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By Roy E. Dickerson

CUBA differs considerably from the other Greater Antilles in many geologic fundamentals. Cuba is geosynclinals; whereas Jamaica, Hispaniola. (Haiti), and Puerto Rico are geoanticlinal. (Scliuchert, Chas., Historical Geology of the Antillian. Caribbean Region, p. 13, 1935.) Rocks of lowermost Cretaceous age exist in large volume in Cuba, where- as they are generally absent in the other islands. Since many of the surface indications of petroleum are intimately associated with lowermost Cretaceous rocks, the Vinales limestone,, this difference is most important. The Vinales limestone in many places in Pillar del Rio and Santa Clara provinces reeks with light tars when broken with a hammer. The late David White and his associates on the U. S: Geological Survey studied

Jan 1, 1937

By AIME

SUPPLEMENTING surveys of the engineering profession regarding salaries and advancement, based upon data from individual engineers, a survey through a questionnaire to employers of engineers has recently been made by a subcommittee of the Engineers Joint Council's Committee on the Economic Status of the Engineer. Its object was to learn directly from employers their attitudes and policies pertaining to the selection, training, placement, advancement, guidance, and professional activities of engineering graduate employes. The questionnaire was sent in May 1946 to 174 employers of engineers, including colleges. Replies were received from 104 employers in nineteen fields of industry, who employ about 2,000,000 persons, about 40,000 of whom are engineers. The following general observations are based on the questionnaires returned. Who Are Hired? Of the co-operators 96 per cent employ cadet engineers directly upon graduation from engineering schools, but only 4 per cent recruit their engineering staffs exclusively from the new graduates. About 43 per cent hire more than half of their new engineer employes after one or more years' experience with other employers. This is evidently a matter of necessity or expediency rather than preference, because more than sixty per cent of those reporting indicate that they prefer to hire the new graduate.

Jan 1, 1947

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

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

Jan 1, 1969

By R. E. Allen

ONE of the most unusual oil field engineering accomplishments of the past two years is the development and rapid advance in the directed drilling of wells. Directed drilling as referred to herein is the controlled steering of the drill stem in the required direction to a given location in the oil sand. The deliberate drifting of holes is an act so far removed from what has been considered good drilling practice that all of the old questions of correlation, drillability and production difficulties are revived. Only a few years ago, during the boom days of Seminole and Santa Fe Springs, the crooked-hole problem, as it was then called, occupied a primary position among the topics of the day in the fields of California and the Mid-Continent. The net result of all the discussion and study at that time was the conclusion that oil wells should be drilled with as little deviation from

Jan 1, 1933

By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By J. F. Ednie

SCRAP metals to the value of more than a billion and a half dollars were recovered in the United States in 1939 for further use in industry. Few people have any true conception of the magnitude of the secondary-metal industry as related to that engaged in the production of the primary, or virgin, metals; of its importance, particularly when a shortage of primary metals exists, as at present; or of the advance that has been made in standardizing and improving the quality of its products. Of the iron and steel produced in the United States in 1939 (the data used in this article are largely taken from Bureau of Mines reports for that year) just over 50 per cent came from scrap and slightly less than 50 per cent from ore. Of the principal nonferrous metals-aluminum, anti-mony, copper, lead, nickel, tin, and zinc-63 per cent came from domestic ores and 37 per cent from scrap. Fig. 1 presents graphically the relative tonnage and value of primary and secondary production of ferrous and nonferrous metals. In this chart only purchased secondary metals are considered, the figures being exclusive of "home" or "plant" scrap which amounts to rather large figures in the iron and steel industry. Incidentally, the chart shows that from the tonnage standpoint the iron and steel industry is some twenty times larger than the nonferrous industry, though with regard to the value of the product the ratio drops to about two to one.

Jan 1, 1941

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Richard W. Smith

Why are we losing our liberties? (1) . . . because our local chambers of commerce come to the National Chamber's annual meeting, vote for a policy on federal economy, and then go to Capitol Hill and ask for a federal project for their area. (2) ... because our mining men ask for a subsidy to mine submarginal deposits that can't be economically mined in a free economy. (3) . . . because 18,000 men and organizations all over the country recently wired or wrote a Congressional committee asking that the Army Engineers be exempt from the President's power to reorganize the Executive Branch of the government under the recommendations of the Hoover Commission.

Jan 1, 1949

By P. E. Busby, C. Wells

FURTHER study of data used in determinations of 1—rates of diffusion of boron in austenite and 2—solubilities of boron in the a and phases of iron and steel' has provided an equation for the diffusion of boron in a iron. In brief, the previously published data were accumulated from the results of deboron-izing (and decarburizing) experiments carried out in the range of 700° to 1300°C. Diffusion coefficients (D?) for boron in austenite were calculated using the Grube solution of Fick's law. However, only solubility values were estimated from the discontinuous concentration-penetration curves, Fig. 1, which are characteristic of diffusion in two phases. Dr. Carl Wagner' has recently provided a solution for calculating D values from penetration curves of this type as follows: Cl1.1 —C8/C8- C11.1 = vp ? e ? erf (?) and D = ?/4?2 t where C11,12, C8, C11, and E have the values shown in Fig. 1. D is the diffusion coefficient, sq cm per sec; t is time of deboronizing anneal, see; and ? is a di-mensionless parameter. For a given diffusion experiment, the value of ? can be readily obtained by graphical solution from a plot of y vs the right-hand part of Eq. 1. D may then be evaluated from Eq. 2. The avplication of this solution to previously re-ported results, of which excerpts are given in Table I, permits the calculation of diffusion coefficients for boron in a iron. On the basis of these meager data, it is tentatively concluded that the diffusion of boron in a may be represented by the equation Da = 1011 e-92,900/RT where R is the gas constant, cal X 0C-1 X mol-1; and T is the absolute temperature, OK. Although the frequency factor, 106 sq cm per sec, is admittedly several orders of magnitude higher than expected, the value of Q, 62,000 cal per mol, appears reasonable and is, in fact, very similar to that for the self-diffusion of iron. It is pertinent to mention at this point that the value of Q obtained for the diffusion of boron in austenite by means of the Wagner solution is 19,000 cal per mol and is in excellent agreement with the value previously reported1 in the equation DT = 2xl0-3 e-21,000/RT [4] which was determined by the application of the Grube solution to other data. The fact that determined constants A and Q in the equation D? = A e-Q/RT were practically the same, independent of whether the Wagner or Grube solutions were used in determinations of D values, strengthened the authors' belief that the computed values of D (Table I) using the Wagner solution are reliable. The relative values in Eqs. 3 and 4 for the diffusion of boron in the a and ? phases, respectively, suggest that boron forms a substitutional solid solution in a iron and an interstitial solid solution in ? iron. The same tentative conclusion has been reached by McBride et al.3 on the basis of relative solubilities, atom diameter, and the size of the interstitial hole in a and ? iron. In connection with the data for test 14 listed in Table I, it is of interest to calculate the solubility of boron in a iron using the D value given by Eq. 3. As might be anticipated from the small movement of the interface in test 14, proper substitutions in Eqs. 2 and 1 give a low value, approximately 0.0004 pct B, at 850°C. Apparently at 835°C (test 13) it is possible to obtain 0.0018 pct B, and at 850°C only 0.0004 pct B into solution in the a phase before a second phase appears. These observations are consistent with the Fe-B constitution diagram proposed by McBride, Spretnak, and Speiser.3 References P. E. Busby, M. E. Warga, and C. Wells: Diffusion and Solubility of Boron in Iron and Steel. Trans. AIME (1953) 197, p. 1463; Journal of Metals (November 1953). 'W. Jost: Diffusion in Solids, Liquids, Gases. (1952) pp. 69-71. New York. Academic Press Inc. "C. C. McBride, J. W. Spretnak, and R. Speiser: A Study of the Fe-Fe2B System. Trans. ASM (1954) 46, p. 499.

Jan 1, 1955

By J. E. Harris

By elimination of other possible nucleation processes, it has been demonstrated, for commercially pure magnesium and a Mg-Al alloy, that at stresses less than that necessary for triple-point cracking creep cavities are most probably nucleated heterogeneously at second-phase particles. Evidence for the existence of such particles is presented and the role of grain boundary sliding in the nucleation process is examined quantitatively. DURING creep deformation of polycrystalline magnesium and its dilute alloys in the temperature range 0.45 to 0.7 Tm (Tm = absolute melting temperature) cavities form mainly along grain boundaries oriented normal to the stress axis and failure eventually occurs by their growth and impingement.' The possibility of low-ductility creep failure of magnesium-alloy reactor cans during service has prompted a number of studies of cavity formation in these materials.2-5 In this paper divergent theories of cavity nucleation6-10 are examined critically and conclusions drawn regarding the most probable mechanism of formation of cavities in magnesium. The paper is divided into two parts. The first section consists of the review and quantitative assessment of the possible role of grain boundary sliding in the nucleation process. In the second part an experimental program is described where an electron-microscope technique has been used to determine if second-phase particles exist in as-received commercially pure magnesium and in a magnesium alloy 1) THEORETICAL REVIEW Possible nucleation sites for creep cavities are: a) high-angle grain boundary triple points,11-14 b) subboundary/grain boundary intersections,15-18 c) ledges in the grain boundary, 19-25 d) second-phase particles. 9,26-30 Each of these possibilities is now considered with special reference to deformation of magnesium. 1.1) Triple-Point Cracking. The stroh31 condition to nucleate fracture is: " > vr [1] where ss = applied shear stress, ? = surface energy, C = shear modulus, L = length of sliding interface. This relationship is independent of the nature of the interface and it is possible to calculate the stress concentration at the end of a sliding high-angle grain boundary and thus deduce, approximately,* the minimum applied stress necessary to nucleate triple-point cracking. Such theoretical predictions for Nimonic alloys have been made by McLean13 and found to agree quite closely with the minimum stress determined by experiment. Stresses capable of nucleating triple-point cracking should also be sufficient to nucleate fracture at a grain boundary due to intragranular slip, for the lengths of sliding interface in the two cases are approximately equal. Thus the minimum stress for triple-point cracking should represent a demarcation between failure due to general "cracking" and that due to cavitation. Hauser, Landon, and Dorn32 have demonstrated that for polycrystalline magnesium in the temperature range 78° to 298°K the fracture stress is inversely proportional to the square root of the mean grain diameter. As pointed out by stroh31 this result indicates that Eq. [I] describes the fracture characteristics of magnesium at low temperatures. Heal3 has reported that for rapid deformation (112 pct hr-1) of polycrystalline magnesium the transition from cracking to cavitation occurs in the temperature range 175" to 275°C. He also presented the fracture-stress values for the same material tested under similar conditions. From Eq. [I] taking G = 1.3 x 10" dynes , ? = 600 ergs . cm-2,33 and L = 0.017 cm, a Stroh-McLean13,31 tensile stress of -266 kg. cm-2 is calculated, corresponding to a transition temperature of -190°C; this is in

Jan 1, 1965

By Earl Oliver

CONTENTS PAGE A.I.M.E. Stabilization Committee Activity 3 Definition of Capture Rule: Robert E. Hardwicke 4 Westmoreland Natural Gas Co. vs. DeWitt 5 Kelly vs. Ohio Oil Co 5 Bernard vs. Monongahela Gas Co 6 Definition of Ownership in Place 7 Prospective Stabilization Remedies 7 Dean Roscoe Pound's Four Tests of Practicability 7 I: Mechanically Feasible 8 Capture Rule 8 Ownership in Place 10 Mechanical Separation Method 10 Engineering Appraisal Method. 11 II. Economically Advisable. ., . 13 Capture Rule 14 Ownership in Place 14 III. Politically Wise 14 Capture Rule 14 Ownership in Place 17 IV. Legally Sound 18 Capture Rule 18 Ownership in Place 19 Dean Henry M. Bates' Analysis 19 Resume 22 THE A.I.M.E. Stabilization Committee was named in 1932 to ascer-tain whether some practical substitute could be devised for the Rule of Capture, which was generally credited with being the major cause of instability in the Petroleum Industry. After considerable intercommittee correspondence a letter was received from. E. DeGolyer under date of Jan. 25, 1935, in which he discussed the possibility of modifying rather than discarding the Rule of Capture. He summarized his proposal as follows:

Jan 1, 1937

What is experience worth? Representatives from the Mining, Metallurgy and Petroleum Societies discussed the question as part of the 1970 Annual AIME Meeting held in Denver, Colo. the week of February 15. Petroleum engineer-consultant, Michel T. Halbouty of Houston, Tex. offered his own clarification of present-day employer-employee relationships in engineering as a whole. "Longevity does not equal experience on the job. Further, when employees are considering salary increases and promotions, job performance is considered all the time; experience two- thirds of the time and length of employment one- half the time." He added, "worth is really what the employee can get for it and experience is essential to survival." Halbouty also noted that salary and responsibility is a function of man's value to his company and is about "as discrediting as grey hair." As far as the engineer is concerned, he reported, the company's ability to pay is, in large measure, not considered. From the company's viewpoint, however, the employee is expected to learn his first year on the job. His second year, he is expected to make his presence felt, Should he require three years to orient himself he might soon be looking for another job. The petroleum engineer pointed out that when the employee wants to know why the salary scale tends to plateau off in later years, most employers react by recognizing that employees "flatten themselves rather than the company flattening them."

Jan 1, 1970

By André G. Journel

Geological study of the Prony Nilaterite (New Caledonia) began in 1969 and included drilling, geological mapping and laboratory studies. The deposit is the product of weathering of basic rocks. From top to bottom, the following zones can be distinguished: a compact ferruginous cover; ore associated with yellow laterite, containing 1.0-1.5% Ni and low in impurities (SiO2, Mg); an intermediate silicated ore containing 1.3-2.0% Ni and higher percentages of impurities; garnierite ore much richer in nickel (2-4%) but high in SiO, and Mg contents (Mg up to 20%) ; and parent rock, largely peridotites. Distinction between types of ore is essential because the high grade ore (silicated and granierites) is penalized for its high Mg contents that demand additional acid treatment. All studies made distinguish two types of ore, laterite and silicated.

Jan 10, 1973

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By L. F. Reinartz

ANOTHER year has rolled by. We are twelve months further away from the start of the depression and. therefore that much nearer to recovery. The accumulated needs and wants 'of our lame, virile population are ready to burst their bonds as soon as confidence returns and credit is stabilized. The steel industry has been harassed by uncertainty of the Government's attitude toward organized labor's de¬mands, and irregularity in volume of production. Steel labor, if left to its own devices, would in most instances, march shoulder to shoulder with the management of steel plants in their effort to pull the industry nut of the ?red.? Cooperation between management and men has improved considerably during; the year.

Jan 1, 1935

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Robert A. Rapp

The standard molar free energy of formation of MOO,was determined between 750o to 1050o C in galvanic cell measurements involving the solid electrolyte Zr0.85 Ca0.15 O1.85. Use of the reference electrodes Fe + FexO and Ni + NiO Provided two independent determinations of FoMoo2. The data may be represented by the equation FMoO2 = -137,500 +40.0T(°K) which is in good agreement with previous CO/CO, gas equilibrium measurements of Gleiser and Chipman. The standard molar free energy of formation of molybdenum dioxide has recently been reported over a large range of high temperatures from the calorimetric experiments of King, Weller, and christensen.' Gleiser and chipman2 have also recently determined ?FmoO2 from 926o to 1068oC in CO/CO2 gas equilibrium measurements. Earlier gas equilibrium studies have been made and reviewed by Gokcen.' Over the temperature range studied by Gleiser and Chipman their values for ?FoMoO2 differed from the calorimetric data by about 700 cal. This investigation was undertaken to resolve this difference and thereby establish the two phase mixture of Mo + MOO, as an electrode of well-known oxygen potential for galvanic cell applications at very high temperatures. The galvanic cell technique involving the Zr,.,, Ca,0.15 01.85 solid electrolyte was introduced for the

Jan 1, 1963