Search Documents

By Ralph W. M. Lai, D. W. Fuerstenau

In aqueous solution, an oxide surface is considered to consist of positively charged surface sites, MOH, neutral surface sites MOH, and negatively charged surface sites MO-. From the mass action law, equations for the distribution of these sites have been derived in terms of the hydrogen ion concentration in solution and the point of zero charge of the oxide. Experiments on the flotation of futile were carried out with sulfonates and amines which are collectors that physisorb, and with oleate, which is a collector that chemisorbs. Flotation response was found to correlate with the site distribution model. A similar correlation was found with published data on iron oxide potation.

Jan 1, 1977

By R. A. RAGATZ

THE preparation of specimens for microscopic examination from metal articles of relatively large cross-section offers no particular difficulty. It often happens, however, that articles submitted for examination are so thin that specimens satisfactory for microscopic examination can not be successfully pre- pared by the methods commonly employed when working with larger articles. Ordinarily, the preparation of metallographic specimens involves the following operations : (1) cutting the small specimens to be examined out of the larger mass of metal, (2) cleaning and electroplating, (3) mounting to furnish support during the grinding and polishing operations, (4) grinding and polishing to produce a scratch-free surface, (5) etching and drying. All of these operations must be carried out in such a manner that when the specimen is finally examined under the microscope, the structure seen is a true and well-defined representation of the structure that the larger mass of metal possesses at the place where the small specimen was removed. It is important that the deformation involved in cutting out the specimen be as slight as possible, in order that the subsequent grinding and polishing operations will completely eliminate the cold- working effects in the vicinity of the cuts. It is also important that the specimen never be allowed to attain a temperature high enough to alter its structure; the maximum permissible depends on the metal being handled. With some metals, zinc for example, consider- able care must be taken to avoid heating; with other metals, annealed steel -for example, no particular pre- cautions need be observed because there is no tendency for structural change to occur at relatively low temperatures.

Jan 1, 1929

By AIME AIME

FEW indeed are the sections of the country where trained or partly trained workers have not already been hired by a war industry plant or will be within the near future. Yet right in the midst of the heavily industrialized East lies the anthracite area, home of a million people, whose productive power has persistently been by-passed either by private industry or by the Government Plant Site Board. The chief reason given for not locating war plants in the area is that it is not within the strategic zone, but in numerous instances elsewhere this rule has been waived. Furthermore, the anthracite region is well protected on all sides by mountains and is at all points more than 100 miles inland. Continued depression in the anthracite industry and a crippling blow dealt by the war emergency to the production of silk and rayon goods, the chief manufacturing activity of the area, have resulted in a heavy migration, particularly of trained young workers, into near-by industrial areas. At least 50,000 people are currently unemployed, with the likelihood of an increase in coming months, and as many families are on relief.

Jan 1, 1942

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By L. P. Durham

DuRing the early mine development period, 1929 and the first part of 1930, a 300-ton pilot-plant concentrator was built at Nkana mine of the Rhokana Corporation, Northern Rhodesia. This plant operated from May 26, 1930 until Oct. 26, 1931, treating 101,080 tons of Nkana ores and producing 4372 tons of concentrate. The plant was built, primarily, as a test unit to determine the grinding characteristics, floatability, etc. of the Nkana ores and other ores of the Rhodesian copper belt and to supply sufficient data on which to base the design of a 5000-ton concentrating plant at Nkana mine. The test unit operated wholly on development ores and no attempt was made to grade or select the ores from any section of the mine. The average assays for the 17 months of operation are given in Table 1. The first ground was broken for the 5000-ton concentrator during June, 1930, and the construction of the plant was completed in November, 1931. The plant started on Dec. 10 and has operated continuously since that date: The whole of the concentrating plant is compact and closely connected, yet with sufficient space for expansion of all sections up to 20,000 to 25,000 tons per day capacity. Mining operations are carried on along a length of about four miles on the easterly limb of the Nkana syncline. This length includes the North orebody, from which all production has thus far originated, and the Mindola orebody, now being developed for production. The ore-bearing measures in the North orebody are leached for some 75 ft. below the surface; the oxidized zone varies in vertical extent from 100 to 150 ft. Practically all the ore below the 200-ft. level is sufficiently

Jan 1, 1935

By AIME AIME

PLANS are now well advanced for the joint meeting of the Institute and over a dozen other engineering societies in Chicago during the week beginning June 26: Engineers' Week at A Century of Progress. All engineers planning to visit the Fair will find it to their advantage to be present at this time so far as the Chicago attractions are concerned, and Eastern members will also have the advantage of special transportation arrangements on June 24 and 25. The tentative program is given at the bottom of the next page. Monday morning, June 26, will be reserved for registration of members and guests and the Woman's Auxiliary at the Stevens Hotel, where special rooms will be provided. A luncheon will also be served there, and in the afternoon, a technical session on nonmetallics. Instead of having the big family dinner that evening at the Stevens, as at first proposed, the local committee has planned to have it at the Fair Grounds, where special facilities have been arranged. A meeting of the Board of Directors and a few invited guests will precede the dinner. All members and guests are likely to be interested in visiting the Museum of Science and Industry, so that will be the sole event on the program for Tuesday morning, June 27. The big attraction there at present is the model coal mine, the first operative coal mine ever built for exhibit purposes. It is based on the Deutsches Museum mine at Munich, but goes far beyond that in realism, and takes the visitor on an extended tour underground. It shows him in half an hour more types of modern mining machinery and coal geology than he would be likely to see in a week's underground study in the coal fields. The Institute members will be the first group to go through this mine.

Jan 1, 1933

By C. C. Harris

An analytical solution of the integro-differential equation of batch grinding is proposed as a first appoximation to the xYt surface. The size distribution equation (xY plane) is a three parameter equation previously suggested. Possible refinements are outlined. Comminution kinetics research is presently following several related courses. Some are equivalent, in that they represent different ways of viewing the same facet of the problem, though the entire endeavor cannot be described as being completely integrated. The purpose of this note is to propose and discuss a framework into which the various approaches might be fitted. This must clearly be founded upon an analysis of the xYt surface.' (See also Fig. 1 of Reference 26.) The investigations referred to above comprise mainly researches into the following: (1) The kinetics of the creation of the finer sizes during relatively small grinding times. This is the Fahrenwald-Arbiter-Bhrany 2-3 approach which leads to equations equivalent to a special case of the charles4 relationship. It emerges that initial production of fines follow essentially zero order* kinetics. (2) Disappearance kinetics of the coarser fractions. This appears to be a first order relationship.5-6 (3) Prediction of the xYt surface via the selection and breakage functions utilizing computer-programmed or approximate solutions of the integro-differential equation of batch grinding.5,8-17 A recent discussion by Mika et al.5 references the relevant literature up to about 1966. In addition to these main-stream researches there is some work on the minor topic of extremely long grinding time considered as a limiting case.18-19 The field is supported by investigations into the size distribution of fragments produced by breakage processes, some of this work being most valuably statistical-mechanical in nature.20-25 Better fitting equations, however, are obtained by statistical and curve-fitting methods.26 This

Jan 1, 1969

By JOHN R. SUMAN

OVERWHELMING proof of the importance of oil in a modern national economy is afforded by the present European War. Treat¬ies and national boundaries have been cynically violated to secure greater supplies of the precious fuel. Petroleum substitutes have been desperately, and far from successfully, sought. The whole German military theory of the drang nach Osten, the drive to the East, is directed at cutting the British supply of oil and securing a supply for Germany. This is a war of machines, and the machines of war feed hungrily on oil. In view of this fact, it is surely comforting to know that we are living today in a nation which has surpassed all the rest of the world not merely in unearthing the raw supplies of petroleum which lie beneath its surface but also in every phase of the industry in mining, refining, processing, production, and distribution.

Jan 1, 1941

By Leon W. Dupuy

Many articles have been written describing peculiar and particular types of drilling. Little correlation has been made between the character of ground to be drilled and sampled and the type of drilling most desirable for procuring satisfactory samples. In development work, the engineer and metallurgist often desire the recovery of a sample in as physically natural a condition as possible, particularly when the sample must provide material for process tests as well as chemical and physical analyses. This paper describes the results of experimentation in drilling unconsolidated materials carrying titanium minerals in the Magnet Cove area, Ark. The drilling was most difficult in that the ground varied much in consistency, and it was vitally necessary to recover a physically natural sample. Ordinary churn drilling recovered a sample that could be analyzed chemically, but the sample was not in its natural state. The problem was successfully solved by utilizing and further developing methods used in the oil and clay industries.

Jan 1, 1949

By R. H. Cox, A. S. Allen, James Paone

The southwestern Illinois communities of Belleville and Maryville lie within the greater metropolitan area surrounding St. Louis. Missouri. They also lie within that part of the Illinois coal basin where the Number 6 coalbed has been mined for more than a century. About half the coal was left as pillars to support the ground surface. Years later, however, damaging movements are affecting buildings, streets, and public utilities in some areas. They are generally believed to be related to abandoned mine workings. The threat of continued or increasing incidence of damage raises the need to explore other subsidence-control measures for protecting affected areas with high population density. Because of experience gained in a subsidence-control program of backfilling abandoned coal mines in the Applachian region and in Rock Springs, Wyoming, the Bureau of Mines was called upon to investigate the subsidence occurrences at Belleville and Maryville, and recommend protective measures. Funds ware appropriated for the Bureau to initiate subsidence-control projects at two residential sites in Belleville and one in Maryville. Subsurface investigation of the sites by diamond core drilling revealed two conditions that differ from those encountered at most sites of previous subsidence-control projects. The mine workings were found to be dry and the mine floor consisted of soft underclay which characteristically loses strength with increase of moisture. It had been anticipated that water would have percolated into the mine workings at one .or more of the sites through cracks resulting from subsidence. Under such conditions Bureau engineers believed that injection of mine waste by the pumped; slurry technique3 would provide support and stabilize any movements initiated by the softening of the clay. With discovery that the underclay deposits at the three sites have apparently not been exposed to water since the mines were operating, hydraulic backfilling of any type was considered inadvisable on the basis of present knowledge. To avoid introducing water, a portable pneumatic system is being devised for injecting minus 0.01 27 m (1/2 in.) mine waste into the mine workings. Machines for pneumatic backfilling have been used in Europe not only for subsidence protection but also for strata control, for reducing spontaneous combustion and methane accumulation, and as a means of waste disposal. The Bureau experimented with a pneumatic machine in the Northern anthracite field of Pennsylvania in the 1950's. Previously pneumatic machines have been installed in active mine workings discharging from horizontal pipelines which conveyed air- borne material into rooms to be filled. In the present adaptation to abandoned mines, the machine and air compressor will be operating at the surface, to impel material vertically down injection boreholes with sufficient air pressure to disperse fill material laterally in mine workings at the base of injection holes. Large diameter access and ventilation boreholes will be provided at one site for entry into mine workings to observe backfilling progress. The Belleville and Maryville projects are part of the Mined Land Demonstration Program of the Bureau of Mines. The Illinois State Geological Survey and Department of Mines and Minerals are furnishing technical support.

Jan 1, 1979

By Robert B. Sosman

ONE of the most neglected fields for physicochemical education as well as for research is that of high-temperature phenomena. Few universities or technical schools give instruction in the physical chemistry of substances at high temperatures. On the contrary such instruction is almost entirely confined to the region between the freezing and boiling points of water. This field should be extended to a much wider range of temperatures, both low and high. Such an extension is logical, sound, feasible, and practical.

Jan 1, 1943

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By C. W. Hall

MINE executives, as a rule, have always been willing to adopt new ideas of operation, or to listen to proposals which might increase the effectiveness of their enterprise, more especially so if they could be shown how definite results might be attained by introducing any conception suggested. In these days of high wages, high cost of supplies, and high taxes, operators are even more inclined to accord consideration to innovations or improvements, and many go so far as to employ men to conduct special investigations and make studies for the purpose of advancing production. Where a man is brought into an organization to do work of an efficiency nature, it often creates resentment among the operative heads because of having their work directly scrutinized, or investigated, and there is a tendency, if not actually to obstruct, to fa.il to cooperate; in which case the investigator is handi-

Jan 1, 1925

By Charles Hart

A STUDY of the various ores that have been discussed impresses one with the need of beneficiation, in many cases. This applies to the ores that have lain dormant, due to necessity for further preparation, or to ores that now find a market due to a changed condition. Processes of beneficiation will come into their own as our richer ores become exhausted. Many efforts at improvement have been commercial failures, due to prematurity. Thomas A. Edison, with characteristic foresight, attempted concentration of the low- grade New Jersey magnetites some thirty years ago. Due to high costs and the discovery of the Mesabi range, his efforts were futile. However, a successful crusher, designed by Mr. Edison, resulted from this attempt. Agglomeration of concentrates had not, at that time, been brought to its present efficiency, when sinters and briquettes of excellent physical condition are obtainable. Recent efforts in the beneficiation of the lean magnetites of the East Mesabi resulted in an excellent sinter, but that operation is also ahead of its time.

Jan 1, 1929

By A. Patton, F. N. Speller

The use of roll scale in the Bessemer process dates back, to the best of our knowledge, at least 20 years. It was first used by the Ohio Steel Go., Youngstown, Ohio (now the Ohio Works of the Carnegie Steel Co.) under the direction of Sam McDonald, Superintendent of the Bessemer Department at these works. Two 10-ton vessels and one blowing engine capable of blowing one heat at a time were employed. The object of using the scale was to shorten the length of the blow, or in other words, to increase the production with the same equipment. Various means were tried out for introducing the roll scale into the bath of molten iron: It was shoveled into the vessel before the heat was charged, so that the metal would flow over the scale; it was shoveled into the bath after the vessel was turned up; it was dumped into the empty iron ladle by the wheelbarrow-load, and at times was dumped on top of the molten metal in the iron ladle. But the practice of introducing the scale into the iron ladle had to be abandoned on account of danger from explosions and of skulling the ladles. It was soon learned that the proper place to charge the scale was in the empty vessel, so that when the molten iron was poured into the vessel it flowed over the scale, causing a considerabIe reaction to take place before the heat was turned up. Eventually, cylindrical chutes similar to those now in use were installed. Into these chutes the scale is dumped and carried into the empty vessel. Before this convenient means of introducing the scale was adopted, the Ohio Works had satisfactorily demonstrated that roll scale would increase production, by blowing 107 heats in one 12-hr. turn (1,087 tons) with one blowing engine, blowing one heat at a time; whereas, prior to the use of scale, the best practice at these works was about 80 heats under the same conditions. In using roll scale and other oxides of iron to facilitate and control the refining of pig iron in the converter, the Bessemer plant has borrowed one of the most active agencies used in the open-hearth process with, as would be expected, much the same results. The effect of such additions to the Bessemer charge may be discussed as to the influence of this practice on quality, production and cost.

Jan 1, 1917

By H. W. Gillett

CLYDE WILLIAMS has reminded me that in the fall of 1929, gave, in MINING AND METALLURGY, an account of the hopes and aspirations of Battelle Memorial Institute, which was then just swinging into initial operation; and that therein I remarked that B.M.I. should stand, as well, for Better Metallurgical Industries, since helping to better them was the Institute's aim. So he has suggested that some of the betterments of the past fifteen years might well be listed. A yearly summary of progress comes pretty close to the ultimate in futility, for everything proved of value in that year had its inception in earlier years, and everything really new has still to be proved. Plenty of things hailed as wonderful achievements for that year, by some enthusiasts invited to contribute to the summary, turn out in later years to be inglorious flops. But over a decade and a half, betterments that are really such become self-evident, and recounting some of them can be done without guesswork or wishful thinking. An inventory of what was known and utilized in 1929 compared to what is now known and used is not too hard to make. Perhaps the most clear-cut picture of what is known and used at a certain date is drawn by the handbooks, textbooks, and equipment catalogs of that date, with scientific periodical literature forecasting what knowledge may later be used when it is verified and assimilated. The tools available for production or for research limit the application of old and the finding of new knowledge.

Jan 1, 1945

By AIME AIME

ENGINEERS in the past have been largely associated with private enterprise and there has been a considerable tendency on the part of some members of our profession to depreciate government service for engineers. We engineers must change our mental attitude about employment in government service, particularly in view of the present most friendly attitude of the U. S. Civil Service Commission toward engineers for major posts in our Government. We must also take a much more active interest in public affairs. It must be realized that the national-defense program, which we are now organizing, will require for its effectiveness large numbers of engineers skilled in a wide range of technical and administrative services. In fact, the success of this undertaking will depend largely upon the extent to which our Government can command expert engineering talent to serve during the emergency. There is an acute shortage of technical and supervisory engineering personnel not only in the industries concerned with national defense but also in the Army, Navy, and other defense agencies of the Government. By an Act of Congress, approved on Oct. 9. 1940. $9,000.- 000 was turned over to the U. S. Office of Education, the regular defense agency of the Government which has co-operated with higher education for

Jan 1, 1941

By AIME AIME

FOR the use of workmen and employees, the company should establish a dispensary and a -hospital where workmen who suffer accidents or professional diseases may be taken care of; and at suitable places in the mine or metallurgical plant it should install first-aid stations. Workmen have a right to receive 75 per cent of their wages while they are unable to perform their work as result of a professional disease; but some companies pay full wages and in the case of natural disease, with the exception of venereal, alcoholism, injuries from fights, and chronic illnesses, 50 per cent of their wages up to a period of two months. The number of diseases the Law considers as professional is large and increases almost daily. Among the professional diseases, the one which has caused greatest harm to the miners and expense to the companies is silicosis. To avoid its propagation, companies should take every possible precaution that the working atmosphere is free from dust, abating this by frequent sprinkling of the workings using, wet drills and furnishing the workmen adequate protective apparatus such as respirators.

Jan 1, 1937

"The Washoe Smelter is situated about two miles east of the City of Anaconda. The smelter site includes about 240 acres and peculiarly adapts itself in topography to the efficient handling of material. By reason of its being on a hill side it is possible to make the level of delivery of the product of one building the level of the charge floor of the next succeeding one.THE ORES: The ore treated comes principally from the Butte district and is hauled by the Butte, Anaconda & Pacific railway, a distance of twenty-eight miles, in trains of fifty 50-ton bottom-dump cars to the railroad yards at East Anaconda. At this point these trains are• split up according to their destination,—that is, as to whether they go to the concentrator and sampling mill ore bins, or to the storage bins. In each case they are made up into trains of eight or sixteen cars, according to the size of engine to be used, and are carefully weighed before delivery to their respective bills.Some idea of the magnitude of the works may be obtained from the following figures:Amount of ore that can be treated in 24 hours…12,000 tonsLime rock from adjacent quarries…2,300 tonsCoke used…500 tonsCoal for reverberatory use…500 tonsCoal for power use…50 tonsWater, per minute, 35,000 gallons.Men employed in and around Anaconda, 3,000. Monthly payroll for above, $300,000.00."

Jan 1, 1913

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