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By John P. Huger

me phase diagram for the system Ag-Si has been established by thermal analysis. The diagram is a simple eutectic type with a eutectic at 3.0 pct Si and 840°C. From the liquidus curve and with the aid of regular solution theory, the thermodynamic properties of the liquid Ag-Si system at 1420 °C have been determined. Silicon exhibits positive deviations from Raoultain behavior at all compositions, while silver exhibits both positive and negative deviations. MEASUREMENTS of silicon activities in liquid iron alloys by means of distribution studies between the immiscible liquids silver and iron have been reported by Chipman, Fulton, Gokcen, and caskey.' The applicability of this technique is dependent, however, on the accuracy of the silicon activity values in the Ag-Si alloys, particularly in the dilute silicon region. Darken and Gurry2 have shown that log ?si/(1-xSi)2 is approximately linear with composition, but uncertainty exists in the extrapolation to dilute solutions. Their calculations are based on the old Ag-Si phase diagram of Arrivaut3 and any variation in the position of the liquidus curves will strongly influence the extrapolation. The purpose of this study is to redetermine the Ag-Si phase diagram and calculate the associated thermodynamic properties. EXPERIMENTAL The Ag-Si phase diagram was determined by thermal analysis of liquid alloys. The alloys were contained in a 35 mm alumina crucible under a protective stream of purified argon. The crucible was placed inside a 64 mm alumina tube fitted with a gas-tight, water-cooled, copper head. The tube and assembly were heated in a manually controlled globar furnace. The temperature was measured with a Pt, Pt + 10 pct Rh thermocouple in a high-temperature porcelain protection tube. The thermocouple calibration4 was checked against the melting point of pure silver at the start and during the course of the experiments, and against both gold and silver at the completion of the experiments. The alloys were prepared from granular silver analyzing 99.95 pct Ag and powdered silicon analyzing 99.88 pct Si and 0.026 pct Fe. Approximately 150 g of alloy were used for each run. The composition of the alloy was determined by withdrawing samples of the liquid alloy with a vycor tube-aspirator bulb device. Analysis of solidified samples agreed, for alloys containing less than 23 pct Si, within ±0.3 pct Si of the calculated composition. Duplicate samples showed a variance within 50.05 pct Si of the mean analysis. The alloy was heated to 100' to 20pC above the estimated liquidus temperature and then the furnace was adjusted to give an average cooling rate of 2" to 7°C per min. A cooling curve was obtained by taking potentiometer readings at 15-sec intervals. Several analyses were made by recording the thermocouple output on a high-speed, Stip-chart recorder, with the exception of run NO. 11, a minimum of two thermal analyses were made for each alloy and the cooling curves then obtained duplicated the liquidus and eutectic temperatures to about 1°C. RESULTS The results of the thermal analysis are given in Table 1, and are represented as the Ag-Si phase dlagram, Fig. 1. The eutectic composition was found

Jan 1, 1963

By D. D. Pollock, D. I. Finch

PREVIOUS work' on a four-component system (Cu-Mn-Ni-Fe) resulted in the development of consistent relationships between the chemical composition and the electrical properties of these manganin-type alloys. The present study was undertaken to develop alloys with temperature coefficients of resistivity and thermoelectric properties more desirable than those of the manganin type, and to determine whether the relationships which had been found for the Cu-Mn-Ni-Fe alloys could be extended to five-and six-component alloy systems. PREPARATION OF ALLOYS The five- and six-component alloys were made from OFHC copper rod, ARMCO iron, electrolytic nickel, manganese cathode chip, and special high-purity aluminum and indium. A Cu-Mg master was used for deoxidation. The compositions of these materials are given in Table I. The alloys were melted and cast as indicated previously,' except that no cover was used and the melts were teemed. EXPERIMENTAL PROCEDURE The finished wire size of 0.0808 in. diam was again selected for the reason that the test specimens would be self-supporting, thus eliminating any extraneous effects which might have been introduced by winding smaller diameter wire on spools or forms. The following tests were performed on the finished wires: A) Chemical Analyses—All of the components of these alloys were determined by premium gravimetric methods. The principle residual impurity contained in these alloys is 0.008 pct Mg (by weight), maximum. Tables II and 111 present the mean analyses computed from at least four determinations of each constituent. B) Electrical Characteristics—The test procedures forthe determination of the thermal emf vs copper, resistivity, and the resistance-temperature relationship are given in detail in Ref. 1. It was also shown that the resistance-temperature relationship is of the form Pt = P,n + At -B/2, [1] where P, is the resistance at t C expressed in percent of a given standard resistance, P, is this per- 0 centage at 0°C, and A and B are constants for a given, properly treated, composition. The results of the electrical tests are also given in Tables II and 111. INTERPRETATION OF DATA The modified Linde2 formula, known to be valid for dilute binary solid solutions, was applied to the complex Cu-Mn-Ni-Fe type alloys. This relationship is of the form where Ap is the increase in resistivity. Zb the valence of the solute, Zn the valence of the solvent, and K and K are designations assigned by Robinson and Dorn3 to the constants for the periodic group to which solute element belongs. The units of K, are -cm per valence difference squared per at. pct; those of K2 are pa-cm per at. pct. For the sake of brevity, these units are not repeated in the following discussion. Calculations were made to determine if this formula was accurate for five-component systems. No experimental studies were made of the Cu-In and Cu-A1 binary systems. The effects of indium additions upon the resistivity of copper are given by Linde. These data, along with those of the effects of Mn and Fe, permitted the calculation of the effects of Al.

Jan 1, 1959

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By Verne E. Hooker, Robert M. Becker

The evaluation of in-situ rock stresses from measurements of the change in diameter of a borehole that is stress-relieved by overcoring has become a common practice. Generally the stress evaluation has been based on isotropic relations whereas rock in varying degrees is aniso tropic. A plane elasticity solution fora circular hole along one axis of an orthotropic medium has been adapted to evaluation of in situ stress. The necessary elastic parameters for this evaluation may conveniently be obtained from static tests on the overcore in conjunction with a consistent orthotropic thick-wall cylinder solution. The method and equations for the laboratory and field evaluations are summarized and illustrated. The determination of in-situ rock stresses from boreholc deformation measurements has gained widespread acceptance. Hastl measured the change in diameter of a borehole that was stress-relieved by drilling a larger concentric core; this overcoring method has produced a major portion of the field data for recent stress evaluations in rock. These evaluations are based on the elastic properties of the rock, which are conveniently determined by testing the overcore.6-8 The stress evaluation and the overcore testing procedures generally assume isotropic relations whereas rock is anisotropic in varying degrees. Recently, an anisotropic plane stress solution was adapted for evaluation of in-situ stress9 and a related plane strain solution was developed for the testing of stress-relief core. 10 The present paper unifies the stress evaluation and overcore testing procedures for a general class of anisotropic rock. Equations are presented for calculating the state of stress in a plane normal to the borehole, and a consistent thick-wall cylinder solution is given for determining the necessary elastic properties. In addition, a complete example of stress evaluation from laboratory and field data is presented, and the order of error in computing the state of stress from isotropic relations is illustrated. Several limitations of the results should be emphasized. All results assume small linearly elastic deformations of a homogeneous medium. Rock characterized by orthotropic, transversely isotropic, and isotropic elasticity is considered; however, the anisotropic results assume a special relation among certain elastic constants in addition to geometric orientation with respect to a plane of elastic symmetry. For some stress determinations in rock, these may be severe limitations. On the other hand, the anisotropic evaluation procedure involves little additional effort and is much more flexible than the corresponding isotropic evaluation procedure. The collection of field data is identical. The laboratory determination of elastic parameters is no more difficult and time-consuming for the anisotropic than for the isotropic model. Only the calculations require some additional effort for the anisotropic evaluation, and this additional effort is eliminated by use of a small computer. The flexibility of the anisotropic procedure is greater because more than two independent elastic constants are available in fitting rock data. For the special relationship assumed among orthotropic constants, five independent elastic constants are available for the determination of in-situ secondary principal stresses as compared with two independent elastic constants for the isotropic model. Much of the material presented is either directly from the literature or adapted from the literature through superposition or the usual transformations. Consequently, only enough detail for clarity of presentation is included. RELATIONS FROM ANISOTROPIC ELASTICITY Materials that have three mutually orthogonal planes of elastic symmetry are called orthotropic. By directing the axes of the coordinates perpendicular to these planes, Hooke's law for an orthotropic solid 11 is

Jan 1, 1970

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By Vernon Read, John K. Hayes

Generally speaking, drilling equipment and techniques presently in use are not capable of meeting the complex technical-and economic-requirements of deep core drilling. Drilling to great depths involves increasing risk, time, and money. And it is especially true that costs increase with depth when conventional core drilling methods are used. Introduction of wire-line drilling techniques has been a great boon to deep core drilling, and is rapidly gaining general acceptance. But, in spite of recent progress, there remains a great need to improve productive drilling time and penetration rates, and still maintain high core recoveries.

Jan 1, 1959

By H. H. Podgurski

Above 200°C the observed increase in the apparent solubility of hydrogen in low alloy steels caused by cold work is attributed to the formation of methane in microvoids. This methane can be isolated quantitatively, and furthermore, the amount of methane is in accord with the equilibrium 2H2 + Fe3C = CH4 + 3Fe. The micro-void volume, calculated from the methane content via the equation of state for methane, corresponds approximately to that calculated from the measured density decrement produced by cold work. THIS investigation was undertaken with the intent of employing the hydrogen atom as a probe in detecting specific crystallographic defects in cold worked steel. It was expected that different degrees of chemical interaction of hydrogen with the various types of defects could be utilized. The original aim was to assign concentration values to defect sites. The success of this approach requires that experimental conditions can be attained under which lattice-dissolved hydrogen equilibrates primarily with only one type of defect. A set of experiments which appeared potentially to embody these requirements was described several years ago by Keeler and Davis.1 They noted in the case of a mild steel (low carbon) that the solubility of hydrogen between 200° and 400°C near atmospheric pressure was notably increased by cold working the steel. The observed solubility was an order of magnitude greater than the normal lattice solubility. * Although the Keeler and Davis studies suggested that the density decrement effected by their cold-working operation might be related to the anomalous solubility of hydrogen, they offered no explanation of the relationship between the two effects. Prior to this work, Darken and smith3 had noted a similar effect of cold work upon enhanced sorption of hydrogen by steel when charged by acid pickling. In the light of present-day concepts, interaction between lattice-dissolved hydrogen and dislocations was strongly suggested. More recently, Hill and Johnson,4 working with a

Jan 1, 1962

By H. H. Stoek

The origin of the Mine-Rescue Service of the State of Illinois can be traced to two distinct sources, the work of the Rescue Station at Urbana and the Cherry disaster. During the early part of the year 1909, the Technologic Branch of the U. S. Geological Survey, now the Bureau of Mines, in connection with the Illinois Geological Survey and the College of Engineering of the University of Illinois, established at the University of Illinois, in Urbana, a branch rescue-station to supplement the work of the Pittsburg station of the Geological Survey. As a result of the work of training at the station in Urbana by R. Y. Williams, mining engineer, and James Webb, foreman of the Bureau of Mines, and the use of the helmets at several mine-accidents in the State of Illinois, the people of the State were somewhat familiar with oxygen-helmets when the Cherry disaster occurred, in November, 1910. The oxygen-helmets were successfully used in connection with that disaster, and upon the recommendation of the Illinois Mining Investigation Commission, the Legislature of the State, assembled in special session during the winter of 1910, passed a bill appropriating $75,000 for the erection and maintenance of three rescue-stations, stipulating that they should be situated in the northern, central, and southern parts of the State. The Act also provided that the stations should be in charge of a Commission of seven, two representing the United Mine Workers of Illinois, two the mine-operators, one the Federal Bureau of Mines, one the State mine-inspectors, and one the Department of Mining Engineering of the University of Illinois. This Commission was called together by the Governor of the State, Aug. 2, 1910, and since that time three stations have been placed, built, and equipped: at La Salle for the northern

Jan 1, 1912

By C. van Dijk

In Sept., 1960, a steam-drive project was started in the solution-gas drive area of the Schoonebeek field. A part(ern of three five-spots and one four-spot was selected covering an area of 65 acres. The pay in the project area has good lateral continuity and dips slightly to the northeut; it is about SO ft thick and permeability increases from 1,000 and at the bottom to approximately 10,000 md at the top. The oil originally in place was 12.6 X 10' bbl. The oil has an in situ viscosity of about 180 cp. At the start of the steam drive the cumulative primary production due to. solution-ga.7 drive amounted id 4 Percent of the oil originally in place. Reservoir pressure had dropped about 120 psi and no significant primary re-.serves remained. Some 11.3 million bbl of steam (all steam quantities are expressed in barrels of water vaporized) have been injected, resulting in production of an additional 4.1 X I0 9bl of oil, or 33 percent of the oil originally in place. This corresponds to a cumulative oil-stearn rario of 0.37 bbllbbl. It appears that the steam preferentially moves r updip while liquids are produced mainly from downdip wells observations indicate that tile steam flows through only the upper part of the formation. The lateral steam distribution in the pattern is satisfacrory since several prodriction wells hardly reacted and, hence, cori tributcd little to the oil production. Production performance and results from material balance calcutlations agree satisfactorily with the results of large-,scale laboratory experiments. On the basis of these experirmental results the .steam drive, together with a cold water follow-up. is expected to bring ultimate recovery to a value of crt leas: 50 percent of the oil originally in place. No serious production problems have been encountered. However, due to mechanical fuilure, two old prodriction wells and one injection well had to be replaced. An extension of the. steam drive in this area is under connstruction. Introduction The Schoonebeek oil field, discovered in 1943 and developed after World War 11, is situated in the eastern part of the Netherlands. The main oil reservoir in this field is the Valanginian sand. A completely sealing fault divides this reservoir into two areas (Fig. 1): the southwestern part of the sand body where primary production is ob- tained by means of a solution-gas drive, and the remain. der where edge-water drive is the production mechanism. In the greater part of the field the reservoir consists of a single, unconsolidated sand body. The net thickness ranges from 30 to 100 ft and the top is between 2,400 and 2,800 ft below sea level. Formation permeability varies from approximately 10,000 md at the top to values of the order of 1,000 md at the bottom, and porosity is about 30 percent. The reservoir contains a paraffinic oil of 25" API gravity with an in situ viscosity of 160 to 180 cp. Initial oil saturation was high (85 to 90 percent). The relatively large quantity of oil in place (more than 10' bbl), and the low ultimate primary recoveries expected from this field — approximately 15 percent stock-tank oil initially in place (STOIIP) for the water-drive area and 5 percent STOIIP for the solution-gas drive area — clearly indicate ample scope for secondary recovery. Because ies-ervoir and crude characteristics made this field suitable for thermal secondary recovery, a hot-water drive project was started in the water-drive area about 10 years ago. A few years later a steam drive and an in situ combustion project were started in the solution-gas drive area. This paper deals with the performance of the steam-drive project, which was started in Sept., 1960, and which is still in operation. Design of Steam-Drive Project, An experimental investigation of the steam-drive process carried out by schenk in 19561 indicated that under schoonebeek conditions steam injection could be an attractive secondary recovery method. the findings and encouraging results of a pilot test in the Mene Grande field in venezuela,i led to the design of a steam-drive project in the schoonebeek field, Pruject Site and Pattern In 1958 the reservoir pressure in the solution-gas drive area had decreased to about 120 psi, and oil production rates of wells in this area had dropped to 7 to 10 B/D. The cumulative primary production was about 4 percent STOIIP, leaving an oil saturation of approximately 85 percent. In view of the large amount of oil left behind in the reservoir, the solution-gas drive area was selected for the planned steam-drive project. The area in the vicinity of Well S1 3 (Fig. 2) was considered to be suitable since it is at least partly isolated from the rest of the field by faults and the sand is relatively thick (about 80 ft).

Jan 1, 1969

By W. G. Woolf, A. Y. Bethune

Filtration of hot (60°C) supersaturated zinc sulphate solution (sp gr 1.540) from slimy leach residues at the electrolytic zinc plant of Sullivan Mining Co., Kellogg, Idaho, is described. Separation of liquids and solids in the finished leach is by Burt filters modified to meet conditions of high-acid, high-density process for electrolytic zinc. Operating characteristics of the Burt filter on this pulp are presented.

Jan 5, 1950

By C. M. Loeb, A. M. Gaudin, J. H. Brown

THE object of most size reduction operations in the mineral industry is to liberate the grains of valuable minerals in the ore from those of the gangue. This is usually accomplished by crushing and grinding the entire mass of ore until there is only a small probability that any single particle contains more than one mineral. During this size reduction only limited control exists over size or composition of the particles exposed to the breaking action, and there is no control over the paths followed by cracks generated during the operation. This lack of control usually results in overgrinding and in production of large quantities of very fine material. The first detriment, overgrinding, is costly in itself, but when combined with the second factor it is doubly so. Not only is the fracture of a free particle unnecessary—the fracture of these particles may also make subsequent separation operations difficult, inefficient, and wasteful. It has been pointed out' that if the object of size reduction is to liberate the valuable mineral component of the ore then, ideally, fracture should follow intergranular paths to the exclusion of trans-granular ones. This would result in liberation of the valuable minerals with as little size reduction as possible. This ideal comminution operation is referred to as intergranular comminution, and it was the object of the investigation to determine the extent to which it could be developed by heat treatments. There are many indications in the literature that heating rocks prior to crushing may be favorable. Reports by Holman,2 Yates3 and Myers' are pertinent. These investigators showed that heating certain rocks prior to crushing them did, in fact, improve their crushing characteristics in that fewer fines were produced, although the fact that intergranular comminution was being effected apparently was overlooked. In addition, Sosman noted that if there is appreciable anisotropism in the thermal coefficients of expansion of even a pure mineral, then considerable permanent separation of the grains of the rock can be expected as a result of heating the rock to a high temperature.' By the same token, if there are ap- preciable differences in the thermal expansion coefficients of the various minerals of a multi-component rock, similar results should be obtained by heating this rock. This has been tested, partially, by Brenner," who obtained patents covering the heat treatment of some pegmatitic rocks in order to facilitate comminution of these materials. It has also been demonstrated that this may occur in taconite." Also, the possibility of causing decomposition of one mineral in a rock as a means of promoting intergranular fracture has been considered. Seigle2 and Schiffman et al. have obtained patents on such processes as applied to calcareous iron ores. These reports all indicate that heat treatments prior to crushing may contribute materially to intergranular comminution, but they also indicate that no organized attempt has been made to determine the controlling factors of the method or to determine its applicability in general. The present article is a report on the initial phase of such an investigation. The authors have reviewed the claims of prior investigators and have attempted, also, to establish the factors that might determine the applicability of heat treatments in the mineral industry. In this work 2000-g samples of various rocks were heated in a small laboratory furnace and crushing and sizing operations were carried out in standard laboratory equipment. All samples of each rock were as nearly identical as possible in particle size, grain size, and composition and contained only lumps coarse enough to contain many grains each. Tests on Granite A number of tests were made on a coarse grained Finnish granite obtained in the form of coarse chips from a local monument yard. This rock exhibited little variation from piece to piece in either composition or grain size. The minerals contained were quartz, orthoclase, small amounts of hornblende, and minute quantities of mica. Grain size ranged from about 1 mm to about 3 mm. Temperature of the Heat Treatment: In some cases the granite was heated to a particular temperature and crushed, hot, immediately upon withdrawal from the furnace—in others the rock was allowed to cool before crushing, but without quenching to room temperature after heating. In most tests on granite the heating period was about 2 hr with the furnace at the highest temperature for about 1 hr. Cases in which these periods were varied greatly will be presented separately.

Jan 1, 1959

By John Garcia

IN some districts of the bituminous coal field the problem of construct-ing bulkheads to seal off water under pressure is becoming increasingly important. Recently this matter has been brought very much to the front by the loss of a large. Illinois mine due to failure of a bulkhead that separated it from several old, flooded mines. As this great misfortune has provoked much inquiry about proper bulkhead design, it is felt that a description of the successful and extensive water-sealing practice at three mines that have different natural conditions will be of considerable interest to those connected with properties having a present or future water problem and to engineers that may have to design safe bulkheads of economical construction. These three mines are the Saxton acid Dresser, near Terre Haute, Ind., and the Hegeler, near Danville, 111. All three have water conditions that make it necessary to regularly seal off till worked-out sections of the mine, and there are considerably over a hundred bulkheads in each. As far as the writers know, these three mines are the only ones in the bitu-minous coal fields of the United States with anything like so large a number of water seals and experience, although a number of other mines are known to have a few bulkheads. More detail will he included herein on the Saxton mine than on the others, as the writers are more familiar with it.

Jan 1, 1937

By H. A. Doerner

PROPOSALS to use hydrocarbon or natural gases for the reduction of zinc from oxide materials may be traced back through Patent Office files to the early years of the present century. Natural gas at rates cheap enough to compete with solid fuels has been available at or near one major zinc district for more than a decade. That the seemingly meritorious and economically interesting applications of these proposals have not devel-oped into workable processes for direct production of zinc by natural gas cannot be completely ascribed to the proverbial conservatism of the zinc industry. It is possible to produce spelter commercially in normal times from zinc oxide and carbonaceous reducing agents without having a very precise understanding of the chemistry of the process. The reduc-tion by hydrocarbons is not, however, in this class, and the technical complexity of this reduction metallurgy and chemistry prohibits solution of the inherent difficulties by the "hit and miss" methods that are some-times thought to be practical. In a thermodynamic study of the chemistry of zinc smelting, Maier1 made a preliminary study of the chemistry of the use of methane for reducing zinc oxide by thermodynamic means, pointing out that the following reactions, the limits of which could be theoretically predicted, were important: ZnO + CH4 = Zn(gas) + CO + 2H2 [1] CH4 = C -I- 2H2 [2] ZnO + CO = Zn(gas) + CO2 [3] ZnO + H2 = Zn(gas) + H2O [4] Other possible reactions, not discussed in the reference quoted, are: CO2 + CH4 = 2CO + 2H2 [5] H2O + CH4 = CO + 3H2 [6]

Jan 1, 1933

By C. H. Mathewson

MICROSCOPIC rnetallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent microstructural mosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atomis or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientations and it is always possible to derive one from the other by some form of rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4'9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13'14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

In reply to inquiries and comments which have reached me since the publication of this paper, and in explanation of some seeming discrepancies between my statements in the text concerning the amount of displacement of the faults, on one hand, and certain figures in the plates on the other hand, I give here, with some additional remarks, my measurements of the displacements in the different sections, which it originally seemed unnecessary to print : By displacement, I mean neither the throw, i.e., the vertical distance apart of the two edges of a faulted bed (what Mr.

Jan 1, 1896

By G. B. Gould

Every mathematical statement of a measure of anything (as distinguished from a count') is followed by a qualification—always implied if not explicity stated—-that the statement is only an estimate, which may vary from absolute accuracy within certain limits, according to the accuracy of the measuring instrument. This basic fact, so obvious to engineers, is not so well understood by many that make use of laboratory coal tests. The tolerances that must be allowed in measurements of coal quality are very important in both their commercial and engineering applications—and the significance of these tolerances depends upon the use made of the laboratory coal test. Only in recent years has there been any intensive study of this question of tolerances as applied to measurements of coal quality. There is very little in our published literature on the subject, and what has been published is not readily comprehended by those who sell coal, or buy coal and use it, unless they happen to have made a study of the subject themselves. There is great need for more widespread understanding of what lias been discovered and how it applies to the use of laboratory coal tests. What follows is an attempt to condense into a few pages the results of the major investigations so far reported, and to explain their meaning in simple nontechnical language, with the addition of some recent illustrative experiments. Determining Deviations in Quality It is necessary at the outset to distinguish between: (I) the accuracy with which one test indicates the quality on one lot of coal; and (2) the accuracy with which a test of one lot of coal represents the average quality of a commercial product, of which the buyer will presumably receive a series of shipments—perhaps many thousands of tons. It is necessary to make this distinction because coal is a variable material—a heterogeneous mixture of a variety of components—the quality of which will vary from one lot to another. Therefore an absolutely accurate determination of the quality (if that were possible) of one lot of a coal is an

Jan 1, 1938

By G. B. Gould

Every mathematical statement of a measure of anything (as distinguished from a count') is followed by a qualification—always implied if not explicity stated—-that the statement is only an estimate, which may vary from absolute accuracy within certain limits, according to the accuracy of the measuring instrument. This basic fact, so obvious to engineers, is not so well understood by many that make use of laboratory coal tests. The tolerances that must be allowed in measurements of coal quality are very important in both their commercial and engineering applications—and the significance of these tolerances depends upon the use made of the laboratory coal test. Only in recent years has there been any intensive study of this question of tolerances as applied to measurements of coal quality. There is very little in our published literature on the subject, and what has been published is not readily comprehended by those who sell coal, or buy coal and use it, unless they happen to have made a study of the subject themselves. There is great need for more widespread understanding of what lias been discovered and how it applies to the use of laboratory coal tests. What follows is an attempt to condense into a few pages the results of the major investigations so far reported, and to explain their meaning in simple nontechnical language, with the addition of some recent illustrative experiments. Determining Deviations in Quality It is necessary at the outset to distinguish between: (I) the accuracy with which one test indicates the quality on one lot of coal; and (2) the accuracy with which a test of one lot of coal represents the average quality of a commercial product, of which the buyer will presumably receive a series of shipments—perhaps many thousands of tons. It is necessary to make this distinction because coal is a variable material—a heterogeneous mixture of a variety of components—the quality of which will vary from one lot to another. Therefore an absolutely accurate determination of the quality (if that were possible) of one lot of a coal is an

Jan 1, 1938

By Saburo Shigeno, Kunzo Amano

As shafts and tunnels move deeper levels in underground mining, development planning becomes more complex. The most serious problem is the aggravation of environmental conditions due to the imposition of higher-than-natural temperatures upon exposed strata. Since such a problem is a potential hazard to health, safety, and production, the authors have developed a system of computer-derived ambient-air temperature data for every major point of an underground mine under a given set of conditions. This system is comprised of two subsystems: 1) Ventilation network analysis, 2) Estimation of air - current temperature. The former is based on the Hiramatsu-Oka method, an improvement of the Scott-Hinsley method. The Hiramatsu-Oka method allows fast convergence and consideration of various fan characteristics. The latter subsystem considers heat radiation from strata, and the humidity. In several tests conducted at Besshi and Sazare Mines of Japan, the computer-derived data correlated with actual conditions.

Jan 1, 1969

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute's influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger's argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.' Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute's influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute's influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968