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By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

Beverley S. Randolph, Frostburg, Md. (communication to the Secretary): It has always appeared to me that each coalseam has its peculiar character or habit, due to the conditions of its formation, by virtue of which it is either persistent or variable in its section over extended areas. One seam will hold its thickness, chemical character, number and position of partings, beds of slate, etc., over a large area, while another will be found to vary in some of these characteristics every few feet. As the position of the outcrop is an accident of the topography, depending on folding and erosion which have taken place since the bed was formed, no one opening in the outcrop, or, in fact, anywhere else, can supply reliable evidence as to the general character of the seam. To determine the character of an untried seam, a number of sections are necessary from widely separated points, in order to show such variations as may exist. Should material variations be developed, more numerous sections are necessary, in

Jan 1, 1901

By Ernst F. Eurich

(Cleveland Meeting, October, 1912.) ALEXANDER PARKES patented in England in 1851-52-53 a process for desilvering lead by means of zinc, making use of the greater affinity of silver for zinc than for lead, discovered by Karsten in 1842. The efforts in England to develop it commercially were not particularly successful, nor was the attempted introduction into the United States. This last was not surprising, as it was about the beginning of our Civil War, and at that period there was very little lead-bullion produced in the united States and there was no field for the process here. There was at that time on Staten Island an establishment that pattisonized lead, probably from Rossie, N. Y., and Chester, Pa., and possibly some Spanish lead, but the production of lead-bullion in the Far West had not yet begun. In 1864, Edward Balbach, of Newark, N. J., patented in this country a process for desilvering lead by means of zinc, and in 1867 Edward Balbach, Jr., patented a " movable black-lead retort with a neck, placed in a furnace," for the purpose of distilling the alloy of zinc, lead, and the precious metals. A brief comparison of the Parkes and the Balbach processes is interesting. The Parkes process as practiced in England consisted in stirring into silver-bearing lead, melted in a kettle, from 1 to 2 per cent. of zinc, cooling, skimming the alloy of lead, zinc, and silver that rose to the surface, liquating it in an iron retort, distilling the residual rich alloy in fire-clay retorts, thus regaining the zinc, and refining the desilvered lead at a low heat in a shallow cast-iron pan that formed the hearth of a reverberatory furnace. If the lead was too impure, it was first softened * Presented also at the Joint Meeting of the Institute and Section IIIa, Metal¬lurgy and Mining, of the Eighth International Congress of Applied Chemistry, New York, September, 1919, and here published by mutual agreement.

Dec 1, 1912

By G. R. Gardner, D. H. Davis

INCREASING realization of the importance of dust control, and the recommendations of various agencies, have led the mining industry to become actively concerned with this problem. The background and necessity for adequate dust-suppression measures have been discussed in a number of publications, including those of the U. S. Bureau of Mines, and the use of spray water to reduce dust at the face and on roadways has been recommended. The problem resolves itself into obtaining adequate dust reduction at a reasonable cost. Inasmuch as the term "adequate dust suppression" has never been clearly defined, nor have permissible limits of dustiness (in terms of dust count) been established, it is apparent that any method selected may be required to meet additional demands. Until the industry has been given some indication of permissible limits of dustiness, no permanent solution is possible. Progress will be somewhat handicapped until such information is available. In addition, dust reduction must be obtained without the addition of any excessive moisture to the coal, since consideration must often be given to: I. Quality standards, particularly reduction in heat value. 2. Handling characteristics, particularly in regard to unloading from railroad cars and bins. 3. Application of dry methods of coal cleaning. 4. Necessity for fine screening within specified limits of oversize and undersize. Little detailed information is available as to the advantages and disadvantages of the several methods of water distribution, the location and protection of sprays, operating data on pressure, quantity of water, and so forth, and results obtained. In 1940 an investigation was undertaken to determine and evaluate the principal factors involved. This paper constitutes a progress report on this work and cannot in any way be regarded as complete on any one of the several phases. CLASSIFICATION OF DUST SOURCES The various sources of underground dust may be classified as primary or secondary. A primary source is one associated with appreciable degradation of size, that is, where the greater part of the actual fines capable of becoming air-borne dust are produced. A secondary source may be considered as one in which the greater part of the fines have been produced at some previous operation and are in such condition that they can be dispersed as air-borne dust. These conceptions appear to be of practical significance, as experience indicates that when dust is controlled at the primary sources the importance of secondary sources is minimized. For these reasons, investigations to date have been concerned principally with the primary sources of dust, and this paper is concerned particularly with one of these-namely, undercutting. In accord with the foregoing definitions, the sources to which the following opera-

Jan 1, 1942

By E. D. Gardner

FIFTY years ago the Utah Copper enterprise at Bingham was just getting under way. An epic in metal mining was in the making. Throughout the West the bonanza deposits were approaching exhaustion and most ore still went direct to smelter. But concentrators were shortly to be constructed for treating milling grade ores, and most important, the pilot plant for the Utah Copper enterprise was being built that year at the mouth of Bingham Canyon. The same decade was to see development at the Inspiration mine in Arizona of the most important new mining method for 50 years to come—undercut block caving. Although the average grade of ore being mined has been declining for 50 years, and wage rates and prices of supplies have been greatly increased, the mining industry has continued to grow and to prosper. Technology has advanced to a point where minerals can be mined under the most severe conditions. The hardest rock can be drilled and broken and the heaviest ground handled. Large or small, an ore-body can be mined successfully, at any desired rate of production. It is possible to pump great volumes of water and to ventilate the most extensive workings; air conditioning has made practicable the mining of ore where the rock temperatures are beyond those that can be borne by man. Mining today in the U. S. is a huge earth-moving operation. In 1953 nearly 2 billion tons of material were mined for direct use or for processing. Stripping at open-cut mines totaled about 1.7 billion cu yd. Table I gives relative tonnages of the branches of the mineral industry in 1953. In addition to the solid materials moved, 350 million tons of petroleum and 340,000 tons of gas were produced in 1953. Fifteen million tons of salt and 5 million tons of liquid sulphur were pumped from wells. An appreciable amount of copper was recovered by leaching old mine workings and dumps. Total value of minerals produced in 1953 was $14.4 billion: oil and gas $7.6 billion, coal $2.6 billion, nonmetallics $2.4 billion, and metals $1.8 billion. Formidable problems face some branches of the industry today, especially pertaining to increased output tons per manshift. The time has come when these problems should be reappraised. With current wage rates, the industry no longer can afford to pay men to do manual labor. It should be recognized, also, that the miner is a skilled worker; efforts to promote the dignity of his calling and his pride of accomplishment have yielded beneficial results. Mineral deposits occur under widely varying conditions. In most instances the degree of support needed by the roof and walls is the deciding factor in selection of an underground mining method. The degree of support needed, in turn, is governed by natural physical characteristics of the ore and its enclosing rocks. Mine operators, of course, learn to judge ground by observation, and an experienced mine boss generally can anticipate what will happen following any given mining operation. A more scientific approach, however, would be advantageous in most cases. More should be known about the strength of the ore and the enclosing rocks, more about stresses set up in the ground when ore is removed, and more about the mechanics of moving ground. Better understanding would work both ways: first, favorable rock conditions could be fully utilized for more efficient mining, and second, hazards of rock falls could be minimized, loss of ore in mining reduced, and expenses caused by ground pressures and subsidence lowered. In general, mining comprises breaking the ore or rock in place, supporting the mine workings, and transporting the ore to the surface. This latter is a materials handling problem. Ventilation, of course, must be provided, and the mines must be kept free of water. Development work at some places is the most important cost item in extracting ore. Drilling and blasting remain the usual practice for breaking ore or rock from place except, of course, at block-caving mines. The drilling and blasting practice at a mine must fit the mining method. In laying out mining procedures attention is being given to

Jan 1, 1956

By W. C. Knopf, G. Samsel

For several years International Minerals & Chem-ical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large-scale plants. Natural potassium is composed of three isotopes —K, K and K. Five other isotopes, artificially produced, have been detected. In natural potassium only the K isotope, with a half life of 1.4x10 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes. Barnes and Salley' measured radiation of potassium salts in solution in 1943. Gaudin and Parnell2 first reported the use of solid salts arranged in a vessel surrounding the ß counter in 1948. Later, Scheel used the method to assay potassium content of various crude and finished potash salts. Experimental: Dip-type Geiger-Muller tubes (TGC-5) supplied by Tracerlab Co. were used in all radiation counting measurements. The tube was encompassed by a glass container about M in. larger in diameter than the tube. This container, which served as a sample holder, was closed at the bottom with a rubber stopper to facilitate removing the samples. Samples were not weighed, but about 40 g of sample were needed for each test. Electrical impulses from the tube were counted on either a Tracerlab scaler or a rate meter. To obviate the need for constant attendance, preset features were incorporated into the scalers, so that at a predetermined time or count the units were automatically deactivated. When rate meters were used, counting rates were read directly from instrument or from a recorder used in conjunction with the rate meter. Each tube was calibrated, according to the manufacturer's instructions, to determine the correct operating voltage to insure reproducible results. A linear calibration plot of percent K2O vs counting rate was also obtained for each tube by recording the counting rate plus background count of several standards of different K2O content chemically analyzed by the chloroplatinate method.' These standards were of approximately the same particle size distribution as samples to be assayed. Specific background count caused by cosmic rays and other surrounding radiation was checked periodically by counting a sample of pure NaCl. Fig. 1 is a representative calibration plot. Assays were determined directly from the standard plot or calculated by subtracting the background count from the counting rate, then multiplying by the slope of the line. Chemical assays of the test samples were made by the Sherril method," a flame photometric technique, or the chloroplatinate method. Data: The radiation assay method has been used for three years by International Minerals & Chemical Corp. in the laboratory and in pilot plants processing ores containing potassium. These dry concentration plants process sylvinite and langbeinite ores at Carlsbad, N. M., and feldspar ores at Top-sham, Maine. Sylvinite ore is predominantly a mixture of syl-vite (impure KCl) and halite (impure NaCl). Contaminants include sulfates, such as langbeinite (2MgSO - K2SO4), kieserite (MgSO H2O), poly-halite (MgSO4.K2SO, 2CaSO, . 2H2O), and slimes. Langbeinite ore is predominantly langbeinite and halite with small amounts of sylvite, sulfates other than langbeinite, and slimes. Several variables, in addition to correct calibration and standardization of tubes, were found to be important in obtaining reproducible results. Particle size distribution of standard samples should be

Jan 1, 1959

We would like to thank Mr. Mandolesi for his informative paper on rails from strand cast steel. The chemical and structural properties of the strand cast steel were of particular interest to us. We would like to supplement his excellent report with some of Inland's findings from our Caster with submerged nozzles and strands reduced in line from 7" x 7" to 5-5/8" square cross section. Inland has conducted extensive segregation studies on AISI 1049 steel - Fine Grain 0.50% carbon and 0.75% manganese. Based on approximately 80 heats, our normal segregation pattern results in analyses of .49% carbon in the center, and 0.50% carbon at the midway and edge position. The sulfur analysis averages .025% in the center, .027% midway, and .026% at the edge. Note the slight negative segregation between the center and midway position. This steel, being lower carbon and probably cast nearer the liquidus, resulted in less segregation than the 0.80% carbon rail steel.

Jan 1, 1972

By Milton Williams

A comparison is made between the amount of interstitial water found by analysis in cores and that estimated from the resistivity curve of the electric log for the corresponding strata of producing reservoirs. It is shown that while the determined and the estimated water saturations are in good agreement in some cases, this agreement may be due to a fortuitous compensation of errors. Estimates of water saturations made from the electric 1og by use of existing relations should, therefore, be employed with caution. Also presented are data on the variation of salinity of interstitial waters in reservoir sands, and on the effect of variation of salinity and porosity on the validity of estimates of water content made from the electric log. INTRODUCTION Throughout the history of electric logging there have been recurrent cycles of optimism and pessimism as to the value of the electric log in the quantitative estimation of reservoir fluid content. The very early days of electric logging were an optimistic period, in which there was widespread faith in the ability of the resistivity curve to reflect fluid content, and in the ability of the potential curve to indicate textural characteristics. In time the accumulation of exceptions to this idealistic behavior brought about a general disillusionment, and caused the more pessimistic of those dealing with electric logs to believe that the sole importance of the log lay in stratigraphic correlation. Within the last several years optimism as to the quantitative use of the electric log has been revived, primarily as the result of the stimulating work of C. E. Archie' on the estimation of interstitial water in sands from resistivity data. Even though the general trend of thought on the quantitative value of the electric log reflects optimism, it is inevitable that there are some widely divergent opinions of the validity of quantitative estimates based on the electric log. A valid method of estimation of fluid content by means of the electric log and a general knowledge of the textural character of the reservoir rock would be of signal importance, not only in that it would save time and money in securing information on reservoirs now being drilled, but also because it would permit the evaluation of reserves in many fields drilled without adequate core data subsequent to the advent of electric logging. Because of this importance, Humble's Production Research Division, in cooperation with various other company divisions, initiated several years ago series of tests designed to evaluate the reliability of estimates of fluid content made from the electric log. The investigation was limited at the outset to sand reservoirs, since it was felt that the inclusion of limestone reservoirs would entail needless complications. In devising these tests it was immediately apparent that the chief difficulty in evaluating the worth of any method of estimation lay in establishing the true value of fluid content. The results of direct analyses of cores cut with ordinary mud were not sufficient, because of the probability of contamination of the fluids by filtrate from the drilling mud; the results of restored state tests on cores were deemed unsuitable because these results can hardly be said to furnish a primary standard. The method adopted was the direct analysis of cores cut with an oil-base drilling fluid. Such cores, when properly handled, are believed to afford the most precise determination of water content available at the present, and, in addition, lend themselves readily to the determination of various other properties which are pertinent to the estimation of fluid content from the electric log. Since it was desired to compare the fluid contents estimated from the electric log run in ordinary mud with cores cut in the same hole, the use of oil-base fluid necessitated the changing over, after all cores were cut, to a conventional mud. This procedure presented several advantages, one of which was that the use of oil-base fluid permitted

Jan 1, 1950

By Hugh J. Leach, J. C. Van de Water

In open pit mining, as in other industries, it has I become necessary to improve operating efficiency in order to combat higher labor and supply costs. Moreover, orebodies are becoming leaner, pits are getting deeper, stripping ratios are increasing, and hauls are getting longer. There has been a steady increase in size, speed of operation, and reliability of the various machines involved in breaking, loading, and hauling ore. Changes have seldom been radical but are rather the result of steady improvement. Drilling: Notable advances have been made in the use of rotary drills and air powered percussion drills for blasthole drilling. Several hundred of these machines are now in use as replacements for churn drills in softer rocks such as limestone and shale. Their application to hard rocks such as iron ore and taconite is under current investigation, but in the Lake Superior iron mining district, open pit blast-hole drilling in ore has been accomplished almost exclusively by standard churn drilling. The only recent advance has been the use of larger machines drilling 9-in. holes. This has increased drilling speed somewhat and allowed wider hole spacing, with consequent cost reduction.

Feb 1, 1956

By Thomas Robins

About six years ago the writer had occasion to visit a large magnetic iron-ore concentrating-plant, and then saw for the first time rubber belts employed for conveying-purposes. These belts were from 20 inches to 30 inches in width, and some of them were as long as 500 feet between centers. When I spoke of the enormous amount of material they handled with a small expenditure of power, the superintendent assented, but at the same time complained that although he bought the best quality of belts, the abrasion of the ore wore them out very rapidly, causing continually very large bills for repairs and renewals. On close examination several interesting points were discovered :

Jan 1, 1897

By Samuel M. Brock

In recent years society has become increasingly concerned with maintaining and improving the quality of environment. Thus, public interest and concern with pollution problems is now high. This is reflected in recent federal and state efforts to formulate new legislation to prevent pollution and strengthen existing pollution laws. In reviewing literature pertaining to pollution problems, it is possible to distinguish many common elements. The most outstanding of these is the failure of the market to guarantee that private firms responding to price signals generated in the marketplace will make decisions leading to optimal resource use. Cases of market failure in allocating natural resources according to the wants of society frequently are due to the presence of technical externalities, or side-use effects.59 These roughly and generally can be defined as interdependencies among production and consumption units, the impacts of which are exerted other than through the market. They are, in other words, extra-market relationships. The economic unit generating external effects does not take them into account in decision-making. Thus, the tendency is for the unit to produce either more than society desires or not enough. In such cases society often has intervened in the decision-making process. This intervention frequently has taken the form of legislation to regulate production and consumption activities. Thus, a body of institutions, which acts as a constraint in decision-making processes, has materialized. These institutions are often far more influential in their effect upon resource use than are the forces of supply and demand acting in the marketplace. The problem of environmental pollution is essentially the problem of handling residuals which are the byproduct of all production and consumption activities which take place in the economy.2 These residuals are emitted into the air and water and disposed of on the land. They are interrelated, in that efforts to control emissions into the air or water can result in the production of solid wastes, which then present disposal problems. It is convenient to separate residuals by the type of pollution they cause-air, water, and land while remembering that these problems are related and that solutions may require coordinated effort.1 Residuals may be produced in both production processes and consumption. Residuals produced in production by the mineral industry, or firms utilizing its products, range from emission of sulfur dioxide by steam generating plants to radioactive mill tailings produced in the course of mining uranium.. Residuals associated with consumption are generated mainly through transportation of members of the household, space heating, and in the disposal of solid wastes, including refuse and junk autos. Residuals associated with both production and consumption receive attention in ensuing sections of this chapter.

Jan 1, 1976

By Augustus Locke

WHY should I, a geologist, be coming before you to talk about finding ore? Certainly, the great discoveries of the past have not been made by geologists, but by men of very different tastes and training. If, in the year 1800, the course of ore discovery could have been foreseen, there would have been no reason to put it into the hands of geologists or other men of technical preparation. It was not geologists but explorers, Indian fighters, prospectors, manual laborers, and hardy financiers, who initiated the American mining industry. Then why this association of geological technique with ore finding? Why this feeling that the way to find ore is to apply to the problem what we call geo- logical principles? Well, to put it broadly, the old method has run out on us. It no longer works. Or, to put it another way, the cost of finding ore by the old method has mounted so high that one old district after another has become, practically speaking, dead, and various other old districts that are still going apparently at full strength are actually beginning to limp, and, with the cost of discovery mounting yearly, to fear, more than they will acknowledge, that the end is approaching.

Jan 1, 1926

William P. Blake, TUCSON, Ariz. (communication to the Secretary): As one who in youth, now nearly half a century ago, had the privilege of participating in the initial explorations which have alreacly resulted, within a single lifetime, in the establishment and Development of a vast continental empire, so well described by Dr. Douglas, I may be permitted to supplement with some additional details the comprehensive sketch given in his paper. Before the War Department, in 1853, sent out the Pacific railroad exploring parties, Fremont had already made his memorable expeditions, exploring the Great Basin and the passes into California; Sitgreaves had traversed, from east to west, the Zuni and Moqui country; and, still later, Emory had examined the region along the boundary-line between the United States and Mexico. The services of these pioneers deserve to be mentioned in even an outline of the history of continental development. Concerning the five practicable railroad-routes, suggested in the Reports of Explorations aid Surveys," etc., as published

Jan 1, 1900

By Claus Goetzel

THE object of this investigation was to determine whether silver alloys could be used instead of the currently employed insert of high-expansion AVERAGE COEFFICIENT PER DE G. C. OVEN RANGE 20° To 200° C. Pure aluminum '31.6 X 10-6 Cast low-expansion Si-Cu-Ni-Al piston alloy 20.0 X 10-6 High-expansion austenitic Cu-Ni cast iron 19.3 X 10-6 Cast steel (0.25-0.35 C, 0.10-1.0 Mn) 12.6 X 10-6 Cast iron (3.15 total C, 2.16 Si) 12.8 X 10-6 Pure silver 18.9 X 10-6 austenitic ferronickel alloy, to reduce the wear of ring grooves in light metal pistons. A typical example of a piston containing a ferronickel insert is shown in Fig. 1. The high coefficient of expansion of silver made it worthy of consideration, while the small size of the insert would render it use feasible in Germany as an emergency in is- tire. The coefficients of linear expansion of several metals and alloys are as shown in the table above. Obviously the melting point of the insert must be high enough to prevent it from melting when the light alloy is cast around it. This imposes a lower limit of about 850° C. for the solidus of the silver alloy. Pure silver melts at about 961° C., so that the Fin. 1.-PISTON CONTAINING tolerable depression in the solidus is rather FERRONICKEL INSERT. small. To avoid deformation of the insert during use a Brinell hardness number of at least 60 appears necessary.

Jan 1, 1937

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By Chikao Nishiwaki

INTRODUCTION The Japanese dependency for mineral raw materials from foreign sources increased rapidly within the 20 years since the Korean war. During this 20 year period Japan has attempted to industrialize and develop her economy while depending mostly on heavy import of nearly all kinds of mineral raw materials. She has fabricated them using energy generated mostly by mineral fuel that are also imported. Fabricated goods are either used domestically to accelerate more fabrication industry or exported after adding more refinement or fabrication. In this paper iron ore as a major raw material for the Iron and Steel industry, three major base metals, copper, zinc and lead, and petroleum as a major energy source have been selected as examples to represent the general features of various kinds of mineral raw materials that are imported. Among other important mineral commodities for which Japan dependa upon foreign sources are: Aluminium, nickel and cobalt, potash and phosphorous 100 percent dependent and tin, tungusten, chromium and molybdenum over 95 percent dependent. IRON ORE Statistics for the important iron and steel raw materials, namely iron ore, coal and scrap iron are shown in Tables 1, 2 and Fig. 1. Iron ore is by far the most important and basic among these three commodities. There has been practically no steel or iron imported as a metal into Japan during this period. Iron ore, including aggregate such as pellets, and metallurgical coal are mostly transported in large ore cargo boats to the port where very efficient port facilities unload them directly at the steel mill site. As a result

Jan 1, 1976

By Harry K. Ihrig

THE hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1/8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was, necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes Co. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.11 The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 DESCRIPTION OF TEST METHOD The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1945

By J. W. Ristori, V. R. Garfias, R. V. Whetshel

During the past eight years, in trying to estimate world consumption of petroleum and related products, the authors have been unable to account for all the supplies available in any one year. There has remained at all times a balance, which at first was thought to represent almost entirely additions to stocks in foreign countries. But as this discrepancy continued year after year-over 148,000,000 bbl. in 1937—it became unreasonable to conclude that corresponding additional foreign storage capacity was continuously being made available. It became therefore clear that the balance in question was due to other causes than to additions to stocks. Last year Mr. A. G. White, Chief Economist of the Petroleum Economics Division of the United States Bureau of Mines, pointed out to one of the authors that an unknown and important factor in consumption of petroleum and related products is to be found in the requirements for military purposes in foreign countries. This paper is the result of Mr. White's timely suggestion. There are no reliable data available either on the storage capacity, and therefore oil stocks, or on the petroleum consumption for military purposes in foreign countries. This information is so closely related to national defense that its divulgation is forbidden. One can therefore but surmise as to these facilities and needs in line with the relative strength of the military land, air and sea forces of the various countries. The authors have assumed many of the component factors that go to make the tables herein presented, such as fuel consumption of fighting ships in relation to tonnage and horsepower, gasoline consumption of air fleets in relation to number of planes, and the consumption of petroleum products by mechanized armies; but in making these assumptions they have availed themselves of the advice and counsel of those whose wide experience in these questions make their views authoritative. The opportunities for error in an estimate of this nature are obvious and ever present; to illustrate: The air fleets in Spain no doubt consumed

Jan 1, 1938

By Roy G. Mead

BECAUSE of its magnitude, and the type of occurrence, the deposit of boron minerals in the Kramer district, Kern County, California, is unlike any other in the world. Discovery of this vast deposit has brought about many changes in the borax industry, so a discussion of the geology, and the occurrence, would not be complete without a brief history of the development of the borax industry. Until the discovery of boron minerals in the desert regions of California and Nevada some seventy years ago, borax was imported from Tibet and India, principally for medicinal purposes, at almost prohibitive prices. Following the discovery of commercial deposits of boron minerals in California and Nevada, and the subsequent development of new uses for borax and boric acid, the consumption has steadily increased until today borax is used in some form or other in every household.

Jan 1, 1933

By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967