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By J. C. Prof. Smock

(Read at the Philadelphia Meeting, February, 1878.) THE fire-clays of New Jersey belong in two geological ages, the cretaceous and quaternary, or post-tertiary. Three very small deposits of plastic clays have been discovered within the limits of the Archoean rocks. These are not refractory and of little importance, excepting in a geological consideration. They have resulted from a decomposition of the feldspars of the rock in situ, and they have been classified as inferior kaolins.

Jan 1, 1878

By Augustus Locke

In 1900, when. the public first heard of "secondary enrichment," the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners' astonishment, they carried chal-cocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales' advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this argument. Especially pertinent was the proof that (1) the deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accomplished more easily than that of pyrite, enargite, or chalcopyrite. The microscopic evidence has been accumulating for ten years and it demands

Jan 1, 1924

By William R. Webster

This is a subject which our Institute has made peculiarly its own. In the first volume of its Transactions the analysis of steel received attention, and every subsequent volume has borne witness to the acuteness and industry of our members in the investigation of this subject. The keynote mas struck, in this as in so many other lines of progress, by A. L. Holley, in his paper on " Tests of Steel," read at the Easton meeting of October, 1873 (Trans., ii., 116)—an essay which may rank as a classic by reason of .its elegant form, logical force, and clear prevision of all the bearings of its theme, Taken together with the brief report of the discussion which followed it (in which Dr. Drown emphasized the effects of heat-treatment and mechanical handling, and Dr. Sterry Hunt the importance of minute variations in chemical composition, and of possible isomeric and allotropic conditions), it constitutes, after the lapse of twenty-five years, an admirable and adequate introduction to the long list of technical papers which have succeeded it. Three years later came the epoch-making papers of Dr. C. B. Dudley on the relation between the chemical composition and physical properties of steel rails, which, with the voluminous discussion they evoked, constitute a special volume, published by the Institute, and full of useful suggestions. If Dr. Dudley could be induced to resume this investigation, he would doubtless be able to solve many points still uncertain or disputed. But I cannot undertake to review the history of this subject, as represented in our Transactions—still less to restate all the contributions to it which have been made in books or in papers before other technical societies, since the initiative was taken by the Institute. My more modest purpose is to indi-

Jan 1, 1899

By J. R. Thompson

It is common practice, and certainly good business as all of us know, to take care of plant operating equipment. Machinery of any type requires periodic inspection and planned maintenance. With this thought in mind a plant operator should at the end of every shutdown period make regular belt inspections and plan for later appropriate care and maintenance. The points mentioned below are understood well by all of us but are sometimes forgotten because belt conveyors are comparatively easy to operate. Maintenance of any conveyor belt is dependent upon the fundamental characteristics of the two component parts-cover and carcass.

Jan 6, 1950

By C. O. Brawner

FACTORS THAT INFLUENCE STABILITY AND STABILIZATION METHOD The most effective stabilization method and design can only be developed if the cause(s) and mechanics of the slide are known. Therefore, it is important that the stability be evaluated by an engineer who has had extensive rock stability experience. The most important factors that influence stability are structural geology, ground water, blasting and the mining method or methods. Structural Geology - The majority of failures in rock slopes occur along discontinuities in the rock (joints, bedding planes, shear or fault zones, etc.). Therefore, on all surface mining projects, the development and maintenance of a comprehensive structural geologic mapping program should be a first priority program that is considered a part of the operations function. This program should include mapping all major features - faults, shear zones and through going joints. All structural features which could influence stability should be mapped and presented in a structural domain format for the entire mine (Canmet, 1977). Where planes, wedges or blocks will be undercut by the mining excavation, shear strength and strain to failure tests should be performed on the joints, fault gouge and gouge-rock contact surfaces. These tests must be performed on the samples in the direction of potential slide movement and must determine the range of peak and residual shear strength values. A preliminary assessment of friction angle can be obtained from measurements of failed surfaces in the field (Figure 1) or from core sliding tests (Barton, 1981). An assessment must be made of the past geologic history of

Jan 1, 1983

By J. D. McBeth, G. M. Potter, Ramon Pizarro

Heap leaching is used by the Carlin Gold Mining Co., Carlin, Nev., to supplement conventional processing of gold ore by agitation-leaching and countercurrent decantation. Selected open-pit ore containing about 0.072 oz Au per ton is crushed to 3/4 inch, dumped by truck on an asphalt pad, and leached by sprinkling with dilute cyanide solution for 7 days. The heap is then drained and removed by front-end loader to tailings disposal. About 70 percent of the gold is dissolved. Leach solution from the heap joins the pregnant solution from countercurrent decantation for gold recovery by zinc precipitation. Four leach pads, each with a capacity of 1,400 tons of ore, are in use. About 10,000 tons of ore are heap leached monthly from about April through October. Heap leaching is recessed during freezing weather. Labor, equipment, and reagent requirements for heap leaching are presented.

Jan 1, 1974

By Samuel B. Christy

Jan 1, 1889

By Joseph W. Roe

MaNY questions arising in the work of the mining engineer may be solved quickly and with suffcient accuracy by the methods of descriptive geometry; but, unfortunately, this subject is more often considered from a mathematical view-point than as an effective tool for solving practical problems. Some of the principles involved are merged into the ordinary operations of mechanical drawing, and are used unconsciously by the engineer in his every-day work. The rest are stowed away on the book-shelf with his forgotten or rarely-used college text-books. One reason for this condition of " innocuous desuctude " may lie in the uifortunate and often cumbersome notation which it has been found necessary to introduce. If some of these principles can be recalled to the engineer's attenti011 in terms of' every-day use they may prove of practical hearing. Recently, in talking with several mining engineers, I used some of the drawing-room methods of a machine-designer, to the evident surprise of those around me. These men were perfectly familiar with the methods, but their application to mining-work had not occurred to them. At their suggestion the present paper is offered, not in ally way as a treatise, but merely to suggest a certain point of view, in hope that it may lead others far more familiar with mining-problems to pursue the subject further. I. To Find the Strike. As the simplest and most fundamental problem, let it be required to find the strike of a vein when the location and elevation of three points on the outcrop are known. It mill be assumed for the present that the rein is a plane.

Jan 1, 1911

By Reno H. Sales

EVERY mine manager, mine geologist, and every prospector in the field who appraises the future of mining properties does so on the basis of a theory of ore deposition whether he recognizes this fact or not. Wherever the ultimate value of a mine or prospect is dependent upon undeveloped ore, any estimate by an engineer or geologist necessarily involves a theory of origin of the deposit. In view of these facts the importance of a thorough understanding of the genesis of ore deposits cannot be overestimated. It well may be that the greatness of our country will depend upon finding reserves of natural resources as yet undiscovered. The genesis of ore deposits offers a fascinating field for study and investigation. This is attested by the large number of geologists who have written at length on the subject. For progress made toward a better understanding of ore genesis we owe much to Kemp, Lindgren, Ransome, Vogt, Emmons, Spurr, Graton, and a host of others. Within my own experience, I have attempted to apply in practice the various concepts and theories that have been advanced by these men.

Jan 5, 1954

By W. J. Reagan

THE problem of increasing output and decreasing percentage of rejections is a vital one in the manufacture of steel of any kind. The making of basic open-hearth steel for use in rolled steel wheels, tires for locomotive and car wheels, and forgings of various kinds, is a highly specialized industry. The increase in weight of railway rolling stock of all kinds, and the high speed that the public demands of transportation facilities, make it imperative that steel for use in this class of material shall be of the highest quality obtainable. During the past few years it has been the writer's good fortune to have opportunity-to study the defects in basic open-hearth steel, and also the results obtained by various changes in open-hearth practice, on such defects. The opportunity for study and the details available are rarely found in the manufacture of steel of any kind. It seems reasonable to assume that many of the results determined here can be applied to the production of steel of other types with a decided improvement in quality, a decrease in the percentage of rejections and an increase in output. All of the material described is basic open-hearth steel with the following range of analysis: carbon, 0.50 to 0.85 per cent.; phosphorus and sulfur, 0.04 coax.; silicon, 0.15 to 0.35; manganese, 0.50 to 0.75. All of this material is bottom-cast, therefore tapping and pouring temperatures are higher than in top-cast production. Ingots used in this type of work are of standard length with varying diameters. The ingot is known as duodecagonal, or twelve-sided. The standard body length is 88 in. and the hot top length, 14 in. Fig. 1 shows a typical ingot of this type. The diameter varies from 13 to 30 in. Ingots for special forgings, which cannot be made in molds of standard size, are made in molds of various sizes and designs. These ingots are sliced cold, into blocks of various lengths, depending upon the weight of the forging to be made. Fig. 2 shows the ingot-after coming from the slicing lathe. Just sufficient metal remains between blocks to hold the ingot in one piece while it is being removed from the lathe; then steel wedges are inserted between the blocks and the blocks are broken apart. This affords abundant opportunity for inspection, as the interior of the

Jan 1, 1930

By G. Pizzi, G. M. Ciucci, G. L. Chierici

The use of the material balance equation to estimate the volume of hydrocarbons originally present in a reservoir, whose producing mechanism is partly due to water drive, has been discussed in the literature by several authors. There is no general agreement upon the possibility of obtaining reliable results by this method. Gas reservoirs in contact with an active aquifer are considered in this paper. Theoretical considerations based on the cybernetic principle of uncertainty (which states that the internal structure of a system cannot be uniquely determined from its observed external behavior) lead to the conclusion that the volume of gas originally present in a reservoir of this type cannot be uniquely determined from its past history. The range of values which encompasses the actual value of the reserves varies from case to case and must be determined by either numerical or analogical methods. Results obtained for six gas fields are reported. All these fields were produced with small fluctuations in their production rates, as is common practice for gas reservoirs; no gas storage fields were considered. Results obtained show that reserves values in a range of 1 to 2, associated with appropriate aquifers, allow the matching of the reservoir past history with mean-square deviations less than the experimental errors involved in pressure and produclion measurements. Similar results have been found in several other partial water drive gas reservoirs. From these results it is concluded that gas reserves cannot be uniquely determined from the past performance of partial water drive reservoirs, at least in cases where the reservoir has been submitted to small fluctuations in the production rates, and pressure data of normal accuracy are available. INTRODUCTION A number of authors have analyzed the problem of estimating the reserves originally present in a partial water drive reservoir from its past pressure-production performance. Literature which deals with this subject can be grouped, according to their conclusions, as follows. 1. A reliable value for the reserves can be obtained even if reservoir data (pressure and cumulative production) are affected by errors within the normal range.'-' 2. A reliable value for the reserves can be obtained only if reservoir data are very accurate'- or if past production performance has been subjected to abrupt variations in the production rate."' 3. No unique value for the reserves can be obtained from reservoir past production performance. This conclusion has been based upon theoretical considerations" and verified in several field cases. The purpose of this paper, which deals only with partial water drive gas reservoirs, is to test the above conclusions against actual field cases. Some theoretical considerations on this problem are also presented. THEORETICAL CONSIDERATIONS As the behavior of a gas reservoir communicating with an aquifer depends on both the aquifer and the reservoir characteristics, the physical system to be studied is the combined gas reservoir plus aquifer. The information which is available for studying the performance of such a system is the well production rates and bottom-hole pressures, all given as functions of time. The external behavior of the reservoir-aquifer system is therefore described by 2n input variables (Gp, Wp,) and n output variables (p,), n being the number of wells in the reservoir. In reservoir engineering it is common practice to consider the reservoir as a whole, disregarding the internal distribution of pressures and of producing wells. This practice is equivalent to substituting the above multi-variable system with a single-variable system, where the average reservoir pressure is the only output variable and the cumulative production G,(t) and W,(t) are the input variables. The internal structure of such a system, defined by initial gas reserves G, aquifer shape and dimensions, boundary conditions and petrophysical parameters distribution throughout the aquifer, is unknown. Therefore, from a cybernetic point of view the system is a "black-box It has been demonstrated" that for a blackbox the indetermination principle holds. Accordingly, the number of different internal structures (or set of parameters) which can account for the observed external behavior is infinite. As a consequence, the initial reserves cannot be uniquely determined from the reservoir past performance. When W,(t) is known, the determination of G from

By Edgar S. Cook

The Warwick furnace at Pottstown, Pa., constructed for anthracite fuel, is, as may be remembered, 554 feet high, with 15; feet bosh. The actual working height from stock-line to bottom is only 474 feet, the bell-and-hopper taking up 8 feet. During the year 1886 we used mixed fuel, in the proportion of three-fourths anthracite and one-fourth coke. The total product of iron was 30,6299 tons of 2280 lbs., being a weekly average of 589 tons, including all ordinary and extraordinary stoppages. Deducting the latter, the weekly average would be about 600 tons. The fuel-consumption for the year was 1.2 tons per ton of iron, while the ore-mixture yielded 52 per cent. of iron. For about two months during the summer of 1887 we were obliged to run on anthracite exclusively, owing to the Connellsville coke strike. In the fall of 1885, in relining the furnace, the crucible had been built 8 feet 9 inches in diameter, with the view of using regularly one-quarter of coke (the largest previous diameter having been 7 feet 5 inches), and we felt somewhat apprehensive of the results when compelled to use anthracite only. The average of seven weeks' run on coal, as compared with the average of the seven corresponding weeks of 1886 (using one-quarter coke), was as follows:

Jan 1, 1889

By Alfred E. Hunt

Tars paper is suggested by the appointment on the part of the American Societies of Mechanical and of Civil Engineers of committees upon the subjects of " Standard Tests and Methods of Testing," and " Uniform Methods of Tests of Material used in Metallic Structures," respectively, and by a study of the report of one of these committees, and other papers. Moreover, the writer has had frequent occasion to hear the complahts of tnanufacturers who furnish structural material subject to specifications, that in the tests prescribed, the number of tests required, and the methods of making

Jan 1, 1892

By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By E. W. Davis

I . OPERATING TESTS 1. CHARACTER OF ORE UNDER INVESTIGATION On the eastern end of the Mesabi Range, in Northern Minnesota, is a large formation of siliceous rock which contains bands and fine grains of magnetite . The magnetite comprises about 35 per cent. of the rock. Fig.. 1 show's graphically that the tonnage of minus 200-mesh material produced varies directly with the tonnage fed to the mill. There is undoubtedly some limit to this relation, but there seems to be no indication of it at 18 T. per hr. Some of the conclusions drawn from this test are that: (a) The ball-mill is naturally a machine of very large capacity; (b) if it is not possible to deliver a large tonnage of original feed to the mill, a closed circuit should be provided so that the mill may crush its own oversize.

Jan 2, 1919

By Paul M. Tyler

MUCH information concerning pegmatites which was thought to be true a few years ago has been proved false, and what is now actually known about some pegmatites is not true of many others. The erratic and seemingly unpredictable structure and variable composition of this class of mineral deposits has been widely emphasized. Even parts of the same pegmatite body exhibit marked differences in texture, mineral composition, width, and attitude. Constructive geological thinking in respect to pegmatites now aims to establish general laws rather than to stress the confusing diversity of features having no special economic significance.

Jan 9, 1953

By Wayne E. Glenn, R. W. French, Lincoln F. Elkins

The Lance Creek Sundance reservoir provides a case history of ro years performance of a reservoir in which unit operation has permitted effective utilization of gravity drainage augmented by primary pressure control with injection of gas into top structural wells. Detailed performance of the reservoir is presented by means of maps of Well status, reservoir pressure, individual well recovery, etc., and by pool-performance charts. Analysis of reservoir performance indicates only minor water encroachment, so that gravity, injected gas, and expansion of gas are the main oil-expulsive agents. A simplified theory of regional drainage of oil from upstructure location to downstructure location due to gravity is presented and checked by means of comparison of "reservoir" permeability and "well" permeability from the pool performance. Good order of magnitude agreement was obtained. Individual well performance and overall reservoir performance indicate possibility that maintenance of pressure makes ineffective those parts of the reservoir in which permeability is too low to permit effective drainage of oil by action of gravity. Oil from these parts can be recovered only when pressure is reduced locally by selective withdrawal or when overall reservoir pressure is finally reduced.

Jan 1, 1949

By Charles F. Brush

THE compression of gases to a very high degree, for purposes of scientific research, has long presented serious difficulties to the physicist. Great advances have been made of late years in the construction of ordinary air or exhaust pumps, while very little has been done towards the improvement of compression pumps. The principal difficulties encountered in the construction of such apparatus are the existence of the so-called "dead space" in the pump barrels, leakage of the piston packings under high pressure, and the trouble arising from the unequal expansion of parts caused by the development of the latent heat of the gas during compression. Of these obstacles to success, the "dead space" is far the most serious, as it fixes a limit to the performance of the pump beyond which it is impossible to carry the compression. The writer having occasion, some time since, to make a series of investigations on gases very highly compressed, and finding no apparatus, or description of apparatus, adequate to produce the required

Jan 1, 1876

By W. P. Sykes

SEVEN years ago, Dr. S. L. Hoyt1 presented a masterful discussion of the hard metal carbides and cemented tungsten carbide. His lecture summarized most of the data then available in the field; many of the details relating to the production, properties and structure of cemented tungsten carbide had never been previously published, for, in fact, this information was only then being acquired. During the intervening years, the cemented carbides have assumed a place of real importance in the commercial field, with an ever widening variety of applications due to constant improvement in the control of production technique and the unremitting search for new compositions that might better the performance of the alloys in one or another type of service. The most recent summary of production methods, properties and guides for the successful application of the cemented carbides appears in the 1936 edition of the Metals Handbook. Of necessity, much detailed information relating to structures and physical properties is not included in such a summary, and it is with such details that the present discussion is concerned.

Jan 1, 1938

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970