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By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.' Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.' Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By Lawrence K. Jetter, Robert F. Mehl

SOME advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory.? Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selected for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatometric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system-a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation ;2,3,4 there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type-the ideal case which Becker5 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1942

By R. C. Temps, G. E. Aiken

Compania de Acero del Pacifico, S.A., the sole Chilean steel producer, is adding to the expanding Chilean economy with development of the El Algarrobo mine. Expected to go on stream early in 1962, Algarrobo is a conventional open pit mine that will include facilities for ore extraction, crushing and screening, rail transport to the harbor at Huasco, modern ship-loading equipment and maintenance shops. CAP anticipates producing 1.38 mil- lion tons annually of high-grade ore for national and world market consumption. Chilean and North American management and engineering teams combined more than a decade ago in the financing and building of CAP'S Huachipato integrated steel plant. A similar performance is being achieved in northern Chile near the town of Vallenar with the opening of a 50-year supply of iron ore from the Algarrobo deposit. This successful intra-American undertaking deserves special mention in these times when some U.S. foreign assistance programs must be defended, particularly with respect to Latin America. North American financial participation in Algarrobo, through the Export-Import Bank of Washington, represents the greatest portion of the $24 million being invested.

Jan 3, 1962

By Boyd Guthrie, J. D. Lankford

A progress report on the oil-shale and shale-oil processing research program at the U. s. Bureau of Mines Oil-Shale Demonstration Plant. Legislation providing for the program and aims are briefly noted. The remoteness and rugged nature of the terrain at the plant site are important factors in construction and operations. Large-scale units now in operation are the crushing plant and two 40-ton N-T-U retorts. These are described in detail. Under construction are several retorting pilot plants and a 200 bbl per day refinery. The refineiy incorporates several types of thermal operation, three-stage low-temperature acid treating, doctor sweetening and rerunning. Data are presented on typical N-T-U retort runs. Yields of 90 to loo pct of assay are realized on 30 gal to the ton shale with a retort cycle time of 18 hr. Data also are presented showing a comparison of a Mid-Continent petroleum and N-T-U shale oil. This comparison indicates that shale oil has a high pour point, low API gravity, and contains about 0.8 pct sulphur and 2 pct nitrogen. The naphtha fraction contains 3 pct tar acids, 9 pct tar bases and jo pct olefins. The problems involved in refining shale oil into usable products are discussed in detail. Introduction The Bureau of Mines oil-shale program now under way at Rifle, Colo., was begun in July 1944 under the provisions of the Synthetic Liquid Fuels Act, which was passed in the spring of that year under the sponsorship of Senator Joseph C. O'Ma-honey of Wyoming and Congressman Jennings Randolph of West Virginia, aided by Michael W. Straus, former Assistant Secretary of the Interior, and others. The oil-shale plant is only a part of the Office of Synthetic Liquid Fuels, Bureau of Mines, which has under way projects to develop synthetic liquid fuels from coal and other solid materials at Pittsburgh and Bruceton, Pa., Morgantown, W. Va., Louisiana, Mo., as well as the Petroleum and Oil-Shale Experiment Station at Laramie, Wyo., and the oil-shale demonstration plant at Rifle. The oil-shale program is entirely experimental. It is not intended that oil will be produced in great quantities. Production will be limited to the volume obtained from plant-scale experimental operations, which will be kept to the minimum size needed to develop techniques and processes and to demonstrate costs. After the passage of the enabling act in the summer of 1944 a survey of the oil-shale resources of the Nation was made to determine the most suitable general area in which to establish the demonstration plant. The most suitable area was found to be in the Rifle-De Bequearea in Garfield County, western Colorado. Bureau of Mines field parties covered this entire area thoroughly

Jan 1, 1949

By F. E. Bachman

Although it has been apparent to me for a long time that too great weight was currently given to the silicon-contents of foundry-iron, and that the theory of the control by silicon of the carbon-contents of cast-iron is unsound, or that, at best, the influence of silicon is too small to be of much practical value as a guide in foundry-work, it never seemed to me desirable to enter the lists against either the " silicon-fad " or the theory, for the reason that I had neither the time nor the facilities to prove my position, nor any better theory to offer. But since Mr. Summers has taken the step, it seems but right that I should give such facts as are at hand in support of his contention. At the same time I do not think these are enough to prove the case if the contrary proposition were not itself, as it seems to me, based on insufficient evidence. Both Keep's and Turner's conclusions seem to be drawn from irons carrying less than the normal amount of carbon; Turner's " base " being, moreover, a steel rather than a pig-iron, and both the white base and the ferro-silicon of Keep being so low in carbon that compounds of them would not give a material approaching the carbon-contents of a normal casting, and having, therefore, little value as showing the effects of silicon on foundry-irons, even if his samples were treated under the same conditions as those to which pig-metal is subjected in making castings.

Jan 1, 1899

By Albert J. Phillips

IT is a privilege and a pleasure to deliver this, the Twenty-sixth Annual Institute of Metals Division Lecture. Eleven years ago C. A. Edwards addressed this audience on the subject "Gases in Metals." In spite of this relatively recent presentation, I propose to, present to you some quantitative considerations of industrial significance on the separation of gases from molten metals because recent observations and measurements, presented in the literature, have made it possible to evaluate mathematically the gases or gas-forming elements and to develop an understanding of the mechanism of gas separation that should permit, in many cases, the control of this baffling phenomenon. DEFINITIONS Before becoming involved in the subject it seems desirable, for the sake of clarity, to state certain definitions and axioms: I. We are dealing only with gases that separate from the molten metal either during cooling or in the transition from liquid to solid. Gases injected by the liquid stream and trapped in the solidified metal, or those forced into the solidifying metal from the mold due to either thermal or cher4ical effects are not considered. Neither are we concerned with the separation of gases within the metal after solidification is complete for the data on this subject are at least complete enough to permit the practicing metallurgist to satisfactorily control the phenomenon. 2. Only where there is a decrease in solubility or a change in equilibrium of either a gaseous element or an element that reacts to form a gaseous compound, can there be a separation of a gaseous phase from the liquid or solidifying metal. 3. The amount of gas separating from the liquid during solidification can be computed directly from the amount of the element contained in the liquid when freezing commences less the amount of the element found in the solid either as a separate solid phase or in solid solution. 4. There can be no separation of gas bubbles unless the told pressure of the gases in the liquid meld exceeds atmospheric pressure plus the hydrostatic pressure of ' the liquid metal head. (In addition, pres- sure resulting from surface tension in- creases the total pressure requirement for initial gas separation. Probably the remarkable differences in appearance caused by different gases in the same host metal are influenced greatly by the rate of diffusion of the gas in the liquid metal balancing the decrease in pressure as the gas bubble size increases and the surface tension effect decreases. Thus hydrogen with its high diffusion rate in liquid copper separates in the form of relatively coarse cavities for a given rate of heat extraction.) 5. Gas separation can take place at less than atmospheric pressure in the voids created by the shrinkage from liquid to solid, but since the voids are not caused by the gas the presence of gas in the voids is of importance only where it

Jan 1, 1947

By Waldemar Lindgren

No one would maintain that all ore deposits or all deposits of useful minerals have been formed by the same processes. Generally they have originated by special processes of concentration but these may be of many different kinds. Some deposits have their origin in chemical or biochemical processes of concentration in rivers, lakes or seas, others developed on land by means of chemical reactions of surface waters on various forms of rocks. Certain insoluble substances remained behind; others were dissolved and precipitated in favorable places. This action proceeded in the realm of the oxidizing surface waters or in the deeper zones to which the waters from the surface could find their way. Examples of the latter kind may be found in the extensive copper and vanadium deposits of some sedimentary beds or in the lead and zinc deposits of certain broad limestone strata. In these instances the evidence for any other mode of origin would seem to be very weak indeed.' Nor does it seem possible to deny that circulating waters may form deposits of the more common metals along fissures after having dissolved many constituents from paths traversed. Another very large class has been formed by magnetic processes of concentration. The last 40 years have been a period of intense activity in the investigation and description of a vast number of deposits; all modern methods have been employed and the result is an accumulation of data, difficult or impossible to master. It has been a period similar to that in petrography. The generalizations, the able deductions, have lagged behind. Evidently several geologists have become weary of this "infinite detail" and a mistrust of the microscope seems to have arisen. Although this feeling of being swamped in microscopic detail is a painful experience, nevertheless only through the detail in combination with the large features, and only by utilizing all the related sciences shall we

Jan 1, 1927

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By Henry Lloyd Smyth, J. Ralph Finlay

The most important area of the so-called Keewatin rocks of northern Minnesota is that which runs westerly from Lake Saganaga, near the national boundary, and finally disappears beneath the drift (or has not been farther traced), in the neighborhood of Vermilion Lake. With this belt we have a general acquaintance, extending back some four years. During the past year we have had the opportunity of studying in considerable detail a small part of it, embracing an area of about 12 square miles on the south and east shores of Vermilion Lake. In this paper we desire to record our observations and conclusions, which seem to us important. II.—Literature. Outside the Minnesota Geological Survey, the list of the investigators who have studied the geology of the Vermilion Lake area is not long. Whittlesey, in 1876,* mentioned the occurrence, in the area about Vermilion Lake, of rocks resembling the Canadian Laurentian. Chester,? in 1884, described the iron-ore at Vermilion Lake as occurring in connection with jasper and quartzite, intimately bedded with the country-rock, chiefly sericite schist, and standing in a nearly vertical attitude. The Vermilion iron-bearing rocks, and those of the Mesabi range, he says, are of the same age.

Jan 1, 1896

By W. H. Emmons

In 1922 Morey made a series of experiments in which he observed the cooling of a molten system containing H2O, 9.1 per cent; K2O, 17.3 per cent and SiO2, 73.6 per cent. This system was confined in a bomb; it was fluid at 500° C. and exerted no vapor pressure. In cooling to 420° C. a large part of it crystallized and at that temperature much of the water had separated from the crystals and remained as steam, which built up a pressure of 4998 lb. per sq. in., a force sufficient to lift nearly one mile of granite.' If granite, cooling at 600°, expels vapor in the process of crystallization it is reasonable to suppose that a considerably greater vapor pressure would result, and it is thought that the vapor expelled from crystallizing granitic batholiths probably has a pressure sufficient to lift two or three miles of granite. This vapor, collecting near the tops of cupolas of batholiths, is believed to exert sufficient pressure to fracture the hoods and roofs of batholiths above the cupolas. If that is true, one would expect to find that the fracture systems above cupolas are arranged in patterns that depend in part on the shapes of the cupolas. The mechanics of the situation seem to require that conical cupolas should have radial fracture patterns, that bluntly rounded cupolas should have fracture systems that are either irregular or rudely conjugated in plan, and that elongated stocks or cupolas should have fracture systems in which the fractu'res lie nearly parallel to the direction of the elongation of the cupolas. Study of essentially all the cupolas of the earth that have associated important vein-filled fractures shows that this is generally true. This

Jan 1, 1935

By W. H. Emmons

In 1922 Morey made a series of experiments in which he observed the cooling of a molten system containing H2O, 9.1 per cent; K2O, 17.3 per cent and SiO2, 73.6 per cent. This system was confined in a bomb; it was fluid at 500° C. and exerted no vapor pressure. In cooling to 420° C. a large part of it crystallized and at that temperature much of the water had separated from the crystals and remained as steam, which built up a pressure of 4998 lb. per sq. in., a force sufficient to lift nearly one mile of granite.' If granite, cooling at 600°, expels vapor in the process of crystallization it is reasonable to suppose that a considerably greater vapor pressure would result, and it is thought that the vapor expelled from crystallizing granitic batholiths probably has a pressure sufficient to lift two or three miles of granite. This vapor, collecting near the tops of cupolas of batholiths, is believed to exert sufficient pressure to fracture the hoods and roofs of batholiths above the cupolas. If that is true, one would expect to find that the fracture systems above cupolas are arranged in patterns that depend in part on the shapes of the cupolas. The mechanics of the situation seem to require that conical cupolas should have radial fracture patterns, that bluntly rounded cupolas should have fracture systems that are either irregular or rudely conjugated in plan, and that elongated stocks or cupolas should have fracture systems in which the fractu'res lie nearly parallel to the direction of the elongation of the cupolas. Study of essentially all the cupolas of the earth that have associated important vein-filled fractures shows that this is generally true. This

Jan 1, 1935

In 1922 Morey made a series of experiments in which he observed the cooling of a molten system containing H2O, 9.1 per cent; K2O, 17.3 per cent and SiO2, 73.6 per cent. This system was confined in a bomb; it was fluid at 500° C. and exerted no vapor pressure. In cooling to 420° C. a large part of it crystallized and at that temperature much of the water had separated from the crystals and remained as steam, which built up a pressure of 4998 lb. per sq. in., a force sufficient to lift nearly one mile of granite.' If granite, cooling at 600°, expels vapor in the process of crystallization it is reasonable to suppose that a considerably greater vapor pressure would result, and it is thought that the vapor expelled from crystallizing granitic batholiths probably has a pressure sufficient to lift two or three miles of granite. This vapor, collecting near the tops of cupolas of batholiths, is believed to exert sufficient pressure to fracture the hoods and roofs of batholiths above the cupolas. If that is true, one would expect to find that the fracture systems above cupolas are arranged in patterns that depend in part on the shapes of the cupolas. The mechanics of the situation seem to require that conical cupolas should have radial fracture patterns, that bluntly rounded cupolas should have fracture systems that are either irregular or rudely conjugated in plan, and that elongated stocks or cupolas should have fracture systems in which the fractu'res lie nearly parallel to the direction of the elongation of the cupolas. Study of essentially all the cupolas of the earth that have associated important vein-filled fractures shows that this is generally true. This

Jan 1, 1935

By W. H. Emmons

In 1922 Morey made a series of experiments in which he observed the cooling of a molten system containing H2O, 9.1 per cent; K2O, 17.3 per cent and SiO2, 73.6 per cent. This system was confined in a bomb; it was fluid at 500° C. and exerted no vapor pressure. In cooling to 420° C. a large part of it crystallized and at that temperature much of the water had separated from the crystals and remained as steam, which built up a pressure of 4998 lb. per sq. in., a force sufficient to lift nearly one mile of granite.' If granite, cooling at 600°, expels vapor in the process of crystallization it is reasonable to suppose that a considerably greater vapor pressure would result, and it is thought that the vapor expelled from crystallizing granitic batholiths probably has a pressure sufficient to lift two or three miles of granite. This vapor, collecting near the tops of cupolas of batholiths, is believed to exert sufficient pressure to fracture the hoods and roofs of batholiths above the cupolas. If that is true, one would expect to find that the fracture systems above cupolas are arranged in patterns that depend in part on the shapes of the cupolas. The mechanics of the situation seem to require that conical cupolas should have radial fracture patterns, that bluntly rounded cupolas should have fracture systems that are either irregular or rudely conjugated in plan, and that elongated stocks or cupolas should have fracture systems in which the fractu'res lie nearly parallel to the direction of the elongation of the cupolas. Study of essentially all the cupolas of the earth that have associated important vein-filled fractures shows that this is generally true. This

Jan 1, 1935

By W. H. Emmons

In 1922 Morey made a series of experiments in which he observed the cooling of a molten system containing H2O, 9.1 per cent; K2O, 17.3 per cent and SiO2, 73.6 per cent. This system was confined in a bomb; it was fluid at 500° C. and exerted no vapor pressure. In cooling to 420° C. a large part of it crystallized and at that temperature much of the water had separated from the crystals and remained as steam, which built up a pressure of 4998 lb. per sq. in., a force sufficient to lift nearly one mile of granite.' If granite, cooling at 600°, expels vapor in the process of crystallization it is reasonable to suppose that a considerably greater vapor pressure would result, and it is thought that the vapor expelled from crystallizing granitic batholiths probably has a pressure sufficient to lift two or three miles of granite. This vapor, collecting near the tops of cupolas of batholiths, is believed to exert sufficient pressure to fracture the hoods and roofs of batholiths above the cupolas. If that is true, one would expect to find that the fracture systems above cupolas are arranged in patterns that depend in part on the shapes of the cupolas. The mechanics of the situation seem to require that conical cupolas should have radial fracture patterns, that bluntly rounded cupolas should have fracture systems that are either irregular or rudely conjugated in plan, and that elongated stocks or cupolas should have fracture systems in which the fractu'res lie nearly parallel to the direction of the elongation of the cupolas. Study of essentially all the cupolas of the earth that have associated important vein-filled fractures shows that this is generally true. This

Jan 1, 1935

By Frank T. Wheby

The cost of tunneling is highly sensitive to the rock characteristics through which the tunnel is to be driven. These characteristics affect in a major way the rates at which tunnels and shafts can be driven and the degree to which the openings must be supported to maintain them in a permanent stable condition. Tunnel and shaft design and cost criteria have been computerized, permitting estimates of tunnel-shaft systems to be made directly from inputs of rock mechanics characteristics and other data. Curves of quantities of steel, rock bolts, and other rock support items as related to tunnel size and rock quality designation are presented. An illustrative example of the use of the program in calculating the cost of a hypothetical tunnel system is included.

Jan 1, 1971

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By K. K. Clark, W. H. Somerton

The feasibility of reducing pressures needed to fracture formations by heating the borehole intensively has been investigated on a laboratory scale. Reductions in fracture pressures of heated Bandera, Berea and Boise sandstone cores were observed at various confining pressures, simulating reservoir stress conditions to a depth of 5,000 ft. Both permeable and impermeable borehole boundary conditions were tested. Three heating conditions were used in the tests. One group of samples was heated in a furnace to a temperature of 600C, cooled to room temperature., and then tested for fracture pressures. Two other groups of samples were heated with a borehole heater to maximum borehole wall temperatures of 625 and 792C, then cooled and tested. In all cases, heated samples showed substantial reductions in fracture pressures compared to unheated samples. The higher temperature borehole heated samples showed the greatest reduction, amounting to 70 per cent in the extreme case. In actual application to wells, it was concluded that fracture pressures may be reduced by 20 to 50 per cent by intensive borehole heating before fracturing. INTRODUCTION Hydraulic fracturing of oil and gas wells is an accepted and effective technique for increasing well productivity in many areas, but is notoriously unsuccessful in other areas. The technique becomes less interesting for production stimulation purposes when excessive fracture pressures are necessary. Formations which do fracture but require high pressures, probably form horizontal fractures. There is good evidence to indicate that some formations do not fracture at all, but yield plastically under high pressure. Thus, any technique which will make formations easier to fracture or will reduce fracture pressures is potentially interesting to petroleum producers. Horizontal fractures generally occur in planes of weakness, such as bedding planes, and at pressures equaling or exceeding the effective overburden stress. In the unusual case where planes of weakness do not exist, a slightly higher pressure must be applied to overcome the tensile strength of the rock. In general, high fluid-loss fracturing fluids are conducive to the formation of horizontal fractures.1 Vertical fractures, when they do occur, are initiated at pressures generally lower than overburden pressure and are favored by low fluid-loss fracturing fluids or impermeable boreholes. The pressure necessary to create a vertical fracture in an impermeable, elastic medium can be predicted from the so-called "thick-walled cylinder" equation: Pf = 2 or+ st.............(1) where pf = fracture pressure or = radial stress st = tensile strength of medium. This equation indicates that to fracture it is necessary to overcome a tangential compressive stress, induced by and equal to two times the radial confining stress, plus the tensile strength of the medium. If the above equation held strictly true for rocks, very little could be done to reduce fracture pressure. The tensile strength of the rock might be reduced somewhat, but any change in st would be small compared to the magnitude of the tangential stress at reasonable subsurface depths. Laboratory tests have shown that actual fracture pressures exceed values predicted from Eq. 1 by factors of 1.4 to 28.6.1,2 Eq. 1 thus does not properly describe the

Jan 1, 1966

By R. V. Higgins

This paper presents a computer method to obtain the shape factors and equal cell volumes of the channels for any well spacing pattern from a potentiometric model. By using this program the authors have processed the data for the seven-spot, direct line-drive and the staggered line-drive patterns. The data for the five-spot pattern had been previously processed by a noncomputer method and are included for completeness. The shape factors and volumes for the channels are presented in tables for those who want to use them to process data using their own permeability relationships and viscosities of their reservoir oils. The authors have used the data and sets of representative permeability curves to process sample calculationr of waterflood performances. The comparison of the calculated results shows that the influence of well spacing is small. The permeabilities of the reservoir rock to oil and water had a greater influence on oil recovery for a given pore-volume throughput of water than the well spacing pattern. The more water-wet the reservoir rock, the better the possibility of permeabilities which are conducive to good recovery. The viscosity of the reservoir oil also influences the recovery more than the well spacing pattern. The reduction in the percentage recovery of oil with increase in viscosity of the reservoir oils is small when oil viscosities are in the range of 0.1 to 3. Above this range the reductions in recoveries are extensive. Sample comparisons of the time required for different patterns to recover the oil are presented. Results of an example calculation are given to show the effect of the permeability profile on recovery. INTRODUCTION The effect of well spacing pattern on the recovery of oil when flooding with either gas or water has been studied by many investigators. Muskat et al.1 presented an analysis using conductivity, sweep efficiency and unit mobility to the time of breakthrough. Dyes et al.2 used experimental techniques (X-ray shadowgraphs) and different mobility ratios. They presented quantitatively the relationship between mobility and sweep efficiency at and after breakthrough. Hauber3 presented a method to predict waterflood performance for arbitrary well spacing patterns and mobility ratios. Craig et al.,4 using techniques similar to Dyes et al. to determine sweep efficiency for a five-spot pattern, added the use of relative permeability curves at breakthrough and thereafter. Douglas et al.5 sed rela- tive permeabilities and continuously changing saturations throughout the entire five-spot flood pattern. In obtaining their solutions they used finite-difierence equations. Hig-gins and Leighton6,7 also used relative permeabilities and continuously changing saturations throughout the pattern before and after breakthrough. They employed techniques that process a flood-pattern calculation on the computer in about one minute. The methods of Douglas et al. and Higgins and Leighton both checked closely the laboratory results for a wide range of mobility ratios. This paper presents some sample performances calculated by the Higgins and Leighton method that show the effect on recovery of different permeabilities and viscosities using the seven-spot, the line-drive and the staggered line-drive, as well as the fivespot flood pattern. No previous paper has presented these data using different permeability curves and continuously changing saturations throughout the flood patterns. The paper also presents (1) the results and analyses of the flood-pattern prediction, (2) the computer techniques for determining the shape factors and volumes from the potentiometric models for the foregoing flood patterns, and (3) the shape factors and volumes of the channels of the flood pattern in the event reservoir engineers may like to process waterflood calculations using their own permeability curves and reservoir oils. DESCRIPTION OF METHOD VOLUMES AND SHAPE FACTORS The use of channels taken from a potentiometric model (see Fig. 1) to aid in calculating the performances of water floods of nonlinear patterns has been thoroughly explained in the literature.0,7 Therefore, very little theory, discussion, or proof regarding this phase will be repeated in this paper. The computer method presented in this paper to calculate the volumes and the shape factors of the channels of potentiometric models employs the trapezoidal rule for the volumes and the Pythagorean theorem (the hypotenuse equals the square root of the sum of the squares of the two sides of a right triangle) for the shape factors. In calculating the volume of a channel, the area of each cell in the channel is determined and then multiplied by the thickness to obtain the volume. In determining the areas of the cells, trapezoids are constructed whose vertical sides are spaced Ax apart, as shown in Fig. 2. The length of the sides is the difference between an ordinate cut off by the top and bottom of the cell — usually equipo-tentials. The coordinates of the points along an equipo-tential or streamline are obtained by Lagrange's8 equation of interpolation for which the constants are coordinate points at the intersections. Three intersections for con-

Jan 1, 1965

By AIME AIME

BERYLLIUM is one of the most interesting of the minor metals and distinctly a modern development, for until the last two decades it had practically no commercial importance whatever. Then it was discovered that when small quantities of it were alloyed with copper, a copper alloy of unusual and valuable qualities resulted. This is by far its major use-in the manufacture of strong, heat-treated copper-base alloys in which the beryllium content varies from about 0.3 to 2.5 per cent. Its second most important use, though much smaller, is in the form of oxide or other nonmetallic products in the fluorescent lamp, X-ray, cathode ray, and television industries. Certain beryllium salts have the quality, in common with several other materials, of transforming short-wave radiation and cathode rays to visible radiation. Such materials are commonly known as phosphors, and the beryllium salts are the most important phosphors now in use. The third largest use for beryllium is for ceramics, including refractories. Beryllium is also used in small quantities in the form of the metal itself.

Jan 1, 1943

By William Colby

INCREASING governmental control of human activities seems inevitable. Within the present generation railroad rates and the public sale of water, gas and electricity have been subjected to rigid regulation. The field of control is slowly but surely being enlarged, and it is the object of this paper to outline in brief space this tendency toward increased governmental regulation, as far as mineral resources are concerned. Our, dual form of government complicates the problem. We must deal not only with the powers of the Federal Government, but also with those of the individual States. In order to approach this question intelligently we must have some conception of the powers and jurisdiction of the States and the United States, respectively, over mineral lands and mineral production. Starting with the Federal Government we find it never owned any public domain within the States that formed a part of the thirteen original colonies and, for historical reasons, the same is true of Tennessee and Texas. The Mid-Western States were erected out of the public domain which was acquired by the United States through cession from the original States or by purchase from foreign nations. Congress early in the last century adopted a policy of leasing public lands containing lead deposits in a portion of this Mid-Western territory, but later abandoned that policy and disposed of such public, lands, mineral and non-mineral, outright so that they long since have practically all passed into private ownership and become subject to the general jurisdiction of the respective State governments. In the great public domain lying west of the Mississippi River, and in portions of some of the Southern States, the Federal Government adopted a new mineral land policy following the discovery of gold in California. (Acts of Congress of 1866, 1870, and 1872.) The mineral lands within these States, instead of being disposed of on the game basis as agricultural lands, as occurred in the Mid-Western States, were segregated from agricultural lands and sold under special laws intended to encourage mining, giving the miner the free right to locate and work these mineral lands without paying any royalty to the Federal Government. A miner could also obtain at slight expense a complete

Jan 1, 1930