Search Documents

E. L. BLOSSOM, New. York, N. Y.-That this paper deals with a real problem is illustrated by a statement made to the speaker a few months ago by the manager of a silver-lead property: "Our ore contains 60 per cent. silica on which the smelters are penalizing us heavily, and they are not able to take all our stuff even then. We have simply got to find some method other than smelting for getting the silver and lead out of our ores. We have had experts down here and have investigated flotation, leaching and volatilization, of which processes the latter is by far the most promising. We are continuing investigation." I was somewhat concerned in certain chloride volatilization experiments which we carried on in Denver in 1903, working on a carload of ore from Butte. Now being connected with the Cottrell process, by which method the fumes will undoubtedly he recovered if they solve the volatilization problem, I have looked into the matter again, and believe it can be developed into a commercial process. On a laboratory scale, working With silver-lead ores, experimenters have obtained a volatilization of over 90 per cent. of the total values in 30 to 60 min, on quantities of 1 to 5 lb., using a roasting dish and a muffle. That looks very good, and would be entirely commercial. On attempting to duplicate these results in a reverberatory furnace, they found that it is more likely to take 8 hr. firing to yield 75 per cent. extraction, which is not commercial at all, as it requires too much time, labor, and fuel, and the whole process is too slow. Of course it can be done, because we have done it in the laboratory.

Jan 1, 1918

By C. M. Weld

The southeastern coast of China, from Ning-Po to .Macao, represents an element in the continental mass of Asia which has at practically all times in the remote past exhibited a tendency to rise rather than to subside.' This strip of land, 1,000 or more miles long by perhaps 150 miles wide at its widest part, has in fact stood above sea level since at least early Cambrian times, while the great basins to the north and west were receiving their massive accumulations of Sinian (Cambro-Ordovician), Carboniferous, and later deposits. We find, .therefore, a coastal fringe of metamorphic and igneous rocks bordering the huge expanses of sedimentary rocks which occupy the interior. Hong-Kong is situated toward the southwestern extremity of this fringe. Hong-Kong is an island of approximately 30 sq. miles, on the north shore of which is situated the city of Victoria, with its 325,000 inhabitants. This island was ceded to Great Britain in 1842. In 1560 the peninsula of Kowloon (about 5 sq. miles), being that part of the mainland lying directly across from the city of Victoria, was added to Hong Kong. Thirty-eight years later, in 1898, a stretch of territory, including the mainland behind Kowloon and. numerous adjacent islands, was leased to Great Britain for 99 years. This last addition is known as the "New Territory of Hong-Kong" and comprises 376 sq. miles in area. A map of Hong-Kong, Kowloon, and the "New Territory" is shown in Fig. 1. My studies of this total area of over 400 sq. miles were devoted primarily to an investigation of the mineral resources. Systematic mapping of the immensely complex exposures of rocks was not possible in the time at my disposal. However, observations in, this. direction warrant a few generalizations.

Jan 2, 1914

By F. Julius Fohs

Centrally located with relation to the largest iron- and steel-producing districts of the United States, the fluorspar-deposits of Kentucky possess increasing interest and importance. As typical of the numerous fluorspar-mines of Kentucky and Illinois, I have selected for description the Memphis, because it and others of its immediate group exhibit the conditions characteristic of all. I. The Memphis MiNe. This mine lies 5 miles NW. of Marion, in Crittenden county, Kentucky, a station on the Chicago and Nashville division of .the Illinois Central R. R. For the first mile and a half out of Marion we see only Birdsville or Middle Chester sandstones of Mississippian age. Then we cross a fault of about 850 ft. displacement, and the Ste. Genevieve oolite sets in. Beyond the fault, oolite is the predominant rock, except that the hills to the north have a capping of Cypress or lowest Chester sandstone, 80 ft. below which is an outcrop of from 6 to 10 ft. of Ste. Genevieve (Rosiclare) sandstone. Occasional sink-holes are noticed, and as the mines are approached evidence of faulting is again seen. A line of .crude head-frames and open-cut dumps, extending for more than a quarter of a mile, marks the Klondike vein. The open-cuts are from 15 to 20 ft. deep, and in most of them, from the surface down, was found the reddish gravel which is really fluorspar—some of it white or purple and crystal-clear (if the red clay is washed off), and some carrying iron and silica, and stained by waters from the decaying limestone walls. In one of these cuts, at a depth of 20 ft., white and purplish honey-combed fluorspar was found, in which the larger cavities are due to the leaching of limestone and calcite, and the minute ones to the leaching of zinc-hlende.

Jan 1, 1910

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000'. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By W. E. Keck, Paul Jasberg

TheRe is a considerable tonnage of iron ore in the Menominee Range of Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a relatively large quantity of finished concentrate would be obtained (deleterious sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal mincrals in a nearly pure state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,0001. Of this quantity and value, Michigan produced approximately 19 per cent1. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1938

By W. E. Keck, Paul Jasberg

TheRe is a considerable tonnage of iron ore in the Menominee Range of Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a relatively large quantity of finished concentrate would be obtained (deleterious sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal mincrals in a nearly pure state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,0001. Of this quantity and value, Michigan produced approximately 19 per cent1. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1938

By Courtenay DeKalb

Revision of the United States mining law is needed chiefly because of the following reasons: 1. The conceptions as to the characteristics of orebodies that were held at the time the statute of 1872 was enacted have since proved to be in many respects erroneous. 2. The operation of the existing law has been found to work unnecessary hardship upon many claimants to mineral land. 3. The existing statute fails in large degree to encourage development of mineral resources. 4. The existing law often produces conflict between placer and lode-claim rights, working unnecessary injustice to placer claimants. 5. The methods of establishing the rights of locators on United States mineral land are defective, and are not uniform throughout the States within which such lands exist. Law of the Apex The objections to the so-called "law of the apex" are so well known as to require no detailed statement. It is sufficient to point out that the apex rule was based upon the notion that ore deposits consisted of well-formed veins included between definite walls, like the slice of ham in a sandwich. The fact is that veins conforming to that simple type are rare. Irregularity is the rule, and the chief metal production of the United States comes from mass? which bear no resemblance to the tabular form of vein. Manifestly the law of the apex fails completely in such cases. Moreover, the tendency is constantly toward the exploitation of ores of lower grade than could formerly be worked, and such deposits exist mainly in the form of large irregular impregnated zones and masses, so that the future development of our mineral resources would be continuously embarrassed by shadowy claims to extra-lateral rights by the locators of so-called apexes.

Jan 1, 1915

By Nathaniel Arbiter

INTRODUCTION Almost seventy-five years ago problems in the recovery of sulfides from then designated slime fractions were the impetus for the development of flotation. The fall-off in recovery by gravity methods below about 200-mesh, and the shift from coarser vein deposits to more disseminated ores, particularly for copper, provided the background for flotation's rapid advances. Although the ensuing years have witnessed major improvments both in flotation reagents and in flotation machines, many problems are still with us. And since, with the exception of the unique leaching of chalcocite ores at Inspiration, flotation is still the exclusive mainstay for primary recovery of all base metal sulfides, the solution of these problems as they arise is vital to the well-being of the mining industry. Before considering the problems themselves, it will be useful to review the current status of sulfide flotation in the United States. The last comprehensive survey by the Bureau of Mines in 1975 (1) showed sulfide ore tonnages treated from 1960 to 1975 as summarized in Table 1; Table 2 gives similar data for the flotation of all non-sulfide ores. Noteworthy is the leveling off in sulfide ore tonnages in 1970-1975, with a probable further decline in the past three years, and the sharp drop in the number of plants floating sulfide ores. In contrast, the tonnages of non-sulfide ores floated, as well as the number of individual plants, has continued to increase. In spite of these trends, two-thirds of the total tonnage of the ores to which flotation is applied is still represented by sulfides. Average grades of sulfide ores in 1975 were: about 0.6 percent for copper; near 5 percent for lead; and near 3 percent for zinc. Recoveries averaged in the low 80's for copper; about 95 percent for

Jan 1, 1979

By Paul Billingsley

The Georgetown mining district is located in Deerlodge county, Mont., about 20 miles west of Anaconda. It lies along the divide between the headwaters of Warm Springs creek, draining eastward, and Flint creek, flowing west and north through the Philipsburg valley. The actual divide is formed by Cable mountain, a narrow ridge running north and south, terminating to the south in low hills overlooking Georgetown lake, and to the north in a high, rugged plateau that falls off to the west to the wide valley of Flint creek. On the eastern, or Warm Springs, slope of Cable mountain is the Cable mine, with the Hidden Lake mine a few miles north. On the western slope is the Southern Cross group, with smaller mines, the Twilight, Cincinnati, Red Lion, and Big Bill, at intervals to the northward. The Georgetown mines lie in the hills south of Cable mountain; the Philipsburg mines, of which the Granite Mountain, Bimetallic, Hope, and Trout are the chief, form a separate group to the north, overlooking Flint Creek valley and Philipsburg. (See Fig. 1.) The region ranges in elevation from 5,000 to 9,000 ft. It is, with the exception of the lower valleys, well timbered with small fir and pine, although Cable mountain and the higher summits to the northward rise slightly above timber line. The main valleys have the smooth contours of glaciation, and their mouths are frequently choked with morainal deposits. General Geology. In a very general way the valley of Flint creek coincides in this region with the boundary between the pre-Cambrian slates of western Montana and the folded Palaeozoic rocks of the Rocky Mountain system. The great limestone formations of the Carboniferous and Devonian, lying at flat dips, extend from Anaconda well toward the head of Warm Springs creek, but on the divide the Cambrian appears, closely folded and intruded

Jan 1, 1914

By W. E. Keck, Paul Jasberg

THERE is a considerable tonnage of iron ore in the Menominee Range of Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a relatively large quantity of finished concentrate would be obtained (deleterious sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beiieficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal minerals in a nearly pure state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,0001. Of this quantity and value, Michigan produced approximately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

EDITORIAL comments on the anthracite report of the Federal Fact-finding Coal Commission, which became public on July 5, together with an analysis of its more important conclusions, will be found on another page of this issue. In this place, only a few extracts from the report, bearing more directly on technical matters, can be quoted, for lack of space. COST OF MINING Mining cost, as it stands on the books of each mining company, represents the average cost of the total output, all sizes, of anthracite. Egg coal has at least five times the market value of barley, but these' sizes are mined together and their costs can not be separated. Mine costs directly reflect the conditions under which these deposits of coal are recovered. Even within the few counties in which anthracite is found there is a conspicuous range of natural conditions. The distinc-tion between the Northern, Middle, and Southern field, or, as they are also termed, the Wyoming, Lehigh, and Schuykill regions, is primarily geologic and topo-graphic, but the effects of the natural conditions largely control costs. The contrast is great between Some of the level-lying beds of moderate but fairly constant thickness under the broad Wyoming Valley, where mining and underground haulage present relatively simple problems to the engineer, and the steeply pitching or overturned and faulted beds of variable thickness in the Schuykill field, where crushed coal' and treacherous roof multiply the difficulties of mining; and increase the unavoidable waste. Even more direct is the connection between geologic processes and the, differences in the character of the coal as mined, the varying proportions of large and small sizes demanding differences in preparation and resulting in different average prices realized for the product of the mines.

Jan 8, 1923

By J. M. Morkowitr

A. Sawatzky (Atomic Energy of Canada, Ltd.)—The detailed criticism by Markowitz of my simple treatment of the thermal diffusion of hydrogen in Zircaloy-2 indicates that my paper was not as lucidly written as it could have been. I would therefore like to reiterate several of the main points of my proposed mechanism and describe in more detail some of the features only implied in the original paper. The distribution equation derived in my paper was stated to hold only for the case where the volume taken up by the hydride was small compared to the volume taken up by the solid solution phase, subsequent work, mentioned below, having shown it to be out by only a few percent up to a hydrogen concentration of about 3000 ppm. Of course, hydrogen in the two-phase region alone is not conserved in my treatment as pointed out by Markowitz. On the contrary, one of the important features of my proposed mechanism is that in the presence of a temperature gradient a two-phase region cannot exist over the whole specimen. For example, if the specimen is entirely a + 6 initially, then on application of a temperature gradient, a single phase (a) region at the hot surface develops from time t = 0 onwards. As mentioned in my original paper, the interface between the a and a+d regions moves toward the colder surface of the specimen with a discontinuity in hydrogen concen- tration developing at the interface and increasing with time. This interface moves at such a rate that hydrogen in the specimen as a whole is conserved. It must be pointed out that my distribution equation (Eq. [5] in Markowitz's paper) holds only for linear geometry. It is easy to show that for the cylindrical geometry of Markowitz the assumptions used in my treatment lead to

Jan 1, 1962

By G. W. Tuffnell, S. Floreen

Three Fe-18 pet Ni-base ternary alloys cortaining carbon, molybdenum, or cobalt were aged to pgroduce hardening by carbides, Ni3Mo, or ordering, respectively. Each alloy was tested in rotating-beam fatigue tests after hardening to 195 ksi ultim.ate tensile strength. The fatigue properties of three alloys soere essentially identical. The results suggest that tlze fatigae strength of an igron-base alloy should depend primarily upon the tensile strength, and not iipon the hardening mecaanisrn. THE fatigue strengths of many steels have been found to be directly related to their ultimate tensile strengths. For ultimate strengths below 200 ksi, the fatigue endurance limit at 107 to 10' cycles is approximately half the ultimate strength. Essen- tially all of the steels that have been tested, however, have been hardened by carbon. Thus it is not certain whether the relationship between fatigue and ultimate strengths is a general one that applies for other types of hardening in steels, or whether it applies only for the particular method of hardening by carbon. The recent developments of the martensitic precipitation-hardened stainless steels and the marag-ing steels have shown that it is possible to achieve high strengths in iron-base alloys by other hardening mechanisms than that due to carbon. Therefore, it is now possible to compare the fatigue properties of several iron alloys having the same ultimate strengths but hardened by different mechanisms. For the present study a binary Fe-18 pct Ni martensite was selected as a base material. This particular matrix composition has been found to have deformation characteristics very similar to pure iron.' Three ternary alloys were prepared by adding either 0.23 wt pct C, 5 wt pct Mo, or 20 wt pct Co to this base composition. After suitable heat

Jan 1, 1965

By Stephen G. Dardaganian

Pore volume compresibilitieu measured in the laborutory on core .samples are reported for typical reservoir .sarrrl.rtorres at reservoir pressure. These cornpressibilities ore different for each reseriloir sample and cannot be correlated to porosity. The compressihilities are a1so functions of presslire. In recent years several authors have pointed out the importance of including pore volume compressibility of the reservoir rock in certain reservoir engineering calculations. Hall' showed that in calculating the hydrocarbon volume of an undersaturated reservoir from the production per unit change in reservoir pressure, the neglect of rock compressibility could, in the extreme case of low porosity rock, lead to results in error by a factor of two. Hawkinsl' and Hobson and Mrosovsky showed that both rock and interstitial water compressibilities must be included to achieve satisfactory accuracy in this calculation. Although rock compressibility is an important reservoir property in these calculations, very few data are available. Hall' made compressibility measurements on a few samples in a small pressure range. No other direct pore volume compressibility measurements have been reported. Geertsma' discussed the elasticity of reservoir rock but did not present any new data. In this paper, rock compressibilities suitable for reservoir calculations are reported for a variety of sandstones typical of U. S. reservoirs. The measurements were made through a range of pressures which is also typical of reservoirs. EXPERIMENTAL PROCEDURE Plugs 1 in. in diameter and 2- to 3-in. long were diamond drilled, 14 from cores from seven oil-bearing or potentially oil-bearing sandstone, one from a quarried sandstone, and another from a shallow, oil-free, pure orthoquartzite. The plugs were extracted in toluene, vacuum dried, and then weighed. The plugs were then saturated with kerosene and reweighed. This gave pore volume. They were then again extracted in toluene. vacuum dried, and jacketed in 0.004-in. thick copper foil. A short length of -in high pressure tubing led from the jacket. The jacketed sample was then saturated with kerosene and placed in the hydraulic pressure cell as shown in Fig. 1. Movement of the mercury slug showed the change in pore volume of the sample under a given pressure change. Temperature was about 72" F for all measurements. Before taking any measurements, the external pressure on the sample was raised to 10,000 psig and kept there for several hours. This formed the thin copper jacket around the plug. 7-he pressure was then removed and the sample left at least overnight, during which time it recovered its original pore volume. An external pressure of 12,000 psig was then applied and held constant. The change in pore volume was noted as the internal pressure was raised in 1,000 psig increments to 10,000 psig. The internal pressure was then reduced to zero, again noting pore volume changes,

By E. H. Snow, B. E. Deal

Instability effects in semicanductor devices have long been attributed to the motion of charges on or within oxide layers on the surface. These effects are of critical importance in metal-insulator-semiconductor MIS) field-effect devices. For this reason, the capacitance-voltage or the conductance-voltage characteristic of these devices can be used as a sensitive detector to study charge transport and polarization effects in the oxide or insulator. A review is given of the results of such studies of thermally grown SiO2 as well as of other insulating films of importance in silicon technology. Three types of effects are distinguished. The first of these is the drift of mobile cations within the dielectric, examples being thermally grown SiO, which is often contaminated with sodium ions, and a variety of other glasses in which the mobile ions are a part of the glass composition. The second effect is a dipole-type polarization which occurs in phosphosilicate glass films obtained by reacting P2O5 with thermally grown SiO2. The third effect involves the transfer of charges between the dielectric and the silicon electrode. This occurs in silicon nitride and other deposited dielectrics. It is concluded that MIS studies have provided a powerful technique joy the study of charge transport and polarization effects in insulating films. The knowledge gained from these studies has led to an understanding of surface effects on conventional transistors and diodes as well as making possible stable MIS transistors. THE metal-insulator-semiconductor field-effect transistor is conceptually the oldest type of active semiconductor device.' The earliest attempts at making this device were frustrated because of high surface state densities at the interface between the semiconductor and the gate insulation.' However, by using a silicon substrate with thermally produced silicon dioxide as the gate insulation, this problem was solved and metal-silicon dioxide-silicon devices with good characteristics were made as early as 1960. 3 Yet it was still over 5 years before these devices became a commercial reality. This delay was largly due, not to surface states, but to stability problems associated with polarization effects within the insulating layer which caused the threshold voltage of the device to drift under temperature and bias treatments. The solution to these problems has not only made possible stable MIS devices, but it has added immensely to our understanding of failure mechanisms in conventional bipolar transistors and has added to the reliability of ali types of planar devices. In this review, we shall first describe the effects of various types of polarization phenomena on MIS device characteristics. Then, since thermally grown SiO, is by far the most important insulator used in these devices, we shall review historically the type of instabilities which have been observed in thermal oxides, the attempts at understanding and eliminating them, and the present status of the problem. We shall then turn our attention to the various deposited insulators which have been used, including lead glasses, phosphosilicate glass, vapor-deposited silicon oxide, and silicon nitride. Interestingly enough, many of these materials show polarization effects which are quite different from those generally observed in thermally grown SiO2. THE EFFECTS OF POLARIZATION PHENOMENA ON MIS CHARACTERISTICS The simplest MIS device and the one which has been most frequently used in the study of polarization effects is the MIS capacitor. Two modifications of this structure with single- and double-layer dielectrics are illustrated in Figs. l(a) and (b), respectively. The capacitance of this structure as a function of voltage applied to the metal gate electrode is plotted in Fig. 2 for the case of an n-type silicon substrate. When the silicon surface is accumulated (positive bias) the measured capacitance is just that of the insulating layer C. When the surface is inverted (negative bias), the capacitance is that of the insulator and a silicon depletion layer in series CoCs/(Co + Cs). Indicated on the horizontal axis of Fig. 2 is the voltage VT at which the silicon surface becomes strongly inverted. This voltage corresponds to the threshold or turn-on

Jan 1, 1969

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By Foster Bain

THE outstanding characteristic of the last hundred years has been the world-wide rise in the standard of living. Man's dominion over nature is increasing with an accelerating pace and more and more the forces and materials of this world are being made to serve man's necessities and his convenience. We demand both quantities and varieties of goods that were beyond the dreams, to say nothing of the reach, of our fore-fathers, and our possession of them has become so much a matter of course that they excite no remark. Literally, thousands of young folks have required an explanation of a recent popular song, "Thanks for the Buggy Ride," for the reason that their own experience does not extend back into the pre-flivver age. This transition from the use of vehicles made mainly of wood and drawn by animal power, to metal made cars propelled by mineral fuels is all but complete and the memory even of older conditions is already fading. This is symbolic of what is happening all around us. In a recent book, Dr. Frank J. Goodenough, president of Johns Hopkins University, referred to Chinese civilization as a ?vegetable" civilization meaning thereby that the Chinese depend mainly upon the plant world for food, clothing and other necessities and luxuries. Our own people did the same hardly more than a hundred years ago. In 1820, this country produced and used only 5 lb. of pig iron per capita, but a quick and enormous change was wrought in the hundred, years that followed, and in 1920 the amount was 119 times as much, or 597 lb. It has since increased even beyond this and touched a peak of 809 lb. in 1923. In that year our output was more than twice that of 1903 and nine times that of 1883. This increase in production

Jan 10, 1926

By Walter G. Perkins

In the assay of copper-bearing material for gold and silver, the elimination of copper before the final cupellation is of course essential, because any copper left in the lead-button will carry gold into the cupel; and a method which will effectively remove the copper with the smallest amount of manipullation is desirable. The scorification method is often rendered long and tedious by the necessity of repeatedly re-scorifying the button— to say nothing of the risk of losing Au—Ag thereby incurred. An ore carrying, for instance, 10 per cent,. of copper and only 0.1 or 0.2 oz. gold per ton, cannot be scorified with accurate results, because so many portions would have to be taken in order to get enough gold for weighing. On the other hand, the crucible method, with potassic nitrate and nails, would not do at all in such a case, because all the copper would be reduced by the nails, and (if the charge were 0.5 A. T.) this would defeat cupellation, by causing cupel-absorption of gold. In matte-assays, more concentrated value permits the determination of gold from smaller portions, and thus diminishes the difficulty experienced with ores. The method here described has been severely tested, during use for more than a year, and hart never failed hitherto, in the assay of any ore or product to which it has been applied. It is not proposed as perfect for every variety of ore or matte—probably no method would be that; but it is believed that, intelligently used, with the modifications dictated by practice, it will give better results, with less expenditure of time and labor, than any other known to the writer.

Jan 1, 1902

By E. J. Dulis, G. V. Smith

AS reported several years ago,' nitrogen may be taken up from the atmosphere by austenitic Cr-Ni steels during creep or creep-rupture tests. This was indicated by chemical analysis and by the appearance of a new microstructural phase, or phases, tentatively identified as chromium nitride (S), at the surface or at the intergranular cracks associated with fracture. The nitrogen pickup was observed to be dependent on time, temperature, and deformation. In a more recent investigation, a sample was obtained in which there was sufficient of the precipitate to suggest that it could be readily identified by X-ray diffraction. This sample had been taken from a 1/4 in. diam creep-rupture specimen of annealed, type 304L stainless steel of the following initial composition: C, 0.03 pct; Mn, 0.65; P, 0.010; S, 0.019; Si, 0.54; Cr, 19.50; Ni, 12.02; N, 0.031; and Al, 0.005. The specimen had ruptured after 10,470 hr at 1500°F (2000 psi). In this case nitrides were distributed across the whole section of the sample, Fig. 1. The precipitate occurred both at the grain boundaries and within the grains; the latter precipitate had in some cases the appearance of pearl-ite, and in others was distinctly Widmanstatten. Chemical analysis of the sample after test showed 0.64 pct "soluble" nitrogen (soluble in 1:1 hydrochloric acid: water) and 0.18 pct "insoluble7' nitrogen (insoluble in the hydrochloric acid solution but dissolved by fuming sulphuric acid). For identification of the precipitate by X-ray diffraction, the matrix in the surface layer of the specimen was dissolved by prolonged attack in an alcoholic solution of picric and hydrochloric acids. The appearance of the specimen surface after such etching is shown in Fig. 1c. The diffraction pattern of the surface-concentrated precipitate was obtained with a recording spectrometer in both the forward and back-reflection regions (the latter by adapting a special fixture to the conventional X-ray unit). The observed X-ray diffraction lines, Table I, show the presence of Cr,N and CrN; the agreement with interplanar spacings calculated from reported data2,3 is quite good. Since it has been suggested' that CrN dissolves only in concentrated sulphuric acid, whereas Cr2N dissolves in dilute hydrochloric or sulphuric acids, an effort was made to distinguish between the two nitrides. This proved possible, inasmuch as etching in a dilute solution of hydrochloric acid gave a sample in which microscopic examination showed that much of the Widmanstatten-pearlitic precipitate within the grains had been eaten out, leaving the grain boundary precipitate in relief, and which, when examined by X-ray diffrac-

Jan 1, 1953