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By C. T. Van Winkle

MINE fires are always dangerous and are frequently accompanied by loss of life during the period of confusion which is apt to follow their discovery. In metal mines, fires may result from the accidental ignition of some combustible material, or they may be of spontaneous origin resulting from the rapid decomposition of sulphide. They occur frequently enough to demonstrate the need of some special equipment and a general plan for controlling them, in addition to measures for their prevention. Nearly all the large copper mines have had fires, and the methods of fighting them have been well described in recent papers, notably-by C. L. Berrien,1 R.. E. Tally,2 and others in discussion. The Copper Queen mine has many shafts, which are connected by underground workings. The deeper parts are ventilated by fans, but in the shallower portions natural ventilation through numerous connecting raises or shafts is sufficient. There have been several fires in the past few years, of which all are extinguished but one, and that is under control. These notes cover particularly the preparations that are being made-to check a new fire, partially or temporarily, and to facilitate the escape of workmen in the interval before a definite plan of fighting it can be established. A fire may occur in a shaft or station, or in some working father away. In case of fire in an upcast shaft, the gas would escape to the surface and the immediate result would probably not be dangerous to workmen, as they could escape by other shafts. In a downcast shaft, however, the gas would be distributed very rapidly throughout a large portion of the mine, and men might easily be trapped and asphyxiated. A fire in mine workings, drift, raise, or stope, would be dangerous in a degree, but the draft there is likely to be less strong than in a shaft and probably a smaller area would be invaded by the fire gases.

Jan 1, 1918

By J. T. Duce

There were no important changes in the producing situation in Colombia in 1930, because the emergency bill passed by the Colombian Congress in 1927 is still in effect, and therefore no change has taken place in the law governing petroleum. At the close of 1930 the Colombian Congress began to consider a new petroleum bill. This measure is an improvement on the preceding bills which had been the subject of so much debate in the Congress. However, it cannot by any means be regarded as perfect, and a number of criticisms may be justly leveled at it. The most substantial one probably is that the royalties on public lands, and the taxes on private lands, while apparently low, are deliverable at seaboard, or payable based on seaboard price at the option of the government. If the government exercises its option to take the oil at the mouth of the well, the cost of the transportation figured back into oil is also deliverable to the government. This phase of the law has the effect of making seemingly low royalties a burden on the operator. The fact that taxes on private properties are deliverable in kind is also an unusual provision for which there is no good precedent. The pipe line provisions are also noteworthy, and the government has authority to fix rates and also to deny permits to construct pipe lines for reasons affecting national economy. There are also clauses enforcing unit operation on both public and private lands, and collecting a tax of 1 c. per 1000 ft. of gas wasted. It remains to be seen whether this bill will be enacted, or whether it will be substantially modified. This much may be said, however, that unless it is modified, it will defeat its own purpose; i. e., promotion of petroleum development in Colombia. Company Activities The South American Gulf Oil Co. shut down its operations during the year, and now employs only watchmen at its camps, Las Monas and El Tigre. The Standard Oil Co. of California continued operations on the Coast at Repelon and Gualapa. At the close of the year Repelon

Jan 1, 1931

Homestake's Bulldog Mountain Operation near Creede, Colorado, in the San Juan Mountains at an elevation of nearly 2,750 m (9,000 ft), is subjected to short summers and long cold winters. Creede’s history dates back to 1889 when silver ore was discovered; and by 1892 production of over a million dollars per month was being shipped from mines located along the Amethyst Fault. The Bulldog Mountain Fault remained relatively untouched by the early prospectors. The United States Geological Survey recognized the potential of this fault in 1960, which led to the staking of many claims over the structure. Homestake leased properties in 1963 and in mid- 1964 a tunnel was started at the 2,956 m (9,700 ft) level with encouraging mineralization being encountered. In 1968 a decision was reached to build a flotation mill of 318 mtpd (350 stpd) capacity. The erection of the mill was completed in early 1969, six years after the first exploration was begun. Since initial start-up, extensive drifting has been done on several separate levels. Two underground hoist installations serve the various levels and many thousand feet of vertical mining operations. Due to the unconsolidated nature of the vein, a new unique underhand cut-and- fill mining method was developed. This procedure is the reverse of the normal cut-and-fill and proceeds from the top down under cemented sand fill, which, while expensive, has greatly reduced s toping hazards. Prior to 1977, a considerable quantity of silver was lost in the slime fraction of the ores processed because of oxidation and other inherent characteristics of individual minerals. Due to Homestakefs favorable experience in treating the slime fraction of the Lead, South Dakota gold ores, experiments with leach methods to recover silver from the slimes by Carbon -In -Pulp offered' the potential for additional silver recovery. Work was begun on the Carbon-In-Pulp plant in April 1976 and completed in December of that year at a cost slightly exceeding $2 million. The C. I. P. plant was designed for 136 mtpd (150 stpd) of current plant slimes plus 227 mtpd (250 stpd) of slimes dredged from the old tailings during the summer season. The sand fraction of the flotation

Jan 1, 1981

By R. Maddin, W. R. Hibbard

A series of X ray experiments conducted by G. I. Taylor' in 1927 and later substantiated in 1939 by J. A. Collins2 both on axially strained aluminum single crystals, revealed evidence that during single slip crystallite rotation occurs in such a manner that " all parts of the material rotated about the transverse direction in the plane of slip."l The actual method of preparing the specimens for X ray examination is not discussed in detail by Taylor except to say that "this specimen was cut parallel to the plane of slip, as calculated from measurements of marks in the surface of the specimen. It was ground and etched till the effect of the new cuts had disappeared. This was verified by applying the same treatment to an un-distorted specimen. The X ray reflectionsl in this case were perfect ones."' Collins, on the other hand, cut his crystals in a mechanical shaper. These surfaces were polished on No. 1, No. 1/0, No. 2/0 and No. 3/0 papers and on a broadcloth lap using No. 600 alundum as a polishing medium. "Finally, the surface was deeply etched in Tucker's reagent. An unde-formed crystal was prepared in the manner described and X rayed to determine whether or not the machining and polishing operations had produced any strain or distortion in the crystal. The Laue spots all seem to be sharp, free from tails and streaks indicating no detectable strains had been introduced in the crystals." Taylor's X ray technique involved the use of "homogeneous X rays from an iron anti-cathode"; whereas Collins used Ka radiation of copper at 31kv and 20 milliamperes. Glancing angle X ray photograms were taken (1) with the axis of rotation of the spectrometer table in the plane of slip and at right angles to the slip direction, and (2) with the axis of the spectrometer table lying along the slip direction. However, eight minute exposures were used in each case and the angle setting of the spectrometer table was increased by one degree for each exposure. With the discovery of the action of three slip systems3 in the plastic deformation of single crystalline alpha brass where, formerly, only one had

Jan 1, 1950

By R. W. Raymond

This name is applied to the present mining law, as enacted in 1872 and since, to indicate its leading characteristic—in which it differs from all previous mining laws of this or any other country. The earlier act, passed in 1866, was practically the first attempt of Congress to deal with the question of mining titles upon the public domain. It was framed after nearly twenty years of acquiescence on the part of the Government in the self-constituted tribunals, officials, rules, and customs of the mining districts. In its recognition of these, and in several other particulars, the act of 1866 was open to serious criticisms. It is the purpose of this paper, not to trace the history of legislation on this subject, or show in detail what were the faults of the earlier law, but rather, by a discussion of certain aspects of the present law, to point out how great a revoluition it has effected in the rights of mining locators, and to indicate some of the difficulties attending its application. In the attempt to correct the vagueness of the act of 1866 an entirely new elernent was introduced into the law, bringing with it a new set of difficulties. Under the act of 1866 and the miners' customs which it followed, the lode was the thing claimed and subsequently acquired by patent. And the claim to a given number of feet on the longitudinal course of the lode was rooted in 'a discovery of any part of the lode in any part of the claim. ("Extensions" could in many districts—perhaps universally—be located and claimed on the strength of the discovery in the principal claim to which they referred; but this is a point not essential to the present discussion.) It was not necessary to find the outcrop or the upper edge of a lode in order to lay a valid location upon it. An explorer, sinking a shaft and intersecting a lode not already discovered and claimed by another, could claim by that discovery the number of feet along that lode which the local laws might permit (not exceeding the maximum set by the United States statute) whether his sur-

Jan 1, 1884

By Thomas A. Wright

No symposium on die casting could be complete without consideration of the methods of formula and impurity control. No consideration of control would be complete without discussion of that new tool of the analytical chemist and inspector, the quartz spectrograph. Just as there is an increased appreciation of the possible applications of the die-casting process and of die castings, so too is there, slowly but surely, of the spectrograph. At present the role of the instrument might well be compared with that of brass or magnesium die castings. Neither is as widely understood or known as they will be. Product specifications are increasing and are getting more explicit and often more rigid. The designer, metallurgist and production engineer or superintendent will be forced to depend more and more on the chemical laboratory. Sampling, as well as analyses, testing and inspection problems will grow. The chemical laboratory must meet its increased responsibility and use of the spectrograph will become more common. Advantages of increased precision, greater speed, lessened labor and often lower costs cannot be ignored. It will be the purpose of this paper in part to outline the respective fields of chemical and spectrographic analyses and to indicate where one may overlap the other and in part to indicate certain possible sources of contamination of zinc-base die-cast alloys in particular. COMPOSITION Aluminum.-Aluminum die castings are expected to conform to the specifications of the American Society for Testing Materials1† and the Society of Automotive Engineers2. The A.S.T.M. has recognized seven

Jan 1, 1935

By F. R. Pyne

The following notes are presented in an endeavor to point out the disadvantages attending the use of chrome brick in reverberatory furnaces in which are conducted the treatment of materials of such a nature that absorption by the brick is of too great value to be wasted, and these values must be recovered, if possible, in order to prevent metal losses that can not be tolerated. Several years ago one of the large Eastern copper refineries decided to utilize basic material in place of siliceous material in the walls of their reverberatory furnaces for the treatment of very foul blister copper, as the latter rapidly corroded the siliceous linings. It was also expected that there would be less slag formation, with a consequent decrease in the cost of treatment and a reduction in the metal losses. Magnesite brick were first used, but while the corrosive action of the foul material was greatly reduced, and the amount of slag formed was very much less, the magnesite proved to be unsatisfactory in certain parts of the furnace, because of its tendency to crack and spall badly when subjected to the alternate heating and cooling that takes place in a reverberatory refining furnace. This made many repairs necessary, and consequent frequent interruption in the operation of the furnace, which, together with the high price of the magnesite brick, ran up the cost of maintenance to an unreasonable amount. It was, therefore, decided to substitute chrome brick for magnesite brick in the parts of the furnace affected. The results, as far as the reverberatory furnace was concerned, were very satisfactory. The corrosion due to the action of the foul blister was small and the amount of slag formed was no greater than when using magnesite, and the tendency to crack and spall shown by the magnesite was eliminated. Gradually the use of chrome brick was extended to all furnaces, those treating blister copper as well as those melting cathodes, and the results were so satisfactory that the siliceous roofs were replaced by roofs of chrome brick except in certain places where experience showed a more satisfactory performance on the part of the silica brick. It was immediately recognized, for both the magnesite and the chrome brick, that the metal absorption was very heavy, but it was felt that the

Jan 1, 1918

By Gordon S. Duncan

The U. S. Geological Survey, I believe, has almost completed a study of the Harney Peak quadrangle, preliminary to the publication of a report on that district. As I was engaged for some months on an investigation of the mode of occurrence of the ore-bearing formation in this area, it has seemed to me timely to make public the results of my study, as a contribution to the consideration of this subject. It seems scarcely necessary to describe the locality and general geology of the Black hills of South Dakota, for since 1846 many have contributed information concerning this region, some of the reports bearing such well-known names as those of Walter P. Jenney, Henry Newton, S. F. Emmons, and C. R. Van Hise, while me have only to glance at Bulletin No. 4 of the South Dakota School of Mines, in which Prof. C. C. O'Harra, of that institution, has given us a bibliography of contributions to the geography and geology of the section, to find that other well-known men have studied the district, and have given us the benefit of their researches. The U. S. Geological Survey has made geological maps of nearly the whole of the Black hills, the only quadrangle yet to be conlpleted being, as stated, the Harney Peak district. During the late summer and autumn of 1910, it was my lot to examine and report on a considerable area in this neighborhood, which once had been prospected, and in some cases exploited, for tin. This paper gives an account of certain geological phenomena, noted at that time, which greatly influenced my conclusions. The predominating formation of the district is pre-Cambrian, represented by a highly-cleaved mica-schist, usually very gar-netiferous, and sometimes hornblendic. Rising like an island from the surrounding schist is a large mass of granite, known as

Jan 1, 1913

By H. E. Cline, D. F. Stein

A fine lamellar structure with interlamellar spacings ranging from 0.I to 3.7 was Woduced by high-speed directional solidification and used to study the interaction of dislocations with an array of bimetallic bound-am.es. The tensile flow properties were measured at elevated temperatures and the results interpreted in terms of an image force model. As the width of the plates decreases the strength increases according to a Hall-Petch relation, suggesting pile -ups. Considerable strengthening was also observed at elevated temperatures. In recent years composites containing a strong but brittle phase and a ductile but weak phase have been studied extensively in the search for a high-strength material with adequate ductility.' However, the strength of these composites has been limited to a volumetric average of the strengths of the component phases. In this paper we will show that a composite made by directional solidification of a Cu-Ag eutectic has strength properties that substantially exceed the strength of either of the metals in the composite, and an explanation for this increased strength will be presented. The Cu-Ag eutectic is a near ideal material to study for several reasons. The eutectic structure is made up of alternate plates of silver-rich and copper-rich phases with the same crystal structure.2'3 In addition, the mechanical and elastic properties of silver4 and copper5 are known over a wide range of temperatures and the eutectic microstructure is stable to nearly the melting point.6'7 Therefore, the properties of the eu-tectic are readily comparable to various theories involving the mechanical properties of copper and silver. The experiments consisted of producing directionally solidified Ag-Cu eutectic material, determining the structure and performing tensile tests at different temperatures and strain rates. EXPERIMENTAL A) Solidification and structure. A cylindrical ingot 2.2 cm in diam and 15 cm long was prepared from 99.999 pct pure materials and cast in argon. The ingot was placed in an alumina crucible and was direc-tionally solidified at 7 x 10"4 cm per sec in a Bridg-man apparatus in argon. Metallographic examination at both ends and along the length of the ingot showed a uniform structure that consisted of fine alternate plates of silver- and copper-rich phases. The plates were aligned parallel to the growth direction, as shown in the longitudinal section, Fig. 1, and were in small randomly oriented domains of parallel plates as viewed in a transverse section, Fig. 2. Four smaller ingots 0.175 in. in diam were solidified at speeds of 2Xlo-', 4.4 xlo-', 4.4 x 10-3, and4.4x10-4 cm per sec to produce a range of lamellar spacings. Replica electron micrographs were taken to resolve the individual plates as shown in Fig. 3. The copper-and silver-rich plates in the larger ingot were about

Jan 1, 1970

By B. B. Cox

Iraq, formerly called Mesopotamia in Asiatic Turkey, became a kingdom under British Mandate after the world war and is expected to gain its independence in 1932 when it enters the League of Nations. The kingdom is shown on Fig. 1 in its relations to neighboring countries, to the Mediterranean Sea and to the Persian Gulf. It is slightly smaller than the State of Texas with its capitol, Baghdad, inland about as far from the Persian Gulf as Breckinridge, Tex., is from the Houston Shipping Channel. The oil fields lie 180 to 225 miles north of Baghdad, or about as far as from Breckinridge to Oklahoma City, and about as far from the Mediterranean as Fort Worth is from Hobbs, N. M. A narrow-gage railway runs from Basra, the Persian Gulf port, to Baghdad. From there another narrow-gage runs into the Kurdish hills east of the Tigris to Kirkuk. A standard-gage, part of the old Berlin-Baghdad system, follows the west bank of the Tigris northward from Baghdad to Baiji, a village about 100 miles south of Mosul. No railway exists between Iraq and the Mediterranean, though the Anatolian Railways in southern Turkey come to within 50 miles of the Iraq frontier and 120 miles of Mosul. Surveys have been completed for a railway through British Mandates from Haifa to Baghdad as well as for a railway through French Mandated Syria from Tripoli to Abu Kemal near the Iraq border. Wagon roads, excepting those constructed by the oil companies, are few and indifferent in Iraq and no road exists across the desert to the Mediterranean, but contrary to prevalent beliefs the surface is firm and free from sand dunes so that motor cars can go almost anywhere in dry weather, with ease. Frequent motor car and airplane service exists between Baghdad and the Mediterranean ports and motor car service may be had between Kirkuk and Nisibin, Turkey, where on two days each week through Wagons Lits service is available to Paris. Baghdad is about 21 days distant from New York City with present transport facilities. The climate is semiarid, similar to Imperial Valley, California, the average rainfall outside the mountainous parts amounting generally to

Jan 1, 1932

By M. T. Worley

This paper reports investigative work conducted to develop a method of estimating the groundwater influx from a homogeneous permeable formation into a vertical mine shaft during sinking. A method of analysis was developed using data obtained from pumping tests and a modification of the Theis non-equilibrium interpretation technique. Excess influx of groundwater into mine shafts has long been one of the more important problems encountered in the development of a mining property. Much work has been done on methods of preventing such influx and on pumping schemes to control inflow if preventive measures fail. The fundamental aspects of the problem, on the other hand, seem to have been neglected. The purpose of this paper is to review the fundamentals of groundwater flow and to propose a rapid method of analyzing hydrologic data in order to estimate influx from a homogeneous permeable formation into a mine shaft. Such an estimate of the quantity of water to be encountered is of value in planning grouting, pumping and other programs designed to control that influx. It is emphasized that the proposed method of analysis should be regarded only as a tool to be used in evaluating the problem before investing the capital necessary to begin development of a property. FUNDAMENTALS OF GROUNDWATER FLOW In order to effectively approach the problem of estimating influx into a mine shaft, a knowledge of the fundamentals of fluid flow through a porous medium is necessary. Darcy, in 1856, developed an empirical relationship to explain the flow of water through sand filters. This relationship V = k (dh/dl), is the basis for all other flow formulae. It has been shown that Darcy's relation is a solution of the Laplace equation and thus is analagous to other natural phenomena such as heat flow. Theis, using the analogy of heat flow by conduction, developed an expression for determining the transient or time-dependent groundwater flow through a homogeneous, isotropic medium. The resulting equation Was also derived by Jacob using hydrologic considerations alone.' The individual terms in the equation are described in Table I. It is important to understand the assumptions upon which this equation is based. 1) The medium through which the fluid flows is infinite in areal extent, homogeneous and isotropic. 2) The well into which the fluid discharges completely penetrates the medium. 3) The characteristics of the medium remain constant at all times. 4) The initial pressure surface is horizontal. 5) The confining media are impervious and horizontal. 6) Fluid is removed from storage instantaneously by a decline in pressure. 7) The diameter of the discharge well is infinitesimal with respect to the drainage radius of the medium.

Jan 1, 1962

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By Samuel Hoyt

THE hardness of annealed copper has been given in the literature and is easily obtained by any of the standard methods of hardness testing. It is not our intention to correct published values or to add to them, but to describe tests of two bars of annealed electrolytic copper in which the methods of Meyer's analysis were employed. MEYER'S ANALYSIS OF BALL INDENTATION TEST The ball indentation test is probably the most valuable hardness test we now have but, as it is carried out in the Brinell or Rockwell test, the result may be seriously in error without the operator suspecting such to be the case. This condition results from the isolated and uncontrolled nature of the measurement. The accuracy depends on the accuracy of the equipment and the care and skill used in the operations; there is nothing in the impression diameter, which is all that is measured, to indicate the presence of error. Meyer's analysis supplies a control of the measurements that goes far toward eliminating unsuspected errors. The principles of this work maybe obtained from elsewhere.1 As this subject has not received the attention of this Institute, it may be well to summarize the more important points as follows.

Jan 2, 1926

By B. H. Cody

The Morenci concentrator of the Phelps Dodge Corporation is a part of the project that was completed after five years had been spent in development of the open-pit mine, equipment and process testing in the former No. 6 concentrator, and construction of the reduction works. The reduction works, of which the concentrator is a part, is about a mile and a quarter southeast of Morenci, on the highway that leads up Morenci Canyon. The concentrator has a nominal capacity for the treatment of 45,000 tons of ore daily. The original plant, which has a rated capacity of 25,000 tons of ore daily and is now in its fifth year of operation, began production on Jan. 30, 1942. The addition, to increase the capacity 80 pct, began operation on Dec. I, 1943. The equipment of the original plant has been described in Mining and Metallurgy (May 1942). NO changes in equipment were recommended for installation in the concentrator extension and only one major change, forced by a shortage of maintenance labor, has since been made. Metallurgical treatment has been altered in some ways as experiments progressed and as labor and economic conditions dictated. No complete description of the operation of the concentrator has been published, so this paper will record such operating and equipment changes as have been necessary, the operating methods that have been developed and the metallurgical results that have been obtained. Descriptions are given in the order of the processes with a flowsheet and an equipment list of each process for convenient reference. The questions asked by engineer visitors have guided the detail in which operation and maintenance are described. During the period Jan. 30, 1942 to Sept. I, 1946, ore milled has totaled 43,595,253 dry tons, from which 1,643,885 tons of concentrate have been made, containing an indicated production of 783,164,-809 lb of copper. The principal results obtained in operation of the concentrator during the years 1942 to 1945, inclusive, and to Sept. I, 1946 are shown in Table I. A graphic general flowsheet of the plant is given in Fig I. Ore The Morenci ore that is now being treated is a medium-hard monzonite porphyry in which the principal sulphide minerals are chalcocite and pyrite. A minor amount of covellite is present. Chalcopyrite and bornite have been observed under the microscope. The chalcocite occurs mainly as a coating on pyrite. Some of the coatings are so thick that the pyrite presents the appearance of being an inclusion in chalcocite. Some are less than one micron thick and are barely visible at 500 diameters magnification of a polished cross section. Some chalcocite is present as a in in the gangue. Various oxidized copper minerals are present as a result of oxidation in place but they represent a minor proportion of the copper minerals of the ore body. Oxidation

Jan 1, 1949

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By R. W. Gurry

WHEN a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. EXPERIMENTAL PROCEDURE Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;1 it suffices to state here that the carburization lasted about 140 hr. at 760°C. (1760°F.) and 44 hr. at 1110°C. (2030°F.), these periods being long enough-on the basis of the calculations presented later-to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941