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By R. V. Ramani, R. Stefanko, P. C. Thakur

The effects of diesel exhaust on mine ventilation systems are discussed. Mathematical models for emission of gaseous pollutants from diesel engines and their dispersion into mine air have been developed. Situations likely to prevail in mines were originally modeled using partial differential equations, but only simplified solutions are presented here. Validity of these models has been established by field observation of the growth of carbon monoxide concentrations in mine air environment. Consequently, these models can be used for air requirement calculations for diesel engines in underground mines.

Jan 1, 1977

By D. Hodouin, T. Gelpe

A digital simulator of classification and grinding circuits is used to evaluate the performance of various flowsheets. For a given flows he et configuration, unit process dimensions, and operating conditions, the simulator calculates the steady-state values of the process variables and determines the conditions that meet the required operation criteria for tonnage and product quality. Calculation examples are proposed for the design of wet and dry grinding circuits. The performance of different configurations of cement clinker and sulfide ore grinding flowsheets is evaluated and discussed.

Jan 1, 1986

By Hugh H. Waesche

Of all the military services, the Signal Corps is the most concerned with piezoelectric minerals because of its function as a supply service to the strategic and tactical military forces. Consequently this paper is written from the point of view of one associated with that organization. The Signal Corps is responsible for the research, development, and supply of communications, radar, and components to the using services of the Department of the Army and to some extent the Other branches of the National Defense Department. Their work therefore includes the study of the sources* characteristics, and application of quartz and other piezoelectric materials. These materials have become a vital consideration in strategic planning and are essential for efficient tactical operation by all the Armed Forces. The Signal Corps at the beginning of world War 11 Was respon-sible for both Army Ground and Air Force electronic equipment. Since that time this Army service organization has probably done more in the development of frequency control devices using piezoelectric materials than any other group. The U.S. Department of the Interior, Bureau of Mines, Minerals yearbook of 1945, shows that during the four war years, 1942 through 1945, 9,598,-410 Ib of quartz crystal were imported for all uses and of this total, 5,168,000 lb were consumed to produce 78,320,-000 crystal units for electronic application. Other government records confirm these data which conclusively show that approximately 53 pct of the crystalline quartz imported was consumed in the production of electronically applied quartz crystal units. It may be assumed that some effort was made to maintain a stockpile over demands for all purposes. and this would mean that the actual percentage of quartz used electronically was considerably over the 53 pct figure. These data only emphasize that electronic application of crystalline quartz was the greatest requirement, and per- haps the actual value in this application to national defense is many times greater in importance than is apparent on first inspection. Current electronic research and development programs of the Armed Forces are planned around the fundamental use of piezoelectric minerals for frequency control and this at present, at least, means quartz. Definition and Early Development The word piezoelectricity is formed from combination of the Greek word "piezein". meaning "to press," and "electricity." It is that property shown by numerous crystalline substances whereby electrical charges of equal and opposite value are produced on certain surfaces when the crystal is subjected to mechanical stress. It appears to be intimately associated with the better known property, pyro-electricity and in fact, the two may be manifestations of the same phenomeuon. This property was discovered by Pierre and Jacques Curie in quartz, tourmaline, and other minerals in 1880 while studying the symmetry of crystals. The converse effect, that is, mechanical strain in the crystal when placed in an electrical field, was predicted by the French physicist, G. Lippman, in 1881, and verified by the Curies almost immediately. As has been the case with many discoveries of similar character in the basic sciences, not much attention was paid to this property for man)- years except as an entertaining curiosity. Between 1890 and 1892 a series of papers was published by W. voigt in which the theoretical physical properties were put into mathematical form. The first practical application of piezoelectricity occurred during World War I when professor P. Langevin of France used quartz mosaics to produce underwater sound waves. The same mosaics were used to pick up the sound reflections from submerged objects which were in turn, amplified by electronic means and used to determine the distances to such objects. This device was intended for use as a submarine detector but development was not completed in time for war service although it was used later for determining ocean depths. About the same time, A. M. Nicholson, of Bell Telephone Laboratories, developed microphones and phonograph pickups using Rochelle salt crystals. A major step in the application of piezoelectric quartz came in 1921, when professor W. G. Cady, of wesleyan university, showed that a radio oscillator could be controlled by a quartz crystal; from that date, this use of quartz has increased steadily, reaching its peak in world war 11 as is shown by the figures previously given. Essentially all American electronic equipment for communication, navigation, and radar, utilized quartz crystals for the exacting frequency control required. Crystalline Minerals with piezoelectric Properties QUARTZ Hundreds of piezoelectric crystalline materials are known, most of which are water soluble. Of these, quartz appears to be without a peer for electronic frequency control. Unfortunately, the quartz must be of superior quality. It must be free of mechanical flaws, essen-tially optically clear, free of both Brazil and Dauphiné twinning and must be, for average uses, over 100 g in weight. Because of these stringent requirements, raw quartz of the quality desired is of rare occurrence. In addition to quartz, several other naturally occurring crystalline materials are known to have the piezoelectric property and could perhaps be substituted for quartz in some applications. These

Jan 1, 1950

Joseph Hartshorne was born in Philadelphia in 1852. He died Aug. 23, 1918. After graduating from Haverford College, he took a special course in chemistry at the Massachusetts Institute of Technology, and later at the University of Pennsylvania. He started with The Pennsy!vania Steel Co. as an apprentice in 1873, working in the laboratory and mills for two years, and then one year as foreman in the Bessemer Department. Next, he was assistant chemist in the second Geological Survey of Pennsylvania. In 1878, he went to Prance to investigate the Pernot open-hearth furnace for the Cambria Iron Co. Upon his return, he assisted in designing and erecting the plant in Johnstown and was foreman of a turn for one year, and superintendent for the next. In 1881, he became superintendent of the Bessemer and rolling-mill departments. In 1884, he went to Pottstown and also made a trip to Europe to investigate the Bessemer basic process. Upon his return he dcsigned and erected the basic Bessemer plant for the Pottstown Iron Co., and was superintendent there until 1893, when the company failed. Since then he has been a consulting metallurgical engineer, and expert in patent cases. The !most important of the latter was that of Krupp versus Midvsle on the armor-plate patent case, in which he was leading cxpert for Midvale. He was a good linguist, having command of French and German, and a fair knowledge of Italian and Spanish. In all, he made eight professional trips to Europe.

Jan 1, 1920

No. 347.-A South African development company will shortly require the services-of a mill superintendent, who has a general knowledge of concentration, particularly of flotation, and is able to take charge of a copper concentrator treating 15,000 tons per month and employing 200 natives and a small number of white men. Salary is £60 per month to start, and the company supplies furnished room or house, including free light, free water and free sanitary service, together with one native house servant. A contract will be made for 6 months, and notice of 3 months by 'either party will be required to terminate the engagement after 6 months. An allowance of £75 for-traveling expenses will be paid on arrival in South Africa to a single man, or £125 to a man who brings his family. Salary begins upon arrival in South Africa, and no allowance will be made for return traveling expenses. No. 349.-A Canadian university wishes to engage a man to teach non-ferrous metallurgy and ore-dressing as well as to direct research work. The instruction work covers 7 months but the research work is continued throughout the year. To a suitable man the rank of professor will be granted. Applicants are requested to state education, experience, salary desired and any other particulars that might assist in selecting a man for this position. No. 350.-Wanted, 60 engineers for ordnance training school, month's training. Salary for first three months $1200 to $1500. After 3 months, up to $2400.

Jan 11, 1918

By F. C. Blare

THE best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld'schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide,† It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter-color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results. * Fresenius, Zeitschrift Air Anal. Chemie., viii, 1. †First noted by Parkes in the Mining Journal for 1861.

Jan 1, 1881

By B. E. Eakin, A. L. Lee

Atmospheric pressure viscosity values For light hydrocarbons were calculated by a simple mixing rule based on the Sutherland constants for pure components. This method was further extended so that the atmospheric pressure viscosity of a mixture may be calculated based on the molecular weight information only. INTRODUCTION A proven method for estimating the gas-phase viscosity of a mixture is the one by Herning and zipperer.l This mixing rule has the following form: One method for calculating the pure component viscosity i is the Sutherland equation,2 which has the following form: The Sutherland constants B and S are determined from experimental data. A set of Sutherland constants for light hydrocarbons based on the data of several investigators3-5 is presented in Table 1. APPLICATION The Herning-Zipperer equation and the Sutherland equation were used to obtain an equation for calculating the gas-phase viscosity of light hydrocarbons. This equation has the form, Eq. 3 was used successfully in the study of methane-n-butane mixtures.6 Further analysis indicated that the Sutherland constants are a function of molecular weight.7 The gas-phase viscosity may be calculated based on molecular weight information only. The following equation was developed: The atmospheric pressure viscosity of ethane, propane, n-butaneand four methane-propane mixtures calculated on the basis of Eq. 6 are compared with the data of other investigators in Tables 2, 3, 4 and 5, respectively. A plot of atmospheric pressure viscosity vs molecular weight based on Eq. 6 is presented in Fig. 1.

Jan 1, 1965

By R. S. Sandhu, L. E. Baker, W. Y. Shieh

The finite element method of analysis was introduced by Clough.1 Within a short period, it has developed into a powerful solution technique in structural and continuum mechanics. It has been used to solve boundary value problems in two and three-dimensional elasticity.2-5 Anisotropy and heterogeneity of materials were allowed for at the earliest stages. 1,4 Its application has been extended to allow for cracks,5 creep and viscoelasticity, 6,7 incremental construction,6-8 nonlinear elasticity3,9 effect of joints in rock,10 and to materials with different behavior in tension and compression.7 Because of its versatility, the finite element method has found increasing application in the field of rock mechanics. In fact, several of the more significant developments have been motivated by problems in this field. Elasto-plastic material behavior based on the incremental or rate-type theory of plasticity rather than the deformation theory was considered by Reyes and Deere11 A material law based on a generalization 12 of the Mohr-Coulomb criterion was used. In this chapter, the formulation of material laws developed by Reyes and Deere 11 is used. An efficient analysis procedure, incorporating recent developments in finite element analysis, is developed for plane-strain conditions. To demonstrate its effectiveness, the procedure is applied to three cases, one for which an exact solution is available, another for which field observations had been made, and a third one for which a parallel study was made, using an accepted limit-equilibrium method.

Jan 1, 1970

By W. L. Watts

The existence of petroleum in California has been known for many years. From time immemorial the California Indians used this mineral, in the form of asphaltum, for various purposes. In the early history of the State the Catholic fathers utilized it for roofing their missions and other buildings. It is said that in 1855 or 1856 Andreas Pico distilled petroleum on a small scale for the San Fernando Mission. He obtained his crude oil from Pico canon, near Newhall, in Los Angeles county; and he was probably the first refiner of petroleum in this State. In 1856 a company commenced work at the La Brea ranch, in Los Angeles county, and tried to refine the crude oil. In 1857 an attempt was made to produce illuminating-oil from crude petroleum at Carpenteria, in Santa Barbara county; and there are records of similar attempts in other localities previous to 1860; but none of them were successful. The first scientific report on petroleum in California was made by Prof. B. Silliman, who published his researches in 1865. He spoke favorably of the possibility of obtaining petroleum in remunerative quantities in this State, and gave the results of his experiments in the fractional distillation of California petroleum. The next decade was marked by a considerable oil-excitement in California; and a great many companies mere formed for the purpose of petroleum-mining and for distilling crude oil. In most instances these companies did not meet with success; but it must be remembered that the pioneer oil-miners did not

Jan 1, 1900

G. R. DELAMATER,* Steelton, Pa. (written discussion t)..-Under the heading, "Preparation of Coal," Mr. Campbell discusses the ad-visability of sizing the coal for the jigs. While I fully realize that conditions alter cases, my method at all times is to do everything possible to avoid sizing. It would be unwise for anyone to say that greater ash and sulfur reduction is impossible by sizing. The thing that can be questioned is, will the greater reduction be sufficient to counterbalance the greater cost? The same thing is true of the proper size of crushing for each individual proposition. In past years many washeries have been built and equipped for wash-ing two or more sizes, but I know of few instances where these plants were operated more than a year before sizing was abandoned. Perhaps in some of these cases this was clue to lack of sufficient development of such scheme of operation; yet I have found that most men engaged in this work, including myself, started into the work with a pretty well-fixed idea that sizing would be beneficial. But trials and tests showed that the mixed size washing is necessary for coals requiring crushing to 1 in. or less. Coal is of low value, compared with other minerals segregated by washing or concentration, for which reason simplicity must be the watchword: simplicity in the machine used to attain the separations of impurities from the coal, in the accessory plant equipment, and in its arrangement.

Jan 12, 1919

By S. R. Gilbert, B. W. Burdett, L. B. Hales

INTRODUCTION Grinding control is currently the most publicized control subject in the minerals industry. Flotation control and crushing control have not as yet received the widespread attention that grinding control has. The primary reasons for this center around the high capital costs of grinding equipment and the fact that grinding mills are extremely energy inefficient. In a typical copper concentrator the energy requirements to produce refined copper are: (1) [Total Energy Distribution (Kw-hr/yr)% Mining4.93 x 10817.3 Mineral Processing9.63 x 10833.8 Smelting and Refining13.9 x 10848.9] One-third of the total energy used for copper production is for mineral processing. A breakdown of this energy into process steps yields the following: [Total Energy Distribution (Kw-hr/yr)% Crushing and Grinding 7.16 x 108 73.8 Flotation 0.76 x 108 7.8 Materials Handling1.78 x 10818.4] It is apparent that comminution operations consume the largest proportion of the energy for processing and as such become major targets for improvements in efficiency. Unfortunately, size reduction operations are extremely inefficient. Efficiency calculations for grinding range from less than 0.1% to about 5% depending on the evaluation criteria. Because of these facts, grinding control has been and will continue to be the focus of major process control efforts. OBJECTIVES AND BENEFITS All benefits achieved as the result of grinding control are derived from modifying physical parameters which improve the efficiency of the grinding mill. These parameters include:

Jan 1, 1982

By S. R. Krom

In connection with perfecting a system of pneumatic concentration I had in view the improvement of machines for crushing and pulverizing ores. A study of the whole subject convinced me that the principle upon which the construction of the Blake crusher, and that of rolls, is based, possessed the mechanical elements which, if perfected and simplified, would make these machines the successful rivals of every other device. It is well-known that until very recently the stamp-battery held undisputed possession of the field; and mill-men and mill-builders almost universally believed that stamps would not be superseded by any other machine for fine crushing. The first step to drive stamps from the field was the introduction of rollers in the Bertrand and the Mt. Cory mills. In both of these mills the great superiority and economy of a system of crushing with rollers instead of stamps has been fully demonstrated. While perfecting the rollers, I had the fact confronting me that they had frequently been tried without success. In fact, the universal opinion prevailed that rollers could be used only for coarse, and not for fine crushing. The secret of the difficulty I discovered to lie in the imperfect and weak character of the rolls heretofore used, due to a misconception of the requirements for a machine for such work, and a failure to appreciate the advantages of continuous, rolling, crshing- surfaces, operating on the toggle-lever principle, which gives the greatest crushing pressure with the least power. expended, and the minimum of wear.

Jan 1, 1886

By Roy Thomas

SOON after the Waelz plant for the fire concentration of low-grade zinc ores was put into operation in the early part of 1929 at Katowice, it was found that the conveyor equipment for transporting the hot residue from the furnace dust chambers was inadequate. Hand tram-ming with water cooling was used for a time, but that method was injurious to the workmen as well as costly. The problem was to find some practical mechanical means of conveying flue dust at temperatures of from 450° to 600° C. as it was drawn from the dust chambers. After considerable preliminary investigation it was decided to install pneu-matic equipment for conveying the hot materials to a central mixing plant, where it would be mixed with slime and from which it would be returned to the furnace feed hoppers. The first pneumatic equipment was installed in 1930, and has been in successful operation since that time. The pneumatic method of transportation has shown a considerable saving in operating costs over the former methods of dust handling and a decided improvement in working and hygienic conditions at the plant, through the elimination of the dust hazard. Additional pneumatic equipment was installed in 1933 for conveying the furnace fume from the baghouses to the roaster plant. At the same time pick-up lines were provided for collecting the cleanings from the vertical and horizontal cooling pipes that are between the furnace dust chambers and the baghouses. The latter installation has practically eliminated a dusty and costly hand-tramming operation.

Jan 1, 1939

By William A. Hustrulid

INTRODUCTION Prior to the mid-1970's, the U.S. Radioactive Waste Disposal Program was focused on salt deposits as the geologic medium of choice, almost to the exclusion of other rock types. These efforts are illustrated by the Project Salt Vault experiment in a salt mine at Lyons, Kansas, in 1965-1967 followed by attempts to locate a repository site in central Kansas. Preliminary evaluation of other geologic media led, in 1978, to the GAIN (Geotechnical Assessment and Instrumentation Needs for Nuclear Waste Isolation in Crystalline and Argillaceous Rocks) Symposium held at the University of California (Berkeley), for the purpose of preparing a state-of-the-art document together with research needs for some of the other possible rock types. Because possible sites had not been selected, nor would they be for some time, the primary emphasis was for research and development focused on generic rocks and generic sites. A basic ground rule at that time was that the host rock formation should provide the primary containment for the waste. Also, the U.S. Nuclear Regulatory Commission (NRC) was just drafting the proposed rules regarding site suitability so that this input was not available. The collection of baseline data, conduction of some critical experiments both in the laboratory and field, and the performance of scoping studies were deemed needed. Such work was indeed undertaken; and to date, a great deal of information has been compiled and much has been learned regarding the characteristics of rock masses, rock behavior

Jan 1, 1984

By D. Pearson

INTRODUCTION In 1975 278x10 3 tonnes of zinc was consumed in the United Kingdom, of which 69.3x10 3 tonnes was obtained from secondary sources. Of this secondary zinc 37.7x10 3 tonnes was used in brass making, the remainder was used in non metallic applications - eg oxides and salts. Many forms of zinc-bearing wastes arise, for example as galvaniser's drosses and residues, fumes from ferrous and non-ferrous metallurgical processes, and filter cakes from rayon manufacture and metal finishing. In the case of zinc-bearing dusts and fumes, the quantities available for recycle are at present restricted by the failure to collect them efficiently, hut environmental factors are leading to improvements in gas cleaning, with the result that quantities collected will increase and then exceed those required for the production of chemicals, so that some dusts may either have to be dumped or processed to metal. The recovery of zinc from steelmaking dusts is practised in W. Germany (1) and Japan (2) employing processes based on reduction in rotary kilns in order to produce sponge iron and a zinc- rich oxide suitable for feeding to the zinc-lead blast furnace. Although the zinc-lead blast furnace is the only zinc-making process used in the UK, no similar treatment of steelmaking dusts is carried out, a pilot scheme was tested by the British Steel Corporation, but development was abandoned for economic reasons. It appears to be cheaper to pelletise suitable dusts and export them for treatment elsewhere.

Jan 1, 1981

By F. R. Hensel

Up to the present time few attempts have been made to produce hard nonmagnetic materials by heat treatment of austenitic steels. The usual result has been to cause them to pass into the martensitic stage, thus destroying to a great extent the typical austenitic properties, since this involves a transition of a portion of the iron from a face-centered to a body-centered type of atomic arrangement. High-strength nonmagnetic materials such as might be provided by properly hardening austenite are required in the electrical industry for different machine parts. In Europe nonmagnetic retainer rings for restraining the end-turns of the rotor windings in turbo-alternators have been developed as a special application of high-strength austenite. In testing1 a 28,000-kva. three-phase Siemens turbogenerator running at 3000 r.p.m. at full load current, the losses in the short-circuit test were 450 kw. for the magnetic ring and 286 kw. for the nonmagnetic, and the difference should be attributable to the magnetic ring. The differences in temperatures during the same test are given in Table 1 and these show the advantage of a nonmagnetic over a magnetic retainer ring. Hardening in this case was obtained by cold working, such as hammering, rolling or some means for stretching the steel while at a temperature near 500" C. One means for stretching2 is to rotate the forged or rolled ring in a centrifugal machine so as to develop within it stress higher than

Jan 1, 1931

By Hewitt Wilson

IN 1903, T. M. and E. H. Alvord, of Marblemount, Wash., built a soapstone-grinding mill in the Skagit River Valley and are reported to have produced "ground talc" during 1904 and 1905, shipping to the paper mills in Wisconsin. Between 1916 and 1920, the Western Talc Co. built and operated a talc-grinding mill north of Mondovi, on the banks of the Spokane River, in eastern Washington, and sold powdered talc to the Inland Empire Paper Co. of Spokane. ? The most active develop-ment in recent years has been by two companies in the Skagit Valley-the Skagit Talc Company, Inc., which has been sawing soapstone block for the soda-recovery furnaces of the pulp and paper companies, and the Asbestos-Talc Products of Washington, Inc., at Burlington, which has been mining and dry-grinding a soft serpentine for the structural filler and insulation trade. Many prospects have been opened in the northern part of the state on both sides of the Cascade Mountains, and these activities undoubtedly are the forerunner of an industry that promises to attain considerable magnitude in the North Pacific States. At the present time, talc is imported from California for use as paper filler, and soapstone block from Virginia for use in the soda-recovery furnaces. A small market has been created locally for tailor and foundry:, pencils, stove grills, and block soapstone for art objects. The results of the present study, as yet incomplete, indicate that the use as a refractory and as a ceramic filler and flux can be expanded.

Jan 1, 1936

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1'4'5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,' basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,'' modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.' These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.' All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By Donald Warren, J. F. Libsch

HIS investigation originated as a result of a pre-vious experimental study' of the magnetic properties of Fe-Co alloys fabricated by the powder metallurgy technique. Densities of powder compacts prepared for the magnetics investigation varied from 7.45 to 7.70 g per cu cm or from 93 to 95 pct of the experimental value of 8.08 g per cu cm for a fused alloy of the same composition.' While this range of density is considered sufficiently high for most applications, the highest possible density is to be desired for maximum magnetic properties. By applying a technique similar to the one described above to a pure electrolytic iron powder, Rostoker³ was able to achieve a density of 7.895 g per cu cm, which is the highest density ever reported for sintered iron. While Rostoker's work involved the sintering of an elemental powder rather than a mixture, it was believed that higher densities should also have been obtained for alloys using the above technique because of the recoining operation and the high sintering temperature. Consequently, it was decided to investigate the various factors affecting the density of this alloy with the idea that such a study might lead to higher densities and, as a result, powder alloys having magnetic properties identical with those of the fused alloys. It was believed that the principal reason that near-theoretical densities for the powdered alloy were not obtained was the interference of gases with the normal sintering mechanism. When present during the sintering operation, gases can exert several harmful effects: they can remain on the particle surface and interfere with surface diffusion and plastic flow; they can be released and, under certain conditions, expand the void spaces through gas pressure; or they can remain trapped in the pores and exert a hydrostatic pressure that retards elimination of the pores. Jones,4 Rhines,5 Goetzel," and others have given the effect of gases in the sintering of powder compacts an extensive treatment. Among the more important sources of gases in the sintering process are dissolved gases, adsorbed gases, air entrapped during pressing, and gaseous products of chemical reactions. During sintering adsorbed gases are partly released at a relatively low temperature, while those gases entrapped during pressing cannot escape until their pressure is increased sufficiently through increasing temperature to expand the interpartjcle openings. The remaining adsorbed gases, gaseous reduction products, and dissolved gases produce a similar effect at the higher temperatures. If, in the sintering process, gas evolution occurs after the interpore channels have been sealed, an exaggerated expansion of the void spaces results. This is particularly true if the temperature is high enough for extensive plastic flow. In his fabrication of powder bars from tantalum, Balke7 had to consider the effect of adsorbed hydrogen and provide for its escape during sintering by limiting the compacting pressure to a maximum of 50 tons per sq in. The effect of gases entrapped during pressing was first noted by Trzebiatowski8 when he found that gold and silver powders decrease in density with increasing sintering temperature if pressed at 200 tsi, while they exhibit the usual increase when pressed at 40 tsi. Recent investigators9-11 have also noted that entrapped gases have an effect on the expansion of copper compacts during sintering. Proper provision for the escape of gaseous products of reduction must be made in order to avoid deleterious effects. Myers" states that in the sintering of electrolytic tantalum powder, the temperature was gradually raised to 2600°F with a pause at 2000°F to permit reduction of the oxides. Experimental Details For the present study, 50 pct Co-50 pct Fe compacts in the form of circular disks 1½ in. in diam and 0.15 in. thick were fabricated by the pressing and sintering of a mixture of the elemental powders. It was decided to follow the sintering process by means of liquid permeability measurements, because it was thought that such measurements might serve as a measure of relative pore sizes, as well as a possible indication of the point at which most of the interpore channels become sealed. However, since the permeability as measured by the flow of a liquid, such as ethylene glycol, does not give an absolute indication of the point where the pores have become isolated, a method for determining the percentage of pores connected to the surface was set up. As an additional cross check on the permeability measurements, metallographic methods were used to study the relative pore size. Finally, the property of ultimate interest, the density, was measured. Raw Materials: The powders used consisted of an annealed, 99.9 pct pure, —150 mesh grade of electrolytic iron powder, and a 98 pct pure, —200 mesh grade of reduced and comminuted cobalt powder. The cobalt powder was not further processed either by hydrogen reduction or annealing. The screen analyses for the iron and cobalt powders are given in Table I, while the chemical analyses for each type of powder are listed in Table 11. Table 111 gives the hydrogen loss measurements for the powders according to the M.P.A. Standard Method and for a higher temperature as well. Preparation of Compacts: Equal amounts of the elemental powders were mixed by rotation for 1 hr and then pressed into compacts approximately 0.15

Jan 1, 1952