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By F. Julius Fohs

WITH portions of two coal basins within its borders and a few scattered fields already developed, the question arises: What is the future of Ken-tucky as an oil-producing State? Is the long list of failures due to lack of 'commercial pools, or unintelligent prospecting? A study of its beds and irregularities of structure points not only to a large waste of development money on unpromising areas, but also to the presence of a few structures well worthy of development. The surface rocks of Kentucky show in succession more than 4,000 ft. of Paleozoic sediments and more than 2,000 ft. of Cretaceous, Tertiary, and more recent deposits. Folding and erosion have brought these beds to the surface, where they have been observed and studied: in detail by my associate, James H. Gardner, myself, and others. This has given opportunity to observe the beds offering suitable reservoirs and having the proper impermeable covering; also the mapping of outcrops and outcrop lines, taken in conjunction with available well records, indicates that certain areas are worth testing, and with even greater definiteness shows areas which should be excluded, as devoid of possibilities. West of the Tennessee River, Cretaceous, Tertiary, and Quaternary sediments occur so that all trace of ancient folding is obliterated, the sediments overlapping unconformably Mississippian rocks. This area embraces 2,000 square miles, or one-twentieth of the area of the State, the Paleozoic rocks covering the remainder. Since there is nothing upon which to base the location of tests for oil and gas in the Cretaceous-Tertiary beds of Kentucky, the Paleozoic area will be chiefly considered.

Jan 3, 1915

By Charles Catlett

Probably no one has had occasion to examine an undeveloped coal property without hearing some hopeful or interested party insist that the bed will improve when opened some distance under cover. When the bed is already in good condition, the opinion is usually advanced that the same character may be expected, at least to the bounds of the hopeful individual's holdings. My attention has been called in this way to the extent to which a bed is affected by its outcrop at the surface ; and having had opportunity to examine a number of openings immediately at the surface, and also a short distance under cover, I submit some observations bearing on this question. Whatever may have been the original variations, we may assume that coal-basins presented in comparatively modern times approximately parallel beds interstratified with fire-clay, slate, sandstone, etc., as represented by Fig. 1. Under the effect of erosion, Fig. 2 would be formed. It is obvious that along the line A, B, C, in Fig. 1, the beds exist under conditions differing from those at A', B', C', or again at A", B", C", in Fig. 2, in their exposures to atmospheric agencies, pressure and erosion. The effect of the first is to decompose and soften many of the strata; of the second, when presented unequally, to cause the movement of such material as was at all plastic towards the point of least pressure ; and of the third, to remove the strata in whole or in part. It

Jan 1, 1901

By James Boyd

REACTIVE metals are not only those sufficiently radioactive to be used as fuels, such as uranium and thorium, but all metals that will find application in power reactors. It is required of such metals that they be relatively inert or chemically unreactive, dimensionally stable at high temperatures and pressures, and either very absorbent of radioactivity or transparent to it. To gain the right perspective concerning these metals it is necessary at this point to explode some erroneous concepts propounded so often they have become accepted as fact. The first of these is that the great industrial nations, especially the U. S., have reached their pre-eminent position chiefly because they possess abundant mineral resources. Some U. S. mineral economists, echoed by the politicians, have taken this position so often that many of their theories and policies are based on the presence of developed mineral resources as a sine qua non to the country's greatness. Actually the reverse is true- under a social and political system granting free rein to the initiative and creativeness of its people, many hidden mineral resources that otherwise would have lain fallow have been developed into productive enterprises to the benefit of the national industrial economy. Again, once the proper incentive was furnished, other countries have also been able to establish valuable mineral enterprises in recent years; resources long dormant for lack of a proper economic environment suddenly have become valuable and productive. It is possible to name immediately several nations where such domestic economic developments have had favorable repercussions within the last decade. The absence of productive mines in any country is no indication that workable deposits do not exist within its territory.

Jan 11, 1957

By J. L. Leland Myer

Some of the early experiments on the oxidation temperature of coal1 were undertaken in England in connection with a study of self-heating, or spontaneous combustion. It was then suspected that coals with low oxidation temperature were most likely to ignite by self-heating, but further experiments showed that many additional factors were involved. The oxidation temperature has importance as a physical property or characteristic of the coal. While only a few of the physical properties have been studied, they appear to have basic significance2 in the ultimate classification of all coals. When reliable data become available on the oxidation temperatures, as determined by standard and adequate methods, it should provide an additional basis for classification and comparative evaluation. Oxidation Temperature Defined For such a heterogeneous substance as coal is known to be, no simple definition of oxidation temperature can be established on a theoretical basis. If coals were homogeneous and of simpler structure, the accepted definition of "ignition temperature " as applied to simple gaseous mixtures might be adopted; that is, the temperature at which self-heating of the mixture sets in. But most coals self-heat slightly even at storage temperature, as evidenced by spontaneous combustion, and the definition for gases cannot be applied to coals with any exactness. By subjecting coals to suitable experimental conditions various oxidation characteristics can be obtained and examined for critical or significant stages of the oxidation process. Oxidation temperature itself must then be defined on the basis of such experimental results. Experimental Methods Attempts to determine critical points in the temperature functions of coal undergoing oxidation have resulted in the following experimental methods:

Jan 1, 1932

By Charles H. Thurman

The data given herein were first included in a paper read before San Francisco Section, A.I.M.E., in October 1940, and are applicable to conditions existing until the gold-dredging industry was temporarily suspended by Order L-208 of the War Production Board in the fall of 1942. There is no doubt that gold dredging will be resumed at some future time, and on a scale equivalent to that of the recent past, but the cost data given herein will be affected to some extent by conditions existing at that time, and by labor rates and prices for materials then prevailing. Dragline vs. Bucket-line Dragline dredges should not be considered for mining large areas of low-grade placer gravel. In such deposits a dragline operator with a 5-cu. yd. dragline would be doing well to maintain an operating cost of 6¢ per cu. yd., while a bucket-line dredge with buckets no smaller than 7 cu. ft. each could be operated for less than 4¢ per cu. yd. By operating costs, I mean only field charges such as direct operating and overhead, which includes pay roll, power or fuel, repairs and maintenance, insurance, land clearing and general expenses, but not including such items as prospecting, depletion, depreciation of equipment, State Franchise Tax, or Federal Income Tax. It is not to be inferred that a dragline dredge cannot make a profit in small low-grade deposits, where the extent of a given property is too small to justify the use of the more costly bucket-line dredge. Consider small deposits of 106 gravel. It is obvious that a deposit of 5,000,000 cu. yd. of such gravel could not be mined profitably with a new 7-cu. ft, bucket-line dredge, costing upward of $250,000, and in operation costs at 4¢ per cu. yd., paying for land or royalties out of earnings; nor could a new combination 5-cu. yd. dragline and washing plant, worth upward of $125,000 and working at 6¢ Per cu. yd., make a profit. These comparisons are made because the hourly capacity of both types of dredges is nearly the same. The bucket-line dredge averages 93 per cent operating time in 24 hr., as against about 80 per cent or less for the dragline dredge. These Percentages of operating time are important factors in making a comparison of this kind- The bucket-line dredge has greater efficiency in cleaning soft bedrock, usually characteristic of dredging deposits, and a 7-cu. ft. bucket-line dredge can be efficient to a total digging depth of 80 ft- (65 ft. below water, 15 ft. above). A 5-cu. Yd. dragline dredge is limited to about 30 ft. of efficient digging depth, 5 ft. of which could be above water. In small areas of gravel not over 30 ft. deep, a 5-cu. yd. dragline dredge could make a profit where a bucket-line dredge could not do so. As an example: compare the dredging of 3,000,000 cu. yd. of 10 gravel 28 ft. deep with bucket line, costin 4¢ Per cu. yd., and with a 5-cu. yd. dragline dredge operating at 6¢ Per cu. yd. Because of small yardage, new equipment is not warranted, therefore we can assume that the dredges of both types are used equip-ment, fully depreciated. Dismantling, mov-

Jan 1, 1946

By R. C. Gifkins

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By Niels Hansen

Dispersion-strengthened aluminum products consist of an aluminum matrix containing finely distributed ceramic or intermetallic particles. Examples of the two types of product are SAP, in which the dispersed phase is aluminum oxide, and materials made from atomized aluminum alloy powder, in which the dispersed phase can be FeA1, particles.' A fundamental difference between the two types of product is that the elongation of aluminum/aluminum oxide products decreases with increasing temperature, whereas the elongation of aluminum- FeA13 products, like that of aluminum alloys, increases with increasing temperature. As regards the structural stability, aluminum/aluminum oxide products are stable to temperatures above 600° C as aluminum oxide does not react with aluminum, whereas prolonged heating at above 400°C of aluminum-FeA1, products leads to coarsening of the intermetallic phase and loss of strength.' On the basis of these results it is supposed that a dispersion-strengthened product combining strength, ductility, and stability at elevated temperatures may be obtained if the dispersed phase reacts with the matrix in such a way that the reaction does not proceed at any significant rate at the application temperature. Different ceramic or intermetallic compounds may be selected as the dispersed phase, and, as alloying of the matrix phase may also influence the reaction, many possibilities exist for each metal. In the present study, aluminum products containing different oxides have been examined. For a reaction to take place between the dispersed oxide and the aluminum the free energy of formation of the oxide (MeO) must be greater than that of aluminum oxide; the difference should, however, not be too great in order to limit the reaction rate. Furthermore the aluminum alloy formed when aluminum reacts with the dispersed oxide should have a melting point near

Jan 1, 1969

By Henry M. Howe

In my original paper, Piping and Segregation in Steel Ingots, I pointed out1 among other things that, in view of the slighter stretching (virtual expansion) of the crust, and greater opportunity for sagging, there should be less piping in broad than in narrow ingots, and less in slowly-cooled ingots, e.g., those cast in pre-heated sand molds, than in those which cool quickly, e.g., those cast in iron molds. A. A. Stevenson said that neither of these predictions agreed with his own experience. In particular, in a picture which he showed of a wide and of a narrow ingot cast from the same ladleful of steel: the wide ingot had certainly piped much more deeply than the narrow one. At the time I did not see the explanation of these discrepancies, but further reflection makes it evident. One of the most important elements in determining the depth of the pipe is the degree of " top-lag," that is, the degree to which the solidification of the top of the ingot lags behind that of the bottom. Through this lagging the steel of the upper part of the ingot is able to run down and fill the pipe below as fast as it forms. To the importance of this lagging I called attention in my original paper.' Sand us. Iron Molds.—If we compare two like ingots, one cast in an iron and the other in a sand mold, we see that the top-lag is much greater in the former than in the latter, because in the former the lower part of the ingot is cooling off fast while the metal is running into the upper part. It is perhaps easier to look at this as a case of the solidification of the hot-

Jan 1, 1910

By Colin C. Rae

The absence of paraffin and other oil hydrocarbons in the soil although they are concentrated in extensive deposits in some localities, the common distribution of plant remains through many formations that are not productive for oil, and many other factors, seem to indicate the existence of an intermediate organic compound between the complex plant compounds and the petroleum hydrocarbons; and much evidence points to the humus acids or associated organic compounds, which are probably collected by surface waters and concentrated in certain areas by means of precipitation by electrolytes, which would be contained in sea water or possibly in various inland seas or lakes. Present-day Evidence There are many present-day evidences of the association of petroleum with humus acids. Binney, in 1912, made observations without explanations on the peat mosses of Down Holland, England, where he found petroleum being formed by decomposition in the presence of an infiltration of sea water. The analysis of a typical peat will show its relationship to the humus acids under consideration. Sample No. 1, SamplE No. 2. PXr Cent. PER CENt. Water......................... 20.0 29.6 Ash.......................... 3.0 3.05 Fiber.......................... 47.0 54.95 Humus acids................ 30.0 12.50 J. D. Haseman and others have noted the association of asphalt and hydrocarbons with the swampy, boggy areas, particularly adjacent to the sea. Many of the rivers carry much humus acid in solution, and some tropical rivers carry in the aggregate millions of tons of humus each year. The amount of humus is a variable factor, depending on climatic conditions, and on the salts and alkalies present in the water, also on the density and temperature.

Jan 1, 1923

By Colin C. Rae

The absence of paraffin and other oil hydrocarbons in the soil although they are concentrated in extensive deposits in some localities, the common distribution of plant remains through many formations that are not productive for oil, and many other factors, seem to indicate the existence of an intermediate organic compound between the complex plant compounds and the petroleum hydrocarbons; and much evidence points to the humus acids or associated organic compounds, which are probably collected by surface waters and concentrated in certain areas by means of precipitation by electrolytes, which would be contained in sea water or possibly in various inland seas or lakes. Present-day Evidence There are many present-day evidences of the association of petroleum with humus acids. Binney, in 1912, made observations without explanations on the peat mosses of Down Holland, England, where he found petroleum being formed by decomposition in the presence of an infiltration of sea water. The analysis of a typical peat will show its relationship to the humus acids under consideration. Sample No. 1, SamplE No. 2. PXr Cent. PER CENt. Water......................... 20.0 29.6 Ash.......................... 3.0 3.05 Fiber.......................... 47.0 54.95 Humus acids................ 30.0 12.50 J. D. Haseman and others have noted the association of asphalt and hydrocarbons with the swampy, boggy areas, particularly adjacent to the sea. Many of the rivers carry much humus acid in solution, and some tropical rivers carry in the aggregate millions of tons of humus each year. The amount of humus is a variable factor, depending on climatic conditions, and on the salts and alkalies present in the water, also on the density and temperature.

Jan 1, 1923

By R. Dawson Hall

THE stresses in the e simplest structures are often those we find most difficult to analyze. The most complex condition in mine stresses is found in simple tunnels where the roof, the sides, and the floor are a monolith. The functions of the parts are like the parts themselves not distinct and specialized, and the problems to be solved are like those in a metal structure with riveted joints or a redundancy of bars. This difficulty explains perhaps why the condition has not been treated. But just because it cannot be discussed in its entirety is no reason why it should be treated as an action of parts with specialized functions as a roof 'beans with supports and a foundation. The problem cannot be ignored on the ground that it is not of sufficient importance to warrant careful consideration, because conditions of complete monolithism, of which the tunnel is the type, are found materially unchanged) in room-and-pillar and in longwall work. This unity between roof, sides, and floor, which to the coal miner is a difficult conception, really deserves a scientific appellation, and perhaps holoid (from holos, whole, and eidos, form) will serve the purpose as well as any other. In a simple tunnel the roof, the sides, and the floor form integral parts of one and the same structure; and the distortion of one cannot be conceived without a consequent strain in the others. Thus when the roof of the tunnel droops by reason of its weight, the upper parts of the sides are drawn in because they are integrally-connected with the roof and must approach each other whenever, by the sagging of the roof, the distance between any two points in it is diminished. (See Fig. 1.)

Jan 9, 1915

By Joseph H. Taylor

The Ducktown district is in the extreme southeastern corner of Tennessee, its principal railroad point being Copperhill, on the Blue Ridge division of the Louisville & Nashville Railroad, midway between Knoxville, Tenn., and Atlanta, Ga. The ore deposits were discovered about 1849 and development work was begun in the early fifties. Only the "black copper" ores, products of secondary enrichment, from beneath the gossan outcrops and overlying the massive sulphide deposits, were then mined and smelted for their copper content. Upon their exhaustion, attention was directed to the treatment of the pyritic ore remaining, resulting in the devising of a process consisting of open-heap roasting, followed by blast-furnace smelting, which was practised until 1903, when semi-pyritic smelting was adopted. In 1908, the companies operating in the district, on account of litigation brought about by alleged smoke damage to forests and vegetation in the adjoining counties of Georgia, were compelled to erect enormous acid plants to prevent the escape of the sulphur dioxide produced in the smelting operations. The utilization of this sulphur dioxide in the manufacture of sulphuric acid as a byproduct has added to the revenues of the companies, and at the same time has furnished a valuable source of supply of sulphuric acid to the fertilizer trade of the South, and more recently to the manufacturers of eyplosives for use in the production of war munitions. The steadily increasing demand for sulphuric acid for the manufacture of fertilizers and explosives, together with the decreasing imports of pyrites, from which the acid is generally produced, now makes it imperative that greatly extended resources of pyrite be developed. While the Ducktown deposits do not predominate in pyrite, they do contain an inexhaustible supply of pyrrhotite, admixed with pyrite, which can be satisfactorily employed to supplement or substitute for pyrite in acid making.

Jan 1, 1918

By Julian Kennedy

THINKING that it may prove of interest to the Institute, 1 have prepared a short; account of the blowing in and subsequent working of the "A" furnace of the Edgar Thomson Steel Works. This furnace was built for the purpose of making spiegel, but has been started and is now running on Bessemer iron. The shape and size of the furnace are shown in the accompanying drawing. It will be seen that the section is formed of lines making very small angles with each other. In fact, an arc of a circle can be drawn, from the top to the tuyeres, which will nowhere deviate more than two inches from the lines given. In building, also, great pains were taken to gradually round the angles, so that the most careful observer, standing in the crucible and looking upward, could not tell at what points the slopes changed. It will also be seen that the widest part of the furnace is almost exactly midway between the bottom and the stock line. The flattest slope is maintained for 20 feet above the crucible, and is about 18 inch to the foot from the perpendicular. The furnace is lined with small brick throughout, and has six tuyeres four inches in diameter, which project seven inches inside of crucible. There are three Siemens-Cowper-Cochrane stoves, each 15 feet in diameter by 50 feet high. Blast is furnished by an upright engine with 32-inch steam cylinder, 84-inch air cylinder, and 48-inch stroke. The steam cylinder has balanced poppet valves, working horizontally. The steam valves are worked by a Porter link-movement in order to obtain a variable cut-off. The exhaust valves are worked by a separate eccentric. It is intended to attach a governor to the cut-off, but at present it is set by hand. The steam cylinder is

Jan 1, 1880

By Donald Barton

THE elastic, earthwaves produced naturally by earthquakes -have been used for a long time as evidence from which to draw conclusions in re-gard to the constitution of the interior and crust of the earth. The elastic earthwaves produced artificially by occasional explosions and recorded by seismological observatories were used to draw conclusions regarding the-geology of the intervening area. Intentionally pro-duced elastic earthwaves in the past five years have come to be used extensively in the investigation of very local geologic structure. The seismic method of work-ing geologic structure, which makes use of artificially controlled explosions and the resulting earthwaves, has developed almost `clairvoyant power in handling certain geologic situations, and in the discovery of salt domes in the Gulf Coastal: Plain region of Texas and Louisiana has 'scored the, most brilliant success. The. first, proposal for the use of artificial earth-quakes in the study-of velocity of elastic earthwaves in the surface formations of the earth's crust was made before 1888 by the English seismologists, Mallet and Abbot. Partly on the basis of their work, A. Schmidt in 1888 proposed- the use of the time-distance graphs of artificial earthquakes to study the variation of ve-locity with depth. Belar in 1902 proposed the practical application of such investigation in connection with boring tunnels. Galitzen repeatedly (1912, 1913) pro-posed the use of explosions to study the velocity of the longitudinal and transverse waves in the uppermost formations and pointed out that the velocity depended in a high degree on the physical character of the beds and that from changes in the velocity, conclusions could be drawn in regard to the compositions of the beds. Somewhat the same thought: was proposed by von dem Borne (1908), by Benndorf, Udden, and others.

Jan 9, 1928

By Sidney H. Haughton

FOLLOWING the discovery of diamonds in 1870 and the Witwatersrand gold fields in 1886 South Africa changed from a predominantly pastoral country with a scattered white population into a land whose economy came rapidly to be based primarily on mining. The total value of the mineral output of the Union in 1944 was approximately $493,000,000, to which gold contributed 84 per cent. Gold furnished some 33 per cent of the Union Government's total revenue in that year, and approximately half the country's population obtained its livelihood directly or indirectly from the gold mining industry. In any review of the Union's mining activities and in any consideration of the country's future, gold mining must occupy a prominent place. It is generally conceded that the present structure is not properly balanced and that an economy based on a preponderance of a single nonpermanent factor possesses potentialities of serious instability.

Jan 1, 1946

By Arthur F. Taggart

Tins paper proposes two units (believed to be new) for designating, respectively, capacity and efficiency for primary and intermediate crushers. CAPACITY Operators know that the tonnage of rock that can be put through a particular crusher in a give time depends primarily upon the crusher setting (open setting for jaw and primary gyratory types; closed setting for cones and rolls), and secondarily on the lithological character of the feed, its maximum size, the amount of fines that it carries, its moisture content, and the method of feeding. The proposed capacity formula states a relationship between all of these factors in one empirical equation, as follows: TR = TR80KK'K" [I] in which Ts, called "reduction tons per hour" is the new capacity unit; T = tons of feed per hour requiring crushing; R80 = "80-per cent reduction ratio"; and K, K', and K" are constants that approximate quantitatively lithological character, moisture content and method of feeding, respectively. T is the hourly weight of material in the feed that is coarser than the coarsest discharge of the crusher. (For marked departures from the normal specific gravity range - 2.5 to 2.7 - T should. be adjusted to corresponding volumes.) In the crushers under consideration, discharge from the crushing zone is limited by the minimum dimension of a particle. Passage of the particle through a square-mesh screen is limited by its intermediate dimension. Sheppard1 has shown that the ratio of maximum: intermediate: minimum average dimensions of broken rock fragments may be taken as about 1.5 : 1 : 0.6 for nonslabby rocks such as are normally crushed, while for slabby rocks, such as thin-bedded sedimentaries, foliated schists and gneisses, and the blocky metamorphics, the ratio is of the average order I.3:I:0.3, with the possibility of an even smaller relative value for the thickness. Gaudin2 finds the corresponding ratio for 150 + 200-mesh pyrite to be 1.4: 1 : 0.6. The hourly tonnage of crusher-plant feed, therefore, should be diminished by the amount thereof that would pass a square-mesh screen of which the aperture is S times the crusher setting, where S is a shape factor with the value 1.7 for rocks that break exceptionally cubic; 2 for ores and rocks that exhibit no appreciable tendency to slabbiness; and 2.5 to 3, or, in exceptional cases, even larger, when the tendency to slabbiness is marked. R80 is the quotient of the theoretical square-mesh aperture that would pass 80 per cent of the feed, divided by the aperture that would pass 80 per cent of the product. It is best determined from screen tests.

Jan 1, 1941

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-'. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5'9 for these high concentrations of phosphorus do not follow Fick's laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1' that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7'8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By Erwin Pink

It has been pointed out in a previous publication' that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e' the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E' is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson's ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

Bill S.1431 for the creation of a Department of Natural Resources has received a propitious hearing before the Senate Committee on Government Operations. Interior Secretary Rogers C. B. Morton was one of the prominent witnesses who testified in favor. The department had been proposed, Morton said, with "the conviction that the development of all natural resources would be harmonized with the most practicable possible means to protect and preserve the environment, consistent with the social and economic needs of the Nation." Another opinion on the pro side came from Atomic Energy Commissioner Clarence E. Larson, who said that a "total picture" had become essential to the establishment of a policy for developing energy resources in the best public interest. Commissioner James T. Ramey, on the other hand, was one of the AEC dissenters. Ramey said he believed the reorganization of resource responsibilities would hinder efforts to deal with energy-environmental problems and prevent the use of AEC "expertise and facilities" to the greatest advantage. As Arnold Weber, associated director of the Office of Management and Budget, pointed out, however, retiring AEC Chairman Glenn T. Seaborg is in favor of the new department. Another supporter, and one who can cast a vote on the bill, is Sen. Frank E. Moss. Final Standards for emissions from new stationary sources will be published by the Environmental Protection Agency on October 27. The initial proposals, appearing in the Federal Register on August 17, called for limiting emissions per million Btu of heat input (maximum 2-hr average) to 0.2 lb of particulate matter, and, where solid fuel is burned, to 1.2 lb of sulfur dioxide and 0.7 lb of nitrogen dioxide. While the new rules are mainly for new plants, the EPA is also proposing them for "existing plants which are modified in such a way as to increase or alter. . . their emissions."

Jan 1, 1971

By F. A. J. Fitzgerald

In any kind of furnace the question of preventing the loss of heat is important, for no matter how the heat is obtained it costs something; and consequently, other things equal, that furnace is most desirable which uses the greatest percentage of the total heat generated for the particular object in view. In the furnace which uses electricity for the generation of heat the importance of preventing losses of heat is very much greater than in any other. To generate 1,000 kg-cal. requires an expenditure of 1.16 kw-hr., and consequently the cost per calorie is always expensive when electricity is used for heating. In heating any material in a furnace a general rule is that the generation of heat should be as rapid as possible. In any given furnace the heat-losses may be expressed as so many watts, and, therefore, the longer it takes to heat the furnace-charge the greater the losses will be. Suppose that a furnace contains a charge to be heated to 1,500°C. and that the average loss of heat is at the rate of 100 kw., then if the process of heating the charge takes 1 hr. the losses will amount to 100 kw-hr.; but if by using a more rapid generation of energy the charge can be heated in 30 min. the losses will amount to 50 kv-hr. An example from experiments on a certain process may be given to illustrate this point. The problem was simply to heat a furnace-charge to a certain temperature, and experiments were made to determine the effect of increasing the rate of generation of energy and comparing the kilowatt-hours required to heat a given charge. Here are typical results : Rate of Generation Energy Per Kg. of Energy. of product 88 kw. 1.7 kw-hr. 93 kw. 1.6 kw-hr.

Jan 1, 1913