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Jan 1, 1902

Jan 1, 1912

By Claus G. Goetzel

PRESSING of powdered metal parts is best done in the direction of the shortest extension of the piece, to avoid too great a loss of pressing force through internal [ ] friction. As long as curved surfaces, recesses, or offsets occur only parallel to this shortest axis of pressure, no special difficulties arise: the cross sections, perpendicular to the pressure, do not vary, nor does the shape of the parts change during compression except for a gradually reduced thickness (Fig. IA). The problem becomes more difficult, however, when the curved surfaces or recesses are perpendicular to the shortest axis of the part (Fig. IB). Two processes for molding uniformly dense parts with complicated shapes from powdered metals are described in detail in this paper. Both can be employed successfully by those trained in the art. The first refers to curved parts; the second is especially adapted to parts having one or more recesses or steps. Both methods, as set forth here, are applied under the condition that presents the more difficult problem. For clarity, before description of the two practical methods, the variable factors in molding powdered metal parts will be reviewed, then an idealized procedure will be considered briefly. VARIABLE FACTORS IN MOLDING POWDERED METAL PARTS Compression Ratio Compression ratio is defined as the proportion of the final relative density of the compact to the apparent density of the powder. For iron powder of an apparent density of 3.0, for example, a compression ratio of 2 1/2 : I would be required to produce a compressed compact of 7.5 density; whereas for another iron powder having an apparent density of only I.5, a compression ratio of 5:I would be required to produce the same density. The lower the powder's apparent density, the greater must be the compression ratio for pressing compacts of high density.

Jan 1, 1945

By S. Kado, G. Derge, L. Yang

Self-diffusion coefficients of silver in molten silver have been measured by means of the capillary-reservoir method in the temperature range 1002" to 1105°C. The results can be .represented by the equation D = (7.10 i 0.06) X 10-4 exp [(—8150 ± 1130)/RT]. The heat of activation agrees within the limit of experimental uncertainty with that for the viscous flow. The validity of the Eyring and the Stokes-Einstein equations are examined on the basis of the self-diffusion coefficients obtained and the known viscosity data of molten silver. MEASUREMENT of the self-diffusion coefficient of silver in molten silver was made in the temperature range 1275° to 1378°K, using the capillary-reservoir method and &"' as the radioactive tracer. The experimental arrangement is shown in Fig. 1. Silver of 99.99 pct purity (fine silver), was melted and degassed in vacuum in a graphite crucible situated inside a McDanel vacuum jacket. The crucible (4 in. tall and 1 in. ID) was protected both at the top and at the bottom with graphite shields and contained about 220 g of silver. The sample holder was a piece of graphite rod (1 in. long and 1/2 in. diam) with 4 capillaries drilled longitudinally into it. The holder was screwed onto a long graphite rod (12 in. long and 74 in. diam) which was connected to a steel disk hanging on a nylon string through a glass pulley. The steel disk kept the sample holder at the center of the McDanel tube and was heavy enough to overcome the buoyancy when the holder was lowered into the molten silver. By turning a handle connected to the pulley through a tapered glass joint, it was possible to raise or lower the sample holder without breaking the vacuum. Two such arrangements were constructed, sitting side by side in 2 Kanthal furnaces. One with non-radioactive silver in its crucible was used for the diffusion run and the other with radioactive silver in its crucible was used for filling the capillaries. To fill the capillaries with radioactive silver, the sample holder was degassed first and then lowered into the radioactive molten silver in vacuum. Purified argon gas was then admitted into the system to push the liquid silver into the capillaries. After cooling in argon, the filled capillaries were polished on emery paper to expose the top of the rod and used immediately as samples for the diffusion run which was carried out at the same temperature as that used for filling the capillaries. During the diffusion run, the samples were degassed in vacuum and lowered slowly into the nonradioactive molten silver before purified argon was admitted into the system. After a predetermined period of time, the samples were raised out of the melt and cooled in argon. The temperature of the melt was measured before and after the run with a chromel-alumel thermocouple inside a McDanel protection tube. Another chromel-alumel thermocouple attached to the outside wall of the McDanel vacuum jacket was used to indicate any fluctuation in the temperature of the furnace during the run, which was found to be less than ± 2°C for the longest run made (93 min). The temperature gradient inside the molten silver was found to be negligible. No significant difference was observed in the results obtained whether the melt was stagnant during the run or was stirred by raising and lowering the sample holder slowly a few times a minute for a distance of about 1/4 in. inside the melt.

Jan 1, 1959

POSITIONS VACANT (Under this heading will be published notes sent to the Secretary of the Institute by members or other persons.) Opening for man as head of laboratory of large brass manufacturing plant in Ohio; must also be competent to manage foundry making brass castings, following practice of malleable iron castings and insulating materials. Good opportunity for right man. No. 36. Professorship in Mining at a Western university; requires man competent to give instruction in ore dressing, in metal and coal mining, and in zinc smelting, and capable of gaining confidence of mining interests. Salary $2,200 to $3,000. No. 37. ENGINEERS AVAILABLE (Under this heading will be published notes sent to the Secretary of - the Institute by members or other persons introduced by members.) Member, graduate engineer, aged 44, with over 20 years' experience in connection with large coal and coke operations in different parts of the country, desires position as general superintendent of large coal company, or will take an interest with the management in a smaller company. No. 206.

Jan 6, 1915

By H. I. Kaplan, C. Laird

Pulsating contpresslon experiments have been carried out on coppev single crystals in order to test the adequacy of mechanisms which have been suggested for stage I cvack grouth when tension-compression loading is the mode of- applying stress. Although dejorrrzation continues slowly for many millions 01 cycles under Pulsating compression stresses both within slip bands formed in the first cycle and by the creation of new bands, the morphology of these bands is not typical of fatigue slip bands in general and neither initiation of cracks nor propagation of artificially induced cracks was observed. It is therefore concluded that 1) initiation and growth of cvacks in fatigue is a consequence of repeatedly reviersed, microplastic deformation rather than intermittent, unidirectional deforma-tion, 2) gvowth of- cracks in polycrystalline specimens FAILURE of a plain specimen subjected to cyclic tension-compression stresses is known to take place by two stages of cracking.1,2 The first stage is characterized by propagation along slip planes roughly at 45 deg to the stress axis, in the outermost layers of the specimen, and at a rate of the order of angstroms per cycle. The average macro orientation of a stage I crack is normally at right angles to the stress axis,3 however, except in a few cases, e.g., single crystals in suitable orientation, when both the micro and macro directions of propagation are at 45 deg to the axis. After a stage I crack has penetrated to such a depth that the stress on the remaining section of metal is significantly increased, stage II crack propagation succeeds stage I, at right angles to the stress axis both micro and macroscopically. Direct evidence of the processes occurring during a subjected to pulsating compression stresses is caused by the setting-up of local tensile stresses due to interactions between grains, and 3) both unslipping mechanisms and operation of the "plastic blunting process " within a single slip band are adequate descriptions 01- stage I growth, being fundamentally similar. The slip mode of a material, however, is considered to control whether unslipping or the plastic blunting process takes place. Thus materials of planar slip mode fauor unslipping while those hacing a wavy mode, and capable of cross slip, can fail in stage I by the plastic blunting process. Similarly, and perhaps more importantly, reversed torsion and tension-compression modes of applying stress may be expected to cause the unslipping mechanism and the plastic blunting process, respectively. single stress cycle4,5 shows that stage II crack propagation takes place by a repetitive plastic rounding and closing of the crack tip. This mechanism has come to be called the "plastic blunting process".6 On the other hand, the extreme smallness of the phenomena occurring in stage I growth prevents elucidation of its mechanism by direct observation. Many suggestions have been proposed for this mechanism,'"-" most of them involving some kind of random or systematic unslipping process. It is possible, however, that the mechanism of stage I growth is essentially the same as that of stage 11, but occurring on a much smaller scale.6 In this situation, it has been observed that cracks propagate along slip bands comprising dislocation cell structures and bounded on either side by regions of different dislocation density and distribution." Since there is evidence that such bands are softer than their matrix, * it may be expected that the plastic blunting process occurs within a single slip band during stage I growth, rather than on two gross bands as in stage 11, when the acting stress is greater.= The blunting of the crack tip allowed by coordinated

Jan 1, 1968

By W. Spencer Hutchinson

THE relative importance of mineral production in British South Africa is about as follows: Gold, $200,000,000; diamonds, $40,000,000; coal, $18,-000,000; asbestos; $3,000,000; chrome ore, $2,000,000. In 1926 the gold mines paid $42,000,000 in dividends, the diamond mines $13,000,000, coal nearly $3,000,000, others less than $500,000. The recorded history of South Africa starts with the visits of the Dutch and the English in the sixteenth century, followed by the settlement of Cape Colony by the Dutch East India Company in 1651: The English acquired Capetown in 1806 and conflicts between English and Boers were a part of the history, from that, time on. Transvaal was settled in 1835, following the Great Boer Trek. The mining of diamonds became im-portant in 1870; the production of gold from the Rand in 1890;' the export of chrome ore in 1910; and the dis-covery of platinum in 1925. South Africa has a race problem, resulting not alone from the disparity of numbers between whites and natives, more than seven blacks to each white, twenty to one in Southern Rhodesia, and three. hundred to one in Northern Rhodesia; but because of the division of the white race between English and Cape Dutch or Afrikaans. The natives are also of many tribes.

Jan 6, 1927

By S. S. Clarke

THE sheet-ground deposits of the TriState district, because they are fairly uniform in thickness (7 to 11 ft.)-rather flat, with an easy dip to the west-and cover a large acreage, offered a problem of improved transportation. Heading advance in this kind of mine is very rapid and track haulage requires a larger crew of trackmen than do other mines, and a heavy investment in track. The use of some type of rubber-tired truck equipment for underground haulage was under consideration for some time by the Eagle-Picher Mining and Smelting Co. The nature of some ore bodies made them not adaptable to truck haulage and some mines that did offer possibilities were equipped with other types of haulage, and the expected savings by the use of trucks did not offset the loss of investment that would be incurred in discarding other equipment. The decision was made to sink a new shaft, designed for skip hoisting, on the Blue Goose ore body, and then develop truck equipment. DEVELOPING TRACTORS AND TRAILERS A study was made of internal-combustion engines for power units in the tractors, but the extreme difficulty of controlling air circulation, and the heavy cost of drilling large churn drill holes for blower installations, led to the adoption of a tractor with a storage battery. The storage-battery tractor that was on the market for mine haulage was impossible to obtain because all were needed for defense work. Several standard electric-truck chassis were purchased and rebuilt in the Eagle-Picher shops. The steering wheel was shortened and set vertical, permitting the driver's seat to be moved forward, and the frame was shortened enough to take the battery box and the fifth wheel support that carried the gooseneck of the dump trailer. The fifth wheel, or turntable, is of the ball and socket type. Fig. I shows the ball fastened to the gooseneck. The socket is split to permit introduction of the ball and is held by through-bolts, and the socket is welded to a ½ -in. plate, which in turn is attached to the tractor frame. Smaller wheels and tires were put on to reduce over-all height. If it had been necessary, the springs could have been reversed, or taken off entirely, to gain additional clearance. The tractors are equipped with 48-cell, 23-plate, 400-A.H. batteries. With the initial tonnage and mileage, the batteries were about 50 per cent down at the end of a shift. Tractors have truck tires 7.50 by 20, 8-ply, front and rear, the rear being dual. After four months of use, the tires are beginning to show signs of failure.* In

Jan 1, 1942

By William A. Longacre

IN a previous paper1 the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4,5,6 THE TWO-LAYER PROBLEM For the configuration shown in Fig. I, and for any electrode separation A, the apparent resistivity is a function of the relative depth [HA], the overburden resistivity pi, and a factor K defined by the equation [ ] where p2 is the resistivity of the lower bed, Thus, by the known theory of electrical images, [ ] THE MULTILAYER PROBLEM As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of [ ] multilayer problems can be worked out in terms of two-layer theory. Hummel,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases, In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. MODIFIED TAGG METHOD OF INTERPRETATION Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1941

University of New Mexico, Albuquerque, N M Requests for publications should be addressed to the Librarian of the University Papers of the Geological Series of the University are bound in volumes: Vol 1, vol 2, pt 1, and vol 2, pt. 2, and vol. 3 are out of print, but separates of the following papers may be had at a uniform cost of 25 cents each. Vol. 1? No. 1, Geology of the environs of Albuquerque (1898); 2, Occurrence of copper and lead in the San Andreas and Caballo Mountains (1898), 3, Geological reconnaissance in western Socorro and Valencia counties (1898); Geology of the San Pedro and Albuquerque districts (1898). , Vol 2: No. 1, Geology of the Albuquerque Sheet (1900); 2, Miscellaneous economic papers by Herrick (1900); 3, Geological reconnaissance in western Socorro and Valencia counties (1900); 4, Geology of the White Sands of New Mexico (1900); 5, Identifi¬cation of an Ohio coal measure's horizon in New Mexico (1900); 6, Cyanide process in New Mexico (1900). Vol. 3. No 3, The oil situation in New Mexico (1920), 4, Geology of Sandia Mountains (1922); 5, Oil and gas m New Mexico in 1923.

Jan 1, 1933

By O. W. Ellis

THE writer has dealt with the effect of various methods of melting copper upon the gas content of the metal.1 The copper referred to in his in his earlier paper was melted in the foundry both in the oil furnace and the electric furnace. As the metal, did not measure up to conductivity FIG. L -INGOT OF OVERPOLEP COPPER. standard, the term "casting copper" was applied to the material in the title of the paper. It was thought that some information in regard to the gases in a sample of overpoled copper might also be of interest, and through the courtesy of C. R. Stevens, superintendent of the copper mill of the Westinghouse Elec. & Mfg. Co., such a sample was obtained. The metal was chill-cast in the form of an ingot about 7 in. long, 2 ½ in. deep (from the base to the raised surface of the ingot) and from 1 3/8 to 1 7/8 in. wide. A photograph of part of the ingot is shown in Fig. 1. The effect of overpoling on the surface of the metal is here quite clearly shown.

Jan 1, 1929

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations' and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)'0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970

By John V. Beall

With some difficulty we framed the picture of the village on the mountain getting in the railroad bridge and tunnel at the base. It was a charming scene of red-tile roofs on a green mountain in the golden autumn sunshine with the black hole of the railroad tunnel looking like something out of the movie, "The Train." We clicked the shutter, advanced the film and started back to our rented Audi. At which point there was a hail from the other side of the railroad bridge. A man in uniform was brandishing an object in the air which looked suspiciously like a rifle. We peered around. We were the only other persons in view. He must be yelling at us. He was now closing the distance at a brisk, determined gait but was still 100 yards away. The car was handy but the road was straight, paralleling the railroad tracks for some distance. We dismissed the idea of running for it. Who knows, he might shoot. When he came up we didn't have much of a conversation because it had taken us a week to learn three words of Yugoslavian-zhiveli, long life, huhvalla, thank you, and schlivavitza, the national drink (plum brandy). None of these seemed appropriate. We got the Idea that photographs of railroad tunnels and bridges were prohibited. The guard, for such he seemed to be, took the Audi plate number, administered a last scowling reprimand and stalked off. This incident was the only one in a 15-day visit to Yugoslavia which we would have associated with "Iron Curtain restrictions."

Jan 1, 1970

ALABAMA. Anniston.-Noble, A. E., 20th St. and Wilmer Ave. Auburn.-Brown, R. L., Box 0. Belle Ellen.-Hutcheson, W. C. Bessemer.-Abbott, C. E., T. C., I. & R.R. Co Dobbs, G. G., Box 97. Ferguson, V., U. S. C. I. Pipe & Fdy. Co. Williams, E. P., Tenn. C., 1. & R. R. Co. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr., 406 Woodward Bldg. Allen, A. W., 1616 S. 14th Ave. Bowron, J., 1401 S, 20th St. Burbidge, T. A., Brown-Marx Bldg. Coxe, E. H. Tenn. C., I. & R. R. Co. Crawford, C. G., Tenn. C., I. & R. R. Co. Crockard, F. H., Brown-Marx Bldg. Ellis, E. E.,1515 Brown-Marx Bldg. Fairbairn C. T., Woodward Bldg. Fies, M. H., 2316 Highland Ave. Geismer, H. S., Keiser-Geismer Engrg. Co.

Jan 1, 1917

By J. Steininger

The Hallimond tube flotation of sphalerite and pyrite with sulfhydryl collectors has been found to be inhibited near neutral pH in the presence of copper salts. Alkalimetric titration studies of the reactions between collector and activator indicate that this effect is apparently related to the formation of basic copper collector complexes. The conditions of formation of these compounds and their stability are in good agreement with the depression observed in flotation experiments. The general procedure employed in the flotation of zinc sulfide minerals requires activation of the mineral surface by heavy metal ions, usually copper, which react more easily than zinc with the common short-chain ionic sulfhydryl collectors.' Commercially, zinc flotation is carried out under alkaline conditions (pH 7 to 10.5), but small-scale experiments indicate that zinc sulfide minerals can also be activated and collected under acid conditions. Selectivity, however, becomes poor at low pH and undesirable materials such as pyrite, silicates and carbonates tend to report in the float. Several years ago, Wark and Sutherland~, measured the contact angles of air bubbles on copper-activated sphalerite immersed in various sulfhydryl collector solutions. When represented, as in Fig. 1, on pH-sodium cyanide diagrams, the results are characterized by 'islands' of non-contact near neutral pH and

Jan 1, 1969

By J. M. Mutmansky, Y. J. Wang, H. L. Hartman

Procedures for determining the operating point that results when a fan is connected to a mine and placed in operation have been a source of confusion for decades. A variety of techniques have been proposed, often to the detriment of the practicing ventilation engineer trying to apply the techniques to the many mine/fan matching problems encountered in the engineering of mine ventilation systems. This paper proposes some different assumptions and definitions that simplify the problems in determining the operating point. As a result, a set of procedures is provided for determining the operating point of a mine/fan system when the outlet areas of the mine and fan are known. To simplify the development of procedures for determining the operating point for a mine/fan combination, the authors suggest that the mine pressures be redefined and then used in such a manner that the conservation of energy is ensured. This provides the basis for the recommendation that the fan operating point be determined using the fan total pressure and the system total pressure characteristics. This procedure can be applied to fans in the blower, booster, and exhaust positions equally well, and to both single-fan and multiple-fan networks. Another advantage is that the method is applicable to fans with or without an evase.

Jan 1, 1986

Discussion of the paper of Ernest Stütz, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1257 to 1265. H. 0. HOFMAN, Boston, Mass.:-I have hunted in vain for a figure which gives a dehydration temperature of cement. I was wondering if Mr. Stütz had a figure of that kind. E. STÜTZ :-No, I am afraid I have not. H. 0. HOFMAN :-I believe some figures have been published that cement disintegrates at 400° or 500° C. It seems tome a very low temperature. Mr. Stütz just made the statement that the disintegration of this briquette begins at the temperature at which the briquette begins to sinter. E. STÜTZ :-Above the sintering point. H. 0. HOFMAN :-The sintering point would be about 1,200° C. E. STÜTZ :-Yes, roughly speaking. I am afraid I have no information about the exact degree of dehydration. H. O. HOFMAN :-I have looked a great deal for such a figure and I have not been able to obtain it. Professor Howe says I might have tried myself. But my interests were directed in another line; although-that is, perhaps, a good suggestion. CHAIRMAN RICHARDS:-Is not Portland cement sometimes used for the test in a cupellation furnace and a drying-out furnace ? H. O. HOFMAN :-Yes, it is used, but that is a higher temperature, of course. But I have been trying to get a figure as to where it loses all its water. I understand it begins to lose water at 500° C. But there are different silicates or hydrosilicates in the cement, so that one would have four or five or sit figures to show the different stages at which the cement loses its water. CHAIRMAN RICHARDS :-I would ask whether the use of this material in blast furnaces has shown increased capacity of furnace or decreased consumption of fuel.

Jan 12, 1913

By Donald M. D. Stuart

It gives me great pleasure to accept the invitation I had the honor of receiving through the Secretary of the Institute, to reply to the criticisms made in discussion of the theory advanced in my work entitled, Coal-Dust an Explosive Agent; and to lay before the Institute a further statement of the views which investigations have led me to form upon this subject,

Jan 1, 1897

By E. H. Rennhack

Phase equilibria of the zinc-rich portion of the Zn-Fe-A1 system containing up to 20.0 wt pct Fe and Al have been investigated at 600°C (1112°F), 450°C (842°F), and room temperature by metallographic and X-ray diffraction techniques. The phase relationships were found to involve only those phases present in the three binary systems. THE presence of small quantities of aluminum (approx. 0.2 wt pct*) in zinc galvanizing baths is known to suppress the formation of Zn-Fe alloy layers within the coating.' As part of an extended investigation of this suppression effect and the alloy reactions involved, the zinc-rich corner of the Zn-Fe-A1 equilibrium system containing up to 20.0 pct Fe and Al was determined at 600°C (1112°F), 450° F (842° F), and room temperature. The present paper reports the findings of this study. The constitution of the Zn-Fe system has been reported by Raynor2 based mainly on the work of Schramm3-3 and Truesdale et a1.6 The solid solubility of iron in zinc is extremely small and lies between 0.0009 and 0.0028 pct in the range 150° to 400°C (302°to752°F). Within the temperature and composition range of interest, a eutectic reaction involving nearly pure zinc, liquid = Zn+FeZn13, is observed at about 419°C (786° F) and 0.018 pct Fe along with a peritectic reaction, FeZn7+ liquid e FeZn13, at 530°C (986° F) and 6.2 pct Fe. The latter reaction is sluggish due to the large proportipn of solid phase involved in the transformation. Halla et al.,7 identified the compound FeZn13 as monoclinic with a = 13.68, b = 7.63, c = 5.07, and B = 128°44'. The structure of FeZn7 was reported by Bablik, et al.,8 to be of hexagonal symmetry, belonging to either the C6v = C6/m mc or D46h = C6/mc space group. Divensions of the unit cell are a = 12.81A and c = 57.6a. The Zn-A1 diagram as composed by Raynor9 and later Gebhardt10 is characterized by a eutectic decomposition, liquid 382°C (720°F) and 95.0 pct Zn and a eutectoid decomposition, at 275° (527°F) and 78.0 pct Zn. The eutectoid reaction cannot be suppressed permanently by quenching. Above 275° (527° F), a and a' co-exist in a closed miscibility gap between 31.6 and 78.0 pct Zn. Both phases are fcc and have nearly the same lattice parameter. The maximum solubility of aluminum in zinc (B) is approximately 1.0 pct at the eutectic temperature. PROCEDURE Materials. The experimental alloys were prepared from both massive and powdered material. Cast alloys were composed from three zinc-base master alloys containing 8.0 pct Fe, 16.0 pct Fe, and 50.0 pct Al which were made from C.P. zinc, Armco iron, and

Jan 1, 1962

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