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By W. F. Shinners

Ozark Ore Co.'s Iron Mountain mine utilizes optimum mechanization to provide ever increasing output from underground as production declines from open pit. Trackless equipment gave flexibility to meet varied mining conditions-required minimum of pre-production development.

Jan 4, 1953

By P. Lindstrom

Retreat mining, using yielding steel friction props, over a 7-year period has been successful at a uranium mine operated by Hecla Mining Co. in southeast Utah. The support system allows good roof control, maximum profit, complete extraction, and good ventilation. Unusual subsidence observations were made in that some of the surface was raised rather than lowered. Longwall mining, commonly practiced in European coal mines, has a potential of broader application because of mechanization possibilities and better roof control and ventilation at greater depths. The Radon mine was one of the first American metal mines to use yielding steel props for supporting the relaxed core of the pressure arch which is induced by retreating longwall mining. Full caving was induced. After more than 7 years of stoping experience, the method has proved very satisfactory for the conditions encountered. The mine and method have been described in references listed in the bibliography. U.S. Bureau of Mines Information Circular 8004 by Wilbert Dare and Philip Lindstrom gives the most information. Stoping experience at this mine indicates that there are many advantages to be gained by using yielding supports; such as in safety, timber cost, roof control, ventilation, ore dilution, and low cost per pound of metal produced. Subsidence measurements show that the surface will rise rather than slump in some areas over the mine. This appears to be an unusual observation and is presented as a new development in subsidence studies. The Radon mine is located 35 miles southeast of Moab, Utah in the north end of the Big Indian mining district in San Juan County. Hecla Mining Co. operated the mine from early 1955 to early 1964 through an operating agreement with Federal Resources, Inc. Development consisted of a 3-compartment, 690-ft shaft, 4 main levels driven on the ore horizon and a haulage level below the ore. Evaluation of physical and economic factors showed that this flat-dipping ore occurrence could be mined by a low-cost coal mining method. The value of the deposit was high and unusual premiums were possible by clean mining. Complete extraction without loss of ore pillars, minimum ore dilution and high production per man were obtained by longwall mining. The principle of working under the relaxed core of

Jan 1, 1964

By W. R. Clough, M. E. Shank

IT has been noted in a study of the flow and fracture of nodular cast iron under biaxial stress conditions (complete results of which will be published later) that when this metal is subjected to stress it may undergo a striking density change. Such behavior was first determined by strain gage measurements made on tensile test specimens, and has since been substantiated by other types of measurement. The chemical analyses and mechanical properties of several nodular irons to be discussed here are given in Tables I and 11. Tensile data for iron A was obtained from a hollow cylindrical combined stress specimen of the same dimension as those used by L. F. Coffin, Jr.1 in his investigation of gray iron properties. Standard 0.505 in. solid tensile-test bars were used for irons B and C. On each specimen type, A-8 wire resistance strain gages were used—two diametrically opposing gages in the axial direction, two in the tangential or hoop direction. By subtracting elastic strains from the measured strains, the plastic strains could be calculated. By assuming that radial and tangential strains are numerically equal, a measure of permanent volume change can be obtained by summing the plastic strains. This appears to be a good assumption, since the metal either fractured, iron A, or readings were discontinued, irons B and C, long before necking took place. This calculated variation of volume increase with stress is given for irons A and B in Fig. 1. Data for iron C is almost identical with that for iron B. The volume change indicated by Fig. 1 has been substantiated by a more direct type of density measurement. A method developed by S. G. Fletcher and' Morris Cohen,' and completely described in the discussion of their article, has been used. The accuracy of specific volume measurement has been estimated as 0.00002 cu cm per gram. Essentially the method consists of weighing a sample in air and then immersed in water. Measurements were made before and after straining the material. The results shown in Table I11 were obtained by means of half-size (0.252 in. diameter, 1 in. gage length, 3/8-16 threads) tensile specimens. Initial measurements were made on the whole specimen before stressing. After stress-

Jan 1, 1955

By Graham John Mitchell

In May, 1919, a crosscut on the 1400-ft. level of the Briggs mine, a Calumet, & Arizona property at Bisbee, Ariz., penetrated a deposit of pyrite and chaleopyrite that had replaced quartzite and limestone and was cut, especially in the quartzite, by numerous fractures. As the drift advanced through these fractured portions, they were found to be free from copper-sulfate minerals although '(sooty" chalcocite was present in the fractures and also as coatings and replacements of pyritc. Howcver, sulfate soon made its appearance in certain fractures, filled them, and began to form stalactites. Several centers of incipient growth were noted for subsequent study, observations in the drift at frequent intervals during the past 17 months affording the opportunity of determining the rate of formation of the stalactites. The one to attain the greatest growth during the period of observation measured 27 in. long and averaged 1 in. in diameter. A close study showed it to be composed of small interlocked crystals of chalcanthite radiating from a small central tube-like opening. The trielinic form of the crystals was evident with prism and pinacoid faces recognixable. Assuming that the supply of copper-sulfate solution was constant (luring the 17 months—-and such an assumption is supported by the fact that the number of drops of excess solution falling, per minute, from the tip of the stalactite at the times of observation checked closely—thc stalactite, it has been estimated, grew at the rate of 1.58+ in. per month. DISCUSSION James I?. Kemp," New Yolk City.—J. S. Curtiss, in the monogr:tpll on Eureka, Ncv., say:: that a stalactite formed in limestonc grew 5/8 in. in three weeks and continued to grow as long as it had a drop of water or solution at the lower end. Another grew at the rate of 3/8 in. in the same time. In the case cited by Mr. Mitchell, the growth was about 136 in. in three weeks. A year ago we had an instance of the formation of cubes of galena on a railroad spike. A mine in northeastern Oklahoma had been idle about two years but on account of pumping of neighboring properties, the circulation of water was active throughout the drift. A cube of galena,

Jan 1, 1922

By T. S. Spicer

The relationship of coal characteristics to the principal types of firing equipment has been known to the coal combustion engineer, but is not as familiar a subject for purchasing agents, salesmen, consumers, and executives of coal-producing and consuming companies. This general survey of characteristics determined by standard laboratory tests, of major types of combustion techniques, and of the relationships between the two is directed toward the latter audience. It will also serve as a review for those actively engaged in the combustion of coal. Although the relationship of coal characteristics to the principal types of firing equipment is well known to the experienced coal combustion engineer, apparently there is need for a summary article on this subject. The author has received numerous requests for such a paper from purchasing agents, coal salesmen, coal customers and executives of coal-producing and consuming companies. Consequently, the scope of this paper will be directed to this audience, with the hope that it may serve also as a review to others actively engaged in the combustion of coal. The magnitude of this subject is so great that only a brief general treatise is possible. The author realizes that because there are so many special cases and exceptions to the generalities which follow, he is in jeopardy of contradicting himself. It is the hope, however, that the many references cited will prove valuable to those who wish to study the details excluded by necessity, due to space and time limitations. Hence, the characteristics of coals as determined by standard laboratory tests will be discussed; the major types of combustion techniques reviewed; and then the characteristics and firing will be related. CHARACTERISTICS OF UNITED STATES COALS The coals of the United States range from lignite to anthracite and each has its own general characteristics. The extensive coal fields of the U. S. are shown in Fig. 1 and the estimated reserve according to rank for each state is illustrated in Fig. 2. Coals may be classified according to rank as shown by Table I from the ASTM Standards on Coal and Coke, D-338-38.1 The basis of this classification is ac- cording to fixed carbon and heating value (Btu per pound) calculated to a mineral-matter-free basis. The high-rank coals are classified according to fixed carbon on the dry basis; and the low-rank coals according to Btu on the moist basis. Agglomerating and slacking (weathering) indices are used to differentiate between certain adjacent groups. While rank is not itself a characteristic it does signify certain characteristics that accompany a class of fuel. Anthracite, for example, immediately implies a hard, free-burning, smokeless coal of low volatile matter, usually having an ash of high fusibility. Coals may also be classified according to grade as described by ASTM Designation D-398-37.1 This quality classification is determined by size, calorific value, ash, ash-softening temperature, and sulfur. This type of classification is not used as extensively by the industry as the rank classification. Fig. 3 shows the heat value of different ranks compared to proximate analyses. Coals may also be classified by sizes, as shown in Tables IIA and IIB, and sizes can be on both top and bottom limits. If this is done, then the coal is called double screened; otherwise, either top or bottom sizes can be specified as a limit. Bituminous coal sizing varies from field to field and depends upon the market demand. The common sizes and their main uses are outlined in Table IIA. Anthracite is usually available in many sizes at the colliery, and Table IIB summarizes standard sizes and names. Although rank, grade, and size designations help identify and describe a coal in question, there still remain other characteristics such as indicated by moisture, free swelling index, grindability tests, etc. A bituminous coal information chart Table III) suggested for use in studying the available coals in a region, lists origin and chemical and physical characteristics. Even this more comprehensive list does not completely spell out all the characteristics of a heterogenous material like coal. For example,

Jan 1, 1961

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle's work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

By Carrol M. Beeson

Reasons are given for using a Boyle's-law porosimeter in conducting core analysis for either routine or research purposes. Among other things, it is pointed out that such a porosimeter permits the measurement of all basic properties on the same sample, thereby eliminating the sources of error inherent in the use of adjacent samples. References are made to investigations of gas adsorption on various porous materials, to show that the use of helium in Boyle's-law porosimeters reduces to negligible proportions the error due to the adsorption or desorption of the operating gas. Two Boyle's-law instruments are described. which permit accurate and rapid measurements of porosity. Schematic sketches and explanation:; are included, along with derivations of equations required in performing precise determinations. Summaries of data obtained during calibration are tabulated and analyses of the data are resented as indications of the precision and accuracy of each device. Comparisons are also shown for measurements made with each of the instruments on the same test pieces and cores. INTRODUCTION An accurate porosimeter, operating on the principle of Boyle's law. is of considerable value in the analysis of cores for either routine or research purposes. This is due primarily to the fact that the measurement of porosity with such an instrument leaves the sample free of contamination by any liquid. When used in conjunction with an extraction apparatus' for determining oil and water saturations, a Boyle's-law porosimeter permits the measurement of all basic properties on the same sample. This eliminates the sources of error inherent in the use of adjacent samples, or the necessity of determining porosity after all other properties have been obtained. Large errors may result from combining measurements made on adjacent samples in order to obtain a single property. This type of error is definitely involved when oil and water are measured with one sample, and the pore vo1ume is measured with an adjacent one. Furthermore, the source of error would be present to some extent, even if the analyst could choose the samples so they were truly adjacent from a geological standpoint. The use of adjacent samples in routine core analysis also necessarily decreases the probability of correlating core properties. For example, the chance of correlating the "irreducible" interstitial-water saturation with permeability, is bound to be greatly reduced by measuring these properties on "adjacent" samples. For research purposes, amplification is scarcely required concerning the greater flexibility of a method for measuring porosity which leaves the core free of contamination by any liquid. Even under those circumstances which require that the core be saturated with a liquid, a previous measurement of porosity with a gas is useful in determining the degree of saturation that has been attained in the process. Furthermore, for comparable accuracy, porosity usually may be determined more rapidly with a gas than with a liquid. This advantage of the Boyle's-law instrument is most outstanding when the determination time is compared with that required in obtaining porosity by evacuation of the core followed by saturation with a liquid of known density. Several porosimeters which operate on the principle of Boyle's law have been described2,3,4,5,6,7 in the literature. No comparison will be attempted between those instruments and the ones described herein. Before helium gas became readily available, Boyle's-law porosimeters were subject to an appreciable error due to the adsorption of the operating gas on the surface of the core solids. There is considerable direct and indirect evidence in the literature to support the contention that the adsorption of helium on porous solids is negligible at room temperature. In discussing the use of Boyle's-law porosimeters, Washburn and Bunting2 stated that "for most ceramic bodies dry air is a satisfactory gas, but hydrogen will be required in some instances. Helium could, of course, be employed for all types of porous materials at room temperatures or above." Howard and Hulett8 obtained evidence that the adsorption of helium was negligible at room temperatures, even on activated carbon ; for the density measured with this gas was unaffected by changes in pressure or by changes in temperature from 25 °C to 75 °C. For oil-well cores, Taliaferro, Johnson, and Dewees" obtained lower porosities with helium than with air, but apparently did not study helium adsorption. From the work of these investigators, it follows that the use of helium in Boyle's-law porosimeters reduces the error due to gas adsorption to negligible proportions. This makes it possible to construct instruments which permit the determination of porosity with (1) a high degree of accuracy, (2) with great rapidity, and (3) without contamination. THE KOBE POROSIMETER The fundamental design of the Kobe Porosimeter was developed by Kobe, Inc., which firm built about 12 of the instruments during 1936 and 1937. Since that time, seven or eight more have been constructed with their permission, making a total of about 20 that have been put into operation.

Jan 1, 1950

By Bryan J. Travis, Thomas L. Cook

INTRODUCTION Our growing concern for adequate and secure sources of energy and minerals has stimulated vigorous exploration for new sources, research toward a better understanding of geological processes, and development of new extraction technologies. The need for control, or at least prediction, of subsurface fluid flow is important for many of these technologies for example: primary, secondary and tertiary recovery of oil; ground water and waste management; in-situ fossil energy extraction (oil shale, coal, tar sands); and solution mining of uranium, copper and other minerals. These technologies, especially the last two, are characterized by highly complex systems. A partial list of the physical processes occurring would include flow in porous/fractured media, multi-phase and multi-component flow with heat transport, chemically active fluids and soils, tracers, diffusion and dispersion, fracturing and dissolution. A great deal of understanding of how these processes behave and interact can be obtained from models. MODELS Theoretical models are valuable because they: 1) provide a frame of reference for interpreting results of laboratory and field experiments; 2) once validated by experiments, allow a variety of geometries, injection/production strategies, etc., to be examined (at relatively low cost) for efficiency and stability; 3) can provide guidance to the design of experiments and field operations. Most models are based on the fundamental principles of mass, momentum and energy balance. But from this starting point, many paths can be taken. For example, there is the theory of Payatakes (1973) which concentrates on the microscale dynamics. In this approach, the rock or soil matrix is represented by a complex of characteristic channels (such as periodically constricted smooth tubes). Detail of flow within the characteristic channel is calculated very accurately. A difficulty with this model is that description of a representative channel can require several parameters which may not be easily measured. Also, it is not clear how the channels can be combined practically to model a large scale flow. Another type of model is the "global" one described by Bear (1972). Here, the continuum equations for conservation of mass, momentum and energy are averaged over a distribution of pore channels, resulting in a set of conservation equations in which the small scale structure of the medium is replaced by quantities such as porosity, permeability, dispersion coefficients and tortuosity. This approach allows computation of large scale flows. However, additional constitutive equations are needed which relate averaged quantities such as permeability to observables such as local saturation, particle size distributions, and others. An important difference between models is the way they handle the momentum equation. Payatakes' model solves the full equation. In others, it is replaced by a simpler relation such as Darcy's law (valid for slow flow rates) or by Forchheimer's equation which extends Darcy's law to higher flow rates. These simple relations can nevertheless match a great deal of experimental data (Dullien 1975). The permeability term which appears in Darcy's law and in Forchheimer's expression has been related to other quantities such as porosity and particle surface area. The Kozeny-Carmen equation is a well-known example, valid for some ranges of porosity and particle sizes and for some materials. Several other semi-theoretical, semi-empirical formulations have been devised, none of which are entirely satisfactory. One goal of researchers has been the ability to predict permeability of a porous material from basic measurable quantities such as grain size distributions without recourse to adjustable parameters. This effort has proceeded from consideration of distributions of idealized, non-intersecting channels, to intersecting channels, to consideration of both distributed pore radii and pore neck radii. This last approach has been used successfully to predict permeabilities (ranging over several orders of magnitude) in sandstones (Dullien 1975). Additionally, studies on explicit networks of channels (e.g., Fatt 1956) and percolation theory (e.g., Larson et. al. 1981) have been used to examine interconnectivity effects in porous media with the hope of eventually being able to predict permeability accurately. To be of more than theoretical interest, a model must be compared s controlled laboratory conditions where boundary and initial conditions and relevant material properties can be accurately determined. Also, extraneous forces can be eliminated so that the interactions between processes of interest can be clearly seen and flow models can be vigorously tested. In contrast to the well-defined environment and

Jan 1, 1982

By William G. Christy

EFFORTS at smoke abatement date back to the year 1273 in England when a law was passed prohibiting the use of "sea cole." The law was not enforced, so King Edward I, 33 years later, appointed a commission "to enquire of all such who burnt sea cole in the city or parts adjoining, and to punish them for first offense with great fines and ransomes, and for the second offense to demolish their furnaces." Many other commissions have since been named to investigate the smoke problem in England, but it still persists in many British cities. In the United States the movement to abate the smoke nuisance started in certain Middle Western cities, and has made considerable progress. Until recently, the coal-producing industry co-operated little in smoke¬abatement programs, taking the attitude that smoke elimination is the dealer's or user's responsibility; and the dealers, in turn placed the responsibility entirely on the user.

Jan 1, 1942

By G. E. Johnson

LEAD SMELTERS AND REFINERS in 1932 were confronted with the problem of adjusting operations and costs to curtailed production and consumption at reduced prices, a problem which has been partially solved at least by improvements in operating technique and increased efficiency. At the Mount Isa properties in Australia, a third blast furnace and additional Dwight-Lloyd sintering machines were installed during the year, designed to increase the production to 6,000 tons of bullion per month. The large proportion of lead carbonate in the ores to be treated has presented metallurgical problems. Of the total lead contained in the concentrates to be smelted, two-thirds is Dresent as carbonates and one-third as sulfides. In the iiitial operations, the resulting Dwight-Lloyd sinter was soft, contained an excessive amount of fines, and was easily fusible. When charged to the blast furnaces it developed accretions in the upper part of the furnace owing to the easily fusible lead carbonates softening and fusing at the top of the charge column. This was remedied by the addition to the sinter feed of diluents of higher melting point, granulated slag and crushed limestone. The sinter feed consists of concentrates, Cottrell dust and wind-box cleanings, totalling 57 per cent of the charge; return sinter fines 15 per cent; granulated slag 23 per cent; and crushed limestone 5 per cent. The sinter produced contains 34 per cent lead and 0.5 per cent sulfur. Experiments indicated that double sintering under these conditions was of no advantage, so the original plan of single sinter treatment was retained.

Jan 1, 1933

By Eugene A. Thiers, William V. Morris

INTRODUCTION Direct reduction processes reduce the various commercial forms of iron oxide (pellets, concentrate, fines, etc.) to metallic iron at temperatures lower than that of molten iron. Thus, this technology includes practically, all iron reduction processes other than blast furnaces and electric pig iron furnaces (whose output in terms of world production is negligible). The product of these processes which is known as direct reduced iron (DRI), or sponge iron, is primarily used as a source of metallic iron in steel-making operations. Interest in DRI, which has been significant since the early 1960s, increased significantly in recent years with the rapid growth of DRI installed capacity throughout the world. The importance of the subject for the Circum-Pacific region stems directly from the influence that DRI has on iron ore consumption and on future steel development for this region. Although there is widespread agreement that electric furnaces will continue to increase their share of global steel output, and especially so in the countries of the Pacific Steel community, some doubts exist about future scrap supplies being adequate to support growth at past rates. The authors believe that such doubts are soundly based. As this paper points out, the total supply of all metallics used in electric furnaces may not be adequate to support the extrapolated rapid growth in electric furnace steel production. This paper seeks to provide perspective on the global and Circum-Pacific prospects for DRI in light of recent energy price developments and the current recession. In this regard, the demand for DRI within the context of recent evolutionary patterns in steel-making, the outlook of DRI supply in terms of prevailing production costs, and the prospects of new technology are discussed. THE DEMAND FOR DRI Although several reports published in the last 10 years predict high rates of growth in DRI, the subject remains a controversial one. Significant growth has indeed occurred, but not to the extent anticipated in the studies summarized in Table 1. The substantial difference between previous expectations and present reality can be ascribed primarily to: (1) lower growth in steel production than formerly anticipated; (2) numerous cancellations of DRI facilities that were previously announced; and (3) a fundamental and probably irreversible change in the economics of DRI production. Note that DRI capacity at the end of 1980 was about 16 million tonnes, a significantly lower figure than any of the projections above. In addition, DRI production was only about half of capacity, reflecting the abnormally low rates of capacity utilization in this industry. [ ] Before examining the current outlook in steel, it is pertinent to note that the market for DRI is usually different in the industrialized countries of the West from that in developing countries. In the former, the available infrastructure and industry's diversification extends DRI's potential markets to numerous steelmaking, foundry, and other industrial applications, although competition from scrap and other forms of metallic iron is constant. Scrap is generally available in these countries and, therefore, DRI competes with it in electric furnace steelmaking, basic oxygen steelmaking (as a coolant), cupola foundry operations, or as an additive in the metallic charge for open hearth and blast furnaces. On the other hand, DRI in developing countries is often allocated exclusively to domestic electric furnace steelmaking or, when capacity exceeds domestic captive requirements, to export. Notwithstanding quality considerations, DRI is being and is likely to continue to be used predominantly as a source of metallics in iron and steel-making. Other uses of DRI, such as in copper cementation represent a marginal market in terms of overall tonnage and can be ignored at this point. Therefore, DRI demand is-determined by the overall availability of metallic scrap in its various forms--a function of steel production and its probable evolution. The Global Steel Outlook Given the present recession, an objective appraisal of the long-term outlook for steel is particularly difficult. On the one hand, historical trends and, especially, the inertial forces associated with such a basic industry as steel must be recognized; such trends suggest that the current stagnation with

Jan 1, 1982

By J. J. Pfeiffer, A. A. Oming, J. W. Myers

The method used to process washery refuse for use as a building material aggregate is described. Results of studies made in investigating this process are summarized. The Bureau of Mines, in cooperation with two commercial coal producers, studied the feasibility of using coal washery refuse in manufacturing lightweight aggregate for building materials. Lightweight aggregate is used in making masonry products of lower bulk density than can be produced from conventional aggregate such as sand, gravel, and crushed rock. Among the advantages of lightweight masonry are reduced deadweight loads which reduce materials cost, lower cost of construction labor, and improved thermal and sound insulation. A process for making lightweight concrete aggregate from coal-washery refuse appeared attractive because of the availability of raw material which contained sufficient fuel to carry out the processing. Vast quantities of such refuse have accumulated throughout the coal-producing areas of the U.S. Generally it is stored in unsightly piles, creating a problem of air pollution and using space that could be devoted to other purposes. Conversion of the refuse to lightweight aggregate could remedy these conditions and effectively utilize a material normally considered waste. The first part of the program was conducted in cooperation with the Truax-Traer Coal Co. to determine the feasibility of utilizing refuse from the company's coal preparation plant at Ceredo, W. Va., in manufacturing lightweight aggregate. The aggregate was to be used in making cement blocks comparable to those known in the building trades as cinder blocks. This project was completed in 1954. Based on the results of this work, the cooperator began commercial development and formed the Trulite Corp. for this purpose. A plant capable of handling 120 tpd of refuse was constructed for approximately $120,000. It began operating on June 1, 1955.' In 1959 a similar study was made, under a cooperative agreement with the Carbon Fuel Co. of Charleston, W. Va., to rrscertain the suitability of refuse from its plant for conversion to lightweight aggregate. Under this program various modifications of equipment were made, and the investigation of process variables begun in the previous project was extended. PROCESSING METHOD The formation of lightweight aggregate from coal-washery refuse js governed, in part, by the fusion characteristics of the mineral constituents of the refuse when heated above their softening temperatures. The heat required for this purpose is supplied by the combustihle matter in the refuse. Some of this combustible matter is coal with high ash content, but most of it is carbonaceous shale. Whereas the density of aggregate prepared from clay or shale depends largely on expansion, the density of aggregate made from refuse is reduced by burning out the combustible matter and, to a lesser extent, by expansion of the residue in the fuel bed. A chain-grate stoker with an updraft air system was chosen for the conversion process in preference to a downdraft sintering machine or a rotary kiln. In down-draft sintering, which operates on the overfeed burning principle, the volatile matter from the refuse would distill off without burning, resulting in inefficient combustion and interfering with proper operation of the equipment. The rotary kiln is designed primarily for processing material that lacks, or is low in, combustihle matter with the heat of reaction supplied from external sources. Washery refuse, which is relatively high in carbonaceous material, could burn at the wall of the kiln causing clinker formation with resultant decrease in throughput and increase in production cost. With an up-draft air stream on a chain or traveling-grate stoker, the volatile matter would be carried into the ignition and burning zones where the heat could be utilized more efficiently. The combustion procedure in this type of unit may be considered as consisting of four periods: 1) initial ignition of the top of the bed by furnace radiation, 2) ignition travel through the bed until the whole bed is ignited, 3) burnout of the combustible material with high air rates to fuse and expand the residue, 4) a cooling period. Investigation of the process required a study of the variables that affect both

Jan 1, 1962

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal' and by Chew and Connally' for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7' API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.' All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

lv. H. Blauvelt, Great Falls, Montana (communication to the Secretary): In his remarks on Mr. Stetefeldt's paper (Trans., xxiii., 587)) Mr. Goetz observes: " Trouble experienced with producers at Great Falls influenced me to try Taylor producers instead of those of Wellman. But recent reports show that the Wellman producers work better, besides coating nearly 50 per cent. less than Taylor producers of equal capacity. Indiana and Illinois coals cannot be used in the Taylor producers by reason of the large size and hardness of the clinkers which they form." I think that Mr. Goetz must have been misinformed regarding the work of this producer in Illinois. One of the large mauafacturing concerns in that State, the Illinois Zinc Company, situated at Peru, which uses a coal mined in the vicinity, tried one Taylor producer, some four years ago, in competition with those of an older type, which it had been using. As a result of this trial, the company has now thirteen Taylor producers, which have been in operation for about three years. A recent report from these works says that the Taylor producers have largely reduced the loss of coal through the grate, and have also improved the quality of the gas, as compared with that produced from the same coal in the producers of the older type. This Illinois coal is, perhaps, the worst in the country for making gas; since, besides containing from 20 to 40 per cent. of ash, it carries a large quantity of pyrites, so that the clinkers are large and extremely hard, and the capacity of the producer is most severely tested.

Jan 1, 1895

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-'. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers' to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,' tenile,'-' electrical reistivity, and thermodyna-mic1',14 studies. Indications of a high bonding strength may be found in the large heat of mixing1' and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750'. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By R. V. Sara

Determination of the Hf-C phase diagram was conducted primarily by metallographic and X-ray diffraction studies on appropriate alloys. The only intermediate phase observed in this binary system was HfC. This phase was found to be homogeneous between 34.0 and 48.0 at. pct C at 2200°c and between 36.0 and 49.3 at. pct C at 3150°C. The lattice-parameter variation was also determined for HfCI-, compositions prepared at 2200° and 3150°C. The most most refractory composition, with a melting point of 3830°c, was established at 47.5 at. pct C from melting-point data. Solidus temperatures of 2240' and 3150°C occur on the high-kafnium and high-carbon sides of the monocarbide, respectively. The invariant point between HfC and carbon is located at 66.0 at. pct C, whereas the 2240°C solidus corresponds to the peritectic temperature at which hafnium is formed from HfC and hafnium-rick liquid. Hafnium has a melting temperature of 2208°C and is capable of taking carbon into solution to the extent of 10.5 at. pct at this temperature. ALTHOUGH the Hf-C phase diagram has not been previously evaluated experimentally in its entirety, the belief has been that the general configuration would resemble the chemically similar Group rV carbide systems, Ti-C and Zr-c.' These binaries are characterized by a single carbide phase with a simple NaC1-type structure which is maintained over wide compositional ranges. This family of carbides has high thermal stability that increases substantially as the atomic number of the metal component increases. This trend characterizes HfC as one of the highest melting materials. According to Agte and Alterthum,2 the melting point for this monocarbide is 3890°C, a value that has been quoted quite extensively for the past several decades. Recently, in repeating the work of Agte and Alter-thum, Adams and Beall3 determined the melting point of HfC to be 3895°C. A significant departure from the commonly accepted version of the Hf-C system was reported by Avarbe and his coworkers,4 who proposed that there is an extreme stabilization of a hafnium in a narrow field to 2820°C, above which it melts peritectically to form HfC and liquid. Their study was also concerned with the melting temperature of various HfCI-, compositions, but the peak melting point was taken from the work of Agte and Alterthum. Avarbe and his associates were not concerned with the high-carbon region of the system. However, three widely varying temperatures have been reported for the HfC-C solidus by other investigators. Cotter and Kohn5 observed approximately 2800°C; Portnoy et al.' reported 3260°C; and, more recently, Krikorian7 indicated 2915°C. Equally as uncertain is the solidus between hafnium and HfC. As noted above, Avarbe et al. report a peritectic temperature of 2820°C, Krikorian7 measured 2150°C, and Benesovsky and Rudy' estimated 2000°C on their diagram. I) EXPERIMENTAL PROCEDURE The starting materials for this study consisted of reactor-grade hafnium hydride obtained from Fair-mount Chemical Co., Newark, N.J., hafnium carbide supplied by Wah Chang Corp., Albany, Ore., and Union Carbide spectroscopic-grade graphite, SP-1. The graphite analysis indicated impurities at levels of only 0.5 ppm or less. According to the suppliers, the hydride and carbide contained the typical impurities listed in Table I. The samples required for these studies were prepared by dry blending either graphite and hafnium hydride or hafnium hydride and hafnium carbide powders for approximately 5 min in a "Spex Mixer Mill". The latter combination was used only for preparing several samples in the HfC1-, melting-point studies. Small pellets, varying between 3/16

Jan 1, 1965

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969