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By Robert Lowrie

Nine intermetallic compounds were tested in tension at various temperatures. Seven exhibited extensive plastic deformation at elevated temperatures. Correlations of tensile strength and elongation are attempted with melting (decomposition) temperature, valence electron configurations of the component elements, heat of formation, crystal structure, density, and volume decrease accompanying compound formation. A LTHOUGH intermetallic compounds have been -tX known for many years, the study of their mechanical properties, particularly in tension, is just beginning. The problem has been unattractive because of the well-known, erratic behavior of brittle materials tested in tension. The strong influence of surface or internal flaws as stress raisers in non-ductile materials and the effect of eccentricity of loading in superimposing bending stresses on the state of tension in the specimen are extremely difficult to mitigate and impossible to completely eliminate. Thus, tensile properties determined for brittle materials, such as intermetallic compounds at temperatures low in comparison to their melting points, are at best only general guides to the values to be expected in an ideal test of a perfect specimen of the material. It is, nevertheless, surprising that apparently no attempt was made to follow up the pioneer work of Tammann and Dahl1 in this field. Working with crude apparatus, these investigators succeeded in showing unequivocally that at temperatures sufficiently close to their melting points (from 75" to 400°C for the compounds tested) intermetallic compounds did exhibit plasticity. This was indicated by the appearance of slip lines on the surface of the specimen. No observations of strength were made in these tests, which were of a compressive or indentation type. Rossi2 in 1932 attempted to study the physical and mechanical properties of single crystals of a group of intermetallic compounds. However, he was able to prepare only one material, Cu2Z8,, in the form of large, defect-free, single crystals. Thus, he was able to report only the relative fragility of the compounds at room temperature. He reported one compound, Ag,Zn,, to be somewhat plastic at room temperature and Cu,Si to be friable, the latter in agreement with results reported herein. Although test results are available only in classified literature, it has also been announced that MoSi, possesses some ductility at elevated temperatures." In 1948 and 1949 Savitskii and Savitskii and Baron -ublished their work on the hot extrusion of Mg-Zn, Al-Mg, and Cu-Zn compounds. Under the favorable state of stress existing for this process MgZn, MgZn,, MgZn,, ß (Al-Mg), ? (Al-Mg) and 0 (Cu-Zn) could be reduced by amounts up to 90 pct at elevated temperatures. These authors also report that hardnesses of Mg-Zn compounds decrease from room temperature values of about 300 kg per sq mm to 30 to 50 kg per sq mm at 325°C. They found that alloys consisting solely of one Mg-Zn compound were most resistant to softening on heating, mixtures of a compound and eutectic less resistant, and mixtures of two compounds least resistant. The more rapid softening of mixtures of

Jan 1, 1953

By Joseph L. Gillson

Bentonite, designating a distinct type of clay, is a young name in mineral nomenclature in the light of the age-old names of most other useful nonmetallics. The earliest references in literature are to "soap clay" (1873) "taylorite" (1888) and finally "bentonite" in 1897, from its occurrence in the Fort Benton series of rocks near Rock Creek, Albany County, Wyoming. Bentonite is a rock term and consists largely of montmorillonite clay. The latter name was proposed in 1847 for a plastic clay found at Montmorillon, France. A clay of apparently identical properties was described by Cronstedt of Sweden in 1788 and a number of other similar clays found in France were given other names in publications from 1853 to 1856. The mineral name montmorillonite was recognized by Dana in 1892. The recognition of "clay mineral" distinctions which led to the present-day classifications of clays by their chief mineral content, dawned in the early part of the twentieth century. Grim6 has aptly said: About 1924, Ross10 and some colleagues of the U. S. Geological Survey began a study of the mineral composition of clays that led to a series of monumental papers on the subject. By the early 1930's what has come to be known as the clay-mineral concept became firmly established in the minds of a great many people actively studying clay materials. The clay mineral concept designates the major clays as kaolins, montmorillonites and illites and by this concept bentonites are now defined as "fine-grained clays containing not less than 85 pct montmorillonite" and a wide variety of clays found all over the world are included in that classification. They could all properly be called "montmorillonite clays" but the common commercial name is bentonite. For a period of over forty years from the time of the earlier discoveries, bentonite was thought to be only the sodium type highswelling clay produced principally in Wyoming. By the clay mineral concept, non-swelling montmorillonite clays also became known as bentonite. In the trade there are two broad divisions-sodium bentonite, often called Wyoming or "western," which expands in water and carries sodium as its predominant exchangeable ion, and calcium bentonite often called "southern," which has negligible swelling and carries calcium as its principal exchangeable ion. There are many intermediate gradations. Properties The mineralogy and chemistry of the clays are so complex that the subject cannot be summarized briefly. The reader is referred to Chapter 12 of this volume in which the subject is treated at some length. Grim6 gave the formula for montmorillonite as (OH)4Si8AL4020.nH2O. He wrote: Montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. . . . Exchangeable rations occur between the silicate layers. . . . The words "tetrahedral" and "octahedral" refer to the coordination number of the cations in the unit cell in the crystallographic lattice. Carroll5a stated: That the montmorillonite structure is the same as that of mica, but the layers are not held together by K+ ions; and water and other polar molecules, such as organic molecules, can enter between the unit layers and cause expansion. Ex-

Jan 1, 1960

By R. L. Manegold

IN RECENT years there has been a decided trend toward bringing ores and coal out of open-pit and underground mines by long, sloping single-stage belt conveyors. Because the high investment cost of haulage conveyors dictates maximum speed and full loading for economy, conveyor belts are running faster than ever before, with a greater burden on the belts. In addition, larger blocks of ore are being mined and conveyed. Rougher use of large mining equipment generates more tramp iron; mechanical loading rejects nothing. Therefore the extraction of tramp iron and other deleterious materials for the protection of haulage conveyors at transfer points, chutes, and idlers is becoming an increasingly difficult job. In our experience, the best method of protecting long haulage conveyor belts is to extract the tramp iron, at least the large tramp iron, ahead of the main haulage conveyor or series of conveyors. It is most practical to collect the tramp iron at the earliest source -possible, usually directly after the primary car unloading dump or after the primary crushers, which are ordinarily not affected by tramp iron, see Fig. 1. The coal or ore from its primary source is fed by chutes or feeders onto a buffer or shock belt conveyor, a short, ruggedly built conveyor system that can be considered somewhat expendable. Its primary function is to bring the ore up to speed for transmission to the haulage conveyor. There is no assured method of protecting this conveyor from tramp iron damage at its feed end. Likewise, there is a possibility, although remote if the magnet applied to this belt is installed correctly, that the tramp iron extraction process will damage the shock belt, which is, however, short and comparatively inexpensive. Magnetic head pulleys with their maximum effective range of about 8 or 10. in. cannot be considered for large installations, even though they are desirable because of the continuous and, automatic tramp, iron removal feature. Further, the most dangerous form of tramp iron with respect to potential damage to a haulage conveyor is the long rod, roof bolt, or rail segment, which is not extracted satisfactorily because of the limited tangential contact of such an iron shape with the magnet. Magnetic head pulleys are also undesirable because the dribble or fines from the head pulley discharge at the same point as the tramp iron. Screens must be used to separate the fines from the magnetics, resulting in additional expense and loss of head room. Magnetic detectors have been used with success, but they only indicate the, presence of iron, and the conveyor belt must be stopped for its manual removal. The, stoppage of any conveyor means that all preceding equipment must be stopped or a cascade of material on the idle conveyor will result. Occasionally combinations of detectors and magnetic, head pulleys are used. The detector precedes the magnetic head pulley and detects only large pieces of tramp iron, while the magnetic pulley subsequently takes out the smaller ferrous metals. Suspended magnets overcome the disadvantages of magnetic head pulleys, detectors or a combination of both. There are several magnetic extraction problems involved in applying a suspended magnet at this

Jan 1, 1952

By Basil B. Zavoico

Production of crude oil in the U.S.S.R. during 1940 is estimated at 222,600,000 bbl., as compared with the revised figure for the preceding year of 220,866,000 bbl., an increase of 0.79 per cent, and at least 20 per cent under the planned output. Baku district (Transcaucasus) remained the outstanding producing area, accounting for 72.33 per cent of the country's production, and this relative importance of the Apsheron Peninsula oil fields will probably continue lor many years to come. In the North Caucasus the Grozny-Dagestan area further extended its decline and the current production in this district amounts to only 6.06 Per cent Of the total U.S.S.R. output, as compared with 35.76 Per cent in 1931 The production of the Kuban-Maikop district remained virtually ullchanged from the preceding year, amounting to 7.64 per cent of the country's total. The Caucasian Province, therefore, in I940 produced 86.03 Per cent of the total production of the U.S.S.R. The promising new Permian Basin district, called Ural-Volga, and referred to sometimes as the "Second Baku," increased its production appreciably during 1940 and the output of that area amounted to 8.31 per cent of the country's total, as compared with 6.35 per cent during 1939. Production in the secondary districts of Russia continued unchanged though some new discoveries in the Emba salt-dome basin suggest that the output of that district may show some increase during the coming years. The drilling operations in Russia during 1940 reached a stage of virtual breakdown and the original footage plans were fulfilled only to the extent of around 50 per cent, while exploration drilling schedules were fulfilled only to the extent of about 25 to 35 per cent. This condition was due to the obvious lack of modern drilling rigs, of good drill pipe and of strong casing. Extended breakdowns occurred with deeper drilling, particularly because with few good drilling rigs available speed was being attempted with rotation rates that the inferior drill pipe and bits could not stand. Twistoffs and endless fishing jobs resulted. The difficulties became so serious a handicap to the Soviet oil industry that it was found imperative to order American drilling equipment and pipe in quantity, a policy that was never favored in the U.S.S.R because it requires expenditure of gold or exchange in major volume, and such exchange usually is reserved only to less bulky key items or to orders directly connected with armaments; also, oil-field machinery is very bulky and the prevailing lack of bottoms makes the transport of the indicated equipment a major problem. But little progress was similarly made in other branches of the Soviet oil industry. NO new major pipe-line construction work was undertaken, consequently the railroads continued to be overburdened with traffic that could be much more effectively handled by pipe lines. No new refinery construction of any magnitude was initiated, though several plants that had been in course of construction for several years were completed during 1940 and operation 554

Jan 1, 1941

By Basil B. Zavoico

Production of crude oil in the U.S.S.R. during 1940 is estimated at 222,600,000 bbl., as compared with the revised figure for the preceding year of 220,866,000 bbl., an increase of 0.79 per cent, and at least 20 per cent under the planned output. Baku district (Transcaucasus) remained the outstanding producing area, accounting for 72.33 per cent of the country's production, and this relative importance of the Apsheron Peninsula oil fields will probably continue lor many years to come. In the North Caucasus the Grozny-Dagestan area further extended its decline and the current production in this district amounts to only 6.06 Per cent Of the total U.S.S.R. output, as compared with 35.76 Per cent in 1931 The production of the Kuban-Maikop district remained virtually ullchanged from the preceding year, amounting to 7.64 per cent of the country's total. The Caucasian Province, therefore, in I940 produced 86.03 Per cent of the total production of the U.S.S.R. The promising new Permian Basin district, called Ural-Volga, and referred to sometimes as the "Second Baku," increased its production appreciably during 1940 and the output of that area amounted to 8.31 per cent of the country's total, as compared with 6.35 per cent during 1939. Production in the secondary districts of Russia continued unchanged though some new discoveries in the Emba salt-dome basin suggest that the output of that district may show some increase during the coming years. The drilling operations in Russia during 1940 reached a stage of virtual breakdown and the original footage plans were fulfilled only to the extent of around 50 per cent, while exploration drilling schedules were fulfilled only to the extent of about 25 to 35 per cent. This condition was due to the obvious lack of modern drilling rigs, of good drill pipe and of strong casing. Extended breakdowns occurred with deeper drilling, particularly because with few good drilling rigs available speed was being attempted with rotation rates that the inferior drill pipe and bits could not stand. Twistoffs and endless fishing jobs resulted. The difficulties became so serious a handicap to the Soviet oil industry that it was found imperative to order American drilling equipment and pipe in quantity, a policy that was never favored in the U.S.S.R because it requires expenditure of gold or exchange in major volume, and such exchange usually is reserved only to less bulky key items or to orders directly connected with armaments; also, oil-field machinery is very bulky and the prevailing lack of bottoms makes the transport of the indicated equipment a major problem. But little progress was similarly made in other branches of the Soviet oil industry. NO new major pipe-line construction work was undertaken, consequently the railroads continued to be overburdened with traffic that could be much more effectively handled by pipe lines. No new refinery construction of any magnitude was initiated, though several plants that had been in course of construction for several years were completed during 1940 and operation 554

Jan 1, 1941

By J. H. Faulk

An examination is made of the various factors influencing drilling rate and drill bit life in various diameter holes. It is concluded that drill bits in the size range 4% to 6 1/4 in. can be used to attain substantially the some daily drilling progress as conventional size bits in soft rock drilling operations. An examination of the most important factors influencing "hazard of losing the hole" in the different hole size results in the conclusion that the smaller hole sizes can probably be drilled at reasonably low risk. However, this risk will be somewhat greater in the smaller diameter holes, requiring that special drilling and mud engineering practices be used to make small diameter holes practicable in soft rock drilling operations. An engineering analysia is made of the power and hydraulic requirements of several drill string-hole combinations to test the feasibility of drilling .small diameter holes in soft rock areas. Large econormies in rig power requirements appear possible by drilling .smaller .size holes in these operations. INTRODUCTION The industry now is re-examining the utility of small diameter holes in the light of substantial technical advances made in recent years. Faced with increasing cost of finding reserves and with proration after developing them, the industry must either develop methods of economizing or receive a lower rate of return on investments. Small diameter holes appear to involve an attractive method of economizing. Our objective is to determine if this is technically possible in soft rock operations. Soft rock, as used in this report, refers to those formations of a "drill-ability" corresponding to that of all Gulf Coast formations shallower than and frequently including much of the Eocene rock system. An important phase of technology which we shall examine is relative drilling rate and bit footage which may be obtained with various size bits. Rig operating efficiency, particularly as influenced by hazard, is also discussed in detail. The technical conclusions resulting from these examinations are used to develop sample drill string design and rig horsepower requirements for drilling holes as smaH as 4 3/4 in. and larger. The principal criterion used for the drill string design is that approximately the same daily drilling progress would be possible in all size holes in soft rock operations. This facilitates a comparison of rig size required for drilling the hole sizes in the range between 4 3/4 and 8 3/4 in. BROAD PROBLEM OF DRILLING RATE AND BIT FOOTAGE The three factors controlling daily drilling progress are: (1) drilling rate of bit while on bottom turning, (2) bit footage, and (3) rig operating efficiency. Let us look now at the first two of these factors. Drilling technology has progressed to the point that a semi-quantitative analysis of the effect of various operating variables upon these factors can be made. Those factors which apparently limit both drilling rate and bit footage for bits now in use are: (1) bit design, (2) weight on bit, (3) hydraulic cleaning capacity for bit cutting surfaces and hole bottom, and (4) rotary speed. (We neglect the effect of mud and formation properties because these factors arc the same for the various size bits.

Jan 1, 1957

By B. L. Landrum, P. B. Crawford

Theoretical and potentiometric model studies have been made of the effect of non-uniform lateral permeabilities on pattern sweep efficiency and production capacity in waterflood and gas-cycling programs. It is shown that a diflerence in directional permeability by a factor of three may result in a sweep efficiency of only 43 per cent for a five-spot pattern or a sweep of either 79 or 38 per cent for a direct line-drive square pattern, depending on the direction of the line-drive flood. Changes in the pattern conductivity varied from about 0.8 to 1.34 over this same permeability variation, depending on the pattern used. It is suggested that measurements be made to determine the possible magnitude and extent of the directional permeability phenomenon early in the field developinent and certainly prior to the initiation of any fluid-injection progmm. INTRODUCTION Irregularities in reservoir sand properties long have been a major difficulty to anyone attempting to explicitly describe the field characteristics of oil production. In particular, it is well known that vertical and lateral permeabilities often differ appreciably; however, the existence of large regions with lateral permeabflity variation is not widely recognized. A number of years ago, extensive studies were conducted by the Secondary Recovery Research Labcratory of the Pennsylvania Grade Crude Oil Association, primarily on the Bradford field. Johnson and Hughes' reported a permeability trend in the northeast-southwest direction. They indicated that flow in the preferred direction may be 25 to 30 per cent greater in that direction than in the northwest-southeast direction. They also reported that similar effects may be found in other nearby fields. The origin of the permeability variation has been discussed by Griffith Hutchinson' described the results of labora- tory tests on limestone cores, pointing out that per-ferential directional permeabilities were significant in one-half of 10 formations studied and that the average permeability ratio was 16:1. Barfield, Jordan and Moore analyzed the fluid-injection displacement performance in the Spraberry and reported that the effective ratio of permeability parallel to the major axis to the permeability perpendicular to this axis was 144:l and that it inclined along an angle of about 30". To prevent the reduction of sweep efficiency which would normally result from flooding or cycling in such reservoirs, well spacing could be varied from the customary square to a diamond-shaped pattern. Johnson and Hughes' presented a method for determining the desired shape. Another method will be discussed in detail in the next section. It is the purpose of this paper to investigate quantitatively the effect of directional permeability upon the sweep efficiency and production capacity of the five-spot and line-drive well patterns. Information currently in the literature will be applied to this particular problem and augmented by a potentiometric model study. It is stressed that the effects herein discussed may or may not be of great importance because field data on this phenomenon are far too scant to form such an opinion. It is suggested that, if conditions similar to those found by Johnson and Hughes frequently exist (as may well be the case), more consideration cdrtainly should be given to this problem.

By W. E. Anderson, T. M. Brady

As part of a larger study to identify factors influencing the practical operating life of wire rope used on large draglines in surface coal mining, field trips to operating surface coal mines were made during late 1975. Wire rope performance information was obtained from personnel at 13 mine sites west of the Appalachians. Seventeen pieces of equipment, utilizing bucket sizes ranging from 30 to 220 cu yd (23 to 168 m), were documented. Draglines at large US surface coal mines can be represented as 120 machines having 60-cu yd (46-m3) buckets, moving 1.8 X 109 cu yd (1.4 x 109 m3) of overburden during 6650 hours of productive availability per year. Based on the limited field study, the calculated downtime resulting from rope-related causes averages 105.6 hours per year for each typical 60-cu yd (43-m3) dragline. The total loss in production from this source alone is thereby estimated at about 25 x 106 cu yd (19 x 106 m3) annually. Although study findings did not reveal anything about dragline rope life that wasn't known or practiced by one operator or another, most operators can expect improved rope life by periodic review of their practices and by adopting one or more life-improvement measures employed at other sites. Since rope productivity was found to vary by a factor of five among the sites studied, considerable improved average performance is possible. As little as 10% overall improvement would increase national productivity by 2 million cu yd (1.5 X 106 m3) of solid overburden removal. Associated savings in rope costs would be some $2 million annually, plus a large reduction of labor-related expenses. This report outlines preliminary findings which may prove useful to many operators in extending wire rope life. Some of these modifications or adjustments in maintenance/operating practices would not require capital investment. During the field survey, no company was found which had tried cost reductions by using presocketed dump ropes, or dump rope sheaves that opened like a snatch block, so these are suggested as possible improvements requiring modest capital input. Data Acquisition During the field visits, mine operators provided rope life information about their machines. Some of the rope life data consisted of gross averages; other data was in the form of detailed records, including rope construction and manufacturer, cutoff and resocketing periods, end-for-end switching, and downtime for rope change-out. Trends of average hoist rope life and average drag rope life determined from the field study are shown in [Fig. 1] as a function of bucket size. The three lines on the graph have slopes of 1, M, and 1/4. A comparison of the data shows that hoist ropes moved about twice as much material as drag ropes prior to retirement, although more than a two-to-one scatter within each category is evident. As expected, the larger machines with the larger buckets moved more total volume of material. The four pairs of solid symbols represent those data for which detailed rope life histories are presented in subsequent figures.

Jan 1, 1980

By E. Teghtsoonian, K. G. Davis

THE preparation of cobalt crystals offers problems: on cooling through 400°C a phase transformation takes place whereby the structure changes from face-centered cubic to the low temperature close-packed hexagonal form. There are a few references in the literature which describe the preparation of cobalt crystals for magnetic work1,&apos; where melt-solidification methods were used. Reasons will be given why such methods were found unsuitable for our purposes. The following techniques were tried: 1) Solid state methods. Any mechanical shaping of tensile specimens would lead to uncertainty with regard to residual strains. With this in mind, following Kaa, strain-anneal and grain growth techniques were extensively investigated. In no Case were useful single crystals obtained. The transformation boundaries, which are crystallographically similar to twin boundaries, are probably extremely stable and inhibit the grain growth. 2) Growth from the melt. Normal melt-solidification methods were tried, using recrystallised alumina crucibles, and also a osoft moldo technique in which cobalt rod was packed in alumina powder. Trouble was encountered with gas evolution on solidification of the melt, giving porosity. Some adhesion of cobalt to the alumina also took place. Only a small proportion of the runs gave single crystals. 3) Zone-refining. Much the best results have been obtained using an electron-beam floating zone refiner. The refiner, based on a design by Calverly et Al .5 had a single-turn tungsten filament. It was operated at 600 v with an emission current around 45 ma. Commercial cobalt rod 1/8 in. in diam was given one pass at a rate of zone travel normally 25 cm per hr, under a vacuum approximately 10-5mm of Hg. Over 50 pct of the runs gave long sections of single crystal. Crystals up to 2o Cm long with good uniformity of cross section and straightness have been grown in this way. Increase in the length of the molten zone resulted in higher single-crystal yields, but control of zone stability was reduced. Sub-boundaries in the zoned crystals were few, and Laue X-ray spots were sharp. The success of the method is believed to lie in two factors, namely i) the absence of crucible restraints during the transformation, and ii) extreme axiality of heat flow during cooling. The axes of the zoned crystals were clustered around the [ 1010] pole, the pole of the basal plane being at least 60 deg from the specimen axis. Crystals grown at lower rates of zone travel showed the same orientation range, Fig. 1. This orientation is similar to that for other hexagonal metals grown from the melt, which is a little surprising when the mode of formation of the hexagonal phase is considered. The preferred orientation is probably caused by anisotropy of heat conduction, i.e., that crystal which can most effectively conduct heat away from the transformation interface will be favored. Fig. 2 shows the area on a standard cubic stereo-gram in which there are no poles more than 60 deg from one of the four < 111> directions. This area

Jan 1, 1962

By E. E. Gardner, P. A. Schumann

A description of a new four-point probe configuration which permits measurement of epitaxial layer resistivity is given. An analytic solution to the potential distribution due to a point current source on a multilayered structure is briefly described. Typical solutions for this probe configuration are presented. Probe spacing, layer thickness, substrate resistivity, and substrate thickness enter into the calculation. Correction factors for typical cases are given. A brief description of the construction of a probe which can achieve a small spacing of 15 is presented. The prohe is constructed so that all points are adjustable by micrometers and the probe spacing and configuration can be easily altered. Measurements of layer resistivity with the four-point probe are compared with those taken with the three-Point probe and diode-capacitance techniques. TWO techniques of obtaining profiles of N/N+ epitaxial structures are given. The reproducihility of the probe spacing and resistivity measurement is discussed. The effects upon the resistivity measurement of errors in the measurement of the lager thickness, substrate resistil)itv, and substrate thickness are presented. SINCE its introduction by valdes&apos; in 1954, the four-point probe has been the most widely used tool for determining semiconductor resistivity. Its usefulness ranges from the evaluation of bulk semiconductor ingots to the characterization of impurity profiles in diffused structures. In general the four points, two current probes and two potential probes, are placed on one surface of the material being tested either in an in-line array or in a square array. Numerous correction factors1 8 have been worked out for these configurations which are dictated by the finite geometry of the sample being tested. One method of evaluating thin wafers has been proposed which has two probesg on each side of the wafer. Further modifications have added a fifth&apos;&apos; and a sixth" probe. One paper1&apos; has discussed the accuracy of the four-point probe and the precautions necessary in its use. With the exception of the method where two points are placed on opposite sides of the wafer, the four-point probe is restricted to evaluation of wafers with a homogeneous resistivity or to the case where an isolating junction exists between the substrate and the layer (epitaxial or diffused) being evaluated. Due to the relative resistivities and thickness, the resistance of the epitaxial layer is much greater than that of the substrate, and consequently a majority of the current flows through the substrate. The potential distribution at relatively large distances from the current sources is determined by the substrate resistance, and hence the AV/I value is a measure of the substrate resistivity and not that of the epitaxial-layer resistivity. In the immediate vicinity of a current source the potential distribution is determined by the layer resistivity among other factors. Consequently, if the potential probe is placed very close to the current source, then with appropriate correction factors it is possible to determine the layer resistivity. This was the theoretical basis for using two closely spaced probes on opposite sides of an epitaxial wafer. However, due to mechanical problems, it is desirable to place the four probes on the same side of the wafer. This paper discusses the potential distribution in

Jan 1, 1965

By L. Himmel, R. F. Mehl, C. E. Birchenall

The rates of self-diffusion of iron in artifically prepared wustites of various compositions have been determined using the decrease in surface activity technique. Similar measurements are reported for artificial magnetites of nearly stoichiometric composition and for natural hematite single crystals. These data, together with appropriate thermodynamic data derived from the present study or from the literature, are used to calculate the rates of oxidation of iron and its oxides, taking as a basis the theoretical rate equations developed by Wagner. The calculations are compared with experimental rate constant data for these same reactions and are shown to provide essential confirmation for the Wagner theory. For the most part, the results are also consistent with the previously proposed transport mechanisms in the oxides of iron. WHEN a metal is exposed to an oxidizing atmosphere at elevated temperatures, a superficial oxide layer is formed which then thickens according to some characteristic rate law. Provided that the oxide layer is dense and continuous and does not present any paths for gaseous diffusion, continued growth must inevitably involve the migration of the reactants—either the metal or oxygen or both—through the lattice of the solid oxide. This is true whether the reaction rate is controlled by the diffusion process itself or by a slow step in a reaction at one of the interfaces. If the overall rate is limited by diffusion, and if the concentrations or thermodynamic activities of the reactants at the boundaries of the oxide layer are independent of time, the familiar parabolic rate law is observed. Under these conditions, Wagner1 has shown that the rate constant may be expressed in terms of the mobilities of the reacting components and the appropriate concentration or activity gradients which are established across the growing oxide layer. In presenting the phenomenological basis for the theory, Wagner has emphasized the role played by lattice defects in diffusion processes in oxides. The essential validity of this theory has been confirmed by experiment for a number of simple systems including the growth of Cu2O on copper.&apos;-&apos; One of the objectives of the present study has been to extend the Wagner approach to the more complex process of the oxidation of iron and its oxides, and particularly to wustite, which is normally the major constituent of the oxide scales formed on iron at temperatures above approximately 570°C. For this purpose the rates of self-diffusion of iron in w?stite, magnetite, and hematite have been measured by tracer techniques and the necessary thermodynamic data have been obtained from equilibrium studies involving the oxides and their atmospheres. These data have subsequently been used to test the underlying assumptions of the Wagner theory as well as the detailed mechanism of the scaling of iron previously proposed by Davies, Simnad, and Birchenall.5 Lengthy treatments of diffusion and conduction phenomena in ionic crystals have been published." * The latest, by Jost,8 also summarizes much of the existing experimental data. In general, however, the oxides of iron have not been considered specifically and hence a brief review of the available

Jan 1, 1954

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By J. B. Newkirk

Results of a Debye-Scherrer X-ray investigation are given which show that the order-disorder transformation is a first-order or heterogeneous reaction in Cu-AU alloys with compositions near CuAu. Evidence was found for conventional tie-line segregation across a usual type of two-phase field separating the ordered and disordered fields in the Cu-Au equilibrium phase diagram. The horizontal and vertical widths of the two-phase fields are about 3 atomic pct and 20°C, respectively, at 43 and 54 atomic pct Au. No evidence for the existence of an ordered structure based on a stoichiometric composition of Cu3Au2 could be found. ALTHOUGH the modern theories relating the de-Agree of order of binary alloys to temperature and composition have met with considerable success, the nature of the transformation from the disordered state to the ordered state and vice versa has never been well understood. It has been assumed by some&apos; that this is a second-order transformation, that is, a homogeneous change of state. Others2 hold that the transformation is first-order and that the effects characteristic of heterogeneous phase transformation apply. Since this subject is discussed in detail in a recent paper,&apos; the arguments will not be repeated here. The present paper summarizes an experiment which was designed to distinguish between these two viewpoints for the case of Cu-Au alloys near the composition CuAu. The Cu-Au system is an important one because it furnishes prototype alloys, the behavior of which has formed the basis of much of the present-day order-disorder theory. It has recently been shown- hat in alloys near Cu3Au there is a temperature range within which the ordered and disordered states coexist in equilibrium and are distinguishable as separate phases. Therefore, the transformation must be first-order for these alloys. A similar demonstration for alloys near CuAu, however, has been lacking. Experimental Method Essentially the experiment consisted of equilibrating Cu-Au samples at various temperatures, quenching them in water to retain the high temperature states, and then examining them at room temperature for the coexistence of the ordered and disordered structures. The thermal gradient method of heat treatment- as used because it was important that all temperatures over the transformation range should be represented in the test. Briefly, this method consisted of holding a wire of the desired composition, sealed under vacuum in Pyrex, in a known temperature gradient for a long enough time to allow each part of the wire to assume the crystal structure characteristic of the temperature at which it was held. The temperature gradient was produced by inserting into an ordinary wire-wound cylindrical laboratory furnace, an 18 in. length of 1/8 in. ID ceramic tube which was heavily wrapped with asbestos. The furnace power was controlled by a Tag-liabue Celectray controller and a chromel-alumel thermocouple with the junction located on the heating elements. During the equilibrating treatment the widest variation of temperature within the gradient tube was approximately 4°C at the highest temperature. The temperature at various places within the tube was determined, before inserting

Jan 1, 1954

By D. H. Woodard

One of the principal uses of polarized light in metallurgy is to show the granular structure of metals by contrasting reflections. This use is confined largely to anisotropic metals, such as beryllium, tin, magnesium, and the like.1 Recently, Hone and Pearson2 have extended the use of polarized light to include the isotropic metal aluminum. This was made possible by the formation of an anodic film that was optically anisotropic and that had a fixed and reproducible structural relationship to the grains in the substrata. With their method, it was possible to indicate localized textures in annealed aluminum sheet. In the course of an investigation of plastic deformation at the National Bureau of Standards, it was found that the isotropic single phase alloy Monel could be made optically anisotropic by treatment with the usual Monel contrast etchant. Experiments soon showed that dif- , ferences in orientation could be detected easily. Previous investigations involving the use of polarized light have been restricted to annealed metals. In this paper it will be shown that inhomo-geneous plastic deformation which results in lattice bending and development of deformation bands, experienced by individual grains in polycrystalline Monel, is revealed in the microstruc-ture. This interpretation of the micro-structure was confirmed by a study of slip lines formed after prior plastic strain. Materials and Procedure The material used was Monel, the chemical composition of which was C—0.17 pet, Mn—1.28 pet, Fe—1.61 pet, S—0.009 pet, Si—0.17 pet, Cu— 30.70 pet, Ni—66.04 pet. The material was divided into 2 lots which were treated as follows: Lot A was heated at 1700°F for 3 hr to produce a fully annealed, coarse grained structure. Lot B was heated at 1400°F for 1 hr to produce a close approximation of a fully annealed structure without appreciable increase in the grain size of the original material. After each of these heat treatments the material was cooled in air. Samples for metallographic examination were cut from tensile and compression test specimens and were prepared by grinding on lead-tin laps, followed by electrolytic polishing, † Etching and the development of ridges were avoided by keeping the voltage above 3.8 and by preventing contamination of the polishing solution with water. Monel, when polished and treated with most etchants, is optically isotropic. However, when given a light etch for about 4 sec with the Monel contrast solution the surface of the metal becomes optically active. The microstructure when observed under crossed nicols* appears different from that viewed by ordinary light. This is shown by a comparison of micrographs made of the same area of a plastically deformed specimen using polarized light (Fig la) and white light (Fig 16). If Monel, which has been lightly treated with the contrast etchant, is slightly deformed by compression, rectangular figures are apparent over the specimen. However, within too short a period to be photographed, these rectangles become circular, probably because of surface tension effects within the etched film. The two observations,

Jan 1, 1950

By H. C. Gatos, J. T. A. Pollock, V. Sadagopan

PREVIOUS investigations on the effect of neutron irradiation on the superconducting properties of bulk transition metals indicated that little or no change occurred in poly crystalline disordered materials, particularly if cold-worked prior to irradiation. Only the superconducting properties of ordered intermetal-lic A15 compounds were found to be sensitive to irradiation, and the observed reduction in Tc and increased magnetic hysteresis or critical current densities were attributed to the introduction of flux pinning vacancy clusters and disorder in the lattice. Since the former would also be expected to be present after irradiation in disordered alloys, the general conclusion was that the disordering effect of the irradiation was the primary reason for the changes observed. The present note reports some unusual effects of neutron irradiation on cold worked Nb(Cb)-Ti-V alloys. Specimens with nominal composition as given in Table I were prepared by repeated arc melting, taking the usual precautions, and homogenized at 1000°C for 24 hr prior to a reduction of 15:l by cold rolling. Samples of size 1 by 1 by 25 mm were sliced from the rolled strips. The sarmples chosen for irradiating were sealed in a cadmium tube (wall thickness 1 mm) prior to exposure in a fast neutron flux of 3.7 x 1019 neutrons per sq cm in the swimming pool reactor of Union Carbide Corporation&apos;s Sterling Forest Reactor. During irradiation the temperature of the samples was maintained below 70°C. The irradiated samples were stored at room temperature for approximately 1 year allowing the radiation levels to reach a safe handling value. Tc measurements were made employing a self-inductance coil technique. Jc data at 4.2"Kwere obtained using a four lead resistivity method. The latter measurements were made at the Francis Bitter National Magnet Laboratory by setting the perpendicularly applied field and increasing the direct current through the sample until a potential of about 10-6 v was detected. Tc values for the nonirradiated samples are listed in Table I together with the change in Tc after irradiation. A decrease in Tc of 0.25 or 0.3"K was measured for three of the four samples, the exception being the Nb-30 at. pct V-20 at. pct Ti alloy which showed a decrease of 0.5K. Jc vs applied field data are plotted in Fig. 1 for the Nb-20 at. pct V-30 at. pct Ti alloy. These curves are typical of the four alloys and surprisingly indicate that a degradation occurred in all the samples after irradiation. Hc2 values, obtained by extrapolation to zero current, are 8 to 15 pct lower than those measured for the nonirradiated specimens. The reasons for the degradation of Tc and jc ob-served in the alloys on exposure to neutron irradiation are not immediately apparent. The temperature at which the samples were maintained during bombardment (<70°C) and stored (20°C) make it highly unlikely that any significant change in the dislocation density of the materials through thermally activated migration and annihilation would occur. The explanation must lie in the type of damage produced by the bombardment. McEvoy et a1. reported no change in superconduct-

Jan 1, 1970

By D. C. Jones

The term "coal-mine mechanization" is definable in several ways. In its general application it can mean the use of machines instead of manpower in each of the various mining activities necessary for the production of coal—so that under this definition a mine that uses mechanical coal cutters could be classed as a mechanized mine. Common usage, however, insists that a mechanized mine is one in which machines are used for the entire process of mining or extraction and transportation of the coal. For the purpose of this paper, then, the second definition of "coal-mine mechanization" will be used, and practices employed in mines where the greater part of the production is obtained through the use of mechanical loaders and conveyors will form the basis for this discussion. Physical Contact Hazards If we were to group all the hazards that accompany the use of mechanized equipment in a mine, the predominant class would be that which, for want of a better name, might be termed the "physical contact" hazards; that is, all the sources of danger that lead to accidents through physical contact of workmen with machines. A survey of accidents in a group of mechanized mines indicated that this class of hazards may be responsible for more than half the number of accidents in mechanized mining. For example, of 21 mining-machine accidents at one mine, 14 were of the physical contact type; of 14 loading-machine accidents at the same mine, 8 were the result of physical contact. Certain of these hazards are controllable through the use of guards— a guard over the cutting-machine bits when the machine is being trammed from place to place, or a chain or some similar locking device around the cutter chain, so that an accidental blow or push against the bit control will not cause the cutter chain to move. Other hazards, such as the possibility of a loader operator having his foot crushed by a crawler tread, or a brakeman being hit by a loader boom swung too far to one side while a car is being loaded, might be subject to control through the use of guard devices, but the reduction or elimination of all physical contact hazards by such methods does not appear feasible. Every accident of the physical contact type should he investigated to discover whether guards could have prevented it, but often the only way in which to combat these hazards will be through the awakened consciousness of each workman as to the danger that exists if he indulges in unsafe practices. A good approach to control of accidents in any mine is the establishment of a set of safety rules or operating rules. The intent of such rules is to provide guides far the workmen to follow in the operation of equipment. Frequently the workmen have no regard for such rules, and observance is obtained only through compulsion on the part of management. An interesting development in connection with-the formation of safety rules occurred during a training program for employees in the

Jan 1, 1947

By D. C. Jones

The term "coal-mine mechanization" is definable in several ways. In its general application it can mean the use of machines instead of manpower in each of the various mining activities necessary for the production of coal—so that under this definition a mine that uses mechanical coal cutters could be classed as a mechanized mine. Common usage, however, insists that a mechanized mine is one in which machines are used for the entire process of mining or extraction and transportation of the coal. For the purpose of this paper, then, the second definition of "coal-mine mechanization" will be used, and practices employed in mines where the greater part of the production is obtained through the use of mechanical loaders and conveyors will form the basis for this discussion. Physical Contact Hazards If we were to group all the hazards that accompany the use of mechanized equipment in a mine, the predominant class would be that which, for want of a better name, might be termed the "physical contact" hazards; that is, all the sources of danger that lead to accidents through physical contact of workmen with machines. A survey of accidents in a group of mechanized mines indicated that this class of hazards may be responsible for more than half the number of accidents in mechanized mining. For example, of 21 mining-machine accidents at one mine, 14 were of the physical contact type; of 14 loading-machine accidents at the same mine, 8 were the result of physical contact. Certain of these hazards are controllable through the use of guards— a guard over the cutting-machine bits when the machine is being trammed from place to place, or a chain or some similar locking device around the cutter chain, so that an accidental blow or push against the bit control will not cause the cutter chain to move. Other hazards, such as the possibility of a loader operator having his foot crushed by a crawler tread, or a brakeman being hit by a loader boom swung too far to one side while a car is being loaded, might be subject to control through the use of guard devices, but the reduction or elimination of all physical contact hazards by such methods does not appear feasible. Every accident of the physical contact type should he investigated to discover whether guards could have prevented it, but often the only way in which to combat these hazards will be through the awakened consciousness of each workman as to the danger that exists if he indulges in unsafe practices. A good approach to control of accidents in any mine is the establishment of a set of safety rules or operating rules. The intent of such rules is to provide guides far the workmen to follow in the operation of equipment. Frequently the workmen have no regard for such rules, and observance is obtained only through compulsion on the part of management. An interesting development in connection with-the formation of safety rules occurred during a training program for employees in the

Jan 1, 1947

By R. D. Pehlke, J. V. Gluck, R. L. Louvet

A study has been made of the effect of small additions of bismuth on the activity of zinc in dilute solution in molten tin. Free-energy interactions have previously been determined between zinc and various third elements where the solvents were molten bismuth or molten lead.&apos;-4 In both of these solvents, the activity of zinc exhibits a strong positive deviation from ideal behavior (at 550°C y° for zinc in lead is 11.4 and for zinc in bismuth is 3.0). The present work, using tin as the solvent, is an extension to a case where the positive deviation is considerably diminished (y°Zn at 550°C is 1.63). Several previous investigators have studied the Zn-Sn binary system; however, little data is available in the range below 0.1 mole fraction zinc.5= Previous high-temperature galvanic cell studies in the Sn-Zn-Bi ternary system included the determination by Gluck and Pehlke of interactions in the bismuth-rich corner1 and separate investigations of the central region by Oleari and Fioriani6 and by Ptak and Moser.7 Yokokowa et al.8 conducted Knudsen effusion studies in the central region; however, their experiments at 625°K were conducted somewhat below the present experimental temperature range. Their results indicated an increase in zinc activity with the addition of bismuth. The present series of experiments was conducted in galvanic cells represented as follows: Zn Zn++ in LiCI-KC1 eutectic Zn + Bi in Sn (pure reference (fused salt electrolyte) (molten alloy) standard) The experimental apparatus. a multi-electrode system employing alumina crucibles and contained in a Vycor tube under a helium atmosphere, has been described previously, as have been the experimental procedures, precautions, and the methods of data reduction.1-4,- The experimental measurements were made over the range from 450° to 650°C. Between thirty and forty measurements were made in each run. The linearity of the electromotive force vs temperature relations was verified by linear regression techniques. The correlation coefficients exceeded 0.99. The experimental results summarized in Table I include the interpolated electromotive force at 550°C and the temperature dependence of electromotive force. Only results from stable and consistent cells containing more than 0.025 mole fraction zinc are reported. Attempts to run cells at 0.01 or 0.02 mole fraction zinc were not satisfactory. This is attributed to the closeness of the free energies of formation of the chlorides of tin and zinc. Calculations employing Wagner and Werner&apos;s criteria for displacement reactions10 indicated that reduction of the zinc content to 0.01 mole fraction places the cell near the borderline concentration for a 1 pct error in measured potential. The compositions shown in Table I are the actual weighed-in amounts. Previous experience has indicated that compositional changes during the running of a stable cell are negligible.&apos; Over the range of compositions studied for the binary alloys, the activity coefficient of zinc was essentially constant indicating that Henry&apos;s law is followed to 0.05 mole fraction zinc. The temperature, OK, de-

Jan 1, 1969

By D. H. Polonis, M. B. Kasen

AN unusual thermal etching phenomenon has been observed on the surface of a Cu-Si alloy. The observations were made during studies of vacancy condensation pit formation which were reported in previous papers.1,2 Figs. 1 and 2 are photomicrographs of the surface of a Cu-4.8 pct Si alloy after heating in vacuo (3 x X mm Hg) to 525°C and subsequently holding at that temperature for 16 hr in an impure (air-contaminated) argon atmosphere. Under these conditions preferential removal of silicon from the matrix by oxidation results in a surface which is entirely a phase overlying an a plus y structure. The light areas of Fig. 1 are regions in which very little thermal etching has occurred, while the majority of the surface has experienced severe etching. Similar regions in Fig. 2 are seen as plateaus above contours produced by net transfer of material from the specimen surface. Twin boundaries are also visible in Fig. 2. The difference in matrix mi-crostructure between Figs. l and 2 reflects the par- ticular orientation of low-index planes with respect to the surface of observation. Thermal etching contours of this type have been studied in detail by Hondros and Moore Both of the photomicrographs show that one or more dark spots are located approximately at the center of every protected area; where two spots are in close proximity, the protected areas have merged. The microstructures indicate that the anomalous resistance to thermal etching is related to the presence of these spots. Williams and Hayfield have shown that local regions of unusually high oxidation resistance can be caused by a surface monolayer of atoms with a work function higher than that of the base material. The result is an inhibition of the rate of electron removal from the base material and a decrease in the oxidation rate. The source of the protected layer may be either surface diffusion from contaminants on the specimen surface or pipe diffusion of solute atoms followed by migration across the surface. In the latter case the driving force is a difference in chemical potential resulting in a Gibbs adsorption phenomenon. In the present case, chemical polishing of the specimen surface precluded contaminants of a strictly surface nature. Consequently, diffusion of impurity atoms from within the lattice appears to be the most tenable explanation of the observed phenomena. The authors propose that the structures of Figs. 1 and 2 reflect the diffusion of impurity atoms along extended dislocations within the individual a phase grains prior to surface oxidation. The central spots within the protected regions are seen as sites of dislocation emergence which have become locally decorated with oxide in the manner discussed in Ref. 1. Williams and Hayfield observed protected regions adjacent to the grain boundaries of iron-contaminated copper which they attributed to the segregation of iron to the grain boundaries coupled with high dif-fusivity along the complex dislocation array at such boundaries. No evidence of such grain boundary protection was observed in the Cu-Si alloy; this

Jan 1, 1964

By Kendall E. Born

Production of crude oil in Tennessee during 1940 was slightly more than 15,000 bbl., a decrease from 1939 of about 36,000 bbl. This sharp decline has been caused largely by curtailed activities in the shallow pools in Clay County, where approximately 3000 bbl. was marketed off the lease during the year as against more than 37,000 bbl. in 1939. The flashy production found in 1938 in the Celina area has been short-lived and the area is essentially abandoned. Failure to find steady production has been the major factor retarding developments in the northeastern Highland Rim area. The Mississippi lime production in Scott and Morgan Counties continued to show a steady decline. The Tennessee production by counties is shown in Table I. Table i.—Oil Production in Tennessee it1 1940 Production. Bbl. Number of County Wells Pumped 1939 1940 Scott............ 4 4,332 3.596 Morgan.......... I: 6,479 5,751 Fentress.......... 3 I,2XX 1,5xz Pickett........... 1 1.2XX Clay............. 8 37.200 3,XXX Developments There were 32 wells spudded in during 1940, four of which were drilling or only temporarily suspended on Dec. 31, 1940. Twenty-eight wells were completed during the year, four of which were commercial producers. The total footage drilled was 3I,214 ft. The more important wildcats are listed in Table 2; the distribution of 1940 oil and gas tests according to physiographic divisions is given in Table 3. Cumberland Platenu.—Thcre was one completion in the coal area of the state, a test that attempted to extend the Mississippi lime production in the Coon Hollow pool to the southeast in Morgan County. This test encountered only slight shows of oil in the producing horizons of the near-by Coon Hollow and Boone Camp pools. Some surface work was carried on by private interests during the year in Scott and Morgan Counties and two wells were spudded in early in 1941 The revival of interest in the Kentucky portion of the plateau will probably result in increased activity in this part of Tennessee during 1941. Several sizable blocks of acreage, some by major oil companies, are held in Scott, Morgan, and Cumberland Counties. Middle Tennessee.—The northeastern Highland Rim continued to be the most active area in the state with 20 completions, although this figure is about one third of the number drilled in 1939. Four oil wells, none with initial productions of more than I00 bbl., were completed in Clay, Fentress, and Pickett Counties. The producing horizons discovered in Pickett and Fentress Counties were in the "Sunny-brookJ&apos; pays of Trenton age. The Clay County producer was an old test drilled deeper in which oil was found at 671 ft. in the upper part of the Stones River group of limestones, a common pay in this area. All four wells were drilled in or close to old shallow production. Deeper testing into the Knox dolomite group in this area was not particularly encouraging, although one well in Fentress County encountered some saturation at 1860 to 1869 ft. in the upper

Jan 1, 1941