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By Bashir Ahmed, Fred D. Wright

Numerous investigators have studied the various factors that influence the ultimate strength of model mine pillars, such as ratio of height-to-least width; restraint or friction on the top and bottom; 1,2 the effect of stress distribution in pillars on their strength;3 and the scaling factors involved in applying the results of model pillars to full-scale pillars. However, the load-bearing capacity of pillars after initial failure does not appear to have been investigated. Yet many mines employ methods in which small pillars or pillar remnants are left systematically; these pillars crush as mining progresses and, of necessity, affect the behavior of surrounding rock even after initial failure. The effect of such crushed or crushing pillars depends largely on their load-deformation characteristics. This chapter presents the results of a preliminary investigation to determine the load-deformation characteristics of a few model mine pillars to and beyond initial failure. Various investigators have also studied the elastic and viscoelastic behavior of mine structures. In such studies, computers are frequently employed to obtain numerical results by the finite difference or finite element methods. It would be entirely feasible to write a program that would approximate the load-deformation characteristics of pillars to and beyond the crushing stage if these characteristics were known. More accurate information on the induced stresses and deformations in overlying strata and on surface subsidence could be obtained, information which should result in better strata control by enabling the engineer to calculate more accurately the effects of changes in pillar spacing, size, and shape.

Jan 1, 1972

By H. M. Fisher, R. E. Snow, S. C. Sun

RAPID colorimetric estimation of the amount of transparent minerals has been applied success- fully to instream mill products at the cryolite flotation plant of the Pennsylvania Salt Mfg. Co., Natrona, Pa. Apparatus used was a Bausch & Lomb monochromatic colorimeter. The optical assembly of the colorimeter, shown in Fig. 1, passes light from a 6-v, 32-cp, prefocus incandescent lamp through two condensing lenses, a heat-absorbing filter, an aperture-control diaphragm, an interference filter, and a sample container. The light finally strikes a barrier-layer photocell and the output current of the photocell is measured by a galvanometer. The engraved index line of the collective lens, located between the lamp and the galvanometer, is imaged upon the transmission scale of the colorimeter by the galvanometer mirror. Reflected light from the galvanometer mirror, the position of which is determined by the output current of the photocell, enables reading of percent transmission throughout the mineral sample being tested. The colorimeter, Fig. 1, was standardized as follows: 1-The colorimeter was connected to a Sola constant voltage transformer, A, of 6-v output operated from a 110-v ac supply. 2-Turning the toggle switch, C, illuminated the transmission scale, B, and the control knob, D, was adjusted with a blank in the optical system until the hairline on the scale read zero. 3-A No. 430 interference filter, E, was inserted into the filter channel, F. &--A test tube, G, containing 7 cc of distilled water was pressed into the sample space, H, and the fine adjustment knob,

Jan 9, 1954

By Thomas L. Watson

MY thanks are due to Mr. Frank Firmstone, Easton, Pa., who has called my attention to the statement in my papers that " Barite, fluorite and quartz, though not observed in the Tennessee area," . . . as possibly misleading to the reader, if construed to mean that such a discovery had never been made. Mr. Firmstone is correct in assuming that this statement referred only to the study of the worked areas of the metallic ores, especially zinc, made in the course of the survey upon which my paper was based. The occurrence of barite and fluorite with lead-ores in Tennessee was reported by Prof. Safford,2 in 1869, and by Safford and Killebrew,3 in 1887, with the further statement that about 1,000,000 lb. of barite were annually mined in Greene, Washington and Jefferson counties, Tenn., and that considerable deposits occur also in McMinn, Smith and other counties. It is also noted that the barite ".usually occurs in veins, associated with galena." The present worked areas of barite are, however, distinct barite propositions, without workable quantities of either lead or zinc, so far as mining operations have gone, and the areas are more or less removed from the present areas of zinc-ores. Mr. Firmstone informs me also that, in 1892, he observed, in the magnesian limestone at Watauga Point, in Carter county, on the left bank of the Watauga river, a little below the mouth of Buffalo creek, small quantities of galena and some fluorite.

Jan 1, 1907

It was a pleasure listening to this paper. Gary Works' problems were a lot more extensive than the trunnion bearing problems encountered at the Weirton Steel Division. In our two-vessel shop bearing failures are critical in that with a bearing failure on an operating vessel and the second vessel under rebuild, we are down until the vessel rebuild is completed or the bearing is repaired. The first bearing problem at Weirton occurred after we had been operating three years. The failure occurred during the 8th heat following "bum-in" of the vessel. Immediate steps were taken to change the damaged float bearing without an extensive search for the reason the bearing failed. Once the campaign was run out the bearings were inspected and found to be damaged. Field checks revealed that the bearing pedestals were not properly located and as a result the freedom of the float bearing was restricted. The trunnion pin end to end dimension had decreased due to distortion and deflection in the trunnion ring. These dimensions were within tolerances. The damage to our bearing was similar to that in the exhibits from U.S. Steel-Gary Works. Steps taken to correct what was found in the field checks were as follows: 1. The pedestals were relocated to center the bearings. 2. 4" diameter pins were installed to locate the housing in the pedestals. 3. The bearing pedestals were opened up to allow the bearing housing to move slightly in the pedestal. 4. Lubrication fittings for greasing between the bearing housing and the pedestal were installed.

Jan 1, 1972

1. Healthy and active Local Section organizations are vital factors in promoting the vigor and growth of the Institute. 2. Activity on the part of Local Sections should be recognized and stimulated by appropriation of funds from the Institute's treasury; and these appropriations should be as large as is consistent with the relative needs for other activities. 3. As between different Sections, the amount of such appropriations should be based primarily on the extent of activities as reflected in the number and character of meetings held and " the attendance of the members at such meetings. 4. In making a request for funds for any year, the officers of a Local Section should submit a report on the printed form approved by the Directors at their meeting on November 19, 1937. 5. A standing Committee on Local Section Appropriations, consisting of one past chairman of a Local Section, one member of the Institute's Executive Committee, and one member of the Finance Committee, shall be appointed by the President and shall pass upon requests for appropriations and authorize payments within bounds of the budget. The committee will be guided by the principles herein outlined, always having in mind the vital importance of healthy, active Sections to the welfare of the Institute as a whole. 6. According to Article XI, Section 2 of the Bylaws, requests for appropriations shall be signed by the Chairman, Secretary and Treasurer of the Section. 7. Requests for appropriations must be in the hands of the Secretary of the Institute by February 15 of the year for which they are desired.

Jan 1, 1940

Department of Conservation and Development, State of North Carolina, Raleigh, N C H J Bryson, State Geologist. The latest list of publications will be sent upon request. Of the many Bulletins, Economic Papers, Circulars and Volumes issued by the Department of Conservation and Development, the following are available and relate to mining and geology of the state ? Bulletin 18, Bibliography of North Carolina geology, mineralogy and geography (1909), 50 cents, 21, The Gold Hill mining district (1910), 15 cents, 22, Report on Cid mining district (1911), 15 cents, cloth 75 cents, 25, Zircon, monazite and other minerals, 15 cents, cloth, 75 cents, 28, Limestones and marls, 15 cents, 29, Kaolins of North Carolina, 50 cents, 31, Deposits of brown iron ore, 50 cents, 32, Magnetic iron ores, 15 cents, 33, The Deep River coal field, 50 cents, 37, Pyrophyllite deposits, 35 cents A series of the Economic Papers review the mining industry in North Carolina for the years cited Those now available are Economic Paper 23 (1908-1909-1910), 10 cents, cloth, 50 cents, 49 (1913-1917), 20 cents, 55 (1918-1923), 25 cents, 60 (1924¬1925), 15 cents, 63 (1927-1928), 25 cents. Other available Economic Papers on geology and mining are No 3, Talc and pyrophyllite deposits (1900), 25 cents; 58, Oil prospecting well near Havelock (1927), 5 cents, 59, Oil-bearing shales of Deep River Valley (1927), 10 cents Available volumes on geology. Vol 1, Corundum and the basic magnesian rocks (1905), 35 cents, cloth, $150, 5, The Cretaceous formations of North Carolina (1923), cloth $1 75

Jan 1, 1933

C. H. BIERBAUM,* Buffalo, N. Y.--I agree with Dr. Merica that the eutectoid has a distinct effect upon the alloy and also that, as yet, it is difficult to say at just what point this eutectoid occurs or the conditions under which it appears; that is, the percentages of copper, tin, zinc, lead, and the other elements together with the temperature of pouring and the rate of cooling that is necessary; all seem to have a contributing effect. Some authorities, Law for instance, gives it as 9 per cent. of tin, yet under certain conditions I have found it with a lower percentage of tin to copper contents than that. The hard delta and the soft alpha crystals are both necessary for a bearing alloy; the one supplements the other. I am not inclined to think that phosphorus has any effect upon the eutectoid forming. The phosphide, PCu3, forms in and around the delta but is and remains distinct and separated from it. Etching with ferric chloride and then with nitric acid shows this very distinctly; it darkens the eutectoid and the other parts and leaves the phosphide bright. The rate of cooling determines the size of the crystals and the eutectoid together with their distribution and orientation. It is possible to chill the alloy to such an extent Where no eutectoid appears. I think it has been positively demonstrated that only an alpha and a beta appear. when this copper-tin alloy has been poured between two polished ingots

Jan 1, 1919

1. Healthy and active Local Section organizations are vital factors in promoting the vigor and growth of the Institute. 2. Activity on the part of Local Sections should be recognized and stimulated by appropriation of funds from the Institute's treasury; and these appropriations should be as. large as is consistent with the relative needs for other activities. 3. As between different Sections, the amount of such appropriations should be based primarily on the extent of activities as reflected in the number and character of meetings held and the attendance of the members at such meetings. 4. In making a request for funds for any year, the officers of a Local Section should submit a report on the printed form approved by the Directors at their meeting on November 19, 1937. 5. A standing Committee on Local Section Appropriations, consisting of one past Chairman of a Local Section, one member of the Institute's Executive Committee, and one member of the Finance Committee, shall be appointed by the President and shall pass upon requests for appropriations and authorize payments within bounds of the budget. The committee will be guided by the principles herein outlined, always having in mind the vital importance of healthy, active Sections to the, welfare of the Institute as a whole. 6. According to Article XI, Section 2 of the Bylaws, requests for appropriations shall be signed by the Chairman, Secretary and Treasurer of the Section. 7. Requests for appropriations must be in the hands of the Secretary of the Institute by February 15 of the year for which they are desired.

Jan 1, 1946

By Charles P. Williams

DURING the fall of the year 1873, attention was redirected to the occurrence of lead ores in Southwestern Arkansas (chiefly in Sevier County), and somewhat extensive explorations of the deposits have since been made in the hope of finding the ores sufficiently argentiferous to be profitably worked. How far the expectations have been realized I am not authentically advised, but samples of the galena ore, yielding 62.09 per cent. of lead, gave on assay at the rate of 15 3-10 ounces of silver to the ton of ore. This was the highest result obtained by myself, though I am informed that higher yields have been obtained by others. Among the samples of ores from this locality, forwarded to me in January last, was one specimen which I at once recognized as stibnite, and, on notification, other specimens of the same from Sevier County were forwarded me. The first specimen of the several received contained 11.51 per cent. of gangue, 57.62 per cent. antimony, 4.57 of bismuth, with small amounts of arsenic and iron. The latest result from a portion of another hand specimen I append in full, with duplicate estimations of the arsenic, bismuth, and gangue. The analyses were all conducted by Mr. C. R. Winters, under my direction, and in the case of those given below the ore was separated as closely as possible from the gangue before analysis. The results are for the mineral freed from hygroscopic moisture, and are as follows:

Jan 1, 1875

1. Healthy and active Local Section organizations are vital factors in promoting the vigor and growth of the Institute. 2. Activity on the part of Local Sections should be recognized and stimulated by appropriation of funds from the Institute's treasury; and these appropriations should be as large as is consistent with the relative needs for other activities. 3. As between different Sections, the amount of such appropriations should be based primarily on the extent of activities as reflected in the number and character of meetings held and the attendance of the members at such meetings. 4. In making a request for funds for any year, the officers of a Local Section should submit a report on the printed form approved by the Directors at their meeting on November 19, 1937. 5. A standing Committee on Local Section Appropriations, consisting of one past Chairman of a Local Section, one member of the Institute's Executive Committee, and one member of the Finance Committee, shall be appointed by the President and shall pass upon requests for appropriations and authorize payments within bounds of the budget. The committee will be guided by the principles herein outlined, always having in mind the vital importance of healthy, active Sections to the welfare of the Institute as a whole. 6: According to Article XI, Section 2 of the Bylaws, requests for appropriations shall be signed by the Chairman, Secretary and Treasurer of the Section. 7. Requests for appropriations must be in the hands of the Secretary of the Institute by February 15 of the year for which they are desired.

Jan 1, 1946

By W. A. Oates, J. S. Blakemore, E. O. Hall

AS part of an investigation into the effect of hydrogen on the serrated yielding of Ni-Cu alloys,' it was necessary to determine the solubility of hydrogen in the alloys of interest. With the exception of the work by Fukusima and Mitui2 who investigated the solubility of hydrogen in solid Ni-Cu alloys at 20 wt pct intervals at 1050°, 700°, and 350°C, the information in the literature is limited.3-10 Alloys were prepared from deoxidized Analar Copper and Mond Nickel pellets.' Wire samples were hydrogenated at 7.8 atm in an autoclave consisting of 5 ft of thick-walled Inconel 600 tube with a resistance furnace around the middle portion. The top end, at room temperature, was fitted with a safety valve, a calibrated pressure gage, and a sample inlet, while the bottom end, again at room temperature, was filled with water. After reaching equilibrium samples were quenched by dropping from the high-temperature region of the autoclave into water. They were then quickly transferred to liquid nitrogen where they were stored until analyzed for hydrogen using an Exhalograph.11 The results, which are shown in Fig. 1, represent the mean of two separate determinations on each sample. Because of the lower level of hydrogen at the high copper end of the series, the results here are of poor precision using this method. Fortunately, the results of Himmler9 using the Sieverts technique are available for these copper-rich alloys (>80 at. pct Cu)

Jan 1, 1969

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

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

Jan 1, 1970

By H. M. Fisher, R. E. Snow, S. C. Sun

RAPID colorimetric estimation of the amount of transparent minerals has been applied successfully to instream mill products at the cryolite flotation plant of the Pennsylvania Salt Mfg. Co., Na-trona, Pa. Apparatus used was a Bausch & Lomb monochromatic colorimeter. The optical assembly of the colorimeter, shown in Fig. 1, passes light from a 6-v, 32-cp, prefocus incandescent lamp through two condensing lenses, a heat-absorbing filter, an aperture-control diaphragm, an interference filter, and a sample container. The light finally strikes a barrier-layer photocell and the output current of the photocell is measured by a galvanometer. The engraved index line of the collective lens, located between the lamp and the galvanometer, is imaged upon the transmission scale of the colorimeter by the galvanometer mirror. Reflected light from the galvanometer mirror, the position of which is determined by the output current of the photocell, enables reading of percent transmission throughout the mineral sample being tested. The colorimeter, Fig. 1, was standardized as follows: 1—The colorimeter was' connected to a Sola constant voltage transformer, A, of 6-v output operated from a 110-v ac supply. 2—Turning the toggle switch, C, illuminated the transmission scale, B, and the control knob, D, was adjusted with a blank in the optical system until the hairline on the scale read zero. 3—A No. 430 interference filter, E, was inserted into the filter channel, F. 4—A test tube, G, containing 7 cc of distilled water was pressed into the sample space, H, and the fine adjustment knob,

Jan 1, 1955

By Charles Y. Clayton

A study of the literature shows that the greater part of research work on annealing of cold-worked iron has been for the purpose of studying the effect on grain-size and properties other than hardness. No reference has been found of experimental work of the same nature as that explained in this short paper. The material used throughout was Vismera iron, an iron containing 0.03 carbon and made several years ago by the Inland Steel Co. One-half inch stock was cut into cylinders % in. long. The cylinders were then compressed for 60 sec. in a Reihle testing machine under loads as indicated below: CoMPressiON, Average Length, Series Pounds Inches 1 10,000 0.693 2 15,000 .599 3 20,000 .501 4 25,000 .426 5 30,000 .378 6 35,000 .351 7 40,000 .311 Fig. 1 shows these cylinders after compression. Each series consisted of 17 specimens lettered 0, B, C, D, E, F, G, H, I, J, K, L, M, N, P, Q and R. One specimen of each series was reserved for study of the properties in the cold-worked condition. The other specimens were annealed in a Hump furnace for 1/2 hr. at the following temperatures: TEmpeRa- TempeRa- Letters tuRe,° C. LettERs tuRe °C. B............................... 250 J.............................. 650 C............................... 300 K............................. 700 D............................... 350 L.............................. 750 E............................... 400 M............................. 800 F................................ 450 N............................. 851 G............................... 500 0. . :........................... 900 H............................... 550 P.............................. 950 I................................ 600 Q............................. L000

Jan 1, 1926

By W. B. Agocs

IN August 1954 a low altitude test geophysical survey was made in the Green Pond area of Morris County, New Jersey, with a Gulf Research and Development Co. Model II total magnetic field variation magnetometer mounted in a Sikorsky S-55 helicopter. The test was made in this area to compare the results of a high precision, very low altitude magnetometer survey with an existing ground magnetic survey in this area having known magnetite concentrations, so that the method could be used in areas of difficult access for the detailing of airborne magnetometer anomalies of interest in place of ground surveys. The load capacity of the Sikorsky S-55 permitted installation of a recording scintillation counter so that a radioactivity survey would be made simultaneously with the magnetometer survey. The area surveyed is located at approximately 41°00'N and 74o28'W, just south and east of the town of Green Pond, N. J. The outstanding topographic feature of the region is Copperas Mountain, a well defined ridge, maximum elevation 1222 ft, which runs the entire length of the survey. The lowest point in the survey, 810 ft, is in the extreme eastern corner. Topography of the area is shown in Fig. 1. The three major rock units outcropping in the area are all metamorphic: the Pochuck gneiss, which has been divided into two metamorphic facies; the Byram gneiss; and the Green Pond conglomerate. The relative ages of the Pochuck and Byram formations, both pre-Cambrian, are in doubt, but it is believed that the Pochuck is the older of the two.' The Green Pond conglomerate is Silurian.' Distribution of the outcrops and mine locations is shown in Fig. 1. Two facies of the Pochuck gneiss can be distinguished locally—the Copperas Mountain and Kitchell members. The Copperas Mountain member is a hornblende gneiss, and all the mines and prospects in the area are in this unit. The Kitchell is a quartz-plagioclase feldspar gneiss. The Byram gneiss is a relatively nonresistant valley formation which is high in the potash feldspar. The Green Pond conglomerate is a well indurated quartzite-conglomerate which forms the Copperas Mountain and the Green Pond Mountain's ridge to the north. It overlies the gneisses with a strong angular discordance that may be a fault. The geologic structure of the Green Pond area is relatively uncomplicated. The foliation planes of the gneisses dip steeply to the southeast, and the Green Pond conglomerate dips steeply to the northwest. Additional faulting in the area is indicated at the contact between the Kitchell member of the Pochuck and the Byram along the base of the topographic spur extending to the southeast from Copperas Mountain. The magnetite mines of Pardee, Winter, Davenport, Green Pond, Copperas, and the Bancroft shaft are described by Bayleyl and Stampe2.' The ore is in the Copperas Mountain member of the Pochuck gneiss. The magnetite veins are 10 to 50 ft wide and up to 300 ft long, dipping to the southeast at angles ranging from 40" to 75". The locations of these mines are shown in Fig. 1. Dip Needle Survey: The dip needle survey shown in Fig. 2 was taken from a U. S. Bureau of Mines Report of Investigations." The figure numbers below the local, individual map area outlines refer to the figures in the aforementioned reports which were not contoured. The area of the dip needle survey was confined almost exclusively to the outcrops of the Pochuck gneiss. The separation between survey profiles was 100 ft and the distance between stations on the profiles was 25 ft in highly anomalous zones to 100 ft in magnetically flat areas. A total of 16 1/2 miles of traverse was surveyed over an area of approximately 1/2 sq mile with 2050 stations. The magnitude of the magnetic anomalies is difficult to determine due to the lack of information concerning the type of dip needle used and the procedure followed in making the dip needle survey. This latter would include the method of "zeroing" the dip needle and the procedure of reading at the stations, whether on the swing or statically. Calibrations made of the Gurley dip needle, Lake Superior type, show a static sensitivity of 385 gamma per degree in the range from —25" to +35o, corresponding to a variation in the total field of —9600 gamma to +13500 gamma in a total field of 57000 gamma, inclination 72". The sensitivity increases to 16 gamma per degree from a deflection of 60" to 76", and from 76" to 172" the sensitivity decreases continuously to a low of 260 gamma per degree. From the above it may be seen that it is difficult to assign an arbitrary sensitivity for the dip needle used on this survey. However, an estimated value of 100 gamma per degree may be assigned. On this basis, the majority of the magnetic anomalies, whose deviation is +20°, would be 2000 gamma. Locally, west and northwest of the Pardee mine the magnetic anomaly is +50°, or 5000 gamma; in the Green Pond mine area deviations of +75" are observed that would correspond to anomalies of 7500 gamma. The areal extent and width of the dip needle magnetic anomalies is comparable to profile and station spacing. Hence it is concluded that part of the detail may be due to control, and the probable cause of the magnetic anomalies is at or near surface exposures of magnetite concentrations in the form of veinlets and disseminations whose locations correspond to the local magnetic anomalies. On the basis of the magnetics, none of the magnetite concentra-

Jan 1, 1956

By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200 °C, a wide range of conveyors is available. Special constructions of rubber conveyor belts, steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400 2F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F. The arbitrary selection of 400 °F as a dividing point undoubtedly can be challenged, as special conveyor belting constructions are available which are suitable for temperatures in excess of 400°F. However, when the relatively short life of such belts and the cost of their replacement, with the attendant down time, are balanced against the reliability and long service life of the properly designed steel constructed units to be discussed, there is little question in any operator's mind that the special belts are more expensive to use. Because the conveyors under study are for the handling of bulk materials, inevitably including a high proportion of fines, obviously wire mesh belts cannot be included for consideration. Even though this type of conveyor is widely used at high temperatures, i.e., for carrying glassware through a lehr, it is unsuited for the conveying of bulk materials, and therefore will be excluded from further discussion in this paper. Preliminary to the study of the conveyor itself is the determination as to whether the material is to be cooled while it is being handled, or whether the processing requires retention of all heat and the maintenance of a given temperature range. In the majority of cases cooling is incidental to or part of the handling process, when the handling, for example, follows completion of sintering, roasting, calcining, refining, or some other process. To meet such operating conditions successfully, the conveying medium used must have: 1—a construction capable of withstanding maximum initial temperatures of the material being handled. 2—a construction providing efficient heat transfer for cooling. 3—a construction providing dependable operation and long life with minimum service requirements, and 4—a construction providing controlled and efficient conveying. Under the usual conditions of cooling during the handling, the construction selected to withstand the initial maximum temperatures does not necessarily involve using alloys, as excellent results can be achieved with normal carbon steels and cast irons, when they are properly applied and proportioned. The earliest and simplest type of conveyor for handling very hot materials is the cast steel drag chain conveyor, still widely used for handling hot cement clinker, as illustrated by Figs. I and 2. Because of the rugged and generous proportions of the chain link design, low carbon steels are entirely suitable for the links. The pins, however, must be alloy steel. The simple, rugged construction of this type of conveyor makes it readily capable of withstanding high initial temperatures, even though the chain is operating buried in the material. The drag-chain type of conveyor has advantages and limitations. Although the efficiency of the heat transfer is relatively poor, the life of the conveyor is reasonably long, and because of its crude simplicity it does not require much servicing. However, as a conveyor, it is limited in capacity, and largely limited to horizontal runs. Furthermore, because of the crude design, heavy weight, and the chain operating at the temperature of the material, greatly reducing permissible operating chain pulls, this type of conveyor is limited to relatively short centers. Another type of conveyor that has been used for very hot materials is the cast pan conveyor. Because of its very generous proportions the cast pan, which is made of either cast iron or malleable iron, can withstand initial maximum temperatures. It also provides efficient heat transfer for cooling. Further, it is on efficient conveyor construction, which can be used for inclines. Because the chain employs rolling friction instead of sliding friction, and is not in the maximum temperature zone, much longer centers are possible. It is this type of conveyor that is frequently used in the casting of various metal pigs, pig iron, and aluminum; it is obvious, therefore, that very high initial temperatures are being handled. With this kind of conveyor the return run is frequently sprayed with water to accelerate heat transfer. The build-up of residual heat in the very heavy cast pans is thus overcome. The outboard roller steel pan conveyor is an improved pan conveyor' which provides high rates of heat transfer and substitutes formed steel pans for the heavy cast pans. It is a very efficient conveying medium. The details of this particular construction are clearly shown in Fig. 3. An early application of this type of conveyor is shown in Fig. 4. In this case the conveyor units are handling roasted phosphate rock at average temperatures of 1000" to 1500°F, and frequent maximum temperatures as high as 1900°F. Several widths are used. The capacity of the unit at a speed of 50 fpm is approximately 30 tph per inch of width at peak loadings, average capacity being about 1/3 of peak loading. The assembled conveyor is shown in Fig. 5, with views of both the top and the underside to show all the construction details. In particular, the following general design principles were carried out in this construction:

Jan 1, 1954

By A. Mitchell

An approximate phase diagram has been developed for the CaF2-CaC2 system, indicating a eutectic point at 1240°C, Ncac2 = 0.13, and no detectable solid solution in either phase. The liquidus line is shown to correspond to a simple c22- ion in solution. A thermo-chemical study of&apos; the reaction between carbon-saturated Ni-Ca alloys and CaC2-CaF2 liquids indicates that lhe Raoullian activity coefficient of CaC2 in dilute solution in Cap2 al 1500°C lies between 8 and 10. Some effects of the stabilily of Cap2-CaC2 solutions at high temperatures on electroslag remelting praclice are outlined. THE alkaline earth acetylides. MIIC2, have a reasonably high thermochemical stability at high temperature in the solid state,&apos; with the exception of magnesium, which forms an unstable acetylide at low temperatures (-500°C) and a carbide, Mg2C3, in the range 700&apos; to 1000°C. The acetylides of calcium and barium have been shown to have limited solubility in their respective chlorides,&apos; and further these solutions contain the acetylide as a C: ion.&apos; The equivalent magnesium solutions have not been studied. Although calcium "carbide" is used as a desulfuriz-ing reagent in steelmaking. and is possibly present as an acetylide-oxide phase in very basic electric arc practice slags, the acetylide ion appears to be substantially unstable in a silicate slag.* As a conse- *This instability arises from equilibria in the reaction: CaC2 + CO = (Ca0) + 3C where the low intrinsic solubility of CaC2 in silicate lattice, and the low activity of CaO in a silicate solution where CaO/Si02 < 1, combine to give a very small equilibrium concentration of CaC2 in solution in such silicate slags at temperatures in the region of I 500°c, even under carbon-saturated conditions. Under highly basic conditions, a liquid CaO-CaC2 phase may separate from the silicate system quence of this, the possibility that reactions involving CaC2 in silicate solutions are of importance to general steelmaking practice is remote. However, in operations involving a slag primarily based on a halide, or alkaline earth oxide, we must take into account the possibility that CaC2 will appear in quantities sufficient to significantly affect both the chemical and physical properties of the slag. The work outlined below presents a study of the CaF2-CaC2 system intended to provide sufficient data to allow an estimate of the importance of this system to electroslag remelting and welding practice. However, we should indicate at this point that there will be other processes, e.g., heat treatment, flux cleaning of castings, fused salt electrolysis, and so forth, where alkaline-earth halide fluxes are in contact with carbon, graphite, or carbides, and where halide-acetylide solutions must be taken into account. EXPERIMENTAL 1) Structural Studies. In view of the difficulty ex-perienced in handling CaC2 prepared from calcium turnings and propane gas at 700°C, it was decided to use solutions prepared directly in the equilibration apparatus, Fig. 1. The starting materials were: a) Ni-Ca-C alloy, prepared by adding calcium to liquid nickel held under calcium fluoride in an induction-heated graphite crucible; b) calcium fluoride, prepared by fusing calcium fluoride powder (British Drug House "EXTRA PURE") calcium fluoride in an induction-heated graphite crucible, in air, followed by electrolysis between graphite electrodes at 1 amp cm-2 density, for 10&apos; coulombs per g CaF2. This procedure decomposes the CaO produced by hydrolysis during the fusion step, replacing it by CaC2; Ca2+ + 2e-Ca*(l) Ca*(l) + 2C(gr)-(CaC2)caF2 O2- -2e-O*(g) O*(g) +C(gr)-CO(g) This results in a composition of between 2 and 5 wt pct CaC2 in CaF2. Fifty grams (in lumps) of this material were placed in a graphite crucible, together with Ni-Ca-C alloy (averaging 20 wt pct Ca), and the equilibration apparatus assembled. The alloy reacted with the crucible at high temperature to give CaC2, which dissolved in the calcium fluoride solution to give the desired composition. Cooling curves were plotted manually for these liquids, with rapid stirring and CaF2 seeding to minimize supercooling, and using a Pt/Pt 13 Rh thermocouple calibrated on the freezing points of nickel and copper. This gave a reproducibility of ±0.l°C. and an absolute accuracy of the thermocouple of ±l°C. An example curve is shown in Fig. 2, with the CaF2 end of the binary system in Fig. 3. The CaF2-CaC2 ingots were crushed, under dry nitrogen, and sampled for chemical analysis and X-ray examination. Analytical details are given in the Appendix. Powder diffraction data indicated that the only phases present in all samples examined were calcium fluoride and tetragonal (Types I and 111) calcium acetylide,4 with no evidence of solid solutions or compound formation. 2) Thermochemical Studies. The apparatus used to obtain activity data on CaC2 in these systems is shown in Fig. 4. It consists of an arrangement whereby the graphite crucible and its contents (CaF2-CaC2. Ni-Ca-C) can be rapidly cooled without exposure to air. Trial experiments to determine an equilibration time by ap-

Jan 1, 1969