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By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world's leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,' Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By Harry Power

THE relative merits of air and natural gas as propulsive agents in pressure drive operations have been discussed for a number of years. When air or gas is introduced into the sand, various factors lead the operator to the selection of what he believes to be the proper propelling medium; but when the question of relative drive effect is raised, several physical and chemical premises must be taken into consideration in arriving at a conclusion as to the superiority of one medium over the other. Dow and Calkins1 and Beecher and Parkhurst2 have contributed fundamental experimental work on the effect of dissolved gas in lowering the viscosity and surface tension of crude oil. Herold3 and Tickell4 have indicated that whatever type of reservoir control obtains, gas plays other important parts in the movement of oil towards the well, namely: 1. The propulsive and expansive force of the gas. 2. The "Jamin effect," or resistance to the movement of oil in a porous media due to the formation of gas bubbles. When quantitative studies are made, parallel conditions must be selected whereby we may say definitely whether air is superior to gas as a driving medium, or vice versa. Examples of similar conditions are not easy to find in the field. However, in the laboratory we can make determinations which may lead to general conclusions when applied to the field. The- experimental and research work described here was started at the laboratories of the University of California in January, 1927, and completed in private laboratories at Tulsa, Okla., in February, 1928. The apparatus used was designed especially for the work.

Jan 1, 1928

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By AIME AIME

ON April 7 the twentieth national Open-hearth Conference of the A.I.M.E. will be held in Birming¬ham, Ala., in conjunction with a meeting of the Committee on Blast Furnaces and Raw Materials. At least 300 engineers and operators are expected to attend. Birmingham, the industrial city and iron, and steel center of the South, has been called the "Magic City." Men actively engaged in business in Birmingham today have seen practically every building in the business district erected, have witnessed the establishment of every existing industry, and have hunted birds cm the site now one of the busiest corners of the business district. Incorporated as a town in 1871, the city today has a population of more than 380,000 in its metropolitan area. It is

Jan 1, 1937

By Eugene W. Pearson

In a marked departure from conventional practice, the Power Plate process combines the two unit operations of leaching and electrowinning into a single continuous step for direct recovery of copper from sulfide concentrates, cement copper, copper scrap, and copper oxide slurries. Considering how environmental controls are pre- venting development of smelters for additional capacity or new construction, the Power Plate process provides a welcome pollution-free alternative to the smelting-electrorefining routes. And its low capital investment and low operating costs also recommend it to copper producers who are now using or investigating various hydrometallurgical methods.

Jan 12, 1974

By J. A. Stachura

Continuous mining machinery provides the coal industry with one way to compete for a larger share of the total energy market. Various types of machines are discussed and some of the problems with continuous miners, encountered by operators, are reviewed. Equipment manufacturers are working with mine personnel to provide solutions for problems that arise. While coal production over the past 25 or 30 years has been on a horizontal plane, coal's share of the total energy market has declined. To participate more effectively in this total energy market, it is necessary to produce coal more efficiently. It is the obligation of all management, employes, and mining departments to gear the deep mining industry to the rapid progress and changing of today's modern industry. This can be accomplished in the near future with the selection of the proper type of continuous miner best suited to each operator's individual situation. In most mining operations there is tremendous incentive to undertake the continuous mining program. It can reduce the size of the mine greatly by permitting a minimum of working places; it makes pillar recovery work more efficient from the standpoint of overall cost, amount of coal recovered, and safety. The work force can be reduced materially permitting closer and more efficient supervision. It simplifies maintenance because equipment can be more readily standardized. The trend of the coal market favors the use of continuous mining machines. Although there appears to be a general feeling that continuous mining is still a relatively new program and will be slow in replacing conventional mechanical equipment, the fact is that tremendous strides have been made since the first machines were installed in 1948. This program is advancing at approximately the same rate that mobile loading machines replaced hand loading. From 1948 to 1955 there were approximately 450 continuous mining machines in service. In October 1959, a survey revealed that there were more than 700 continuous mining machines in service. Many operators have expressed a desire to undertake this program, but they feel that they could not do so at this time because of one or more of the following reasons: 1) the thickness of their coal seams, 2) seam characteristics, 3) soft bottoms, 4) bad roof conditions, 5) size consist, 6) insufficient flexibility in machines, 7) difficult ventilation problems, and 8) high maintenance costs. With the realization on coal about the same today as it was in 1948, or slightly less and since coal is still failing to participate to a greater degree in the total energy market, it is not surprising that the coal industry is desperately exploring more economical methods for deep mining. The manufacturers are aware that the coal industry is willing to invest in continuous miners if the equipment is built for maximum flexibility, will produce higher tons per man, and assure long life between overhaul programs. CONTINUOUS MINING MACHINES Before discussing details regarding the selection of a continuous miner, let us have a preview of some of the continuous mining machines which are available to the coal industry today. Jeffrey Manufacturing Co.: The machine shown is the Jeffrey 76 A.M. Colmol. This is their most widely used miner, and has been particularly successful in central Pennsylvania and in high-wall mining in western Kentucky. One of the outstanding features of this auger-type miner is its portability. The entire mining range can be changed from its lowest point to the maximum height without stopping the mining operation. Jeffrey 76 B.M. Colmol: This machine is similar to the 76 A.M. model; however, it is built bigger and stronger for a mining range of 50 1/2 to 72 in. This is the model that is now available (Fig. 2). Jeffrey has added two arms to the top row, omitted the odd arm in the bottom row, thus permitting a 50 pct larger throat opening. This eliminates one

Jan 1, 1961

By Leo Brewer, Gerd M. Rosenblatt

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At

Jan 1, 1962

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By Giovanni Barla

In engineering analyses, rock is frequently treated as a homogeneous, isotropic, and linearly elastic medium. However, rock material exhibits, in most cases, physical nonlinearity, time-dependency, and anisotropy. In some instances, anelasticity due to nonmechanical effects, such as density and temperature changes, must also be taken into account. The influence of these different anomalies in the physical behavior of a rock material is often neglected. An estimate of the discrepancies which are introduced when classical theory of elasticity is used is consequently required. The easiest theoretical path by which these discrepancies can be analyzed is to vary the constitutive equations of the rock material. The constitutive equations, representing various physical experiences with different types of media, define a class of ideal substances. Assuming different constitutive equations for the description of the rock physical behavior, one can establish a sensitivity analysis to determine how much information is contained in elastic theory for reliable design purposes. The method may be applied also using numerical techniques (e.g., finite element or finite differences) which, because of the nature of the formulation, require one to assume in each case the rock constitutive equations. Theoretical and experimental work is needed to be able to perform such analyses with confidence. Adequate and practical procedures for the determination of the material functions which enter the various constitutive equations must be established. This paper presents such an attempt with respect to the simulation of some behavior patterns of rock material. It is felt worthwhile to stimulate activity in this field and it is hoped to contribute to this objective.

Jan 1, 1970

By M. D. Flavel

The paper describes the physical aspects of the compression and impact crusher types along with the information needed to apply, install and operate them to best achieve designed performance levels. It reviews key performance parameters such as energy size relationships for crushing processes and how automation devices can optimize machine productivity. Weaknesses of existing application engineering methods are discussed. The use of pilot plant information and appropriate laboratory testing procedures are reviewed from the point of view of the application design engineer so that the best type of machine can be selected for a proposed installation.

Jan 1, 1982

By D. W. Jessup

ONLY during the past few years, have the old-fashioned methods for treating ores and byproducts progressed to any marked degree. The advent of multiple-hearth roasting, blast roasting, the baghouse, and the Cottrell plant indicate this change. It is the ability to roast and smelt sulfide ores and concentrates that gave this later advance. Further investigations that will solve the problem of efficient handling of flotation concentrates and their attendant ills are of the utmost importance. With future developments, the metallurgist will be able to smelt more economically and to treat still more refractory ores, making the early methods appear small by comparison. GROWTH OF SMELTING Well within the memory of pioneer smeltermen, the ore was charged directly into the blast furnace as it came from the mine;, only the richer, ores were smelted, the lower grade and sulfide ores were undesirable. Matte was, at first, thrown away and only two products) were desired-slag and lead bullion. Scores of the early smelting companies failed because of improper reduction of ores, high costs, short- furnace campaigns, inability to treat sulfide ores, and ores containing-zinc. With the failure of weaker companies, consolidation eliminated many others, until today the field is dominated by a comparatively few organizations, each strong financially. Formerly, a few thousand dollars would erect a small plant, whereas the modern smelter costs over a million dollars. Ore and products to which formerly no attention was paid are now treated with comparative ease and at a good profit. Mechanical improvements have modernized smelting, furnace tonnages show an increase, and metal recoveries have made enormous strides. Even though costs have decreased, they have not dropped in proportion to the improvements, because of the higher wages, greater costs of fluxes and coke, more undesirable ores smelted, etc.

Jan 8, 1925

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

By P. H. Mell

AMONG the minerals exhibited at the Atlanta Exhibition of 1881, soapstone, kaolin, and asbestos were well represented. The first two occur in large quantities, of very pure quality, throughout the South. The last is somewhat limited in amount, get in certain localities it exists in masses sufficiently large to pay for working; in North Carolina, Georgia, and Alabama it has ken mined with some profit. I would, in this paper, call special attention to the minerals soapstone and kaolin, because their many valuable qualities seem to have been almost entirely overlooked by our Southern manufacturers. Steatite, particularly, occurs in such large quantities, and generally in such close proximity to the great iron regions of Alabama and Georgia, that it is anlazing that the iron companies will persist in sending abroad under heavy expense for firebrick. It would require a much smaller sum of money to quarry this rock and place it at the various furnaces ; and the results obtained, I am sure, would prove its superiority over the majority of firebrick brought into this region. Soapstone, as well as kaolin, is found throughout the metamorphic regions of Alabama, Georgia, South Carolina, and North Carolina. Below will be found seven analyses that I have made of this mineral, taken from various points in the four States above mentioned. I have also subjected these same specimens to severe fire-tests, and the results were very satisfactory. The tests mere canducted in the following manner: Small portions of the compact variety were carefully weighed and placed in a Fletcher's new crucible furnace for gas, and subjected for half an hour to a heat that will in 12 minutes fuse iron. The only effect upon these specimens was a slight change in color to a darker shade, a small loss in weight, due evidently to the evaporation of water, and, in one or two specimens, a slight degree of fusion on the sharp edges. The first specimen subjected to investigation was taken from a large outcropping in Tallapoosa County, Alabama. Specific gravity, 2.88 ; hardness, 1.9; color, blue gray. Composition: Water,....2.68 Silica,..........65.48 Iron oxide,.........2.10 Alumina,.........15.02 Magnesia,... 15.35 10061

Jan 1, 1882

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By S. A. Herres, A. R. Elsea

Temper brittleness refers to the loss in the notched-bar impact resistance encountered in most medium- or low-alloy steels when they are tempered within the temperature range of 700 to ll00°F or slowly cooled from a higher tempering temperature. Temper brittleness is important because it impairs the service properties of otherwise suitable steels over the range of hardnesses obtained at medium tempering temperatures and because it is impractical to cool pieces of large section rapidly enough from higher tempering temperatures to prevent temper brittleness. The problem of temper brittleness has always been closely associated with ordnance manufacture because armor plate and gun steels require good shock resistance and are often heat treated in heavy section. However, it is now realized that many brittle failures in structural alloy steel parts are attributable to temper brittleness, and there is little question that it contributes to the low impact resistance of alloy steels used in the hot-rolled or normalized condition which are slowly cooled from the hot-rolling or normalizing temperature. Recently Hollomonl has presented a comprehensive summary of the literature on the subject and an excellent description of the manner in which temper brittleness affects the notched-bar impact resistance and other mechanical properties of steel. Carpenter and Robertson2 have given a good analysis of the probable mechanism of temper brittleness, which is similar in many respects to the precipitation-hardening phenomenon. Fig 1 is their diagram illustrating the response to tempering of a susceptible steel. Three changes are recognized as the temperature of tempering a previously quenched steel is raised: (1) pre- cipitation occurs more rapidly and to a greater extent and the notched-bar impact value falls to a minimum; (2) coalescence of the precipitated particles begins to be effective and the impact values for both rapidly cooled and slowly cooled specimens increase; (3) the precipitate goes back into solution at higher tempering temperatures and the impact values of specimens cooled rapidly enough to retain the solution increase, while reprecipitation occurs in slowly cooled specimens and their impact values decrease again. No change must proceed to completion before the following one begins and there is overlapping in temperature ranges. Although there have been a large number of experimental investigations of temper brittleness, insufficient evidence has been accumulated to permit definite identification of the precipitate wnich causes temper brittleness nor have the specific effects on it of various alloy elements and impurities in steel been definitely established. This lack of evidence is largely a result of the lack of a suitable measure for temper brittleness. Temper brittleness is evidenced by an increase in the temperature of brittle failure of notched-bar impact specimens, but most of the data are in the form of an arbitrary susceptibility ratio of the room-temperature impact value for specimens quenched from a high tempering temper to that of similar specimens furnace cooled from the temper. It is obvious that this numerical ratio is dependent upon the type of specimen used and the specific conditions of testing rather than the characteristics of the steel. In general, manganese, chromium, and nickel alloy steels are most susceptible to temper brittleness and molybdenum has heen used to decrease

Jan 1, 1950

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

By V. O. Struebing, K. A. Johnson, F. H. Ellinger, C. C. Land

The system Pu-Ce-(Pu,Ce)Co2 has been investigated by thermal, micrographic, and X-ray diffraction methods. The principal characteristics of this system were found to be: 1) a "eutectic" valley extending across the phase diagram from the 6 Pu/Pu3 Co eutectic at 408°C to the 7 Ce/Ce24Co11 eutectic at 42Z°C, the maximum temperature in the valley being 443°C; 2) three ternary inter mediate phases, each having an appreciable mutual solid solubility for plutonium and cerium; 3) eleven four-phase equilibria comprising one eutectic, four peritectics, and six Class II reactions; 4) a pseudobinary section between the ternary phase A and the y Ce solid solution, and another such section between the 6 Pu solid solution and the 77 phase (Pu3 CO) containing cerium in solid solution. ALLOYS of plutonium that are completely molten at temperatures in the vicinity of 500°C are of interest for use in the liquid state as fast reactor fuels. Since exploratory work1,2 on Pu-Ce-Co alloys had indicated that a "eutectic" valley extended across the ternary system between the Pu-co[6 Pu/n (Pu3co)] and the Ce-CO[? Ce/? (ce24co11)] binary eutectics, thus allowing alloys of any plutonium concentration to be selected within the temperature limitation, the present investigation was begun for the purpose of accurately defining the "eutectic" valley. However, when the existence of three ternary intermediate phases and the consequent complexity of the liquid-solid equilibria were discovered, the investigation was expanded to cover the complete system, except for the corner between the isomorphous series PuCo2-CeCo2 and pure cobalt. 1) EXPERIMENTAL The purities of the alloy components are given in Table I. Alloy buttons, each weighing about 5 g, were prepared by arc melting the accurately weighed components (±0.1 mg) under a purified He-Ar atmosphere. Weight loss as a result of melting was usually less than 1 part in 1000; therefore, the buttons were not chemically analyzed. One half of each button was re-melted by induction heating in vacuo in a magnesia crucible and furnace-cooled, so as to produce a somewhat coarser microstructure than that of the rapidly cooled arc-melted button. About 20 g of each alloy to be examined by thermal analysis were remelted in vacuo in a tantalum crucible of the inverted thermocouple well type. The thermal, X-ray diffraction, heat treating, and micrographic methods used in this investigation were essentially the same as have been described in earlier reports.3,4 Two etchants for these alloys were found to be satisfactory: A) 8 (parts by volume) orthophosphoric acid, 5 ethanol, and 5 glycol; B) 7 tetraphosphoric acid, 36 water, and 57 2-ethoxyethanol. Etchant A was used at 5 to 6 v for 15 to 20 sec, and etchant B was used at 10 v for 10 sec. 2) THE LIMITING BINARY SYSTEMS 2.1) Plutonium-Cerium. The phase relationships of this system have been investigated by Ellinger, Land, and Cramer,5 and by Selle and Etter.6 The over-all agreement of their phase diagrams is good, but there are some discrepancies in the positions of some phase

Jan 1, 1967

By J. T. Crawford

Although nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth-Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal bri-quetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the world's largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis., waterfront and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned, General History In the summer of 1871 a small sailing vessel entered the harbor of Duluth-Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1949