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By O. M. Schaus

GRATIFYING progress continues towards the elimination of the hazards confronting health and safety in and about mines. Employers and employees are diligently co-operating. One of the outstanding movements towards this end is the National Safety Competition conducted by the U. S. Bureau of Mines. William W. Adams, of the Bureau, has stated that "Through 1936 there has passed by a dozen years of this National Safety Competition, as it started in 1925 with an enrollment of 210 mines and quarries in 28 states and 68 million man-hours of employment. For 1936 it covered 328 mines and quar-

Jan 1, 1938

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950

By T. W. Guy

THE increased moisture due to water¬spraying for coal dust control is of interest even for mines from which the coal is to be wet-washed before screening, because in many cases wet coal dust materially decreases the loading efficiency of men an equipment at the faces. It also causes serious increase in the normal wear and deterioration of all equipment with which it comes in contact. It is important to the consumer if it increases his as-receive moisture. No attempt will be made in this paper t cover the entire subject of water-spraying of coal for dust control. It will be confine to discussion and data on (r) percentages c dust in bituminous coals, (2) moisture increases due to spraying for dust control in mines or plants by methods which have proven satisfactory for periods of one to five or more years, and (3) a few suggestions for research. SIZE AND PERCENTAGE OF COAL DUST The U. S. Bureau of Mines1 classifies a coal dust all bituminous coal passing 20-mesh sieve (0.0328 in. square opening; The percentage of such dust to be found is ROM coal, of course, varies widely wit. the characteristics of the seam, and with the methods used in the mining and in the preparation of the coal. ROM screen analyses of 12 U. S. coals selected at random from personal files given in Table I show: A few other screen analyses examined indicating 40 pct or more of 2o-mesh X o dust in 3/8 in. X o-sizes were not included because of uncertainty that they were representative. The number of results in Table I is not sufficient to give a reliable estimate of the average, or of the range to be expected, but it indicates that in every case the coal dust is a relatively large percentage of the total ROM coal, and, of course, a progressively larger percentage of resultants as the larger sizes are separated for marketing.

Jan 1, 1948

By R. R. Estill

THE rank of the Ruhr coal ranges from a high volatile bituminous coal to an anthracite, depending to some extent on the original depth of the seam. The average Ruhr coal corresponds to a soft bituminous American coal of a coking quality. The average thicknesses of individual coal seams being mined are also comparable (59 in. against 65 in. in the United States). However, consideration of seam conditions and mining conditions other than those just mentioned emphasizes differences rather than similarities with United States soft coal. In general, the Ruhr seams now being mined are much more folded and inclined than American seams. Dips of 20' and 30" are common in seams now being worked, and 30 pct of the coal reserves in the district are in seams dipping more than 35". Only on the tops and bottoms of folds do we find rather flat coal seams. In addition to the folding there is extensive displacement by cross faulting plus a certain amount of strike faulting of an overthrust nature, which results locally in doubling or omission of seams. Because of the long history of mining in the Ruhr, nearly all coal lying near the surface has long since been mined out, and we find that the average depth of mining is at present about 2300 ft below the surface. Deep mining, folding, and faulting result in seam conditions requiring a great deal more roof support than one finds in American soft coal mines. In fact only in the anthracite district and the Rocky Mountain and Pacific coal fields do we find somewhat similar conditions. It is easy to say, therefore, that the problem of mechanization of coal cutting and loading in the German mines is quite different from that which we have so effectively met in America with our mobile cutters and loaders, duck bill loaders, and a room and pillar system of mining our drift and slope mines. Partly because of more limited coal reserves, the traditional German mining system is largely the longwall method, which gives an almost complete coal recovery. Backfilling must be extensively practiced to protect the longwall faces, the over and underlying seams and workings, and especially the surface industrialized areas and barge canals. The German engineers have accordingly concentrated their efforts on the design of cutters, loaders, and conveyors suitable to longwall methods rather than room and pillar methods. Undercutters with cutter bars like American models have been in use in the Ruhr since well before World War 11. In 1941 they accounted for 8.5 pct of the production. This percentage, of course, includes coal which was undercut but nevertheless had to be broken down with air hammers or with explosives. The most common of these cutters is the Eickhoff Standard cutter (see fig. 1). This machine does about 95 pct of the undercutting in the Ruhr today, and is available with either compressed air or electrical power and in at least four different sizes. A variation of the cutter is this one with two cutter bars (fig. 2). At the end of 1947 about 200 of these machines and similar cutters were accounting for 13.2 pct of the total production, a production which was, however, only 60 pct of the 1941 production rate, so that the actual cutter tonnage was only up to a small amount over 1941. In 1941 about 3 pct of the production was accounted for by shearing machines making their cut perpendicular to the longwall face. They were similar to those used in the States. These machines are today considered obsolete and now account for only 0.7 pct of the total production. They are located at only a few mines and at present do not seem to have much of a future in the Ruhr. For the future, the Ruhr miner is looking forward to rather extensive mechanization of face work, with two major types of equipment being developed almost simultaneously. On one hand there is the development of cutter loaders for use in relatively hard coal. They represent the further extension of ideas developed after relatively long experience with the Eickhoff cutter. On the other hand there has been since 1942 an intense interest in the Ruhr in the development of face-stripping methods, particularly by the Kohlenhobel (coal plow) and its modification. At the end of 1947 these cutter loaders, Kohlen-hobels and scrapers together were actually accounting for only about 1.4 pct of total production while air hammers still broke 77.1 pct and as much as 1.2 pct was actually broken by hand picks. However,

Jan 1, 1951

By R. R. Estill

THE rank of the Ruhr coal ranges from a high volatile bituminous coal to an anthracite, depending to some extent on the original depth of the seam. The average Ruhr coal corresponds to a soft bituminous American coal of a coking quality. The average thicknesses of individual coal seams being mined are also comparable (59 in. against 65 in. in the United States). However, consideration of seam conditions and mining conditions other than those just mentioned emphasizes differences rather than similarities with United States soft coal. In general, the Ruhr seams now being mined are much more folded and inclined than American seams. Dips of 20' and 30" are common in seams now being worked, and 30 pct of the coal reserves in the district are in seams dipping more than 35". Only on the tops and bottoms of folds do we find rather flat coal seams. In addition to the folding there is extensive displacement by cross faulting plus a certain amount of strike faulting of an overthrust nature, which results locally in doubling or omission of seams. Because of the long history of mining in the Ruhr, nearly all coal lying near the surface has long since been mined out, and we find that the average depth of mining is at present about 2300 ft below the surface. Deep mining, folding, and faulting result in seam conditions requiring a great deal more roof support than one finds in American soft coal mines. In fact only in the anthracite district and the Rocky Mountain and Pacific coal fields do we find somewhat similar conditions. It is easy to say, therefore, that the problem of mechanization of coal cutting and loading in the German mines is quite different from that which we have so effectively met in America with our mobile cutters and loaders, duck bill loaders, and a room and pillar system of mining our drift and slope mines. Partly because of more limited coal reserves, the traditional German mining system is largely the longwall method, which gives an almost complete coal recovery. Backfilling must be extensively practiced to protect the longwall faces, the over and underlying seams and workings, and especially the surface industrialized areas and barge canals. The German engineers have accordingly concentrated their efforts on the design of cutters, loaders, and conveyors suitable to longwall methods rather than room and pillar methods. Undercutters with cutter bars like American models have been in use in the Ruhr since well before World War 11. In 1941 they accounted for 8.5 pct of the production. This percentage, of course, includes coal which was undercut but nevertheless had to be broken down with air hammers or with explosives. The most common of these cutters is the Eickhoff Standard cutter (see fig. 1). This machine does about 95 pct of the undercutting in the Ruhr today, and is available with either compressed air or electrical power and in at least four different sizes. A variation of the cutter is this one with two cutter bars (fig. 2). At the end of 1947 about 200 of these machines and similar cutters were accounting for 13.2 pct of the total production, a production which was, however, only 60 pct of the 1941 production rate, so that the actual cutter tonnage was only up to a small amount over 1941. In 1941 about 3 pct of the production was accounted for by shearing machines making their cut perpendicular to the longwall face. They were similar to those used in the States. These machines are today considered obsolete and now account for only 0.7 pct of the total production. They are located at only a few mines and at present do not seem to have much of a future in the Ruhr. For the future, the Ruhr miner is looking forward to rather extensive mechanization of face work, with two major types of equipment being developed almost simultaneously. On one hand there is the development of cutter loaders for use in relatively hard coal. They represent the further extension of ideas developed after relatively long experience with the Eickhoff cutter. On the other hand there has been since 1942 an intense interest in the Ruhr in the development of face-stripping methods, particularly by the Kohlenhobel (coal plow) and its modification. At the end of 1947 these cutter loaders, Kohlen-hobels and scrapers together were actually accounting for only about 1.4 pct of total production while air hammers still broke 77.1 pct and as much as 1.2 pct was actually broken by hand picks. However,

Jan 1, 1951

By A. G. Journel

Accurate prediction of recoverable reserves are key to the development and planning of a mining operation. Recovery functions for tonnage, quantity of metal, and ore grade are defined and two approaches for their estimation are proposed. The indicator kriging (IK) approach draws on the data rank orders, whereas the multigaussian (MG) approach relies on a grade multivariate distribution hypothesis. Although based on different premises, both approaches yield remarkably similar, and reasonably accurate, estimates for recoverable reserves.

Jan 1, 1986

By C. R. Fischrupp, M. D. Helfrick, W. A. Straw

In the manufacture of telephone apparatus a number of nonferrous sheet metals arc blanked and formed to produce a wide variety of parts, which are generally small in size because of space and weight requirements. Many are given sharp bends in forming, so that they may be assembled into compact units. This study covered sheet metal of the alloys of brass, phosphor bronze and nickel silver that are most extensively used by our company. In general, the sheets range from 0.005 to 0.100 in. in thickness and from 1/4 hard to extra spring temper in hardness. As many parts function as flat springs, and others require the maximum stiffness for structural reasons, a large percentage of the metal is used in the hard and spring tempers. So, because of the necessity for the minimum radius of bend consistent with the maximum in hardness, there has been a need for information as to the forming characteristics of these sheet metals in the various alloys, tempers and thicknesses. The literature yields relatively little regarding such forming characteristics, so that designers of apparatus and tools have been largely dependent upon past experience or tool tryouts for guidance. In presenting tabular data intended as a basis for selecting the temper of the metal and radius of the bend, we recognize the influence of many other factors which are not covered in this study. For example, the angle of the bend and conditions of the metal, such as grain size and presence of impurities, as well as conditions of the fabricating process, such as rate of forming and adjustment of the tools, may all affect the result. In addition, a bumping operation subsequent to forming, which is frequently used to set the bend, increases the strain on the metal. We wish to emphasize the fact that this is not considered a scientific investigation of the formability of materials or an attempt to correlate forming characteristics with various other properties of the metals, except in so far as such properties are controlled by commercial limits on composition and temper. It is expected, however, that the data presented may serve some useful purpose in estimating the relative formability of different thicknesses

Jan 1, 1931

By William S. McAleer

Two major trends in the coal industry today focus attention on the need for heat-drying equipment of a simpler, more flexible and less expensive type than has been considered standard equipment for drying coal. These trends are: I. The tremendous growth in the use of mechanical equipment to load coal both in underground mining and strip mining, which necessitates efficient mechanical cleaning of the fine as well as the coarse coal and thus means a growing tonnage of washed fine coal? with its attendant moisture problems. 2. The growing consumer demand for the smaller sizes for use as domestic stoker coal, with increasingly rigid specifications covering size, ash, and moisture analyses. ACCEPTED PRACTICE In the past, when, for example, 4 in. too coal has been washed, there was little trouble in producing a washed product 4 to o with a satisfactory resultant moisture. The 4 to 3/8-in. could be taken from dewatering screens at a surface moisture ranging from 2.5 to 3.5 per cent, depending upon the size consist. The 3/8-in. to o coal was generally dewatered satisfactorily with centrifugal driers, to final surface moistures from 5.5 to 8 per cent, again depending upon size consist. The centrifugal type of drier has definitely proved itself to be the most economical type of machine to handle coal approximately 3/8 in. to o as recovered by dewatering screens or drainage elevators with 15 to 25 per cent surface moisture and turn out a product with moistures as stated above. Sometimes such moistures (5.5 to 8.0 per cent) in the product are satisfactory. If not, an ultimate moisture, lower than 3 per cent, is seldom required and the centrifugal drier removes 70 to 85 per cent of the total moisture to be removed. In certain districts there has been a growing tendency to circumvent the use of centrifugals or other types of driers, by dewatering over screens of the wedge wire type and wasting all the finer sizes. Sometimes all the minus 28-mesh has been wasted and often the size wasted has been as large as 1/8-in. By wasting these finer sizes, a lower moisture can be obtained in the finished product, but taking into account the cost of the tonnage so lost, plus the added cost of ultimately disposing of this wasted tonnage, often the cost will be greater than the cost of heat-drying in a modern plant, which makes possible the recovery of all the tonnage. Moreover, with the moisture standards for domestic stoker equipment even these wasteful approaches to its solution do not solve the problem and there remains only the alternative of heat-drying. HEAT-DRYING Until about four years ago, heat-drying of coal at the preparation plants was confined chiefly to drying the fine sizes (approximately 3/8 in. to 0). Occasional

Jan 1, 1941

By Wm. Reuben Webster

THE greatly enlarged demand for small sizes of seamless copper tube which has recently occurred, due particularly to the rapid growth of the electric household-refrigerator industry, has emphasized the superiority of phosphorized to tough pitch copper for the purpose of producing this commodity. In the manufacture of this material exceedingly heavy reductions by cold drawing are employed, customary practice involving as much as 90 per cent. reduction of cross-sectional area in four runs without intermediate annealing. Although this superiority has long been recognized by tube makers, no quantitative expression of it has heretofore been published. It is believed that the data herewith presented will serve this purpose. Recent investigators are not in agreement as to the relative mechanical properties of copper containing small amounts of oxygen as compared with copper containing sufficient oxygen to produce that condition known as tough pitch. Hanson, Marryat and Ford' found that "oxygen has a relatively small effect on the properties of copper." Johnson,2 on the contrary, states "it cannot be denied that it (tough pitch copper) is inferior, to deoxidized copper where severe mechanical manipulation is concerned." These authorities in the reports of their investigations, as might be expected from their conclusions, do not present data of a character requisite to a conclusive determination of the question.

Jan 1, 1927

THAT the march of civilization has synchronized with progress in the art of utilizing minerals is a proposition that needs no proof. It is a truism. Historians conveniently divide the time that the earth has been inhabited into the Stone Age, the Bronze (more accurately the Copper) Age, and the Iron Age. As archeologists are not entirely in accord as to dates, and as a few centuries make no difference whatever to this particular story, it may be approximated that the Age of Copper began about 8000 years B.C. and that it gave place to the Age of Iron about 1000 years B.C. The logic of this succession-stone, copper, iron-lies in the fact that copper first displaced stone, then iron displaced copper as the standard material out of which the utensils, implements, and weapons, the utilitarian articles of antiquity, were made. After the advent of iron, the mining and smelting of copper continued. Copper and bronze found use particularly in objects of artistic and ornamental nature; but the superior qualities of iron for many purposes were recognized. Useful manufactures of those days consisted principally of knives, hammers, chisels, spear-heads, arrow-heads, and battle-axes. First these were made of stone, then of copper and bronze, then of iron-particularly as there was plenty of iron ore, and the metallurgy was comparatively easy of accomplishment. Of course, the periods of transition dragged slowly. Definite as were the three Ages dominated by the mineral substance from which they get their names, ten or fifteen centuries probably elapsed from the time the first iron was smelted in a small charcoal furnace until it became the accepted material from which to shape a battle-axe. Contrast this with the pace of modern progress. In a brief span, half a dozen more or less deserving candidates for the distinction of having their name

Jan 1, 1933

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By L. A. Tarshis, H. E. Cline

A stability criterion for a lamellar eutectic interface was derived previously1 assuming that the wavelength, A,. of the perturbation which grows most rapidly is much larger than the lamellar spacing. A. This assumption was required to permit averaging of both the interface temperature and composition over the complicated geometry of a lamellae. If this assumption is invalid, as has been suggested.2,3 then the problem becomes too complicated to solve completely. The first of these analyses1 did not calculate the wavelength. A,. of the initially unstable perturbation. whereas the more recent analysis.' which led to a contradiction of this assumption. did not include one of the key factors for determining this wavelength. To rigorously determine the wavelength, the effect of the curvature of the perturbed interface (not considered by either of the above treatments) must be included. By omitting this term, one would be led to an incorrect conclusion regarding the magnitude of A,. but to an accurate criterion for stability as evidenced by the excellent agreement with experimental observations.' In the case of single-phase alloys. the critical wavelength. A,. for instability can be calculated from the Mullins and Sekerka4 (M.S.) analysis which includes the effects of capillarity. In the following discussion, the M.S. analysis is applied to lamellar eutectics and the critical wavelengths calculated for reasonable growth conditions in Pb-Sn eutectic alloys. In order to apply the M.S. analysis to eutectics. one may substitute i) the effective liquidus slope.1 m*. for the single-phase liquidus slope and ii) the ratio of the bulk alloy composition. C,. to the average interface composition in the liquid (Ci = CE where CE is the equilibrium eutectic composition) for the distribution coefficient to give:

Jan 1, 1970

By C. Dinis da Gama

In order to reduce the complexity of mechanisms influencing rock. fragmentation by blasting a simulation approach is proposed, using the capabilities of microcomputer interactive graphics. Situations involving cratering end bench blasting are simulated, and both jointed and intact rocks can be subjected to explosive action, taking into consideration its breakage mechanisms. Size analysis curves relating rock distribution before and after the blasts are determined and compared with field data.

Jan 1, 1984

By Waldemar Lindgren

CONTENTS. [ ] I.-CHARACTER OF THE DEPOSITS. 1. Principal Features. IN many schemes of classification and description the term contact-deposit has been somewhat loosely applied to all accumulations of useful minerals (other than those of unquestioned sedimentary origin) which are enclosed between two different rocks. As thus used, the term may include deposits of widely differing origin, and, unless qualified, is not in place in a genetic classification. The present paper deals with a special class of contact-deposits. In many geological provinces, granular igneous rocks, such as granite, diorite and syenite, have broken through and invaded sedimentary rocks. The molten magma may in part have reached the surface and there solidified with relative rapidity as a lava. The largest masses of it, however, did not reach the surface, but cooled very slowly at considerable depth under great pressure, and eventually consolidated into a rock of granitic texture. Uplifts and extensive erosion may have followed; and at the present day, in many places, thousands of feet of material have been removed, bringing to the surface the intrusive granular rocks and their once deep-seated contacts with the sedimentaries which they shattered at the time of in-

Jan 1, 1902

By F. P. Nichols, F. A. Renninger

At one time, mineral aggregates were considered physically and chemically inert substances whose junction was that of an inex-pensive, easily obtainable source of bulk. This philosophy applied regardless of the use to which the aggregate was put. Research approaches dealing only with such gross physical properties as hardness, toughness, impact resistance, etc., dominated the early growth years of the industry and influenced specifications to a large extent. The accelerated pace of highway construction, which began toward the end of the depression years, focused attention on the need for extensive aggregate research. The realization in the early 1940's that aggregates interacted chemically as well as physically with their environment provided the stimulus necessary to translate the drab, systematic aggregate technology of the early 20th century into the changing, dynamic, challenging field it is today. Current research problems are discussed in detail. These efforts being pursued by contract research organizations, universities, governmental agencies, and industry transcend many fields. The mineral aggregate industry is the world's largest mining and processing endeavor, yet it is graced with little of the romance or public awareness that accompanies mention of gold, silver, iron, copper, uranium, or aluminum mining efforts. Much of this reaction is undoubtedly due to the fact that the uses to which crushed stone and sand and gravel are normally put are not fully recognized or appreciated by the general public. Almost 2 billion tons of mineral aggregates are quarried or mined, processed, and sold yearly in the United States alone.= The largest uses to which this vast tonnage is subjected are as ingredients of portland-cement concrete, bituminous concrete, and dense-graded aggregate-base course mixtures in the highway and building construction fields, two industries closely related to the expenditure of public funds. It is for these uses, partially in justification for the expenditures of vast sums of public funds, that mineral aggregate research truly finds its emphasis. The research efforts expended relative to the highway and building construction uses to which mineral aggregates are subjected are those of primary concern to the industry. These efforts, while of direct consequence to the industry due to the volume market represented, are of interest as well to public agencies, universities, and contract research firms. All actively conduct research, exchange information, and make contributions to the overall knowledge relative to aggregate usage and limitations. The research efforts of the mineral aggregate industry is the subject to be discussed throughout this paper. It covers all aspects of highway and building design, construction, and technology. The effects of research pertaining to quarrying and mining methods, blasting and processing techniques, storage and handling facilities, and equipment employment and development have left their mark on the crushed stone and sand and gravel industries. Such specialized efforts have resulted in dramatically increased production rates which in turn have served to keep costs, and hence prices, down. Despite the many inflationary pressures over the years, the cost of a ton of aggregate today is little more than it was 25 or 30 years ago. Mention is made of these efforts simply to emphasize the diversity of research in the mineral aggregate field. The remainder of this paper focuses on the complexity of what might be termed "product knowledge" research.

Jan 1, 1971

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard' showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.' Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y' eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y' pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By Robert D. Pike

IN November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: [ ] Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2,3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depend¬ing upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1947