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By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By James Terry Duce

Production of oil in Bahrein for the war years was as follows: YEAR BBL PER YEAR Prior to 1939 . . . . . . . . . . . . . . 22,287,055 1939 . . . . . . . . . . . . . . . . . . . . . . 7,588,554 1940 . . . . . . . . . . . . . . . . . . . . . . 7,073,919 1941 . . . . . . . . . . . . . . . . . . . . . . 6,794,157 1942 . . . . . . . . . . . . . . . . . . . . . . 6,240,627 1943 . . . . . . . . . . . . . . . . . . . . . . 6,571,609 1944 . . . . . . . . . . . . . . . . . . . . . . 6,713,795 1945 . . . . . . . . . . . . . . . . . . . . . . 7,308,938 Total to Jan. 1, 1946 . . . . . . . . 70,578,654

Jan 1, 1946

By C. R. St. John, R. W. Lindsay, Charles R. Austin

Many of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys.l,2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)= and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650" to IOOO °F. as a consequence of additions of 0.40 to 0.60 per cent of this element in carbon steels of the order of 0.25 to 0.35 per cent carbon content. Babcock and Wilcox Tube CO.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or I per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to1000°F. 4

Jan 1, 1945

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

WHEN one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed' that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others.2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between , phase layers formed by diffusion, in the Cu-Zn system, § and furnishes further evidence in support of the principle. MATERIALS AND METHODS The Cu-Zn system is especially suitable for these studies since the high vapor pressure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals-and with various loads, then the plates were annealed for .4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold worked layers from the finished crystals

Jan 1, 1944

By O. W. Walvoord

A Definition: An ore feeder is a mechanical device that, by virtue of its motion, causes ore to be supplied or carried forward at a desired metered rate to other milling equipment. From the viewpoint of economics there can be little question, even for small tonnage operations, as to the advisability of using mechanical feeders in the place of manual labor. Only a few short years ago, it was common practice to employ crusher men for the feeding of crushers, thus eliminating the capital expenditures required for mechanical feeding equipment. Having been a crusher man in several instances, the author does not favor such practice. The high cost of labor today eliminates the crusher man, and feeders become an economical capital expenditure when considered against the importance of obtaining maximum production efficiency from all the machines in a process flowsheet.

Jan 2, 1955

HE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given composition and quality. In comparison with other steelmaking methods, the basic open-hearth process is one of the most versa- tile, both from the standpoint of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. With some types of liquid-metal charges, the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO). This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SiO2) , manganese oxide (MnO), iron oxides (FeO and Fe2O3), and phosphorus oxide (P2O5) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course

Jan 1, 1951

By Francis H. Crockard

DURING the past five years we have probably witnessed greater technological advances than in any similar period. Industry and science have steadily marched ahead. The makers of iron and steel products have watched with great interest the development of stream-lined trains, faster and safer airplanes, the entirely new science of air-conditioning and the widespread use of stainless steels. Since 1930, we have witnessed the erection of the world's largest suspension bridge, the largest and fastest ocean liner and the spectacular Boulder Dam, while even greater things are planned in these particular fields. Other industries, too, have been moving ahead rapidly. This advance in a few years has been caused primarily by the fierce competition of the depression. Now, more than ever, is the emphasis placed upon quality and service. Makers of southern merchant pig iron have been no exception and have been confronted with increasingly strict chemical specifications and with much greater stress on physical characteristics than ever before. For example, sulfur in the iron must be held very low, competition demanding that it be in the 0.020's and low 0.030's; silicon content must be held within a very narrow range, and definite requirements of phosphorus and manganese are an essential part of the specifications. Physical characteristics are becoming of increasingly greater importance. The introduction of triple-skimmed, slow-cooled iron several years ago was the first step in this direction. Now there are a few customers who buy iron by chemical analysis and physical appearance, having found that the analysis alone is an insufficient guide to their requirements.

Jan 1, 1935

By William Schriever

The flow of a gas-free liquid through a spherical-grain sand has been investigated by S1ichter.l By theoretical considerations involving a rather large number of approximations he arrives at the following flow-formula: V = CPd2At NLB{1 - m) where V is the volume of liquid delivered in time t through a cylindrical column of sand of length L and cross-sectional area A by a pressure-drop P when the sand grains of diameter d are packed to a porosity m and the coefficient of viscosity of the liquid is n. C and B are constants which were determined from geometrical relations; B was in reality a function of . Values of B(l — m) for various values of m were given in a table. In the same Annual Report of the U. S. Geological Survey, King reported the results of his experiments on the flow of water through porous media. He found that there was a departure of about 86 per cent. from a linear relationship between rate of flow and pressure, for a specimen of Dunnville sandstone for pressure drops not exceeding 60 cm. of mercury. The specimen was approximately 4 cm. in diameter and 5.1 cm. in length. Over the same range of pressure he found a departure of 45 per cent. for a specimen of Madison sandstone. For unconsolidated sands he found departures as great as 49 per cent. for pressure drops of 70 cm. of mercury; for pressure drops not exceeding a few inches of water he obtained a close approximation to a linear relation. He also investi-

Jan 1, 1930

By Arthur Phillips

The progress made in recent years in the art of dispersion-hardening has naturally led to an intensive study of alloy systems capable of yielding supersaturated solid solutions at ordinary temperatures. In general, the investigations have been confined to rather precise determinations of solubility limits and to experimental approaches designed to furnish more complete information regarding the rate and nature of precipitation under appropriate thermal conditions. Efforts are being made to focus more sharply on the atomic changes that are a direct consequence of the instability of the supersaturated solution. Here precision X-ray methods have come to be of considerable importance because lattice parameter measurements indicate very precisely the concentration of solute atoms in the solvent lattice. In spite of the general acceptance of parameter values as a criterion for the placing of solubility limits, it may be suggested that no thorough appraisal has been made of the several factors that conceivably may affect such measurements. More specifically, little attention has been devoted to the significance of surface energy conditions, specimen size and method of preparation, with particular regard to the genesis of the grains and the surface concentration changes as a consequence of heat treatment and etching. Stenzel and Weertsl recently published the results of a detailed study of precipitation reactions in aluminum-rich copper alloys. They found that, although copper lowers the lattice constant of aluminum, a 5 per cent copper alloy quenched from 150" and 225' C. had parameter values unquestionably higher than that of pure aluminum. Their results seem to substantiate, at least qualitatively, the earlier work of von Göler and Sachs,2 who indicated a parameter value, for the same alloy annealed for 24 hr. at 200° C., some 0.0008Å. larger than that of pure aluminum. Stenzel and Weerts attributed the abnormal lattice dimension to the effect of strain induced by the precipitation of CuA12. Weerts3 later

Jan 1, 1934

By Eugene McAuliffe

The management of The Union Pacific Coal Co., which operates a group of coal mines in Southern Wyoming, believes in the value of applied psychology as a productive factor in the work of getting out coal. Operating almost wholly through the medium of mechanical loading machinery, the company has for some years paid a bonus, equivalent to one-half the labor saving made above a determined average output per shift worked, on a given machine. No penalty is attached where the established output is not obtained, but in 1933 the men on one class of machines earned an average premium of $0.633 per shift on 56.4 per cent of the tonnage loaded. On another class of machine, the men earned an average premium of $0.686 per shift on 28.4 per cent of the tonnage loaded An increase of 36 per cent in tons loaded per man-shift has resulted since the program was instituted. This coal company has also been very successful in reducing mine accidents through prizes awarded in an unusual way. At the close of the year, every man whose particular mine section passes through the year without a lost-time accident is given a ticket entitling him to participate in a safety drawing where an automobile is awarded as first prim.. There are also a number of cash safety prizes which are similarly awarded. Some 1500 persons attend the drawing, which excites much interest and attention. The particular plan employed, the payment of production bonus awards and safety prizes, is foundationed upon collective. rather than individual effort, and, once gotten under way, has proved to be substantlally self-cnforcing.

Jan 1, 1934

By David S. Cahn

Pilot-plant and laboratory tests were made on blends of steel plant flue dust and portland cement to determine whether the flue dust could be pelletized for use as a source of iron in dry process cement manufacture. Strength and setting time results showed that an acceptable agglomerate can be made with a Type II portland cement binder. Abrasion-resistant and well-sized pellets were made in a horizontal drum, using a simulated closed circuit, with a binder content of 7.5% and a moisture content below 15%. Pellet quality was found to be relatively insensitive to changes in binder concentration above 5%. Simulations of stockpiling and weathering indicate that little difficulty would be encountered with use of the flue dust pellets in cement plants.

Jan 1, 1972

By Geo. H. Ashley

THE year 1923 saw a decline in the production of crude oil and a strong advance in the production of natural gas. The production of petroleum in Pennsylvania has been remarkably uniform for many years, but with a slight average decline. Until 1918, production was maintained above 7,500,000 bbl. Four of the six years from 1918 to 1923, inclusive, saw a yield of between 7,400,000 and 7,500,000 bbl.; 1923 gave only 7,253,000 bbl. The production of natural gas in Pennsylvania has been variable, reaching a maximum of 138,000,000,000 cu. ft. in 1906 and nearly reaching that figure again in 1907 and 1917. In 1921 production dropped to 86,000,000,000 cu. ft., and it seemed that a rapid decline had set in. Prices were raised by most of the gas companies, and -these raises sustained by the Public Service Commission. Possibly as a result of this and the better prices realized, drilling in the gas fields has been active. The year 1923 has not been prolific in large oil wells. The largest single well was drilled by the Manufacturers Light & Heat Co. on the William Auld farm near Prosperity, Morris township, Washington County. This well started at 225 bbl, but quickly dropped to 60 bbl. A 100-bbl. well was struck in September in Springhill township, Greene County. Three wells in the Tidioute pool started at 50 bbl. or better, and a well near the 28th Ward, Pittsburgh, came in at 60 bbl. One well in Washington County started at 50 bbl., but all of the other wells started at less than 20 bbl. The Tidioute pool, which was the sensation of 1922, had by Jan. 1, 1923, dropped in daily total production to 1430 bbl., by Feb. 1 to 1040 bbl., and by May 1 to 700 bbl. At that time, most of the wells were still flowing naturally, though, as the gas pressure was rapidly decreasing, it was not anticipated that such a flow would long continue. As the wells in this pool started at from 500 to. 800 bbl.. a day, it is evident how rapidly they fell off. In August, 1922, the average production per well per day was 44 bbl. ; in February, 1923, 4 bbl.

Jan 3, 1924

By Wilbur Nelson

ALL of our accounts of the discovery of copper ore at Ducktown, Tenn., state that the discovery was made in August, 1843, yet it would appear that samples of copper from this district were found by the Spanish explorer, DeSoto, when he wandered into Southern Tennessee, in 1539, in his four years of exploration through the Southern States. The following quotation is taken from his diary: "Towards the north there was a province named Chisca; and that there was a melting of copper, and of another metall of the same colour, save that it was finer, and of a farre more perfect colour, and farre better to the sight, and that they used it not so much, because it was softer. And the selfe same thing was told the governor in Cutifa-Chiqui, where we saw some little hatchets of copper, which were said to have a mixture of gold. But in that part of the country it was not well peopled; and they said there were mountains, which the horses could not passe; and for that cause, the governor would not goe from Cutifa-Chiqui directly quicker." DeSoto sent two of his company to try to find these mines, but after five days' wandering through the mountains they returned, stating that their guides had become lost. Although the Ducktown area may have been known to the ancient Indians, it was not until August, 1843, when a Mr. Lemmons, who was panning for gold on Potato Creek, in the Ducktown basin, found some reddish-brown decomposed rock, which he supposed to be gold, that the copper deposits were actually discovered. His disgust on finding that this yellow metal. was not gold was so great that he did not. try to develop his find. In March, 1847, B. C. Dugger erected an iron forge at this same place, but was unable to work the iron as it contained so much copper that on cooling it would break to pieces. The finding of copper in the iron ore by Mr. Dugger led to further explorations; and in April, of the same year, A. J. Weaver, who was passing through that country, told the people that the black rocks they had dug out were rich copper ore. Mr. Weaver began the first mining in this district.

Jan 10, 1924

By Thomas Chance

ALL gravity methods for the separation of ore from gangue, or of slate and other refuse from coal, are based upon differences in the falling velocities, in some fluid medium such as air or water, of the materials to be separated. As all materials falling in a vacuum have the same velocity, independent of the size, shape, weight or specific gravity of their individual particles, it would be more accurate to describe the operation of these methods as depending upon the. retardation of falling velocities effected by the resistance of a fluid medium, this retardation being greater for small or light particles than for large or heavy particles. This generalization is true also of those appliances utilizing centrifugal force to replace or to supplement the action of gravity. The separation of materials of different specific gravities by means of a fluid having a specific gravity greater than that of the lighter particles and less than that of the heavier particles has not been applied commercially, or on a large scale, to the separation of ores or to the washing of coal, the method being limited to laboratory experimental work or to laboratory determinations for the purpose of checking up the work of jigs, classifiers, and other types of concentrating appliances. A solution of zinc chloride has thus come into general use inn the laboratory to separate coal, bony coal and slate, both to check up the work of coal-washing plants and for the purpose of making tests preliminary to the designing of coal-washing plants. The use of a heavy solution of some chemical in water has often been proposed for making such separations, especially in connection with the washing or preparation of coal. Practically insuperable difficulties, however, have prevented the commercial development of any such process, the difficulties being both physical and financial. The cost of the chemical used to make high-gravity solutions is usually prohibitive, and the freeing of the coal from all traces of the chemical is found to be practically impossible. Such solutions inevitably penetrate the individual lumps and particles of coal, transfusing into the pores and saturating the joint-planes, and very large quantities of wash water

Jan 2, 1918

THERE has been a lot of talk about the shortage of engineers and we have done our share of it; but recently we heard a spot radio commercial-between broadcasts-urging high school seniors to study engineering. We think this is going too far. Engineering is an exacting profession requiring the highest personal qualifications. Publicity for the purpose of interesting capable young people in choosing courses in engineering should emphasize qualification. The opportunities for a career in a great constructive profession which is the basis of our high standard of living should be properly evaluated. Although there is a need for more engineers today, nobody knows what the employment potential is going to be four years hence. The profession may do itself a grave disservice by attempting mass recruitment in the face of an unpredictable national economy. The mining and metals industries are in a special position as fewer engineers are needed in these fields. Only 10 pct of all engineers are mining and metallurgical engineers. Today's shortage is not so much in recent graduates, but in trained practicing engineers. The shortage has served the profession to good effect because it directed the talents of engineers into more productive channels. In some areas high school graduates have been put into routine jobs such as, surveying. If there is one thing the mining profession does not want, it is an oversupply of graduates which would relegate college men to years of work and discouragement in routine jobs. The public has a clear cut picture of the legal and medical professions and thus the respect knowledge imparts. But the engineer is variously thought of as a man who pulls the throttle lever on a locomotive, tends a furnace, or builds a bridge. The term engineer is too loosely used. For instance we have heard of "crowd engineers" and "exterminating engineers." In some unions an engineer designation has been established to describe a person doing routine checking or other control job. We do not disparage these positions but they are different from the work done by the man qualified by years of experience and study. Many of these so-called engineers are not engineers at all. The engineering profession has cooperated closely on a program of recruiting high school graduates for engineering study. It should start a cooperative public relations program to enlighten the public on the accomplishments and work of engineers. This type of publicity need not be of the bombastic type. It can be educational and dignified. Radio, television, and the periodicals can be used to convey information. It is time that laymen and interested young people learn to make a distinction between the true engineer and the technician. Such a program would instruct parents and high school students and thereby interest the right type of people in the engineering profession. The Centennial of Engineering sponsored by the American Society of Civil Engineers is a step in the direction of instructive public relations. This fine start should not be allowed to remain as a one pass venture. The engineering profession as a whole should follow this exposition with a sustained, well directed effort to inform the public of the engineer's work and the possibilities it holds for a constructive career.

Jan 1, 1952

GOVERNMENT ESTABLISHES DIVISION OF ENGINEERING Government supervision of employment for technical men has been inaugurated by the United States Employment Service, through the establishment of a Division of Engineering, with A. H. Krom, of Chicago, formerly Secretary of the American Association of Engineers, as Director. War demands on the engineering profession have already caused a serious shortage of men with mechanical designing experience and those with practical experience in chemical engineering. At present the professional organizing mediums reach less than 20 per cent. of the estimated 300,000 technical men in the country. This is not a satisfactory arrangement for war times. All the technical men of the country must be reached and, in addition, all men with technical experience must be carefully registered so that they will be immediately available. The advantages of such a governmental registering and systematizing of employment will be apparent at once, to the engineer. Considering that this is principally an engineer's war, the importance of Federal direction of distribution and conservation of the technical service of the country is apparent. The Service will he started through the office of the Director of Engineering, 29 S. LaSalle St., Chicago. All technical men desiring to register for emergency Government work or permanent advancement in positions meeting their qualifications, are urged to volunteer at once for registration, classification and employment.

Jan 8, 1918

By Vito J. Colangelo

The primary object of this study was to determine the effect of ferrite and its orientation upon the mechanical properties of a precipitation -hardening stainless steel with particular attention to the short-transverse properties. The investigation consisted of Jour major parts : the preliminary investigation of billet properties, the effect of forging reduction and ferrite content upon mechanical properties, the effect of notch orientation upon impact strength, and the relationship of heat composition to ferrite content. Low ductility and impact strength in the short transverse direction were found to he associated with the orientation and shape of- the ferrite plates. It was also determined that impact strength varied with notch orientation. The test values obtained with the notch perpendicular to the plane of the ferrite plate were lower than those obtained in the notch-parallel condition. The over-all investigation showed that high ferrite contents in general had a deleterious effect upon mechanical properties and that the ferrite content could he minimized by exercising rigorous control of the heat composition. A careful balance of elements, nitrogen in particular, must he maintained in order to reduce the formation of ferrite. THE precipitation-hardening stainless steels were developed to fulfill a need for high-strength corrosion-resistant alloys. In the annealed condition they are soft and ductile and possess many of the desirable characteristics of the austenitic stainless steels. In the hardened condition, the alloys exhibit the high strength and hardness of the martensitic stainless steels. The alloy under consideration in this investigation has a nominal composition as follows: C Mn Si Cr Ni Mo N 0.13 0.95 0.25 15.50 4.30 2.75 0.10 The hardening mechanism is identical to that of other hardenable steels in that it depends upon the transformation of austenite to martensite. This alloy because of its annealed structure and its ability to be hardened combines the desirable forming and corrosion properties of the austenitic grades with the high hardness and strength levels attainable with the hardenable grades. The reason for this apparent duplicity of proper- ties can be explained by considering a basic metallurgical difference between the hardenable stainless steels and those of the austenitic group. Both types are austenitic at 1800°F but, while the martensitic grades transform to martensite upon rapid cooling to room temperature, the austenitic grades remain austenitic even when cooled to temperatures below room temperature. The major difference then is in the degree of austenite stability. This stability can quantitatively be described by the Ms temperature. The Ms is defined as that temperature at which austenite begins to transform to martensite. The austenitic grades for example may be cooled to -300°F without producing significant quantities of martensite. The hardenable stainless steels on the other hand have an Ms temperature in the vicinity of 400" to 700°F. In cooling to room temperature, these alloys traverse the entire Ms-Mf range and show almost complete transformation to martensite. The semiaustenitic stainless steel, however, occupies an intermediate position with respect to its austenite stability. The analysis is so balanced that the Ills temperature lies at or slightly above room temperature. The resulting alloy retains much of its austenite at room temperature and yet responds to hardening heat treatments. Achieving this delicate balance of elements is therefore of great importance. Slight imbalances of the equivalent Cr-Ni ratios frequently result in the presence of 6 ferrite. It is the effects of this ferrit with which we are concerned, more specifically the effect of the quantity and ferrite orientation upon mechanical properties, particularly ductility. PROCEDURE A) Preliminary Investigation of Billet and Forging Properties. In order to determine the effect of ferrite on billet properties, billet stock from three heats with various ferrite contents was utilized. Tensile specimens were obtained in the transverse and longitudinal directions from this material and heat-treated as shown in Tables I and 11. Forgings were made from these same heats, the purpose being to determine what effect, if any, the ferrite might have upon the mechanical properties. These forgings were made in such a manner as to elongate the ferrite in the longitudinal and transverse directions. The method of forging was as follows. A section was cut from a 6-in.-sq billet of Heat A and flat-forged to 1-1/2 in. thick. Working was done from one direction only with no edging passes as shown

Jan 1, 1965

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

(The paper by L. H. De Wald-Tech. Pub. No. 429 was presented at the Boston meeting, September, 1931.) W. A. SCHEUCH, Chicago, Ill.-Since starting up our Hawthorne copper wire plant we have found that wire bars from certain suppliers perform quite differently from those of other suppliers. In attempting to evaluate these bars, we made cross-sections, and in making these cross-sections we found considerable variation in the crystal structure. Indications were that there was some preference in the type of crystal structure. In attempting to find the reason for that we discussed it with the various producers and-also reviewed the literature. Mr. DeWald was assigned to determine the various factors that enter into copper wire bar crystal structure, on the basis that the product was a horizontally cast wire bar of practically identical composition and of recognized good composition for the present quality product sold in the market. Mr. DeWald has asked me to say that he should have made reference to Mr. Dalzell's paper on a theory concerning gases in refined copper. D. K. CRAMPTON, Marion, Conn. (written discussion).-Mr. DeWald has set forth an interesting and thorough exposition of the factors controlling macrostructure of this material. It is particularly interesting to us as it somewhat parallels work we have done on macrostructure of round copper billets for piercing into tubes. Our findings as to the effect of the several variables on macrostructure check Mr. DeWald's. The general principles underlying the two are precisely the same. The fact that we worked with copper deoxidized with phosphorous instead of tough-pitch copper, and round billets cast on end instead of wire bars, does not influence the results. We have found that round billets cast so as to produce large radial grains have greater soundness and density than those with a fine macrostructure. Further, and more important, we have found that the billets with large radial grains show markedly different performance on piercing from those having a fine equiaxed structure. With a given temperature of billet and adjustment of piercing machine, the coarse-grained material requires appreciably lower power for piercing and goes through the operation inn appreciably less time. These two differences are of sufficient commercial importance to warrant exercise of great care in maintaining the coarse structure. It seems probable that much the same phenomenon should hold in the hot rolling of tough-pitch wire bars. We would expect that, other things being equal, the coarse-grained wire bars would roll more readily and require less power than fine-grained ones. Moreover, we believe the differences in initial structure of the wire bars should be largely eliminated in the hot rolling process and during the subsequent drawing and annealing, of wire would be entirely eradicated.

Jan 1, 1932

By C. A. Rowland, R. C. Nealey

Wet grinding rod mills have been used for 50 years to grind ores and to make specification sand. The application of wet grinding rod mills is well understood. Until recently, there have been very few installations of dry grinding rod mills. The selection of dry grinding rod mills follows the basic principles established for the selection of wet grinding rod mills. The basic Bond Formulae1 [ ] is used to select mills when using grindability test results as the basis for selection. W is multi- plied by the 1.3 wet to dry grinding factor established from wet and dry ball milling experience, and then by any other applicable inefficiency factors.1 Dry grinding rod mills have also been selected by scaling up bench scale continuous rod mill tests and pilot plant tests.

Jan 12, 1968