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By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By F. D. Weeks

The Salida smelting plant, owned by the Ohio & Colorado Smelting & Refining Co., is situated at an altitude of 7,000 ft., about 2 miles west of Salida, Colo., and 215 miles southwest of Denver. Salida is a division point on the Denver & Rio Grande R. R. where the narrow-gage line serving the San Juan region joins the through standard gage. This narrow-gage road also serves the coal and coke companies at Crested Butte and the lime quarries and mines at Monarch and Garfield, which are only 20 miles distant. These facts, together with the possibility of an appropriate site, doubtless influenced the builders to locate at this point. The smelting plant and yard occupy 80 acres of land on the northeast side of the Arkansas River. The slope of the ground is such as to permit of the ore being delivered by cars at a point 25 ft. above the feed floor; and in front of the furnaces there is a fall of 50 ft. for the slag dump. A recent purchase of river bottom has provided slag room for 20 years. As originally constructed, the plant consisted of four blast furnaces, 40 by 144 in. at tuyéres, two copper-matting furnaces, dust chamber, stack, power plant, blowers, sampling works, and one railroad trestle about 16 ft. from bed floor to rails. Later 12 hand roasters of excellent design were added and the practice of smelting leady matte in a copper-matting furnace was abandoned. Since the plant passed under the present management the equipment has been increased so that the following is a brief description of the same at this date: Two lead blast furnaces, 48 by 180 in. at tuyéres, 17 ft. 6 in. tuyéres to feed floor; four lead blast furnaces, 40 by 144 in. at tuyéres, 17 ft. 6 in. tuyéree to feed floor; two copper-matting furnaces, not used; blast-furnace flue, 900 ft.; area 245 sq. ft.; blast-furnace stack, 150 ft.; above furnace floor, 190 ft. When smelting a 500-ton charge per day, the gases approximate 63,700 cu. ft. per minute and travel at a speed of 260 ft. per minute. The slag is hauled by a 10-ton electric locomotive; the slag shells and settler refuse are elevated to a bin on the feed floor by an electric hoist. The matte is tapped in 1,600-lb. cakes and loaded into cars

Jan 1, 1916

By Felix Shay

THE Agua Fria mine is in eastern Honduras at Lat. 140° 06' N., Long. 86° 36' W. Danli, the seat of the local municipal government, is the nearest town. The property is approximately 44 miles east of Teguci-galpa, the terminus of a truck road from the Pacific coast. The mine lies at an altitude of 3300 ft. with surrounding elevations as high as 6000 feet. For 20 years the oxidized croppings of the Agua Fria vein had been worked intermittently when in 1927 an attempt was made to open the property. A shaft was sunk 300 ft. and considerable ore was blocked out, but before a mill could be installed financial difficulties arose and the mine reverted to the original owners. Erle P. Halliburton, of Los Angeles, purchased the property in 1934. At that time a careful consideration of all factors involved showed that air transport was the only practical method of moving the equipment and machinery necessary to commence production. The other alternative was by muleback, which required sectionalizing all equipment to a maximum load of 200 lb., and during the rainy season this type of freighting was subject to serious delays. It was decided to purchase a trimotor Ford powered by three Pratt and Whitney Wasp B motors developing 400 hp. each. There were several reasons for the choice: (1) this type of plane was available at a reasonable price, owing to its replacement by faster models on most of the airlines in the United States; (2) the ship was capable of carrying a pay load of 3000 lb. over the required distance; (3) since this airplane had been widely used there would be no difficulty in securing competent personnel or in purchasing spare parts. It was necessary to rebuild the plane for cargo service. The windows were removed and the fuselage was entirely covered. A hatch was cut in the top of the fuselage to receive heavy crane loads and pieces of freight that were too large or too long to go through the rear door. The seats were removed and the interior of the plane was lined with Duralumin sheets. A heavy-duty landing gear was installed and the floor was reinforced.

Jan 1, 1940

By George Otis Smith

The Secretary of the Interior in his recent report to the President has defined the new public-land policy, which is in fact "but a new application of an old policy." His words may be more acceptable on this subject of land classification than the repetition of phrases which have served some of us for several years. Secretary Lane says of the past: 1'Congress has always been most generous as to the disposition of the national lands.... There was land for all, and it was the government's glad function to distribute it and let those profit who could.... And this generous donor was not so petty as to discriminate between kinds of lands, the uses to which they could be put, or the purposes which those might have who got them. Land is land, save when it contains minerals; this was roughly the broad principle adopted. To classify was a task too difficult or not worth while. The lands would classify themselves when they arrived in individual ownership. And so the door was opened for monopoly and for fraud." Of the reaction and the evolution of a new policy, the Secretary con. tinues: • ' " A reaction was inevitable. If lands were to be withdrawn from public service, why might not the government do the withdrawing itself? The old philosophy that land is land' was evidently unfitted to a country where land is sometimes timber and sometimes coal; indeed, where land may mean water—water for tens of thousands of needy neighboring acres. For the lands of the West differ as men do, in character and condition and degree of usefulness. We had not recognized this fact when we said 'land is land.' Lands fitted for dry farming and lands that must forever lie unused without irrigation; lands that are worthless save for their timber; lands that are rich in grasses and lands that are poor in grasses; lands underlain with the non-precious minerals essential to industry or agriculture; lands that are invaluable for reservoir or dam sites— these varieties may be multiplied, and each new variety emphasizes the fact that each kind of land has its own future and affords its own opportunity for contributing to the nation's wealth.

Jan 1, 1915

By B. F. Bush

THE coal-fields of Missouri, situated hi the northern and western portion of the State, are distributed, in whole or in part, over 57 counties, embracing an area estimated by Mr. Broad-head to be practically 23,000 sq. miles, including small detached beds and outliers in St. Louis, St. Charles, Lincoln and Warren counties in the eastern part of the State. This area includes about 8,000 sq. miles of Upper or Barren Measures, 2,000 sq. miles of exposed Middle, and 12,420 sq. miles of exposed Lower Measures. In a general way, the Missouri coal-field is bounded on the east by an imaginary line entering the northern part of the State just east of the 92c1 Meridian and passing across the State in a southwesterly direction to a point on the Kansas-Missouri line a little below the southern boundary of Barton county. An important part of the field overlaps this line and extends down the northern side of the Missouri river, under¬lying the greater part of Randolph, Howard, Boone and Audrain counties. In all, 34 counties produced coal during the year 1903. Fig. 1 shows the position of the coal-fields in Missouri. GEOLOGICAL FEATURES. The Coal Measure formations, all of the Carboniferous age, rest unconformably upon the rocks of the sub-Carboniferous or Mississippian series, and, in some cases, upon the rocks of the Devonian and Silurian ages. From their outcrop on the eastern and southeastern borders of the field, the Measures dip west to northwest at the rate of 10 ft. per mile, reaching a maximum thickness estimated by

Jan 1, 1905

By M. A. Goudie

The deposits occur in a large salt basin of Middle Devonian age. The potash, the final deposit in the salt basin, results from several interrupted cycles of evaporation and dessication. The deposits are extensive, and, at first glance, relatively undisturbed. With more and more wells being drilled, it has now become evident that salt solution has played a large part in changing the original deposits, resulting in some cases in partial to complete removal of the potash and the underlying halite. The most dominant factor in the removal of salt by solution appears to have been tectonic movement and consequent faulting, probably of relatively minor dimensions but of major importance. Evidence which indicates the tilting of the evaporite basin to the north and northwest is shown by the changing pattern of the basin during succeeding eras of potash deposition. The potash minerals of most importance economically are sylvite and carnallite. Reserve calculations indicate that 6.4 billion tons of recoverable high grade potash in K2O equivalent exist in the basin. The Devonian salt basin, which contains the Saskatchewan potash deposits, extends from just east of the foothills in Alberta, north as far as the Peace River area, across Saskatchewan and into Manitoba as far east as Range 10 west of the First Meridian and south into Montana and North Dakota (Fig. 1). The basin is closed everywhere except to the northwest. The known potash deposits are confined almost entirely to the Province of Saskatchewan, with the exception of a small area in western Manitoba bordering the Saskatchewan boundary. The following discussion will concern only the Saskatchewan part of the basin. The evaporite series in the basin is defined as the Prairie Evaporite Formation of the Elk Point Group, of Middle Devonian age. Recent work done by potassium-argon dating methods has indicated an Upper Middle Devonian (Givetian) age of from 285 to 347 million years for the potash. The Elk Point Group consists in ascending order of the Ashern, Winnipegosis, and Prairie Evaporite Formations. The Ashern formation, with an average thickness of 30 ft, sometimes called the Third Red Bed, consists of dolomitic shales and shaly dolomites. The Winnipegosis, is a reef-type dolomite, usually with good porosity, and in many cases oil-staining, although to date no production has been obtained. The thickness varies from 50 to 250 ft. The Prairie Evaporite formation, varying from 0 to 600 ft in thickness, consists of halite with interbedded anhydrite and shale, with considerable amounts of potassium salts in the upper part of the formation. The potassium salts are chiefly chlorides, although very minor occurrences of sulfates have been re- ported. The anhydrite beds do not appear to be continuous, although generally one or two bands of anhydrite underlie the lowest potash zone and are used as marker horizons. The shale occurs as seams interbedded with the salts, as large irregular inclusions in the salts and as very fine particles in intimate mixture with the salts. The Prairie Evaporite Formation is overlain by the Second Red Bed member, the Dawson Bay Formation and the First Red Bed Member of the Manitoba Group, listed in ascending order. The Red Beds are shales which vary in color from red to green, maroon, grey, grey-black, and reddish purples. They serve as marker horizons for coring the potash. The Second Red Bed averages 14 ft in thickness, the First Red Bed 35 ft. The Dawson Bay Formation, which everywhere overlies the First Red Bed and the Prairie Evaporite Formation in the area under discussion, is a reef type of carbonate, in some places limestone, in others limestone and dolomite, with vugular to pinpoint porosity averaging 130 ft in thickness. In some parts of the area, it has a salt section near the top of the formation, usually with interbedded shales and limestones. In other parts of the area, it is waterbearing and the salt is absent. Detailed mapping has indicated that the areas in which the Dawson Bay is water-bearing are areas which have been disturbed by faulting. Where the Dawson Bay is salt-bearing, the porosity has been plugged by salt. The total thickness of the salt varies from between 600 to 700 ft in the center of the basin to zero at the northern edge of the basin (Fig. 2).* The salt-free area in the center of the Province is believed to have resulted from removal of salt by solution. Evidence from several wells suggests that salt removal has been a continuing process from the time of deposition to the present day. One well drilled between the Quill Lakes for potash information encountered

Jan 1, 1961

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-'. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.' The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By A. S. Appleton, M. B. Bever, G. E. Dieter

A gold-silver alloy was deformed by explosive loading at shock pressures up to 510 kbars. The stored energy and hardness increased over the whole range of pressures; the largest rates of increase were observed between 120 and 150 kbars. In this range, markings rkavacteristic of defornation twins first appeared; higher pressures produced markings in all grains. These effects are compared with those of conventional deformation processes and are discussed in relation to probable structural changes. In recent years, increasing efforts have been devoted to the investigation of the effects produced in metals by the passage of high-intensity shock waves of explosive origin. By properly utilizing the energy released by the detonation of a high explosive, it is possible to generate pressure pulses of the order of 500 kbars and higher. (One kbar equals l0 9 dynes per sq cm or approximately 1000 atm.) The passage of a shock wave through a metal occurs at pressures which are very much greater than the yield strength. As the shock front passes a point in the metal, the pressure rises almost instantaneously, and continues to act at the point for a few microseconds. Thus, metals subjected to explosive shock loading experience a nearly instantaneous increase in pressure, and a subsequent release of pressure, which is almost as rapid. Under these conditions mechanical twinning and shear transformations occur readily. smith1 has investigated the metallurgical changes in copper and iron resulting from exposure to explosive shock waves. He found an appreciable increase in hardness in both metals. In copper, a hardness greater than that resulting from 95 pct reduction in thickness by rolling was obtained, yet in the explosive deformation, the thickness of the specimen decreased only a few percent. After explosive loading, the micro-structure of copper showed markings characteristic of mechanical twins. The amount of stored energy resulting from explosive loading is of interest. Measurements of the stored energy of cold work as a function of strain, temperature, strain rate, and composition have been made with gold-silyer alloys deforyed by rolling, orthogonal cutting,3 drilling,4 filing, wire drawing, and torsion. The investigation reported here was also carried out with a gold-silver alloy and its results can be compared with those for the deformation of this alloy by more conventional methods. EXPERIMENTAL PROCEDURES An alloy containing 82.6 wt pct Au and 17.4 pct Ag was purchased in several batches from Handy and Harman Co., New York, as annealed rod 1/4 in. dim. The rod was cold-rolled to a sheet approximately

Jan 1, 1962

C. W. GENNET, JR.,* Chicago, 111. (written discussion?).-Since the Lehigh Valley accident, transverse fissures have become a source of constant anxiety to railroad officials, because such defects, only infrequently detected by the trackmen, may appear under a moving train entirely without warning. The number of actual accidents resulting from rails containing fissures is no doubt a small proportion of the total, but the serious losses that have been directly attributable to fissures, coupled with the continual possibility of repetition, creates an alarming situation which demands a full investigation of the cause of fissures; apart from other types of rail failures. Mr. Howard's position gives him a field for action and an opportunity for laboratory examination and research that are unsurpassed, and the results. of his investigations must be received with the utmost attention and respect. His admirable paper, summarizing his previously published studies and analyses of the transverse fissure problem, constitutes a convincing treatment of the subject chiefly from the standpoint of stress and strain to which rails are subjected. The intricacies of the problem are so great that seemingly any theory advanced for the cause of fissures may be attacked from some angle; and although Mr. Howard's deductions are logical in the direction followed, it is apparently necessary for considerable work to be done along other lines before his theories can be fully accepted. It is generally conceded that fissures, whether fundamentally clue to fatigue or something else, are of a progressive character, their ultimate size' being the result of growth from an originating nucleus or point of rupture. Abundant proof of this lies in the variable sizes of the fissures found, and there can be no doubt that their development or growth is the result of the strains to which rails are subjected in the track. Obviously, therefore, the most important factor in investigating the cause for fissures lies in determining the conditions that exist at the point or

Jan 4, 1918

By Felix B. Shay

THE Agua Fria mine is in eastern Honduras at Lat. 140° 06' N., Long. 86° 36’ W. Danli, the seat of the local municipal government, is the nearest town. The property is approximately 44 miles east of Tegucigalpa, the terminus of a truck road from the Pacific coast. The mine lies at an altitude of 3300 ft. with surrounding elevations as high as 6000 feet. For 20 years the oxidized croppings of the Agua Fria vein had been worked intermittently when in 1927 an attempt was made to open the property. A shaft was sunk 300 ft. and considerable ore was blocked out, but before a mill could be installed financial difficulties arose and the mine reverted to the original owners. Erle P. Halliburton, of Los Angeles, purchased the property in 1934. At that time a careful consideration of all factors involved showed that air transport was the only practical method of moving the equipment and machinery necessary to commence production. The other alternative was by muleback, which required sectionalizing all equipment to a maximum load of 200 lb., and during the rainy season this type of freighting was subject to serious delays. It was decided to purchase a trimotor Ford powered by three Pratt and Whitney Wasp B motors developing 400 hp. each. There were several reasons for the choice: (1) this type of plane was available at a reasonable price, owing to its replacement by faster models on most of the airlines in the United States; (2) the ship was capable of carrying a pay load of 3000 lb. over the required distance; (3) since this airplane had been widely used there would be no difficulty in securing competent personnel or in purchasing spare parts. It was necessary to rebuild the plane for cargo service. The windows were removed and the fuselage was entirely covered. A hatch was cut in the top of the fuselage to receive heavy crane loads and pieces of freight that were too large or too long to go through the rear door. The seats were removed and the interior of the plane was lined with Duralumin sheets. A heavy-duty landing gear was installed and the floor was reinforced. The nearest site for an airport was two miles north of the mine. The necessary grading was done by a small track-type tractor with a wheeled grader, which was brought in overland. Six weeks was required for bring-

Jan 1, 1940

By J. C. Bayles

It is seldom the privilege of one who contributes to the Transactions of a technical society, to describe a new industry in which, by processes employed for the first time, are attained results of conspicuous value. There are but few such patches of virgin soil worth the tilling, within the area circumscribed by the industries which have experienced a regular and uniform development. New and startling methods in production are often announced as about to be introduced; but, as a rule, they take their place among the " large desires with most uncertain issues," or give new significance to the historic words of an eminent statesman concerning " the bright beginnings and the bitter end of a halcyon and vociferous proceeding." In this paper I shall have the pleasure of briefly describing a new industry which has been established without announcement or proclamation — the manufacture of serviceable pressure pipes of great strength, from strips of steel or iron wound spirally, heated only along the overlapping edges, welded by hammering and finished into tubes of uniform diameter, and of such length as mag be found convenient in handling and transportation. As such tubes are now manufactured on a considerable scale, in a range of sizes which will soon include everything between 4 inches and 30 inches, and as much larger as may be needed, both process and product are likely to be of interest to engineers in all departments of professional work. The raw material of the industry is the ordinary sheet-iron or steel of commerce, of such lengths and widths as it is convenient to roll. The range of the ganges of the metal which can be employed has riot yet been determined. The lightest metal thus far successfully made into pipe is No. 29 iron, and the heaviest a steel gauging somewhere between 12 and 14. Heavier machines are now building which will bend steel .165 of an inch in thickness, or No. 8 of' the Birmingham gauge. Probably No. 20 or No. 22 will be the lightest used in making commercial pipes; hut the experiment with No. 29 was interesting as showing the readiness with which the flame can be controlled. To get a welding heat with such thin

Jan 1, 1888

It is always the case with heavy and cheap materials that the area within which they can be economically used depends upon the cost of transportation, and in those days of poor roads and no mechanical means of haulage on them, coal could only be moved a few miles from the mine by any other means than water. The need of better means of transport to the areas west of the mountains had been urged by Washington and many other leaders, but the first turnpike over the Alleghenies only reached the Ohio River at Wheeling, W. Va. in 1818. The James River and Kanawha road reached the Ohio in 1831, that from Winchester, Va. to Parkersburg in 1838, and the road through the Cumberland Gap was completed in 1797. None of these affected the coal industry excepting indirectly by building up some of the river towns which coal could reach. The inadequacy of roads alone to carry the traffic of the rapidly growing interior communities was demonstrated only a few years after the National Pike was completed, and in the early 1820's several of the states embarked upon the construction of a canal system, which had been under discussion for some years. The Erie Canal was opened in 1825 from Lake Erie to the Hudson River through New York; Pennsylvania, Virginia and Maryland had already started similar projects designed to bring traffic to their principal cities from the interior. The Pennsylvania Canal was started from Columbia, as a railroad extended from Philadelphia to that point, and it followed the Susquehanna and Juniata Rivers to Hollidaysburg; thence to Johnstown, a distance of 36 miles, where it consisted of partly railroad and partly inclined planes, the boats being hauled up, and lowered down the planes; from Johnstown the canal followed the Conemaugh, Kiskiminitas and Allegheny Rivers to Pittsburgh, 104 miles. Boats first reached Pittsburgh by this route in 1834. The Chesapeake and Potomac Canal followed the Potomac River from a point above Alexandria above the falls, to Cumberland. This canal was chartered in the eighteenth century and a portion of it was used by traffic in 1800. It was too small to be of much use and was abandoned, and later after many legal and financial vicissitudes was completed to Cumberland, traffic from there starting late in 1850. This date, however, was long after the Baltimore and Ohio Railroad had been completed to

Jan 1, 1942

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946

By A. Lee Barrett

THE Maintenance Committee of the Coal Division of the American Institute of Mining and Metallurgical Engineers is presenting as a part of this report the second of a series of maintenance cost comparisons. The committee's purpose is to assemble maintenance costs on all equipment connected with mechanical operations at the face of coal mining and to arrange these costs by districts so that comparisons can be made between districts and within districts. The committee, this year, sent 35 questionnaires to representative coal companies who either reported last year or had advised specifically of the inability to report to last year's questionnaire primarily because of limited time. The response to the questionnaire this year was not as good as last year, only 20 of the 35 selected companies returning a completed questionnaire. This year's data has been .compiled and combined with last year's data to present a comparison of the 1945 and 1946 costs of loading machines, shortwall cutting machines, universal cutting machines, service locomotives, shuttle cars, and mine cars. The same tabulation by districts is used as was used for 1945. As was indicated by last year's report there is considerable variation in the maintenance cost of mining machinery in the various coal mining districts and due to this high variability it was not felt practical to attempt to Arrive at weighted averages. Consequently, all average figures used in this report are straight averages. An analysis was made of companies reporting both this year and last year in an attempt to determine the trend in maintenance costs for different classes of equipment. Ten representative companies are used in this computation. Table I shows the average cost for 1945 and 1946. It is felt that the negative trend in the maintenance cost of universal cutting machines probably represents the effect of the purchase of a relatively large number o new machines in 1946 with little maintenance cost appearing during the first yeas of operation. The grand total figure indicates an upward trend amounting to plus 18.7 pct. However, this figure is viewer with some suspicion because of the effect of the universal cutters decreasing maintenance cost and it is concluded that direct application of percentage increase should be made to types of equipment. In Table 2 covering maintenance costs of various types of mining equipment for 1945 and 1946 the results, obtained in Table I indicating trends were applied to those

Jan 1, 1948

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers'-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,' reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By R. Wang, N. J. Grant, B. C. Giessen

By crystallographic and X-ray methods, the existence and isonzorphism of Ti3Rh5 and Hf3Rhs were confirmed. Both phases are of the orthorhombic Ge3Rh5 type; lattice parameters and refined positional parameters are given. The structure is related both to the filled-up NiAs-B8 and Cu-AI types. An analogous phase with zirconium does not exist; the effect of ternary substitutions for titanium ad hafnium suggests a size factor limit to be active. A recent survey of phase diagrams of the T4 metals titanium, zirconium, and hafnium with the T, noble metals rhodium and iridium indicated the existence of the A3B5 phases Ti3Rhs, ZrsRhs, and HfsRhs. Ti3Rhs and Hf3Rh5 were found to be isostructural, based on the line-rich powder patterns which had not been analyzed. Zr3Rh5 was considered to have a substructure of the NbRu type (orthorhombically distorted B2-CsCl type).&apos; Because, in combinations with other transition metals, hafnium and zirconium are generally more likely to form isostructural phases than hafnium and titanium (with the significant exception of the Ti2Ni-"E93" type phases based on T4 metals2), the reversal of this relation for the A3B5 phases was of interest. As shown in the following, the nonexistence of Zr3Rhs has been established, the structures of Ti3Rh5 and Hf3Rh5 have been worked out, and crystal chemical relationships and stability criteria are reported. EXPERIMENTAL METHODS AND RESULTS Alloy Preparation and Phase Diagram Work. Alloys were prepared from high-purity (99.99+ pct) elements by arc-meltin3,4.Heat-treated alloys were annealed in a vacuum of 3 x X torr for 24 hr at 1300DC. Metal-lographic samples were etched electrolytically in concentrated HCl with 5 v ac for 5 min.3 X-ray diffraction powder patterns were taken on a GE XRD-5 dif-fractometer with Cum radiation at low scanning rates (0.2 deg per min for 28). It was confirmed that Ti3Rhs and Hf3Rh5 have similar diffraction patterns, and that an alloy with the composition Zr3Rhs has a different pattern. Six Zr-Fh alloys with 59 to 69 at. pct Rh were therefore prepared and investigated in the as-cast state by X-ray diffraction and metallography. Alloys at 59 and 61 at. pct Rh were found to be a single phase, with the distorted B2-CsC1 type structure typical for the off-stoichio- metric region of the phase (Zr,-,Rh,)Rh. This phase forms a eutectic with ZrRhs at about 66 at. pct Rh: accordingly, alloys between 61 and 69 pct at. pct Rh consisted of two phases. There is no evidence for the existence of Zr3Rh5. Based on the results in Rafs. 1 and 5, on the present work on Zr-Rh, and on several additional alloys investigated, the portions between the AB and AB3 stoi-chiometry for Ti-Rh, Zr-Rh, and Hf-Rh are as follows: Further, several ternary alloys near Ti3Rhs and Hf,Rhs were prepared in which it was attempted to replace titanium and hafnium partly by zirconium, niobium, tantalum, and germanium. The results will be discussed in a later section. Structure Determination of Ti3Rh5. Since Ti3Rh5 and Hf3Rh5 are isostructural, the following discussion will largely deal with the former. Although the powder pattern of TisRhs is complex, as found previously,1 it could be indexed by comparison with other structures of A3Bs stoichiometry. Ti3Rh5 was found to be isostructural with Ge3Rh5, whose orthorhombic structure had been elucidated by Geller.9 As both the sizes and atomic numbers of germanium and titanium are comparable, the unit cell volume and the peak intensities could be expected to be similar; however, significant differences exist in the atomic positions, as will be shown. All lines in the powder patterns of Ti3Rh5 and Hf3Rhj could be indexed with primitive orthorhombic unit cells with the lattice constants: The fractional errors are 10 The low-angle portion of the indexed powder pattern of Ti3Rh with sin2 8 < 0.30 is listed in Table I. The extinction laws Okl only with k = 2n and hOl only with h - 2n are compatible with the space group Pbo2 and the more symmetrical space group Phnm of Ge3Rh5. Finally, the positional parameters of Ti3Rh5 and HfsRhs were refined under the assumption that titanium and hafnium occupy the germanium positions in Ge3Rh5. Integrated intensities were obtained from the diffraction patterns by planimetry. Intensities of overlapping reflections were separated by an iteration process incorporated into the least-squares positional refinement program according to a method described previously. The intensities of Ge3Rh5 were used in the first separation cycle, while the atomic parameters of Ge3Rh5 were used as starting values in the first refinement cycle. Absorption due to specimen

Jan 1, 1970

At the University Club, New York, Jan. 23, Chairman George E. Hale and other officers of the National Research Council, gave a dinner to officers of the national engineering and other societies. About thirty persons were present, including officers of the National Research Council, the four Founder Societies, American Society for Testing Materials, Society of Automotive Engineers, Inc., Illuminating Engineering Society, United Engineering Society, and Engineering Foundation. Letters were received from the Western Society of Engineers, which also had been invited. Gano Dunn, vice-chairman of National Research Council, was toastmaster. The proposed permanent organization of the National Research Council and possible methods of connection with the national engineering societies, either directly or through Engineering Foundation, were outlined. It was suggested that not only the four Founder Societies be represented in the Engineering Division of National Research Council, but also that the other national engineering societies be admitted to membership. It was proposed that the Engineering Division should have a chairman who should be an engineer of wide reputation and of the highest professional attainments who should devote his whole time to the establishment and development of the Division. Methods of organizing industrial research were discussed. At a subsequent meeting of the National Research Council, an invitation was issued to each of the national societies to form a research committee encouraging that committee to become active in the promotion of research within its respective field. Due recognition is to be given each committee in the general organization of the National Research Council. Dr. H. M. Howe, in a very interesting and comprehensive address, told of much important work that had been clone by the various sections of the Research Council, as that of mechanical engineering in developing the often rather nebulous devices for helping win the war and putting them in such form that they could be of direct use to the military service. The section on metallurgy, till lately under Bradley Stoughton and now under G. H. Clevenger, did much valuable work in the improvement of helmets and body armor and made very extensive ballistic tests with refractory steels for this purpose. Important work was done in investigating the fatigue of metals and results of great moment were achieved. The committee on ferro-alloys, under J. E. Johnson, Jr., did important work in effecting economy of manganese in steel manufacture with a view to reducing the necessity for importation of manganese ore, thus releasing ships for other purposes. , The section on electric welding has accomplished valuable results in the development of electric welding for ships, a new branch of industry of very great promise.

Jan 3, 1919