Search Documents

Jan 1, 1943

I-Mine Ventilation A. C. CALLEN, Chairman E. A. HGLBROOK, Vice-chairman H. I. SMITH, Secretary CLARENCE E. ABBOTT ALFRED W. HESSE FRANK H. PBOBERT GAM BRIGHT G. R. JACKSON GEORGE S. RICE THOMAS H. CLAGETT JAMES F. MCCARTHY E. J. RISTEDT . OSCAR A. GLASSER W. B. PLANK GERALD F. SHERMAN Coal Mining M. D. COOPER, Chairman HOWARD N. EAVENSON JOHN A. GARCIA THOMAS D. THOMAS CHARLES ENZIAN JAMES W. PAUL C. M. YOUNG JOHN J. RUTLEDGE

Jan 1, 1929

New York Holds monthly meetings, except June, July and August J E SPURR, Chairman A D BROKAW, Vice-chairman SIDNEY ROLLE, Vice-chairman M H MERRISS, Secretary-treasures, Nichols Copper Co, 25 Broad St, New York M F CHASE KARL HOFFMAN Boston Meets first Monday of each winter month C R HAYWARD, Chairman E C GEITHER, Vice-chairman D H McLAUGHLIN, Secretary-treasurer, Rotch Bldg, Harvard Univ Cambridge, Mass GEO H GILMAN GEO A PACKARD

Jan 1, 1923

By James S. Browning, B. H. Clemmans

BERYLLIUM, obtained mainly from the beryllium-aluminum silicate, beryl, is one of our most strategic and critical metals. Strategic because suitable substitutes for many of its alloys have never been developed. Strategic because of certain uses and potential uses of a classified nature in our nuclear energy program. In this field, substitutes have been developed, but only at the expense of a reduction in efficiency.

Jan 8, 1953

By C. E. Turner, J. R. Elenbaas, R. D. Grimm, J. A. Vary, D. L. Katz

A technique is presented by which well samples and core plugs of dolomite formations are classified by microscopic examination into seven different porosity grades. Quantitative values of porosity and permeability are determined for each grade by a statistical correlation of the core plug test data with the porosity grading system. These quantitative values are applied directly to the grades exhibited in the well samples for the purpose of estimating the reservoir void space for wells that were not cored. The procedure is described for estimating the gas reserves per unit area lor the South Hugoton gas field. but a reserve estimate for the field is not given. INTRODUCTION The miscroscopic examination of well sample; and the graphic recording of their lithologic qualities and other distinguishing characteristics of various geologic formations drilled is both a science and an art of long standing and wide application. Usually the primary objective of a geologist who "sits on the well" and examines the samples are: to identify the formation being drilled, determine the total depth, casing point. and completion interval. In most cases the porosity is described. if done at all, in general terms. such as: trace, scattered, fine, poor, fair, medium. good, excellent, or in some other relative terms. In fields where various geologists have examined samples and recorded observations on many wells considerable variations in lithologic terms and porosity descriptions occur unless there is primary effort to establish uniformity of logging observations and standards of recording observable porosity. When an estimate of the pore volume of a reservoir is made a geologic concept of the processes that control the magnitudes of porosity and permeability is developed by microscopic examination of well samples. The characeristics and appearances are then mentally related to rather general quantitative units of porosity based on physical core data from the same reservoir or on such data or experience in other reservoirs that have similar qualities. The reliability of such estimates depends largely on the variations of the lithology of the formations, the geometric properties of its void system. the extent of comparisons of sample appearances with porosity data, as well as the uniform recording of all relevant characteristics. This statement is particularly significant for dolo-mitized limestone formations of substantial thicknesses and heterogeneity such as the Permian Dolomites of the Hugoton gas field. Jn this field, as well as in most of the Permian Dolomite fields, the producing formations are of relatively great thicknesses in which the porosity and permeability of the reservoir varies substantially in all directions, depending on the crystalline structure. degree and kind of impurities, kind of fossils anti cementation thereof, degree of dissolution. and fracturing. The variations of the lithologic texture of the dolomites and post deposition alterations have resulted in porosities and permeabilities of such magnitudes that only a part of the gross thickness can be counted as "pay." At the time of this study insufficient gas production had been experienced to apply the pressure decline production method in the South Hugoton Field and the electric logs are not definitive enough. The problem of estimating gas reserves in the south part of the Hugoton Field is primarily one of determining the pay thickness and porosity from well samples and core data. The area studied embraced all that part of the field lying south of an east-west line through Guvmon, Okla., anti containing approximately 1.000,000 acres. This paper describes a technique of correlation of physical core data with well samples so that quantitative values of pay thickness, porosity. Permeability, and connate water may be assigned to well samples that are representative of a given interval, and thereby permitting the estimation of gas reserves lor a given unit area. The procedure was developed by a uniform microscopic qualitative porosity grading of the dolo. mite core plugs.. and relating these grades to the respective physical core data on a statistical basis The well sample-were also graded in a Similar manner in order that the quantitative values established lor the core plugs could be applied to the well Sample for wells that were not cored. GRADING OF DOLOMITE A group of experienced geologists was given the assignment of examining the samples on all wells in South Hugoton in order that they could log their observations in a uniform and standardized manner and grade the observed porosity so that it could be related quantitatively to the core data. The group initiated the study 011 chips from cores which bad been tested for porosity and permeability. This study continued until all of the geologists developed a common knowledge of lithologic terms and of the characteristic appearances of the samples and their relations to measured porosity. The characteristic appearances of the dolomite samples under twelve-power magnification as related to their qualitative porosities afforded a classification of the dolomite into :even grades of porosity, ranging from dolomite of no-visible porosity under twelve-power magnification to dolomite of excellent porosity. The assigned grade for a specific 10-ft interval is a weighted average of all visible grades of porosity exhibited by the cuttings representing that interval. The porosity characteristics were recorded by a color graph adjacent to the lithology column in conjunction with a numerical system for further definition of relative porosity as shown in Fig. 1. The three vertical lines to the right of the lithology column each represent 33 1/3 per cent. which lines were used to record the percentage of the samples, for any particular interval. that showed porosity under the microscope. The colors were used to denote actual pore size. i.e., orange. blue and I-ed for pore diameter of one-fourth or less. one-fourth to one-Ilalf. and greater than one-half millimeter, respectively. The area colored 1)). one or more colors represents the percentages of the samples exhibiting pores of the respective size or sizes. The numerals from one to six inclusive shown on the log in

Jan 1, 1952

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By T. A. O’Hara

SINCE May 1948, when tungsten carbide bits were introduced at the Flin Flon mine, they have been popular with the miners because of their fast drilling speed and low gage loss. The high cost of commercial carbide bits and tipped drill steel, however, prevented their use except for the hardest rock. In an effort to extend the use of tungsten carbide on a basis economically competitive with detachable steel bits, experimental work was begun in 1950 to test the feasibility of making tungsten carbide tipped drill steel in the mine drill steel shop. This work showed that tipped drill steel could be made locally at less than half the cost of the commercial product. The performance of the local tipped drill steel was comparable to that obtained with commercial carbide bits and tipped drill steel and the cost per foot drilled was much lower. Local tipped drill steel was adopted for all mine drilling in November 1951. Since then drilling costs per foot have been sharply reduced and footage drilled per manshift has increased markedly. Experience at Flin Flon has shown that production of satisfactory carbide tipped drill steel is not difficult and that highly skilled labor and costly equipment are not required. As long as wise selection of brazing materials is made and certain simple precautions are rigidly maintained, there is no reason why small mines with relatively unskilled labor cannot produce a satisfactory product. The following description outlines the technique used at Flin Flon for making carbide tipped drill steel and discusses characteristics of the brazing process that make special precautions necessary. Drill steel is forged to four-wing shape in a conventional steel sharpening forge. Standard steel dies are modified to minimize forging cracks around the central waterhole and to forge a blunt bithead on the steel. The steel is preheated to 1500°F and held at this temperature for at least 2 min. When the temperature has equalized throughout the steel section, the drill steel is transferred to the forging furnace and heated rapidly with a reducing flame up to 2000°F. This two-stage method of heating minimizes the grain growth and decarburization of the steel while ensuring that the steel temperature does not vary greatly throughout the forging zone. After forging the steel is allowed to cool in air to about 1600°F before being annealed in a bath of vermiculite. Despite the high hardenability of the 3 pct Ni-Cr-Mo drill steel used, this simple treatment anneals the drill steel sufficiently for milling. The forged and annealed drill steel is slotted on a plain horizontal milling machine that is equipped with a quick opening chuck and a slot depth stop. The full depth of the slot is milled in a single pass of the 3-in. milling cutter which is fed at 33/4 in. per min across the crown of each bit wing. The slots are cut to a width of 0.342 to 0.344 in. Maintenance of this slot width is necessary to ensure that the optimum brazing clearance of 0.002 in. will result after assembling of shims and carbide in the slot. Prior to March 1953, when the milling machine was installed, drill steel was slotted on a small manually fed ¾ hp milling attachment mounted on the bed of a lathe. Over 16,000 drill steels were slotted on this unit, and in view of its small size and low cost it gave excellent service. Brazing of Tipped Steel Drill steel that has been milled and cleaned in carbon tetrachloride is mounted in a rotating cradle holding six drill steels, the length of which may be from 2 to 12 ft. The slots in the drill steel, the shims, and the tungsten carbide inserts are thoroughly fluxed with a fluoride flux and assembled as shown in Fig. 1. Fig. 2 shows the brazing equipment in use. As the ring burner is lowered over the bithead a spring valve opens the gas lines, and the gas mixture, preset to give a slightly reducing flame, is fed to the ring burner where it is lit from a pilot flame. The ring burner heats the drill steel over a zone about 1 to 2 in. below the bithead, which becomes heated by conduction through the steel. By this means the bithead is heated rapidly and evenly, and contamination of the brazing joint with soot from the flame is avoided. The bithead is heated to the melting temperature of the brazing alloy within 1 min. This rapid heating minimizes the disadvantage of a non-eutectic brazing alloy. The brazing alloy, a nickel-bearing quaternary alloy, is placed at the bottom of the slot below the carbide insert, as shown in Fig. 1. As the brazing alloy melts it is drawn by displacement by the carbide and by capillary action into all parts of the joint to displace liquid flux from metal surfaces. As soon as the brazing alloy melts, each insert in turn is wiped by being moved back and forth along the slot. This action assists wetting of the carbide by the brazing alloy and assists in displacing molten flux from the joint. After continuous heating for about 75 sec, when the bithead has reached a temperature of about 1500°F, the ring burner is raised and the gas supply is shut off automatically by the spring valve. As soon as heating is stopped a hand press is placed on the bithead and the inserts are squeezed down firmly. This action minimizes the clearance between the bottom of the insert and the slot. Correctly brazed steel should maintain a clearance at the bottom of the slot of 0.001 to 0.002 in. After six steels have been brazed they are removed from the cradle and allowed to cool in air. As soon as each drill steel is cool it is dressed on a grinding wheel to remove excess flux and braze and is ground to the gage appropriate to the length of the drill steel.

Jan 1, 1955

By S. D. Strauss

Mr. Strauss takes apart the double threat of monopoly and failing resources in this article. Originally presented before the American Electroplaters Society, the basic contents o f his message are a warning that traditional trust-busting and mineral shortage concepts have been outdated by the broadened scope of competition. But to the miner, stoic before the cyclical predictions of feast and famine, traditional markets aren't getting any easier.

Jan 8, 1961

By William A. Prichard

After a study of the excellent geological reports and maps prepared by the United States Geological Survey,? and after practical experience in working the ore-deposits in this field,

Jan 1, 1904

By G. Knight

In most mines the major contribution to the dust exposure of miners arises from rock hand- ling. Scooptrams are frequently used and produce 8 to 1300 mg of respirable dust for each ton of ore loaded. It is shown that sprays at drawpoints are not fully effective in wetting the rock and suggestions for improved wetting techniques are given. Techniques for improved dust control by ventilation and local filtration are described. The problem of dust from ore- passes and dumps on tramming levels are outlined.

Jan 1, 1981

By John W. Stevenson

In gassy coal mines, abandoned worked-out areas are natural reservoirs that may contain air- methane mixtures. The quantity of such mixtures is continuously increasing or decreasing as atmospheric pressure falls or rises. This is in accordance with Boyle's Gas Law, which states that the volume of a perfect gas varies inversely with the absolute pressure. In large, open gob areas without a bleeder ventilation system, atmospheric pressure is a static force acting in all directions. Changes in atmospheric pressure may occur rapidly or slowly, but any change will result in a change in the quantity of gob air-methane mixtures.

Jan 6, 1968

[ ]

Jan 1, 1938

Jan 1, 1931

Jan 1, 1943

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-' the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:' and, if some simplifying assumptions about particle shape are allowed, the total number of particles.'2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.' Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400'F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y' precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y' precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10' to 10' cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975'F for 4 hr.

Jan 1, 1970

By W. C. Hellyer, R. A. Campbell

In single-stage autogenous grinding, the buildup of a critical size fraction in the media can be corrected by removing this material through pebble ports, crushing it below the critical size range, and recycling the crusher product back to the mill. The rate at which the critical sire fraction is crushed affects the size distribution of the grinding media and this in turn affects the sire distribution of the grate discharge. This provides a means for controlling the grind produced by a single-stage autogenous grinding unit. The pilot-plant investigations on a very hard copper ore were carried out at the facilities of the Institute of Mineral Research, Michigan Technological University. In an autogenous grinding circuit in which feed at approximately 9 in. top size is reduced to a size suitable for subsequent processing, the build-up of a "critical size" fraction in the media causes problems. A "critical size" fraction has been defined as, "media too small to effect reduction by impact grinding of ore coarser than a quarter of an inch and too large to be broken by the largest size of media in the charge."' The buildup of a critical size fraction reduces the capacity of the mill, increases the grinding power requirements per ton of finished product, and generally produces a finer grind than is desired. It is general practice to overcome this problem by the addition of large-diameter steel balls to the grinding charge. This has certain disadvantages, such as 1) an increase in mill liner wear, 2) wear on the steel balls, and 3) some loss in flexibility in grinding circuit opera-tions resulting from difficulties in removing the steel balls by means other than by grinding out. A number of investigators' have suggested the use of a small crusher as an alternative to the use of large steel balls for control of a critical size fraction. With this technique the critical size fraction is removed from the mill continuously through suitable-sized pebble ports, crushed below the critical size range, and returned to the mill. An external crusher would cause no increase in mill liner wear, the wear on the crusher would be less expensive than the wear on the steel balls, and the flexibility of the grinding circuit operations would be enhanced since the crusher can be cut into and out of the circuit at will. This paper describes an autogenous grinding pilot plant investigation on a very hard copper ore, which led to the selection of an autogenous grinding flowsheet incorporating a crusher in the circuit as the preferred method for grinding this ore. Further development of the technique demonstrated that the crusher could be employed to control the product produced by an autogenous grinding unit. Description of Pilot Plant These investigations were carried out at the pilot-plant facilities of the Institute of Mineral Research, Michigan Technological University, Houghton, Mich. The autogenous grinding unit was a 6-ft-diam by 2-ft-long Hardinge Cascade mill with %-in. slotted steel grates. Pebble ports cut into the grates allowed passage of pebbles having a top size of approximately 21/2 in. The grate and pebble-port discharge material passed over a 3/16-in, trommel screen with the trommel under -size being pumped to the classification device. DSM screens were employed for classification in the early investigations, but were replaced later by a small Dorr rake classifier. The trommel oversize material returned to the mill via scissor conveyors. When the crusher was incorporated into the circuit, the trommel oversize material passed to a double-deck vibrating screen fitted with 2-in. and 3/4-in. square mesh screen cloths. The $ 2-in. and the —2 +3/4-in. size fractions were combined and crushed to a nominal 1 in. in a 4 x 6-in. jaw crusher. The crusher discharge and the —3/4-in. screen undersize returned to the mill. In the final investigation, a flap gate fitted to the top deck of the screen directed the — 21/2 +2-in. size fraction to the crusher or back to the grinding mill. The flap gate operated manually on a 15-min cycle, with this material being crushed for so many minutes out of each cycle. This was found to be a more reliable method of controlling the amount of — 21/2 +2-in. material crushed than attempting to make a split of a small weight of material on a continuous basis. Operational Techniques: Each sample was sized into three fractions and the Cascade mill feed was reconstituted from these size fractions in the proportions existing in the original sample. Sufficient feed for 15 min operation was weighed out and fed by hand over a 15-min period. The gross mill power draft was recorded every 15 min, corrected for tare power and drive efficiency, and reported as net kilowatt-hours per ton. A recording kilo-watt-hour meter provided a continuous visual record of the power drawn by the mill. Pulp densities of the trommel undersize and the classifier overflow (or DSM undersize) were taken every 15 min. The classifier overflow was sampled automatically. Timed samples of the classifier sands were taken every 15 or 30 min, weighed, and returned to the circuit. After correcting for moisture content, the weights were converted into percent circulating load. Timed samples of the +2 in., the —2 + 3/4-in., —3/4-in. screen fractions, and the crusher discharge, were

Jan 1, 1971

By G. Derge, Ling Yang, G. M. Pound

The specific conductance and its temperature dependence were measured over the entire composition range of the molten Cu2S-CuCI system. At a typical temperature of 1200°C, 10 rnol pet of the ionically conducting CuCl reduced the specific conductance from about 77 ohm-lcm-l for pure Cu2S to about 32 ohm -1cm -1, and 50 mol pet CuCl reduced the conductance to that for pure CuCI—about 5 ohm 1cm1. The nature of electrical conduction in molten Cu2S, FeS, CuCI, and mixtures was studied by measuring the current efficiency of electrolysis at about 1100°C. The Cu2S, FeS, and mattes were found to conduct exclusively by electrons, but addition of 1 5 wt pet CUS to Cu2S produces a small amount of electrolysis. Addition of CuCl to Cu2S suppresses electronic conduction, and ionic conduction reaches almost 100 pet at a CuCl concentration of about 50 mol pet. These facts are interpreted in terms of electron energy level diagrams by analogy to the situation in solids. RESULTS of electrical conductivity studies on molten Cu-FeS mattes as a function of composition and temperature have been reported.' The specific conductances ranged from about 100 ohm-' cm-' for pure Cu2S to 1500 ohm-' cm-1 for pure FeS. This is in sharp contrast with the low specific conductance of molten ionic salts for which the transfer of electricity is by migration of ions in the field. In general, these ionically conducting molten salts, such as NaC1, KC1, CuC1, etc., have a specific conductance of the order of magnitude of 5 ohm-' cm-'. It was concluded on the basis of this evidence that molten FeS and Cu,S exhibit electronic conduction. Pure molten FeS has a small negative temperature coefficient of specific conductance, resembling metallic conduction, while pure molten Cu2S has a small positive temperature coefficient, resembling semi-conduction. The molten Cu2S-FeS mattes follow a roughly additive rule of mixtures, both with respect to specific conductance and temperature coefficient. Savelsberg2 has studied the electrolysis of molten Cu2S and Cu2S + FeS. He concluded that while molten Cu2S is an electronic conductor, there is some ionic conduction in molten Cu2S + FeS3 owing to the formation of the molecular compound 2Cu2S.FeS and its dissociation into Cu1 and FeS2-1 ions. The present work does not verify his results. Chipman, Inouye, and Tomlinson" have studied the specific conductance of molten FeO and report a high specific conductance, about 200 ohm-1 cm-1 of the same order of magnitude as that found for molten mattes, and a positive temperature coefficient. They interpret these results in terms of p-type semiconduction in the ionic liquid by analogy to the situation in solid FeO.1 imnad and Derne' detected appreciable ionization in molten FeO by means of electrolytic cell efficiency measurements. In order to verify the conclusion that electrical conduction in molten Cu2S and mattes is electronic, and to gain further insight into the structure of molten sulfides, the following investigations were carried out in the present work: 1) The specific conductance, s of the molten system Cu2S-CuC1 was measured as a function of temperature over the entire composition range. As discussed later, molten CuCl is an ionic substance. It was thought that if molten Cu2S were simply ionic in nature, addition of small amounts of CuCl might not have a catastrophic effect in lowering the high conductance of the Cu2S. On the other hand, if much electronic conduction occurs, addition of the ionic CuCl should have a large effect in destroying the electronic conduction. 2) The electrolytic cell efficiency of the following molten systems was measured at about 1100°C in specially designed cells: Cu3; Cu2S + FeS, 50:50 by wt; FeS; Cu2S + CuS, 15 wt pet; Cu2S + CuC1, 5.9 to 46.4 mol pet; and CuC1. This gives a direct measure of the fraction of current carried by ions in these melts. Further, the cell efficiency, extrapolated to zero ionic current, is given by cell efficiency = (s leasile + s elexstronic). [1] s lucile for molten CulS would be expected to be no greater than that for molten CuC1, whose s lonle is about 5 ohm-' cm-1, as will be seen in the following. u,.,,.,.,.......for molten Cu,S is of the order of 100 ohm-' cm-'.' Thus, a large increase in cell efficiency from 0 to values of 10 to 100 pet upon addition of CuCl to Cu2S would indicate destruction of the electronic conductance. Conductance Measurements Experimental Procedure—The apparatus and experimental method were the same as those described in detail in connection with the study of electrical conduction in molten Cu,S-FeS mattes.' A four terminal conductivity cell and an ac poten-

Jan 1, 1957

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970