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By Alexander R. Troiano, Eugene P. Klier

Since the very early work on quenched structures, where the products of the martensite transformation had been recognizedl this transformation has provoked much interest and study. Theoretically it was desirable to account for the extreme changes in physical properties resulting from the formation of martensite, as that information might lead to results of practical importance. Desirable information, therefore, was on the kinetics of transformation from austenite to martensite as well as on the physical constitution of the martensite. It has been known for years that certain steels quenched to room temperature will contain persistent austenite as well as martensite. Other important and now well-established features of the martensite reaction are the Progress of the reaction on cooling only and the independence of Ar" with cooling velocities exceeding the critical velocity. These facts have been experimentally determined by various methods and investigators. Notable among the early investigators were Tammann and Scheill and Wever and Engel.2 Unfor- tunately, all investigators did not fully interpret their results, which, coupled with several investigations that yielde. conflicting resultsl caused a state of confusion that was not clarified until quite recently. X-ray investigations of martensite in steels3-6 indicate it to be a supersaturated solid solution of carbon in alpha iron. This supersaturation is evident from the appearance of a body-centered tetragonal structure with the addition of sufficient carbon. The dimensions of this tetragonal structure are a linear function of the carbon content within the limits of accuracy of the determinations. Slight tempering of tetragonal martensite leads to the destructi,, of the tetragonal structure, which is converted to a body-centered cubic strutture. This phenomenon has precipitated a controversy concerning the nature and mechanism of the tempering of martensite The facts in the case have been outlined by Epstein7 and more recently by Antia, Fletcher, and Cohen.8 The significance of Ar" on theoretical grounds is not clear, however, although considerable study has been devoted to its determination. The precise position of Art' aS a function of carbon content was first stated by Greninger and Troiano9 for steels covering a range of approximately 0.7 to 1.8 per cent carbon. The effect of alloying elements on Ar" has recently been the subject matter of investigation by various methods.

Jan 1, 1945

By K. G. Kreider, J. H. Brophy, J. Wulff

The technology of nickel-activated sintering of tungsten powder has been successfully applied to the densification of plasma-sprayed tungsten. Nickel was added by infiltration in a zinc solution followed by evaporation of the solvent. After sintering one hour at 1300°C density 95 pct of theoretical and transverse rupture strength of 74,000 psi were obtained. Shrinkage was found to be anisotropic and the mechanism of densification was comparable to that found in the nickel-activated sintering of tungsten powder. 1 HE use of a plasma spray gun for the fabrication of massive tungsten parts has become increasingly interesting. Applications now exist where a deposit in the as-sprayed condition is satisfactory. However, these deposits are generally characterized by a lamellar anisotropic microstructure containing 15 pct porosity of which, typically, two-thirds is open to the surface. Mechanically, the as-sprayed deposits fail at relatively low stress levels with a biscuit-like fracture. As a result of these problems the possibility of improving structure and strength by sintering treatments subsequent to spraying is particularly attractive. Preferably this sintering treatment should be adaptable to large bodies of sprayed metal. The similarity between the as-sprayed tungsten structure and that of a powder compact suggests that the relatively low-temperature activated sintering technique1 might be profitably employed in the densification of plasma-sprayed tungsten. It was the purpose of the present investigation to develop a technique for introducing the nickel-activating agent into the sprayed structure, to evaluate the amount and mechanism of densification obtained as a function of time and temperature, and to obtain an indication of the relative strength before and after sintering. EXPERIMENTAL PROCEDURE Powder used for spraying was purchased from the Wah Chang Corp. in several size fractions ranging from an average size of 4 to 150 . These powders were sized further for an explicit study of the influence of average feed size on densification. All powders were dried at 200°C before use. Spraying was accomplished with a Plasma Flame unit manufactured by Thermal Dynamics Corp. Several modifications of the unit were helpful in conducting the investigation. A variable speed auger feed mechanism coupled with the carrier gas mecha nism facilitated the use of fine particle sizes. A coil of ten turns of copper tubing in series with the arc power and concentrically would around the nozzle improved nozzle life and extended the range of operating currents available. The function of the auxiliary coil was to cause the arc to spin and to prevent impingement at only one point in the nozzle. Normally air sprayed deposits were made with an arc maintained at 400 amp at 50 to 70 v. The arc was blown by a gas mixture containing from 5 pct H, 95 pct N for the finest powder feed sizes ranging to 20 pct H, 80 pct N for the coarsest size. The flow rate was maintained at 100 cu ft per hr NTP through a nozzle of 0.25 in. ID. When apraying in air, the powder stream was directed toward an aluminum substrate for ease of mechanical removal of the deposit. The substrate was cooled by diverting the plasma flame with an air jet, and a second jet was directed on the deposit surface. In this configuration a gun-to-work distance of 2 to 3 in. was found to be satisfactory. Fig. 1 represents a typical as-sprayed deposit micro-structure. Laboratory studies of protective atmosphere spraying were carried out in cylindrical chamber 8 in. in diam by 18 in. in length. In operating the nozzle attached to such a chamber, particular care was required to avoid nozzle burn out due to reduced gas flow. The structure and density of the chamber sprayed deposits varied over wide ranges depending on substrate temperature. For the purposes of this investigation, flat deposits were made approximately 2 in. sq by 3/8 in. thick. From these deposits individual samples were cut an ground to a rectangular shape typically 1 1/2 in. by 1/8 in. sq such that the long dimension was perpendicular to the spraying direction. For the study of shrinkage anisotropy deposits up to one inch thick were produced. From these, rectangular samples were cut having a longer dimension parallel to the spraying axis. Prior to the addition of activating agent, the samples were deoxidized in hydrogen at 800°C for 20 min. No detectable dimensional or microstructural change was observed after this treatment. The addition of nickel was accomplished by infil-

Jan 1, 1963

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By H. E. Mauck

The many factors that control bumping must be carefully studied for each coal seam where bumps occur, and specifications known to exclude bumping should be incorporated in the mining plans. This calls for complete knowledge of the seam's characteristics and its adjacent strata, and in many instances these characteristics are not revealed until the seam is actually mined. Pressure and shock bumps, the two general types, occur jointly and separately. In this discussion no differentiation will be made. Whether pressure or shock, they are treated as bumps, and both must be eliminated. Bumps in mines have occurred in several places throughout the coal fields of the world. A study of many of these occurrences indicates that geologic characteristics, development planning, and mining procedure have contributed. But more specifically, there are conditions usually associated with bumps: thickness of cover, strong strata directly on or above the seam, a tough floor or bottom not subject to heaving, mountainous terrain, stressed and steeply pitching beds, and the proximity of faults and other geologic structures. Mine planning should incorporate these known factors (not necessarily in order of importance): 1) Main panel entries should be limited to those absolutely necessary to ventilate and serve the mine. This reduces the span over which stresses may be set up that will later throw excessive pressures on barrier and chain pillars when they are being removed. 2) Barrier pillars should be as wide as practicable so that they will be strong enough to carry the loads thrown on them when final mining is being carried out. 3) Pillars should never be fully recovered on both sides of a main entry development if the barrier and chain pillars are to be removed later. The excessive pressures placed on the main chain and pillar barriers by arching of the gob areas can result in bumping when these barriers are being removed. 4) Full seam extraction is better accomplished by driving to the mine boundary and then retreat-drawing all pillars. If there are natural boundaries in the mine—such as faults, want areas, and valleys —retreat should be started there. 5) Pillars should be uniform in size and shape. The entire development of the mine should call for uniform blocks with entries driven parallel and perpendicular. Only angle break-throughs should be driven when necessary for haulage, etc. 6) For better distribution of rock stresses and reduction of carrying loads per unit area, both chain and barrier pillars should be developed with the maximum dimensions. 7) Pillars should be open-ended when recovered. If they are oblong, the short side should be mined first. Both sides of a block should not be mined simultaneously, but under no circumstance should the lifts be cut together. 8) Pillar sprags should not be left in mining. If they are not recoverable, they should be rendered incapable of carrying loads. 9) Pillar lines should be as short as practicable. (Three or four blocks are adequate). Experience has shown that rooms should be driven up and retreated immediately. The longer a room stands, the more unfavorable the mining conditions. This contributes to bumping. 10) Pillars should not be split in abutment zones (high stress areas lying close to mined out areas) and if slabbing is necessary, it should be open-ended. 11) Pillars should be recovered in a straight line. Irregular pillar lines will allow excessive pressures thrown on the jutting points. Experience has shown that the lead end of the pillar line can be slightly in advance. 12) Pillar lines should be extracted as rapidly as possible. This appears to lessen pressures on the line and render abutment zones less hazardous. 13) Extraction planning should call for large, continuous robbed out areas. Robbing out an area too narrow to get a major fall of the strata above the seam tends to throw excessive pressures on a pillar line. 14) Timbering in pillar areas should be adequate but not excessive. Too heavy timbering or cribbing is likely to retard roof falls and throw excessive weight on the pillar line. 15) Experience has shown that when pillar lines have retreated 800 to 1000 ft from the solid, bumps can occur. Because this distance may vary in different seams, impact stresses should be studied for each individual condition. In any event, extra precautions should be taken against bumps in this area. This list of controlling factors may or may not be complete. It probably is not, but it covers most of the problem's significant aspects. The question is whether or not bumping can be eliminated. The answer is that bumping can be minimized and possibly eliminated if these and other established factors are thoughtfully considered and incorporated in the mining and extraction plans. If a mine has already been developed or the pattern set so that little change can be made, then it will be necessary to adjust to the most nearly practicable system that can incorporate the known factors.

Jan 1, 1959

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

By T. Sterry Hunt

IT is now five years Since I called the attention of the Institute to the industrial importance of the coal and the iron ores of the Hocking Valley in Southeastern Ohio, and in a pamphlet on the region published Soon after, in 1874, endeavored to resume the principal facts then known respecting it, including the observations of the geological survey of Ohio, made and published up to the time by Professors Andrews and Wormley, together with an estimate of the probable future of the region, and its relations to the coal and iron markets of the country. Since that time the labors of the Geological Survey have included a further Study of the coal by Prof. Edward Orton, the results of which will be awaited with much interest. I may say from my knowledge of them, that while confirming the general conclusions of his predecessors, he has been enabled to add much to our knowledge as regards the correlation of the various members in different parts of the coal-field, and to Show more clearly the positions and the importance of the ore-beds in the Hocking Valley region. The only ore mined in that vicinity previous to 1874, was below what is called the Great Vein or No. VI coal, and to the west of what is known as the Hocking Valley coal-field, and although experiments in a few furnaces in the State had Shown that this coal could be used with advantage in iron-Smelting there was not a single blast furnace within the field. My observations at that time, however, impressed me with the abundance of iron ore, not only below but above this important coal Seam, and I then ventured to express the opinion that this region, from its cheap and easily mined Smelting-coal, its native ores and limestones, and its geographical position and relations to the great markets of the West, and to the supply of rich iron-ores from Lake Superior, was destined at no distant time to become a great metallurgical centre, where iron could be made more cheaply than at any other equally accessible point in the country. The object of the present communication is to report progress, and to State how far my observations made in the region last month have justified the predictions of 1874. The five years which have elapsed have been, as all know, most unfavorable to the iron trade, and especially to new enterprises in untried regions, yet they have not passed without important industrial developments in the Hocking Valley, where not less than thirteen blast furnaces have been erected

Jan 1, 1879

By C. L. Shapiro, R. Schempp

DuRing the past few years, general interest in the steel-producing and steel-consuming industries has been centered on the so-called "inherent characteristics" of steels. While often vaguely described, these characteristics are known to influence the response to heat-treatment and the hardening characteristics of the material. Although most of the recent papers and discussions have associated the "inherent characteristics" with the austenitic grain size and emphasized the importance of it, comparatively little is known of the variables that may affect the size of the austenite grain. The work to be described in this paper was carried out during the course of a study on the inherent characteristics of tool steel containing one per cent carbon. The discrepancies encountered in the determination and classification of the austenitic grain size led to an investigation of some of the variants influencing the austenitic grain size as determined by standard methods. Methods of Determining Austenitic Grain Size The present methods used for the determination of the austenitic grain size may briefly be classified in two groups: 1. Etching at room temperature to reveal the austenite grain size prior to cooling. 2. Etching at elevated temperatures, cooling to room temperature, and observing the structural conditions that existed at the temperature from which cooling occurred. The outstanding methods of the first group are: (1) the McQuaid-Ehn test, (2) optimum rate of cooling, (3) quenching and etching. McQuaid-Ehn Test.—This established and accepted test does not need much elaboration. It consists of pack carburizing at a definite temperature for a standard period of time and slowly cooling in the furnace. The temperature is 1700" F. (925' C.) and the time is 8 hr. The interpretation and evaluation of this test are fairly well defined in the A.S.T.M.

Jan 1, 1937

A. M. Strong, Bishop, Cal. (communication to the Secretary*) :—The paper of Mr. Eeyes gives us the most complete account of the geology of the borax-deposits in the Death Valley region that has yet been published, and is a valuable addition to the geological literature of a very interesting though little-known territory. During the past ten years I have been over much of the northern part of the country described by Mr. Eeyes and the region immediately north of it.

Jan 1, 1910

By AIME AIME

WHEN the present Chairman of the Coal Division, A.I.M.E. applied for membership in the Institute 28 years ago one of his endorsers was Howard N. Eavenson, with whom he has now been associated as a partner in a Pittsburgh consulting coal - mining engineering firm for 22 years. Back of that association was some ten years of operating work in Kentucky. Mr. Alford was born in Philadelphia on Dec. 11, 1887, and was educated in Quaker schools, graduating from Swarthmore with an A.B. in 1909, later receiving a B.S. and an E.M. from the University of Pittsburgh. In the summers of 1907 and 1908 he had his first taste of coal mining as a chainman for the U. S. Coal and Coke Co. in Gary, W. Va. Upon graduating in 1909 he got a job on the by-product coke ovens of the Illinois Steel Co. at Joliet, Ill., but a year later went to Kentucky as superintendent of the Shamrock mine of the St. Bernard Mining Co., by which company he was employed for the next ten years. Successively he was assistant chief engineer, chief engineer, and assistant to the president. His duties were varied, including all the engineering duties commonly associated with coal mining, both underground and on the surface, construction of washing plants, prospecting, reports on new properties, power plants, safety work, and labor relations.

Jan 1, 1942

By Nathaniel Herz

(San Francisco Meeting, September, 1915) THE use of zinc dust for precipitating the precious metals from cyanide solutions is well established now in many places, and has many advantages over the shavings method of precipitation. Although much work has been clone on methods of testing zinc dust, as yet no absolutely positive test has been devised to determine the value of the material. Certain facts are known, but often it happens that results on a working scale are not as expected from the laboratory tests. The purpose of this paper is to record some observations made while testing. a large variety of zinc-dust samples in the laboratory. W. J. Sharwood1 has described standard analytical methods, which have been followed, with the changes noted. The regular determinations include zinc oxide, by solution in ammonia and ammonium chloride, lead, and precipitating efficiency. In some cases cadmium was determined by a method similar to that described by J. E. Clennell.2 I will discuss the precipitating-efficiency test in detail. The procedure is as follows: "A solution of potassium silver cyanide is prepared by dissolving 10 grams of silver cyanide (AgCN) and 5 grams of `99 0' potassium cyanide in a little water and diluting up to 1000 cc. It is then adjusted by addition of a little more KCN or AgCN until the solution indicates from 0.12% to 0.15% free KCN by titration with standard silver nitrate. The titration is best made by using a 10-cc. or 20-cc. sample, adding 1 cc. of 2 % potassium iodide, and a slight excess of ammonia, as the end point is then sharper. Or 15 grains of pure crystallized KAg(CN)2 may he dissolved in a liter of water and 1.5 grams KCN added. "Weigh out 0.5 grain zinc dust into a 300-cc. beaker. Add a few cubic centimeters of water and stir until, zinc is well mixed, then pour in 250 cc. of the prepared solution, stirring vigorously. See that all lumps are broken up, and continue stirring for fully five minutes. Stir occasionally (at least every 10 minutes) until the end of two hours from the addition of the solution. Then filter upon an 11-cm. filter, wash precipitate thoroughly, sprinkle with test lead, wrap it carefully in the paper, plaice in a scorifier with about 20 grams test lead, burn paper cautiously in muffle, scorify five minutes, cupel at low temperature and weigh silver. Milligrams silver obtained from 0.5 gram zinc X 0.0606 = percentage precipitating efficiency."'

Jan 8, 1915

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

By B. B. Gottsberger

A NOTABLE feature of the practice of the American mining engineer is the fact that 'his field has been world wide, and the results of his work may be found in all countries. For this reason, the mining engineer is particularly interested in any legislation tending to restrict his freedom in this respect. In their zeal to improve the status of the professional engineer, those responsible for the enactment of the registration laws now in effect in various of the United States may have introduced a practice that will result very much to the detriment of the American mining engineer. He is preeminently interested in the maintenance of the professional "open door," and fame may be the reward of him who calls the first "International Conference for the Limitation of Restrictive Legislation." There is no reason why these United States should be the only country to regulate the practice of professional engineering and, in fact, the movement is spreading beyond its borders. Already, it is necessary for the mining engineer to be thoroughly conversant with the various state laws in order to insure his right to pursue his calling. It may soon be necessary for him to make sure of his status in foreign countries before undertaking work in them.

Jan 1, 1921

By H. R. Wheeler

CREATION of a "committee on promotion of student interest in coal mining" has an encouraging implication for the coal industry. It is indicative that mining men, both in the field and in the educational centers, realize that the problems of the industry require the best talent available. Young men are being invited into coal on the premise that it needs them, that it offers opportunity for creative work and the realization of their objectives. In initiating a movement which purports to meet the objectives of any young man who spends four or five years of his life in college, the industry does so with a full realization of its obligations.

Jan 1, 1940

By C. M. Ball

The very considerable progress made during the past three years in the crushing and concentration of ores, lends special interest at the present time to any means of a more efficient character than such as are already generally known and in use, for the rapid and regular reduction of large quantities of the harder and heavier grades of mineral-bearing rock. Such means are of exceptional importance in connection with the preparation of iron-ore for separation by the magnetic process, since in this operation the capability of dealing with large volumes of material and of securing by ready means of adjustment, a granulation of the material under treatment to any required mesh or fineness, is of the greatest possible value. With these, however, must be coupled the further considerations of the amount of power expended for the work done, and the wear and tear, represented in the cost for renewal of parts of the crushing machinery, per ton of material reduced to a given degree of fineness. In general terms it may be stated that the operation of a crushing train, capable of reducing an ore-rock of average density and hardness, from the condition of mine lumps to pass 1/16-inch screenopenings at the rate of 20 tons per hour, should not call for an expenditure of more than 125 horse-power, and that the wear and tear of the crushing machinery, all told, should not exceed 2 cents per ton. In the design of a crushing-train for an ore-dressing plant, there are, moreover, considerations of great importance which relate to the simplicity or complexity of construction and arrangement, the wear and tear of few or many elements, the easy ability or difficulty of maintaining the working adjustment of the various elements of the train, and the number of hands required for the operation of the system. With these points in view, it is thought that the Cummings ore-

Jan 1, 1893

by their overdogmatic picture of geology and their resulting drastic oversimplification and idealization of geologic features. I am in hearty disagreement with the recommendation that geophysics should be done by cooperative work between a geologist and a geophysi-cist. That arrangement would be comparable to doing petrography by having a physicist at the microscope and a geologist sitting by his side. The interpretation of the geological significance of geophysical data can be done efficiently only by a physicist who has become also a good geologist or by a geologist who is also a good geophysicist. Less Well-trained Men The rank and file, composing perhaps two-thirds of the personnel of exploratory geophysics, is not, and should not be, composed of highly trained men. The routine, stereotyped character of the work and the impossibility of promotion of more than a few from these lower ranks even under the best circumstances justify companies in filling the bulk of these rank and file positions with men having only a bachelor's degree at the most. There can be a wide range of training for such positions, although certain lines of study are preferred for certain kinds of work, and different employers have different preferences. For work in gravitational and magnetic prospecting, first preference will be for men having geological training and second for men with civil engineering training. In seismic work, men with geological training are preferred by some employers for computers; physicists, electrical engineers and all whose technical education has covered radio circuits are preferred for the other technical positions. Collegiate training in geophysical prospecting brings no preference and by many employers is given a slightly inferior rating. One large company seldom hires men who have just graduated with a major in geophysical prospecting. This prejudice is based on the reasoning that much of what is learned in college is obsolete or obsolescent, that most of the techniques learned in college will have to be unlearned, because different from those used by the employing company, and that in the long run additional courses in basic physics, mathematics and geology are of more value to a man than the courses on geophysical prospecting. DISCUSSION [This discussion refers to the five papers beginning on page 23 and ending on page 74.1 L. W. Blau,* Houston, Texas.—I have had some rather sad experiences with forecasting. For example, I could not foresee 10 years ago my present occupation, and I do not profess to be able to look ahead 10 years and tell anyone what he will be doing then. Referring to the point raised in the discussion, I do not know, for example, what the price of oil will be 10 years from now. If an appreciable number of

Jan 1, 1940

by their overdogmatic picture of geology and their resulting drastic oversimplification and idealization of geologic features. I am in hearty disagreement with the recommendation that geophysics should be done by cooperative work between a geologist and a geophysi-cist. That arrangement would be comparable to doing petrography by having a physicist at the microscope and a geologist sitting by his side. The interpretation of the geological significance of geophysical data can be done efficiently only by a physicist who has become also a good geologist or by a geologist who is also a good geophysicist. Less Well-trained Men The rank and file, composing perhaps two-thirds of the personnel of exploratory geophysics, is not, and should not be, composed of highly trained men. The routine, stereotyped character of the work and the impossibility of promotion of more than a few from these lower ranks even under the best circumstances justify companies in filling the bulk of these rank and file positions with men having only a bachelor's degree at the most. There can be a wide range of training for such positions, although certain lines of study are preferred for certain kinds of work, and different employers have different preferences. For work in gravitational and magnetic prospecting, first preference will be for men having geological training and second for men with civil engineering training. In seismic work, men with geological training are preferred by some employers for computers; physicists, electrical engineers and all whose technical education has covered radio circuits are preferred for the other technical positions. Collegiate training in geophysical prospecting brings no preference and by many employers is given a slightly inferior rating. One large company seldom hires men who have just graduated with a major in geophysical prospecting. This prejudice is based on the reasoning that much of what is learned in college is obsolete or obsolescent, that most of the techniques learned in college will have to be unlearned, because different from those used by the employing company, and that in the long run additional courses in basic physics, mathematics and geology are of more value to a man than the courses on geophysical prospecting. DISCUSSION [This discussion refers to the five papers beginning on page 23 and ending on page 74.1 L. W. Blau,* Houston, Texas.—I have had some rather sad experiences with forecasting. For example, I could not foresee 10 years ago my present occupation, and I do not profess to be able to look ahead 10 years and tell anyone what he will be doing then. Referring to the point raised in the discussion, I do not know, for example, what the price of oil will be 10 years from now. If an appreciable number of

Jan 1, 1940

By Grover J. Holt

A detailed description of the many variations in iron mining and transportation practice in Minnesota would require much space. Since a fairly detailed description of the practices then in use was published in the guidebook issued in connection with the meeting of the Institute on the iron ranges in 1920, and subsequent developments have been described by E. E. Hunner, M. H. Barber,2 and A. E. Anderson, J. M. Riddell and G. J. Holt,³ it will not be necessary here to do more than review the highlights of current practice. Details on any points of interest can be obtained through correspondence with the operators involved. † The iron ores of Minnesota, which have been formed through enrichment of the iron formation in which they occur, largely by the removal of silica, are usually covered by a blanket of glacial drift known locally as "surface." Surface material, including sand, clay, hardpan and boulders, makes up the greater portion of the stripping in open-pit operations. In some instances, stripping also includes taconite and paint rock," directly below the surface material and overlying the ore. Tacenite is the iron formation, a ferruginous chert with inter-bedded slate layers. :'paint rock" is a local term for oxidized slate layers inter- bedded in the iron formation, high in phosphorus, alumina and moisture. The iron ores fall into two classes: (I) direct shipping (merchantable ores or ores requiring no treatment except possibly crushing or screening to make an acceptable sized product), and (2) ores requiring beneficiation (such as sintering, drying, washing, jigging, high-density treatment, or magnetic separation in the case of magnetite). The Mesabi Range produces chiefly soft Bessemer and non-Bessemer ores. The Cuyuna Range produces mainly low-manganese brown ore and high-manganese black ores, with some iron ore. The Vermilion Range yields mainly Bessemer and non-Bessemer iron ore, with some hard or lump ore that finds use in the open hearth. Open-pit mining is limited to the Mesabi and Cuyuna Ranges but underground mining is done on all three. The choice of mining methods is determined by the relative economics of overburden-removal and shaft-mining costs. Stripping Practice Common practice has been to remove the bulk of the overburden during the winter season and to mine during the summer, In- the present emergency many operators are forced to forego the economies attained by year-round utilization of paper. and to equip for, and carry on, stripping and mining simultaneously. In the normal years or lean years to come, most properties probably will be overequipped and high depreciation charges Will have to be absorbed.

Jan 1, 1943

By Grover J. Holt

A detailed description of the many variations in iron mining and transportation practice in Minnesota would require much space. Since a fairly detailed description of the practices then in use was published in the guidebook issued in connection with the meeting of the Institute on the iron ranges in 1920, and subsequent developments have been described by E. E. Hunner, M. H. Barber,2 and A. E. Anderson, J. M. Riddell and G. J. Holt,³ it will not be necessary here to do more than review the highlights of current practice. Details on any points of interest can be obtained through correspondence with the operators involved. † The iron ores of Minnesota, which have been formed through enrichment of the iron formation in which they occur, largely by the removal of silica, are usually covered by a blanket of glacial drift known locally as "surface." Surface material, including sand, clay, hardpan and boulders, makes up the greater portion of the stripping in open-pit operations. In some instances, stripping also includes taconite and paint rock," directly below the surface material and overlying the ore. Tacenite is the iron formation, a ferruginous chert with inter-bedded slate layers. :'paint rock" is a local term for oxidized slate layers inter- bedded in the iron formation, high in phosphorus, alumina and moisture. The iron ores fall into two classes: (I) direct shipping (merchantable ores or ores requiring no treatment except possibly crushing or screening to make an acceptable sized product), and (2) ores requiring beneficiation (such as sintering, drying, washing, jigging, high-density treatment, or magnetic separation in the case of magnetite). The Mesabi Range produces chiefly soft Bessemer and non-Bessemer ores. The Cuyuna Range produces mainly low-manganese brown ore and high-manganese black ores, with some iron ore. The Vermilion Range yields mainly Bessemer and non-Bessemer iron ore, with some hard or lump ore that finds use in the open hearth. Open-pit mining is limited to the Mesabi and Cuyuna Ranges but underground mining is done on all three. The choice of mining methods is determined by the relative economics of overburden-removal and shaft-mining costs. Stripping Practice Common practice has been to remove the bulk of the overburden during the winter season and to mine during the summer, In- the present emergency many operators are forced to forego the economies attained by year-round utilization of paper. and to equip for, and carry on, stripping and mining simultaneously. In the normal years or lean years to come, most properties probably will be overequipped and high depreciation charges Will have to be absorbed.

Jan 1, 1943

By A. E. Gorum, J. Washburn, E. R. Parker

Experimental evidence was obtained in support of the idea that cleavage fracture can be initiated by dislocation pile-up. The high ductility of MgO crystals when tested in bending comPared to their relative brittleness in tension was explained on the basis that large pile-ups are more likely in a tension specimen. CLEAVAGE fractures have been a problem of major concern for many years. A number of large steel structures have failed in a brittle manner, usually suddenly and without warning; often the failures occurred for no obvious reason and at nominal stress levels well within the generally accepted range. A great deal of data have been collected about factors that contribute to failures,1 but the physics of the fracture process has never been revealed. cottrel12 has recently developed a theory of brittle fracture in ductile materials which was based upon the concept that dislocations moving on two intersecting planes can unite to form a crack nucleus. This theory accounts for the known effect of grain size and for the effect of testing temperature. There has, as yet, been no experimental evidence published that would substantiate this or the earlier theories based on stress concentrations due to piled-up dislocations. The study reported herein was conducted to obtain information that would either substantiate or disprove the

Jan 1, 1960

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969