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By James P. Kimball

AMONG the curious results of the recent advance of prices in the iron trade of the United States, one of them at least is to be regarded as of great importance. I allude to the utilization of mill cinder as a cheap and almost costless substitute for high-priced iron ores in many blast furnaces, situated within easy reach of such raw material. It has been, with but few exceptions, the practice in this country, based upon tradition rather than upon authority or European precedents, to waste this material on 'account of its high proportion of silicic and phosphoric acids, although known to contain more iron than most ores, and although also known to be sometimes applied to the blast furnace in greater or less quantities without serious detriment to the iron for specific purposes. While in use to a limited extent in the Hocking Valley and Hanging Rock iron regions of Ohio for several years, its use in Western Pennsylvania has only become general of late, under the exigencies of high prices and a short supply of ore. Especially has mill cinder largely entered into the stock of furnaces attached to rolling mills in and about Pittsburgh. Under such circumstances the cinder pig has been paddled on the premises, and the malleable iron produced has been unexpectedly good. Cautiously as at first mill cinder has been applied, it is evident that the temptation to use it freely is a strong one whenever the commercial rates for high-class ores are out of proportion to the general conditions of the iron trade, as sometimes happens in this country, especially as the free use of it is apparently justified by the quality of the iron produced from this cheap and abundant material. Indeed the consumption of cinder pig has., not been wholly confined to mills using up the production of furnaces belonging to the same plant. One furnace at least on the Ohio, at Covington, for several' months has been making foundry pig from "all cinder." The iron has gone into the general trade. It is probable that malleable iron of good quality can he made from the poorest cinder pig, but with what degree of economy will

Jan 1, 1881

Jan 1, 1897

By Open-Hearth Steel

We have a very high-powered organization up here this morning, headed by Kenneth C. McCutcheon, general superintendent of the Ashland Division of the American Rolling Mill Company, and L. A. Lambing, superintendent of the open-hearth and Bessemer departments of Jones & Laughlin Steel .corporation of Aliquippa, Pa., representing the open-hearth men. Also, we have P. F. Dolan, assistant general manager of the Maryland plant of Bethlehem Steel Company, of Sparrows Point, and Harry E. McDonnell, superintendent of blast furnaces of Weirton Steel Company of Weirton, W. Va., representing the blast-furnace section.

Jan 1, 1940

By R. S. Newlin

IN reality, the Butte district is the birthplace of the Anaconda Copper Mining Co., for it was here that strength was gathered and means provided for later expansions of the Company. The Butte district was organized at a miners' meeting on Aug. 20, 1866, primarily for gold placer-mining operations. Substantial amounts of placer gold were recovered from gulch gravels during the period 1862 to 1868. The earliest lode claim locations in the district were recorded in July and August 1864. Copper ore was first shipped, to Swansea, Wales, in 1866. In November 1866, according to the Montana Post, construction of a smelter was started to treat the silver

Jan 1, 1948

Jan 1, 1881

Jan 1, 1940

By Edward H. Robie

THE registration badges gave out, there were not enough programs, the Pioneer Hotel's rooms were insufficient, and some hundred applicants for banquet tickets had to be turned down at the Institute's Regional Meeting in Tucson, Nov. 1-5. Minor inconveniences these, however, occasioned by the fact that, optimistic as they are in Arizona, about half again as many partook of the week's activities as were expected. For this, the local program committee can be blamed-both the technical and social features were too attractive in quantity and quality. Seriously speaking, though, the Institute has probably never had a more successful Regional Meeting than this one. It being the first that has been held in Arizona in 22 years, no effort was spared to make it the distinctive gathering that it was.

Jan 1, 1938

By Donald H. McLaughlin, John H. Moses

IN the latitude of Lima, the broad uplifted block that forms the Andes is made up of a complex sequence of folded and faulted sediments and volcanics, broken by large and small bodies of granitic rocks and porphyries with which the principal mineral deposits are closely associated in both time and space. The intrusives are a final episode in the geologic history as revealed by the consolidated rocks, for after their emplacement and after the formation of the primary ore deposits in and about them the record is simply one of long continued erosion and uplift.

Jan 1, 1945

By Herluf P. Nielsen, Robert I. Jaffee

IN recent years much attention has been given to high-melting alloy systems, It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. PAST WORK Müller1 determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from 1771°C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Müller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at 1000°C. Vines and Wise3 report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. MATERIALS The platinum powder used in this work was kindly supplied by the research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio, It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HCI. the resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1948

By J. E. Breen, J. Weertman

The creep rate of polycrystalline tin was studied as a function of temperature and stress in constant stress experiments. The temperature was varied from room temperature to almost the melting point of tin. Activation energies were calculated from tests run at the same stress. It was found that on a log creep rate vs inverse temperature plot the experimental points did not fall on one straight line but on a line which changed its slope in the 90° to 160°C region. Two activation energies for the creep of tin can be calculated from the data: a value around 26,000 cal per mol at high temperatures and a value around 11,000 cal per mot at low temperatures. It is suggested that the discrepancies between the creep activation energies and those of self-diffusion can be accounted for if self-diffusion takes place predominately by Zener's ring mechanism rather than through vacancy or interstitial movement. SHERBY, Orr, and Dorn' and Dorn' have recently reviewed some of the data on high temperature creep of metals. -The data show that the activation energy of high temperature creep is approximately equal to the activation energy of self-diffusion. This same correlation has also been successfully made between the activation energy of grain boundary relaxation and that of self-diffusion.3,4 The metal tin does not fit into this simple picture. Its activation energies of self-diffusion differ appreciably from that of grain boundary relaxation and of creep. Fensham,5 from a precisely performed experiment, has determined that the activation energies of self-diffusion of tin are 10,500 and 5,900 cal per mol along the C and A axes, respectively. There are two energies because of the anisotropic nature of tin. Rotherham, Smith, and Greenough6 have shown that the grain boundary relaxation activation energy is 19,000 cal per mol (measurements made from room temperature to 100°C). Puttick and King7 found the same activation energy for grain boundary slip in bicrystals of tin (180° to 225°C region). Until recently, there was no high temperature large strain creep data on tin suitable for activation energy calculations. At rather small strains (up to 0.01), Tyte8 had made a series of measurements on tin from which activation energies can be calculated. In Fig. 1 are plotted some of his data on a log creep rate vs inverse temperature graph. It can be seen that Tyte's work indicates that at a relatively low temperature the activation energy is around 7,400 cal per mol but at higher temperatures the activation energy increases. Since Tyte measured the creep only for small strains, it is doubtful if a

Jan 1, 1956

By Oliver Bowles

AUTOMOTIVE TRANSPORT by highway, which has become indispensable to modern life either in peace or war, involves the use of powerful machines, many of which travel at high speed. To start, accelerate, and stop each motor vehicle demands the use of clutch and brake. Friction is applied intensively to both these mechanisms, and their linings must therefore be of materials that will resist wear and that will not ignite with the heat of friction. Asbestos, that curious fire-resisting: natural fiber that may be woven into unburnable cloth, is eminently suitable for this special' use, and no satisfactory substitute for it has yet been found Because- asbestos is regarded as absolutely essential to all types of motor transport on land, and in addition is indispensable to. many .other kinds of machines and equipment, the situation of the- United State's with respect to supplies of-raw-material-is of special interest: From the standpoint of national self-sufficiency, conditions are far, from satisfactory, for United States mines furnish only three to four percent of the total domestic require-

Jan 1, 1938

By A. D. Hughes

C. W. MERRILL*-Mr. Hughes' paper not only is very well presented but is most timely in that it covers a subject of vital interest to the United States. Tin is one of the strategic metals which has not been found here in appreciable quantities. The total United States tin output since the first recorded production over 100 years ago would not supply current consumption for a fortnight. On the consumption side, tin is extremely important in national defense because of its use in tin plate which, in the form of tin cans, makes it possible to feed properly the armies that the United States recruits from its civilian population in emergencies. Moreover, the internal combustion engines so important in powering tanks, planes, and other war machines, require large quantities of tin alloys for bearings and for soldering. These considerations, along with the fact that Malaya, historically, has been the leading source of tin to the United States, make the kind of information that Mr. Hughes has presented so ably, a matter of vital interest.

Jan 1, 1949

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.' Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-'. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By E. H. Rose

IN the realm of ore dressing the most pregnant feat of all time was announced in 1945: the winning of the mineral raw materials which made the harnessing of atomic energy possible. Lost in the stupendous implications of the end result, in the two billion dollar hugeness of the project, and in the famous names attached thereto, the fact that crude uranium ores had to be concentrated received relatively little notice in the press. Only the final link in the concentrating chain was publicized-ether extraction of uranyl nitrate, developed by Hoffman and carried on by the Mallinckrodt Chemical Works, or methods developed by the Ames group under Spedding. Some of the earlier links represented less glamorous but equally difficult and exacting research. One may only speak a word of admiration for those who worked hard, accomplished much, and said nothing. The universal lament for most of the year was "man shortage." A group of Canadian engineers expressed it as "being so short of labor that no labor was available to develop laborsaving devices." . Despite this, an outstanding amount of mineral-dressing progress was made in 1945. Necessity allowed no alternative. The insatiable demand of war for minerals forced the exploitation of lower and lower grade ores, and of others not before considered of commercial character or use, requiring the mineral dresser to fight for and win new bridgeheads on the home front.

Jan 1, 1946

By Orville R. Lyons

THE Russellton preparation plant of Republic Steel Corp., located north of Pittsburgh, Pa., prepares 3 1/2x0-in. Thick-Freeport coal by means of a 13-ft 6-in. diam Chance cone and 16 No. 7 Deister tables. The plant feed ranges between 370 and 410 tons per hr, of which approximately 31 pct is ¼x0-in. size, and the plant reject ranges between 14 and 16 pct of the feed. The 3½xY4-in. washed coal, the cone product, is dewatered and desanded by a double-deck Parrish-type shaking screen 46 ft long and 7 ft wide. The 1¼x¼-in. portion is further dewatered by two 4x12-ft single-deck vibrating screens. The ¼x0-in. washed coal from the tables is distributed to three 54x70 in. Bird centrifuges. The dewatered centrifuge product is combined with the product of the de-watering screens prior to loading into railroad cars. During the early part of 1951 complaints were received from officials at Republic's coke ovens concerning the moisture content of Russellton washed coal. The records revealed that during the first half of 1951 the shipped washed coal moisture averaged

Jan 1, 1954

The House Committee of the Engineering Societies Building has lent to he members of the three welfare committees a room on the ground floor of the building where they can carry on some of their war activities. Two sewing machines and two knitting machines are installed there and ladies are invited to sew for the Foreign War Relief Committee and knit for the Emergency Committee, which is working for the 27th Engineers, a special mining regiment. The Emergency Committee, Mrs. H. Norman Spicer, Chairman, reports the formation of a committed of 21 members. The organization meeting was held March 7, and plans were made for future activities as follows: A letter was read from Mr. Ingalls asking for 72 sweaters, 72 helmets, 66 pairs of wristlets as well as 772 pairs of socks, 272 being for immediate delivery. To meet this request it was decided to secure the helmets and wristlets from the Navy League, and to undertake the making of the sweaters and socks ourselves. Accordingly Mrs. H. N. Spicer and Mrs. J. H. Devereux were empowered to buy wool in sufficient quantities, and woven material for the 72 sweaters, sending the bills to Mr. Ingalls, who had guaranteed the money from the Engineering and Mining Journal. This was attended to promptly, and the materials were ready for distribution to the committee on March 13. After considerable difficulty, knitting machines for the socks were discovered and the agent came to demonstrate them. Mrs. Spicer gave one to the Committee and Mr. Ingalls has guaranteed the money to buy two when the manufacturers can deliver them. Up to April 6, 130 pairs of socks, machine and hand-knitted, have been handed in-also 68 sweaters, 80 helmets and 90 pairs of wristlets. It has been calculated that it needs five women knitting behind each man at the front to keep him continuously supplied with knitted garments.

Jan 5, 1918

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