism for the electrolysis follows. Ionization of Cryolite Na3AlF4 = 2Na + 2F + NaAlF, Na + AlF-AlF+Na + F [4] Addition of Alumina 2Na2AlF+ 2AL2O4 6Na + 3A12O3F4 [5a] Al2O2F 2AlOF2 [5b] Cathode Process AlF, + 3e+ 4F + Al. [6] Anode Process AlOF2 + 2F AlF1 + 1/20, + 2e or A12O2F + 4F-2A1F; + 0, + 4e. [7] Although both Rolin&apos;s and the present mechanism of the Hall process may be qualitatively satisfactory, present data are not adequate for quantitative tests of the theories.

Jan 1, 1959

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick&apos;s law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert&apos;s law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick&apos;s Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970