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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

By B. M. Larsen, T. E. Brower

For some years we have been carrying on a rather comprehensive investigation of the occurrence of oxygen in liquid open-hearth steel. This investigation was interrupted by the war emergency and is therefore incomplete, with many questions still answered only partially, if at all; yet it seemed worth while to present a report of progress on this difficult field of research, if for no other reason than to promote discussion and further investigation of this important problem. The significance of such studies depends in large measure upon the accuracy of measurements of oxygen content in liquid steel while it is still in the furnace or as it flows into the ladle, or thence into the mold and there is, as we shall show, good reason for believing that the main source of uncertainty is in the sampling, not in the analytical method as such. The difficulty arises from the fact that any method of sampling is of itself apt to alter the amount of oxygen in solution in the liquid steel, because this oxygen is in a readily reactive condition. On the one hand, being usually present at a concentration appreciably in excess of that corresponding to equilibrium with the carbon then present, it may decrease rapidly in percentage by reaction with carbon and evolution of CO, especially if the liquid metal is in any way shaken or brought in contact with a cooler solid surface. On the other hand, it may increase rapidly by ab- sorption of oxygen from a slag, a furnace atmosphere, or from air. These circumstances, which are inherent in the problem, as well as our conclusion that, despite the considerable amount of careful work already done, there is still no method of sampling liquid steel acceptable as an unquestioned standard, ed us to undertake systematic comparisons of oxygen content of large numbers of samples taken: (I) by a single method at different positions and levels in the bath; (2) at the same place by different sampling methods; and (3) from bath, tapping stream and pouring stream. The different sampling methods yield somewhat different values and there is as yet no way to tell with certainty which is the most accurate. But the general reproducibility and consistency of the results give us some confidence in certain inferences we draw from them: namely, that the "spoon" method of sampling, properly carried out, gives somewhat more consistent results than the "bomb" method, as it has usually been practiced; that, in the bomb method, an aluminum cap is preferable to a steel cap; that the oxygen content of liquid steel in a finished heat is substantially the same all over the bath at the same level, and tends to decrease at lower levels further from the slag interface; also that it tends to decrease, and to decrease erratically, from furnace bath to tapping stream entering the ladle. Accordingly it seemed desirable to report these observations in detail as a first step, so that the reader may judge their significance as a contribution towards solution of the main problem, which is to find a means of pre-2

Jan 1, 1945

By Hugh S. Spence

In the winter of 1941-42, muscovite mica was discovered by a young prospector, Justin Purdy, in the township of Mat-tawan, Nipissing District, Ontario, a few miles north of the small settlement of Eau Claire, which lies on the main Transcontinental Highway (No. 17) between Mattawa and North Bay. Muscovite had been known for many years to occur in the general Mattawa region, and various small efforts at production had previously been made by individuals working scattered deposits in the area. These minor activities, however, had never led to production of any consequence or the discovery of any important mica bodies. The Purdy finds were made in a heavily timbered, mountainous area lying about three miles north of the low-lying settled land along the highway, and in a section not hitherto prospected. The mica taken by Purdy and two partners from surface outcrops proved so remarkable in point of size of trimmed sheets that the find attracted considerable attention, and the area surrounding the three claims taken up by the prospectors was quickly blanket-staked by various interests. Though a number of other mica-bearing pegmatite dikes were found later on these stakings, none proved as rich as those on the original Purdy ground; very little commercial mica was obtained from them and attempts to develop them were short-lived. Purdy and his partners sold their initial production to dealers in Ottawa and Hull, where the Canadian mica industry long has centered. Young Purdy, unfortunately was killed in a motor accident in the early summer of 1942. His father continued mining operations for a few months and produced and sold a considerable amount of mica. In October 1942 the Purdy holdings were acquired by lnspiration Mining and Development Co. of Amos, Quebec, which had been active in staking in the area. This company formed a subsidiary, Purdy Mica Mines, Limited, to develop the property. Under the energetic management of Joseph R. Norrie, rapid progress was made, and production soon attained important proportions. Realizing from the outset the unusual character and potential value in the war effort of the Purdy discovery, the Metals Controller, Department of Munitions and Supply, at once arranged with the Department of Mines and Resources for an official geological report on the area, and also drew the attention of the War Production Board in Washington to what seemed likely to prove a highly important source of strategic-quality mica. Officials of WPB were sent up in the Summer of 1942 to inspect the property, and so impressed were they with the possibility that it might become of high

Jan 1, 1948

By Hugh S. Spence

In the winter of 1941-42, muscovite mica was discovered by a young prospector, Justin Purdy, in the township of Mat-tawan, Nipissing District, Ontario, a few miles north of the small settlement of Eau Claire, which lies on the main Transcontinental Highway (No. 17) between Mattawa and North Bay. Muscovite had been known for many years to occur in the general Mattawa region, and various small efforts at production had previously been made by individuals working scattered deposits in the area. These minor activities, however, had never led to production of any consequence or the discovery of any important mica bodies. The Purdy finds were made in a heavily timbered, mountainous area lying about three miles north of the low-lying settled land along the highway, and in a section not hitherto prospected. The mica taken by Purdy and two partners from surface outcrops proved so remarkable in point of size of trimmed sheets that the find attracted considerable attention, and the area surrounding the three claims taken up by the prospectors was quickly blanket-staked by various interests. Though a number of other mica-bearing pegmatite dikes were found later on these stakings, none proved as rich as those on the original Purdy ground; very little commercial mica was obtained from them and attempts to develop them were short-lived. Purdy and his partners sold their initial production to dealers in Ottawa and Hull, where the Canadian mica industry long has centered. Young Purdy, unfortunately was killed in a motor accident in the early summer of 1942. His father continued mining operations for a few months and produced and sold a considerable amount of mica. In October 1942 the Purdy holdings were acquired by lnspiration Mining and Development Co. of Amos, Quebec, which had been active in staking in the area. This company formed a subsidiary, Purdy Mica Mines, Limited, to develop the property. Under the energetic management of Joseph R. Norrie, rapid progress was made, and production soon attained important proportions. Realizing from the outset the unusual character and potential value in the war effort of the Purdy discovery, the Metals Controller, Department of Munitions and Supply, at once arranged with the Department of Mines and Resources for an official geological report on the area, and also drew the attention of the War Production Board in Washington to what seemed likely to prove a highly important source of strategic-quality mica. Officials of WPB were sent up in the Summer of 1942 to inspect the property, and so impressed were they with the possibility that it might become of high

Jan 1, 1948

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

ONLY a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about I per cent of copper, with or without additions of elements such as magnesium,1 and die-casting alloys containing about 4 per cent of aluminum with small amounts of magnesium and sometimes copper.2 A number of elements are capable of forming alloys with zinc, which do not enter into solid solution except in limited degree. The present paper considers one such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. ZINC-TITANIUM SYSTEM The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor of the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. ALLOY PREPARATION All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C. until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount of this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidation. HOT-ROLLING TESTS Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections revealed a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By Rex W. Woods, Morris Muskat

A leastmsquare analysis procedure has been developed and applied for the study of the deviations in estimations of oil in place as given by the material-balance equations. The data used were those obtained from field observations on the Jones sand in the Schuler pool, Arkansas, and the Monroe dolomite in the Reed City pool, Michigan. Possible effects of water intrusion were taken into account by expressing the cumulative water influx in terms of various functions previously proposed in the literature. Formulas were developed and values calculated for the minimum deviations and minimal percentage deviations in the calculated volumes of oil in place from the average values, as could be obtained by suitable choice of the water encroachment and initial gas-cap volume parameters. The results show that the fluctuations in these calculated volumes are very insensitive to the values chosen for the rate of water intrusion and initial gas-cap volume, and hence cannot be safely used in discriminating between spurious values for these parameters and such as actually pertain to the producing reservoirs. Moreover, the exact form of the water-intrusion function seems to have but little effect on the fluctuations in the computed oil in place. Accordingly, it is concluded that the material-balance method does not of itself provide a satisfactory criterion for determining the basic physical unknowns of producing reservoirs or in making conclusive decisions regarding the production mechanism, unless independently established geological control data are available for eliminating unreasonable values for the reservoir parameters, even though they may still satisfy the material-balance formulas. If, however, from core or logging data the initial oil in place and the gas-cap volume can be established in advance, the material-balance formulas can be inverted to find the water intrusion. Moreover, by determining by such calculations the water-intrusion coefficient, the iuture production performance can then be predicted by the aid of the materiaI-balance formulas for specified operating conditions. This type of application may be of particular value in predicting the results of Pressure-maintenance operations. Introduction The evaluation of the forces acting upon an oil reservoir is a problem of considerable interest to the operator as an aid in determining the proper method of operation for the reservoir to obtain an optimum recovery of oil. In many pools, the nature and magnitude of the forces acting upon the reservoir remain unknown until an appreciable amount of ultimate recovery is obtained. To be of value to the operator, a reliable interpretation of reservoir performance should be available in the early life of the pool to permit an optimum plan of operation. Progress has been made in an understanding of reservoir behavior and the importance of the different factors involved. The material-balance method of estimating oil in place has been proposed as a tool in analyzing reservoir-performance problems.l The solution of such problems by this method ordinarily involves two or more unknown values relating to the nature of the reservoir, and the results

Jan 1, 1945

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-' deg-'), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer' and further confirmed by owell.' However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

By Maurice C. Fetzer, Charles R. Austin

It has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A1 critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publicationsl,2 have shown that the factors controlling graphitization below the A1 are different from those operating above the A1 inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemical analyses. Many years ago it was recorded3 that the rate of graphitization at subeutectoid temperature is not a maximum just below the A1 critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is impossible to spheroidize certain steels in the temperature range of 650° to 710°C. without the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A1 (720°C.) these same steels may be completely sphe-roidized at constant temperature. In previous studiesl,2,4 on I per cent plain carbon steels graphitization was encountered during prolonged tempering. The limited number of steels studied did not provide sufficiellt data to permit adequate study of the factors controlling this graphitization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, furnished by four steel companies, who also supplied information regarding the history of manufacture. An extensive program of research is being carried out on these steels, including the effect of pretreatment and atmosphere on the nature and extent of graphitization, and the possible correlation of graphitization with such characteristic properties as hardenability, grain size and mechanical behavior. In the present paper discussion is restricted to a study of the correlation between graphitizing tendency at 670°C. after quenching from several temperatures above the critical, and (I) the minor variations in the chemistry of these steels of "similar" chemical composition, and (2) the deoxida-tion practice employed. The state of the lead bath, oxidized or protected from oxidation by charcoal, used in the tempering treatments is also considered. Materials Eighteen plain carbon steels of about I per cent carbon, and containing similar amounts of each of the other common elements usually found as impurities, were obtained in the form of rods % in, in diameter from four steel manufacturers. The analyses for ordinary and special elements of all the steels were made on the rod stock as received in the laboratory, and the re-

Jan 1, 1941

By Maurice C. Fetzer, Charles R. Austin

It has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A1 critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publicationsl,2 have shown that the factors controlling graphitization below the A1 are different from those operating above the A1 inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemical analyses. Many years ago it was recorded3 that the rate of graphitization at subeutectoid temperature is not a maximum just below the A1 critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is impossible to spheroidize certain steels in the temperature range of 650° to 710°C. without the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A1 (720°C.) these same steels may be completely sphe-roidized at constant temperature. In previous studiesl,2,4 on I per cent plain carbon steels graphitization was encountered during prolonged tempering. The limited number of steels studied did not provide sufficiellt data to permit adequate study of the factors controlling this graphitization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, furnished by four steel companies, who also supplied information regarding the history of manufacture. An extensive program of research is being carried out on these steels, including the effect of pretreatment and atmosphere on the nature and extent of graphitization, and the possible correlation of graphitization with such characteristic properties as hardenability, grain size and mechanical behavior. In the present paper discussion is restricted to a study of the correlation between graphitizing tendency at 670°C. after quenching from several temperatures above the critical, and (I) the minor variations in the chemistry of these steels of "similar" chemical composition, and (2) the deoxida-tion practice employed. The state of the lead bath, oxidized or protected from oxidation by charcoal, used in the tempering treatments is also considered. Materials Eighteen plain carbon steels of about I per cent carbon, and containing similar amounts of each of the other common elements usually found as impurities, were obtained in the form of rods % in, in diameter from four steel manufacturers. The analyses for ordinary and special elements of all the steels were made on the rod stock as received in the laboratory, and the re-

Jan 1, 1941

By John J. Schanz

INTRODUCTION The two prior Seeley W. Mudd books on mineral economics devoted their final chapters to themes having to do with the future. In 1932, the last chapter in Mineral Economics8 was "The Future Value of Mineral Property" by J. R. Finlay. Both the first edition (1959) of Economics of the Mineral Industries7 and the slightly revised second edition (1964) closed with "Minerals and Man's Future" by Zay Jeffries. We are not inclined in this third AIME volume on mineral economics to ignore the tradition of the prior volumes. Moreover, it always is fitting and proper to close a book about the mineral industries by examining in a rather general way the challenges and uncertainties that are perpetually strewn in our path as we pick our way into the future. Unlike its predecessor volumes, which were written to acquaint the nonspecialist with the economic characteristics of mineral resources and to provide data about the mineral industries, this edition was also designed with the mineral economics student and practicing specialist in mind. Thus it is anticipated that it will be both a reference as well as suitable for use as a textbook. Consequently, this closing examination of our changing perspectives about mineral resources devotes some space to the past events and current status of mineral economics as a field of study. The fears and forecasts of the past can be a perceptive and usually deflating way to begin an examination of the future. As we look up and down the track of time from the 1975 platform, we find that many of the past views of the future were transient in character, others were imperfect in their prognosis, while others were based on fears that now seemed unfounded. But down through the years some of the observations or expressions of concern have a persistency which perhaps reflects some elemental characteristics of mineral resources. On these "truths" rest our contemporary understanding of the economics of the mineral industries. The uncertainties and priorities for the next 25 or more years, not surprisingly, have a somewhat different mix than those that seemed most compelling to our predecessors in 1932 or 1959. So it is appropriate that we review how the perspective of the mineral economist has changed over the span of a half century. In light of the particular interest of AIME on the role technology must play, it is fitting that we close with some observations on that topic. THE EMERGENCE OF MINERAL ECONOMICS AS A FIELD OF STUDY The publication of Mineral Economics by the AIME in 1932 as a Seeley W. Mudd volume marked the end of emerging interest in

Jan 1, 1976

By Frank Somogyi, Donald H. Gray

Techniques for in-situ dewatering of tailings and slimes include evaporation, decantation, drainage under self weight, drainage by surcharging, and electro-osmosis. A promising technique for increasing drainage efficiency is a vertical, wall-drain system, which can be constructed in an impoundment concurrently with deposition of slurried tailings. The vertical drains, which can be constructed from sand or from the coarse fraction of a tailings stream, greatly speed the rate of consolidation of the fine tailings or slimes. The performance of a wall drain system and the semitidy of consolidation efficiency to certain variables or system parameters are examined. These parameters include the slime deposition rate, ratio of drain to slime permeability, drain width, and drain spacing.

Jan 1, 1979

By Walter R. Hibbard, Harold Margolin

The effect of ten ternary additions on the aging of a Cu-Ag alloy was measured by X ray, microstructure and hardness. A supersaturated copper-rich transition structure was found. The effect of the ternary element was related to differences between transition and precipitate lattice parameters and analogies with solution and strain hardening. IN addition to the prerequisite of diminishing solid solubility with falling temperature, the theory of coherency hardening1 proposes that the principal source of hardening during precipitation is strain caused by coherency between the matrix and precipitate. For a given system greater coherency hardening would result from lengthening the period of coherent growth and/or increasing the number of nuclei, other things remaining equal. However, the hardness change during aging is a function of a number of phenomena in addition to coherency hardening, such as dispersion hardening, loss of coherency, solute depletion, matrix recovery or recrystal-lization, coalescence, and their relative time sequences. The present investigation was undertaken to study the effect of ternary additions on the age-hardening of Cu-Ag alloy. For this purpose a series of alloys were made containing as ternary constituents Mg, Al, Si, P, Mn, Ni, Zn, As, In, and Sb. These elements were added to a master 5 wt pct Ag in Cu alloy in such amounts as to obtain alloys listed in Table II containing the following approximate atomic percentages: 96 pct Cu, 3 pct Ag, 1 pct ternary addition. A 97 atomic pct Cu, 3 atomic pct Ag alloy was used as a comparison standard. There have been numerous investigations of age-hardening in Cu-Ag alloys2-lo but few of ternary Cu-Ag alloys. Pfister and Weist" found that 1 wt pct Ni reduced the solubility of Ag in Cu above 600 °C and that the rate of precipitation was slower than in polycrystalline Cu-Ag alloys of similar silver content. More recently Hodge, Jaffee, Dunleavy, and Ogden12 investigated the effect of ternary additions of Mg, Li, P, Cd, Zn, Zr and Be on strength properties of Cu-Ag alloys. Mg, Cd, and P were found to increase strength in the aged and cold-worked condition. Experimental Procedure Charges weighing 7.5 lb were melted in a closed carbon crucible under a reducing atmosphere* of nitrogen and hydrogen. A Durville-type casting procedure with a hot-top arrangement was used to obtain a sound casting, 2x2x43/4 in. Prior to rolling and annealing of the ingots, a trial solution anneal of rolled sections of the hot-top portions indicated that at 780°C melting was avoided except for the Cu-Ag-Sb alloy. This alloy could not be produced as a single phase within the limits of temperature control. i 3" to 5oC, since melting occurred at 64O °C, and below this temperature precipitation was

Jan 1, 1952

By Oscar A. Glaeser

The purpose of this paper is to present specific applications of the fundamental principles of mine ventilation and the means that are at our disposal to accomplish the task of maintaining a healthful atmosphere in small mines and prospect openings. Need for Ventilation The range between the maximum oxygen content of normal air and the minimum safe content is extremely narrow, approximately 5 per cent. Furthermore, normal air must not be contaminated with irrespirable gases beyond definite limits, and mineral dusts are equally dangerous, although health impairment is slower. Tables 1 and 2 present the more common respiratory hazards encountered in mines. Adequate ventilation is the most effective means available to reduce or eliminate these hazards. Mechanical ventilation has reached varying stages of perfection in coal mines and in many large metal mines. The small mines and prospects rarely have a definite plan of ventilation. As a consequence underground workers are frequently exposed to health and accident hazards. The annual reports of fatalities in mines in the Western States record yearly many deaths due to asphyxiation and deaths caused by men falling down shafts and raises after being overcome by gas. At times mining operations are slowed up because there is no means of driving out the gas after blasting. For that reason only one shift is worked, or men wait from one to several hours for the "smoke" to clear out. Methane gas in varying quantities is widely distributed throughout California. It has been encountered in explosive concentrations in the coast range. It has been found on the Mother Lode and in quicksilver mines near the coast. Methane explosions have not been uncommon in underground operations and in tunneling jobs. These conditions and records indicate that there is room for improvement in mine-air conditions.

Jan 1, 1937

By C. N. Reid

Slip-line studies on deformed chromium single cvystals showed the usual bcc behavior. At room temperatuve, cross slip was prevalent—slip was not confined to a given plane, but the slip direction was (111). At -10O0K, slip occuvred on (110) planes, twins on(112) planes, and cleavage on (1001 planes. A single-crystal tensile specimen with an axis close to [011] showed a pronounced yield drop and high strain rate sensitivity which zclere used to derive relevant parame tevs in a dislocation dynamics treatment. Transmission electron microscope studies confirmed the existence of (110) slip planes and showed ecidence of loops punched out by precipitates and of grown-in dislocations promoting tangling. OF recent years experimental studies have been made of the deformation characteristics of single-crystal molybdenum and tungsten, but very little has been published on the behavior of single-crystal chromium. During a study of the mechanical properties of chromium, single-crystal studies were made which have already been partially described.&apos; However, additional information was generated which was not directly relevant to the main theme of Ref. 1, and, therefore, was not reported. In view of the need for complete documentation of deformation modes, the experimental observations made on the deformation of single-crystal chromium are summarized here, together with an electron-microscope study of the associated dislocation structures. It was found that, in terms of the deformation modes, chromium is a conventional bcc metal, showing a very pronounced yield-point phenomenon. Further, it was found that the flow strength of these crystals is very sensitive to the strain rate. Finally, the crystals were observed to contain many unidentified precipitates, which often were associated with prismatic dislocation loops. EXPERIMENTAL METHODS Single crystals were grown from rods of wrought chromium by the method of zone annealing. Rods of "1/4in.-diam were supported vertically in an argon atmosphere while an induction coil was moved up the rod at 1 in. per hr. The power was adjusted to just below that required for melting, and the process produced single crystals in about 30 pct of the rods used. The orientations of the crystals, in general, lay near [011] and are summarized in Fig. 1. Before this treatment, the wrought material contained 35 pprn C, 68 ppm O, and 12 ppm N.* An analyzed single crystal *Usual metallic impurities found in iodide chromium are: Al, 5 ppm; Ca, A ppm; Cu, 2 ppm; Fe, 75 ppm; Yg, 0.5 ppm; Yn, < 3 ppm; Mo, < 3 ppm; Ni, 4 ppm; Si, < 20 ppm; Ti, < 1 ppm; V, 4 ppm; Zr, < 3 ppm. contained 10 pprn C, 79 ppm O, and 50 pprn N. Tension and compression specimens were shaped from the crystals by mechanical grinding, followed by the electrolytic removal of about 0.010 in. from the surface in a perchloric/acetic acid bath. All specimens had a gage length of 0.75 in., and tension specimens had a diameter of 0.100 in., while that of the compression samples was 0.200 in. Mechanical tests were carried out at a rate of 1.3 pct per min, and temperatures below 0°C were attained by means of a nitrogen cryostat similar to that of Wessel.2 EXPERIMENTAL RESULTS Modes of Deformation. In addition to the tensile properties of these crystals, which are described in Ref. 1, deformation markings on the surface were studied. Crystals A and F, Fig. 1, were deformed in tension at 300°K to 10 and 16 pct strain, respectively. The surfaces contained visible slip lines, about 1 C( apart, composed of both straight and wavy segments. They did not define a single plane, and so determination of the slip plane was not possible. However, the slip direction was deduced by comparing the axial orientations of the crystals before and after deformation. Fig. 2 is representative, and shows that the axis ro-

Jan 1, 1968

By Thomas Fraser

UP to the present, there has been no large coal-producing industry in any of the South American countries. Since colonial times, the great mineral and agricultural wealth of that continent has led the people to activities other than the development of manufacturing industries based on coal; and climatic conditions are such that there has been very little demand for solid domestic fuel. However, there are extensive and widely distributed reserves of coal in South America that would make the development of a modern coal industry feasible. That factor is of the utmost significance now, when it is believed that the South American countries are entering the pioneer phase of a broad industrial development. Coal Fields Great areas of coal-bearing formations of Cretaceous and Tertiary ages occur generally throughout the Andean uplift and extend into the coastal range of the Caribbean region far east of Caracas. Thus the west coast countries have adequate reserves of coal, which include a wide range of types and classes. In the eastern part of South America, east of the Cordillera, as in North America, the coal measures are of Carboniferous and Permocarboniferous ages. The principal known deposits in this area are in the southern States of Brazil. Permocarboniferous coals ranging in rank from lignitic to anthracitic are found in the States of Rio Grande do Sul, Santa Catarina, Parana and Sao Paulo. In the great.interior plateau of Brazil, south of the Amazon River, are extensive areas of Carboniferous strata that may contain coal deposits. There are widely scattered reports of findings of coal in&apos; wells and stream beds in northern Piaui and Goias. In the Rio Fresco Valley, explorers have observed outcrops of two beds of anthracite and have brought to Rio de Janeiro samples from these beds. The Fresco is a tributary of the Xingu River that enters the Amazon from the south, but coal could not be shipped by water since the Rio Fresco area is in the upper part of the Xingu Valley, and there is a formidable series of rapids between that area and the lower level of the Amazon River basin. It is doubtful if coal deposits in this general area will be of economic importance for many years to come. Fig. 1 shows the general location of known coal fields of South America that have been explored sufficiently to indicate the presence of workable reserves. The coal deposits of the Andean region are similar in occurrence and general characteristics, as well as in age, to the coals of the Rocky Mountain region of North America. Although the coal fields obviously

Jan 1, 1952

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber&apos; in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman&apos; has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By Reynold Q. Shotts

Chemical methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods on duplicate samples of the same coals, but to the author&apos;s knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published. This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation.

Jun 1, 1955

By A. T. Shurick

THE present economic crisis in bituminous coal is substantially the most insidious, and critical, in the modern history of the industry. The large consumption deficit that has gradually developed (almost unawares), has culminated in a situation that has forced home the urgent necessity for prompt and radical remedial measures, such as the various mergers now in course of negotiation. Conditions today are sufficiently comparable with those in the iron and steel industry, preceding the formation of the United States Steel Corpn., to suggest the possibility of a sweeping super-consolidation, that all but staggers the imagination. The important function of the banker in this, and lesser projects, is too well known to require comment, and it is important that we understand clearly just what these functions are. Certain features in banking practice came up for consideration in connection with a rather exhaustive economic study into the prospective future of the coal industry, upon which I was recently engaged for an Eastern bituminous interest. This survey was made for the purpose of effecting a decision on certain pressing questions of policy, involving considerable capital expenditures, that would be compatible with the flattening out in the curve of production in recent years. An examination of the TRANSACTIONS, and the coal literature generally, failed to disclose any pertinent, and authoritative data, on this subject. This was more or less characteristic of the whole survey, which had involved a large amount of original research, and measures were taken to procure the required information. The following notes have been compiled largely from the data thus collected, supplemented with material, suggestions and criticisms, by several of the larger banking houses active in coal, together with personal memoranda of my own.

Jan 1, 1928

By D. W. Brunton

The maps of our large mines are usually prepared with the greatest care; and it is somewhat singular that, in compari~on with the great amount of time and money spent in surveying and platting, 80 little actual use is made of them. Almost the only purpose for which a completed survey-map is afterwards consulted, is the determination of the relative position of the different workings to each other, and to the boundary-lines of the property. After the completion of such a map, it should be made the beginning of another, and in most cases a far more important undertaking, namely, its utilization as a starting-point for a complete inventory of the company&apos;s underground possessions. The ordinary mine-survey map, being nothing but a record of what has been done, is, in one sense, only ancient history. To increase its value, such additions should be made as will render it a complete statement of the amount and value of ore in sight at any particular time, and a guide for future development. Comparatively little extra labor is involved in this undertaking, since the larger and most expensive part of the work has already been completed when the mine has been surveyed and mapped. The necessary additions consist in working out and platting on the maps, the geology of the mine as exposed in the workings, in such a manner that the geological survey may be of daily use in the development and operation of the mine. The first step towards the production of a geological map consists in tracing individual level-sheets from the general or composite map. The area to be included, outside of the property in question, will depend very much on local conditions; but, for geological, legal and commercial reasons, it should be extended as far as reasonably practicable. The scale to be

Jan 1, 1906