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By H. J. Beach, W. C. Goins

The laboratory development and field use of oil well cement compositions* with high resistance to drilling mud contamination are described. Resistance is obtained by adding a I-lb mixture composed of three parts paraformaldehyde to two parts sodium chromate tetra-hydrate for each sack of cement. This mixture neutralizes the cement-retarding properties of quebracho and other tannins, starch, sodium carboxymethylcellu-lose, Ignite, and monovalent salts of lignosulfonic acid. The retarding properties of calcium lignosulfonate are unaffected. The decontaminating mixture may be used in common cement (designated Type I by ASTM specifica-tions,' Class A by API Std. 10A2) or in a slow set slurry prepared from common cement by addition of calcium lignosulfonate. No changes in slurry viscosities or thickening times are caused by the protecting reagents. The method has been used in 185 field jobs where an improved success ratio has been obtained in plug setting. INTRODUCTION Field experience and laboratory investigations have established contamination by drilling mud as a major factor in oil well cement failures. During 1955, 12 attempts were required to set six open-hole cement plugs in the Timbalier Bay field, La. Eighteen to 30 hours elapsed between placing and testing the plugs in preparation for sidetracking operations. Considerations of rig time expense required immediate resetting where soft cement was drilled after a reasonable waiting period. Sea water drilling mud was used in each well and daily additions of thinners, usually lignites, had been required. Sodium carboxymethylcellulose had been added regularly to control fluid loss. The 50 per cent plug failures were attributed primarily to contamination by the mud. Similar experiences can be found in other fields along the Texas and Louisiana coasts where drilling muds normally contain large quantities of organic treating materials. Cement contamination was the subject of a survey by the Mid-Continent District Study Committee on Cementing Practices and Testing of Oil-Well Cements of the API.3 Data collected from member laboratories and released in Sept., 1951, reported the effects of a number of drilling mud treating chemicals on cement. The study revealed that many of the additives, notably the organic materials in relatively small quantities, had marked effects on the properties of cements tested. Severe losses in strength and erratic thickening time resulted from small additions of mud treating chemicals such as quebracho, starch, sodium carboxymethylcellulose, and lignite. The report included no recommendations of methods for overcoming the problem. One investigation of the contamination problem reported the successful use of activated charcoal in setting cement plugs after conventional slurries had failed.4,5 The investigation indicated that an optimum concentration of 5 per cent activated charcoal was effective in combating contamination from 16.7 volume per cent of treated mud. Laboratory and field muds were included in tests and contained varied quantities of ode or more of the following: quebracho, caustic, starch, lime, and calcium lignosulfonate. The function of the charcoal appears to be physical, removing the organic materials by adsorption. The method may be employed in API Class A or Class D (unretarded slow set) cements. The chemical approach presented here is based on

Jan 1, 1958

By Harold M. Mooney

WHEN apparent resistivity data are taken with the symmetrical Wenner 4-electrode spread, a fixed center position is used and readings are taken for values of electrode separation. Basic data consist of apparent resistivity plotted against separation of adjacent electrodes . The interpreter attempts to infer geologic structure, such as the depth to discontinuities and the nature of subsurface earth materials. An earlier paper' described methods for interpreting resistivity data. All of these involve a severe assumption, namely that the earth in the region of interest consists of horizontal layers, electrically homogeneous and isotropic. The actual earth never satisfies this assumption exactly and may deviate from it so much that none of the above methods can be applied. Attempts in three directions have been made to modify the assumption so that it approaches known geologic complexity more closely. First, curves have been calculated for dipping discontinuities. Stern' and Aldredge hose a few widely separated dip angles. Trudu confined his attention to small dips. Berel'kovskiy and Zubanov computed gradient curves for widely separated dip angles. Unz as given the most complete solution, with a brief attempt to treat the three-layer case. Second, anisotropy can be taken into account. It seems geologically probable that layered materials have different vertical and horizontal conductivities. Cagniard, Maillet, and Pirson et up methods for finding an equivalent hypothetical isotropic medium. Standard interpretation methods can be applied to this, and the actual medium can then be deduced. Belluigi'" discounts the practical importance of anisotropy; Geneslay and Rouget do not agree with his conclusion. Third, the effect of variable resistivity in a layer can be considered. Keck and Colby" examine the mathematics of an exponential increase in a surface layer. Several authors, for example, Stevenson,'' consider a continuous variation of resistivity with depth. The present paper deals with a linear variation of resistivity in a surface layer. Geologically, surface variations should be expected. Unconsolidated materials such as glacial drift show marked irregularities over short distances. The effects of weathering change with depth. The moisture content of material above the water table may vary from a dry sand to a saturated clay, and both of these will be changed by rainfall. Figs. 1 to 6 present apparent resistivity curves to show the effect of a variable surface layer. In all cases resistivity varies linearly with depth down to a depth of one unit. Material beneath this depth has constant resistivity. Electrode separation is plotted in depth units. Insets on each figure show the corresponding cross-sections, plotting true resistivity against depth. To illustrate, consider curve A of Fig. 1. The true resistivity of material at the surface of the earth is taken as 0.4 units. Resistivity increases with depth, reaching a value of 1.0 at 0.5 depth units and 1.6 at 1.0 depth units. Below a depth of 1.0, all the material has very low resistivity (zero, for purposes of calculation). Curve A in the main part of Fig. 1 shows how apparent resistivity varies for this case as the electrode spacing is increased. To illustrate further, curve E of Fig. 4 corresponds to true resistivity of 1.2 units at the surface, 1.0 at a depth of 0.5 units, 0.8 at a depth of 1.0, and 1.5 for all depths greater than 1.0. Apparent resistivity curves have been plotted logarithmically so that the shape of the curves becomes independent of the units, giving the curves wide validity. A certain drift-covered area, for example, shows a gradual decrease of resistivity from 230 ohm-meters at the surface to 150 ohm-meters at the bedrock surface, 275 ft down; bedrock resistivity is 800 ohm-meters. Curve E of Fig. 5 indicates that true resistivity decreases from 1.2 units at the surface to 0.8 at a depth of 1.0, then increases abruptly to a constant value of 4.0 units. Since resistivity and depth ratios are the same, this can be used to predict the field curve. For Fig. 5, multiply true resistivity and apparent resistivity by

Jan 1, 1955

By A. M. STROKG

Discussion of the paper of Charles R. Keyes, presented at the Spokane meeting. Bulletin o. 34, October, 1909, pp. 867 to 903. A. M. STRONG, Bishop, Cal: (communication to the Secretary*) The paper of Mr. Keyes gives us the most complete account of the geology of the borax-deposits in the Death Valley region that has yet been published, and is a valuable addition to the geological literature of a very interesting though little-known territory. During the past ten years I have been over much of the northern part of the country described by Mr. Keyes and the region immediately north of it. Mr. Keyes seems to give the impression that Furnace creek is the northern end of these borate-bearing deposits, but such is not the case. Of the seven principal marsh-deposits which for years furnished the greater part of the borax supply in the manner described by him, four are north of the boundary-line as given on his map. The entire territory immediately east of the Sierra Nevada is composed of a series of sinks, each with a well-defined drainage-area.. Of these, Death valley is the deepest, and its drainage-area one of the greatest. The section given in the paper is typical of any line drawn eastward from the Sierra Nevada. At the lowest point of each of these sinks is a marsh, which, in times of heavy rain-fall in the mountains, is converted into a lake. These marshes always contain borax, which is now considered to have been derived from the washing of the Tertiary lake-beds in the surrounding mountains, of which they form a considerable part. Additional territory which I have studied shows that the boundaries given on Mr. Keyes's map should be considerably extended to the north. Just how far these borate-beds extend I am not prepared to say. J. E. Spurr says of them : 1

Feb 1, 1910

[United Engineering Trustees, Inc. A. L. QUENEAU, '45 ALBERT ROBERTS, '47 RALPH B.. WILLIAMS, '48 The Engineering Foundation F. F. COLCORD, '46 E. A. PRENTIS, JR., '48 A. L. QENEAU, '45, Chairman Engineering Societies Library Board J. W. LAIST, '48 W. A. MUDGE, '45 A. B. PARSONS, Ex-officio T. T. READ, '46]

Jan 1, 1946

By R. S. French

THE purpose of this paper is to present data that have been obtained during the past two years concerning the effects of prior cold-work and temperature and time of anneal upon the recrystallization and grain growth of 70-30 cartridge brass. It was desirable to study certain of these phases so that an accurate picture of the principles of the subject could be shown. The work is not intended to provide explicit annealing data, but to provide material examples that may help to clarify analogous problems concerning this alloy. Specifications often set limitations upon the grain size of annealed materials because of the importance of grain size upon subsequent manufacturing operations. It was, therefore, worth while to study the variables that affect the recrystallized grain size of this material. C. H. Mathewson and A. Phillips,1 W. R. Webster,2 and others have presented annealing characteristic curves of this alloy. A recent typical curve presented by R. S. Pratt3 is shown in Fig. I. The tensile properties and grain sizes are shown as functions of the annealing temperature. Such curves serve as a useful guide in determining the physical properties of annealed material, but as they are made generally under carefully controlled laboratory conditions they do not indicate the performance of metal annealed in a mill muffle, where conditions are different and the amounts of metal require necessarily longer heating times and temperatures. Study of the effect of time and temperature upon grain growth and subsequent recrystallization was made with a coil of metal having the following analysis: 70.04 per cent copper; 0.007 lead; 0.007 iron; 0.00 tin; 0.00 silicon; 0.001 nickel; 0.000 phosphorus; balance zinc. The sample coil was obtained from metal that had been rerolled from hot-rolled mill stock, and was received at 0.228-in. gauge, soft, with a grain size of 0.125 mm. This material was then rolled 43.5 per cent to 0.125-in. gauge and annealed to a 0.053-mm. grain size. In this condition, samples were cut and used in all of the experimental work reported in this paper. TIME The first study was of crystal growth at a constant temperature over a moderate length of time. Material was cut from the stock coil at 0.129-in. size and rolled 75 per cent hard to 0.032-in. gauge. From this piece small samples were cut ½ by 2 in., suitable for grain-size determinations. Twelve samples were placed in an electric furnace uniformly across the width, approximately an inch from the floor, A thermocouple was wired to the center sample, so that the approximate metal temperature could be followed. At various

Jan 1, 1944

By R. S. Hoch, Roy A. Bobo

Maintenance of desirable plastic flow properties of weighted drilling muds may be greatly simplified by use of centrifugal classification to control the drilled solids content. The new application of a decanting type centrifuge to separate and reject the low density solids from the weighting material results in a drilling mud of greatly improved quality with lower values of yield and rigidity. Its practicality and economy has been proven in field operation. The degree of separation of light and heavy solids is not limited by the machine, but by the particle size distribution of the solids in the mud. Removal of the low density component of drilling mud that makes chemical treatment necessary permits a marked reduction in chemicals. The main uses of the centrifugal process are the treatment of muds while drilling, the reclaiming of discorded muds, cleaning up of workover muds, and the reduction in lime content of mud for completion. INTRODUCTION Drilling mud in any circulatory system is made viscous and difficult to pump by gradual accumulation of drilled solids which pass through the shale shaker and are continually reground. In a weighted mud containing a large proportion of barite by volume, the amount of drilled solids that may be tolerated is greatly reduced. Much effort has been expended to control by chemical treatment the effects of such solids. Though chemical treatment is quite effective, the time eventually comes at deeper depths after enough drilled solids have entered the system when a portion of the mud must be discarded and replaced with water and more weighting material. Once begun, this process is generally continued at frequent intervals with resultant high maintenance costs. At the termination of drilling, mud highly contaminated with light solids and spent chemicals is poorly suited for completion operations.' It is likewise limited in utility for other drilling operations. This investigation was conducted for the primary purpose of determining an acceptable mechanical means of removing the lightweight solids from weighted drilling muds in order to maintain viscosity at a minimum. A decanting type of centrifuge was selected from the various possible methods of mechanical separation. The centrifugal process has been employed in this country for this purpose in central mud reclamation systems in California in earlier years. It also was used for treatment of weighted muds on the Gulf Coast.' In more recent years only sporadic attempts have been made to employ it in the field on weighted muds. DISCUSSION OF PROCESS Selection of Apparatus Two factors favor mechanical procedure for the separation and removal of drilled solids or clays from the mud circulatory system. First, the greater specific gravity, 4.1 to 4.3, of the barite would promote more rapid settling than the clays whose specific gravity range is from 2.5 to 2.7. Second, the relative coarseness of the barite particles also facilitate faster settling of this phase. A decanting type of centrifuge was preferred for this process over other possible methods for these reasons: 1. Requires no costly additives or excess dilution. 2. Centrifugal force affords greatly accelerated separation as compared to gravity.

Jan 1, 1955

By W. W. Dudley

Inflow of ground water is an important engineering and safety consideration during construction of large openings underground. The initial step in predicting groundwater inflow involves hydraulic tests in exploratory drill holes. Zones within the area of interest are isolated in the drill hole by inflatable packers and are tested by measuring the water level responses to applied hydraulic stresses. These responses may then be translated into significant hydraulic characteristics of the tested rocks such as transmissivity, hydraulic conductivity, hydraulic potential, and storage coefficient by using a type-curve solution. Once the geometry and necessary hydraulic characteristics have been determined for the rock in the vicinity of the proposed opening, a model can be developed using certain assumptions that will lend itself to treatment with available mathematical methods. The mathematical method applied to the model considers conditions of partial penetration and nonsteady-state, leakyartesian, constant-drawdown discharge of ground water. A type-curve solution results in a curve that gives the variation of discharge (inflow) with time. This technique of predicting ground-water inflow has been used in planning construction of cylindrical chambers for use in underground nuclear experiments by the U.S. Atomic Energy Commission. These chambers have been constructed in low-permeability rocks at depths as much as 6000 ft and under hydraulic heads of thousands of feet.

Jan 1, 1973

United Engineering Trustees, Inc. W. D. B. MOTTER JR., '44 A. L. QUENEAU, '41 ALBERT ROBERTS, '43 The Engineering Foundation GEORGE D. BARRON, '44 F. F. COLCORD, '42 A. L. QUENRAU, '41 Engineering Societies Library Board A. T. HASTINGS, '41 J. W. LAIST, '44 A. B. PARSONS, EX-Officio T. T. READ, '42

Jan 1, 1941

By Jack D. Arthur

The Surface Mining Control and Reclamation Act of 1977, as amended, and related regulations take blasting safety into consideration by requiring compliance with existing state and federal laws. The regulations are based on blasting practices developed by the industry, as well as research and experimentation by the US Bureau of Mines and explosive manufacturers. Residential areas in the proximity of surface mines have made it mandatory that blasting operations be conducted under restrictions and requirements designed to protect the public and structures located within 0.8 km (0.5 mile) of any surface blasting activities. Restrictions against blasting apply where dwellings, schools, churches, hospitals, or nursing facilities are within 305 m (1000 ft) of blasting operations. They also apply where wells, petroleum or gas storage facilities, municipal water storage facilities, fluid transmission pipelines, gas or oil collection lines, and sewage lines are within 152 in (500 ft) of blasting operations.

Jan 11, 1979

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.' Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

By F. Kurata, A. F. Bertuzzi, P. C. Davis, T. L. Gore

The phase and volumetric properties of 10 very volatile mixtures are presented for temperatures from — 200°F to above the critical points. These mixtures consisted of natural gases and of mixtures of natural gases with methane and nitrogen. Existing correlations of compressibility factors have been extended to apply to these mixtures. Existing correlations of critical pressures and temperatures do not apply to these mixtures. Methods have been developed for estimating critical temperatures of these mixtures to ± 4°F and critical pressures to 2 5 per cent. These methods apply to other volatile and very volatile mixtures. The results of this work are particularly applicable to the separation of nitrogen from hydrocarbons by low-temperature distillation. INTRODUCTION Knowledge of the low-temperature phase and volumetric properties of natural gases and of other mixtures of the light hydrocarbons is becoming increasingly important as interest in low-temperature separation processes increases. Low-temperature distillation has been used to separate ethane and ethylene from natural gas and from refinery gases for petrochemical uses. Removal of nitrogen from natural gas by low-temperature distillation has been proposed 7,20 as a means of increasing the capacity of existing gas transmission lines and of improving the marketability of the gas. Further application of low-temperature separation processes has been retarded by lack of data on the phase and volumetric behavior of mixtures at low-temperatures and at high pressures. This paper presents the results of determination of the phase and volumetric properties of 10 very volatile mixtures at temperatures from - 200 °F to above the critical point. These mixtures consisted of natural gases with methane and nitrogen. Generalized methods are presented for estimating the critical temperatures, critical pressures, and the densities of such mixtures. EXPERIMENTAL APPARATUS AND PROCEDURES The apparatus and the experimental procedures have been described in an earlier paper13. The method consists of displacing the mixture from a reservoir which is maintained at constant temperature and pressure into an agitated glass equilibrium cell which is maintained at constant temperature. The liquid level within the glass equilibrium cell was visually observed, and the pressure was measured to within & 3 psi with a calibrated Bourdon gage. COMPOSITIONS OF MIXTURES STUDIED The compositions of the mixtures studied are summarized in Table 1. The measured properties included in Table 1 will be discussed later in this paper. The sources of these gases are described below: Gas "A-1'' was obtained from the Phillips Petroleum Co. Its composition was reported in connection with earlier work." The properties of this gas were reported in an earlier paper.13 Gases "A-2, A-3, A-4" were prepared by mixing nitrogen with gas "A-1." Gas "AB-1" was prepared by mixing methane with gas "A-1." The properties of this gas were reported in an earlier paper.'" Gases "AB-2" and "AB-3" were prepared by mixing nitrogen with gas "AB-1." Gas "B" was obtained by W. W. Bodle of J, F. Pritchard & Co. from the primary separator of a well in western Kansas. Gas "C" was obtained from a Cities Service Co. pipeline at Lawrence, Kans. Gas "D" was prepared by mixing gas "AB" with gas "C."

Jan 1, 1955

By C. A. Heiland

IN the third year of war, geophysical oil exploration broke all records to keep pace with the demand for increased reserves. Geophysical prospecting for strategic and other minerals also grew in scope. The trend of geophysical oil exploration throughout the war is indicated in Fig. 1. This figure resembles the one presented in the last annual review issue of M&M (February 1944, p. 62), corrected for data on-operations in the last months of 1943 and extended into 1944. The average number of geophysical oil prospecting crews in the field in 1944 was 451, whereas the total in 1943 was 340. An upward trend in the use of all geophysical methods is clearly evident throughout the year. Seismic operations were 67 per cent, gravimeter surveys 28 per cent, and other methods 5 per cent of the total. Seismic reflection and refraction crews increased 181/2 per cent over the 1943 average, gravimeter operations increased 73 per cent, and other methods gained 92 per cent. The increase in seismic and gravimeter operations, particularly the latter, is probably due to an increased production of equipment and the organization of new service companies. Miscellaneous methods gained largely through a revival of magnetometer work, and an increase in the use of torsion balances and electrical equipment. In comparison with the prewar average of 1941, it is noteworthy that seismic operations increased 58 per cent, gravimeter operations 88 per cent, and miscellaneous other methods gained as much as 283 per cent. Unfortunately the expansion in the number of geophysical crews does not indicate a proportionate increase in efficiency or in areal coverage, as will be brought out later.

Jan 1, 1945

By Freeman Bishop

Mercury is the latest ecological disaster. It was believed to be no pollution problem because it is heavier than water and expected to fall to the bottom of streams. But the Food and Drug Administration (FDA) found that mercury in a dozen states and several Canadian provinces was being ingested by fish. A Deadly Dose First to sound the alarm was Canada when a graduate student's research revealed that mercury contamination in Lake St. Clair had reached 1.4 pmm. which is almost three times the 0.5 ppm the FDA's allowable maximum.

Jan 1, 1970

[United Engineering Trustees, Inc. W. D. B. MOTTER, JR., '40 A. L. QUENEAU, '41 ALBERT ROBERTS, '41 The Engineering Foundation GEORGE D. BARRON, '44 F. F. COLCORD, '42 A. L. QUENEAU, '41 Engineering Societies Library Board J. W. LAIST, '40 A. B. PARSONS, Ex-officio T. T. READ, '42 F. F. SHARPLESS, '41]

Jan 1, 1940

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

By E. C. Simmons

Uranium is an incompatible element with respect to the major rock-forming minerals crystallizing from granitic magma, entering instead trace minerals such as zircon. The relationship between the saturation limit (SL) for such a mineral and the bulk distribution coefficient (Do) for U is central to understanding the distribution of U and its availability to late-stage fluids that can form ore deposits directly, or labile U that can be remobilized later. Low SL values imply early crystallization of zircon, but in very small proportions, minimizing Do and maximizing the degree of enrichment of U in late-stage fluids. Thus, granitic rocks with low Zr contents (due to a low saturation limit for zircon) are most likely to evolve U-enriched differentiates; this will be reflected in a high U content of the zircons (but not necessarily high U abundances in whole-rocks). Thus, the ratio of the U content of zircon to the Zr content of the corresponding whole-rock is potentially a very useful parameter in identifying granitic rocks most likely to have U-enriched solutions associated with them. The granitic rocks associated with the U deposits of the Midnite mine area, Washington, have geochemical characteristics that fit the model presented very well. The rocks are very low in Zr (100 ppm) and contain zircons with extremely high U contents (3,000-4,000 ppm).

Jan 1, 1984

Mining Methods J. MURRAY RIDDELL, Chairman Guy N. BJORGE, Vice -chairman Alluvial Mining CLINTON BERNARD BENERE H. GRANT H. R. NORSWORTHY

Jan 1, 1937

By Minoru Sasabe, Mayurni Sorneno, Kazuhiro Goto

I) The Object of the Present Experiment. When the oxygen chemical potential in the gas phase is changed, the oxygen chemical potential in the liquid metal or in the liquid oxide phase will be subsequently changed. The object of the present experiment is to develop a method of measuring the change in the chemical potential of oxygen in liquid metals and in liquid oxides with respect to time, when the oxygen potential in the gas phase changes. II) The Experimental Method. The following types of the oxygen concentration cells with the solid electrolyte of Zr0z-CaO are used: KAZUHIRO GOTO, MemberAIME.MINORU SASABE,and MAYUMl SOMENO are Associate Professor, Research Associate, and Professor, respectively, Department of Metallurgical Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo, Japan. Manuscript submitted March 12, 1968, EMD. Igas phase liquid Ag or Pb ZrO2-CaO electrolyte!, The measured reversible electromotive force can be expressed by the next equation, provided that the transference number of the oxygen anion in the electrolyte is unity: E = RT/nF log (at electrode I)/P~ (at electrode 11) where is the electromotive force, R is the gas constant, T is absolute temperature, n is valence of oxygen anion, and Pq is the oxygen pressure at the electrodes. As shown in the previous work1 of the authors, the electromotive force is determined by the difference in the chemical potential of oxygen at the vicinity of the interfaces between the solid electrolyte and the electronic conductors used for the two electrodes. Fig. 1 shows the two kinds of the cell assembly used to measure the change of the chemical potential of oxygen in liquid metals and liquid oxides with respect to time. In both cases, the change of the oxygen pressure in the gas phase is measured by the independent oxygen concentration cell located above the

Jan 1, 1969

By E. F. Sumner, C. K. Eilerts

A partial differential equation was developed and programmed to compute the cumulation and flow of the liquid phase of a gas-condensate fluid. It was found that such cumulation near the wellbore may attain saturations permitting liquid flow within periods of the order of 1 day. The radius at which this saturation obtains advances toward the external reservoir boundary with continued recovery, although it may move only 2 to 5 percent of that distance during the productive life of the well. This relatively high saturation can cause a serious dimunition in delivery capacity. The pressure dilferential required for flow of gas through a formation with such saturation may be as much as three times greater than the corresponding differential in a formation where saturation is less than 2 percent. Because of the radial geometry, total reservoir pressure differential required for flow with a zone of relatively high liquid saturation about the well was indicated to be two to three times greater than without the saturation. INTRODUCTION A computing program developed by the authors 1 to integrate the partial differential equation for transient radial flow of gas-condensate fluids required a prevalued function, W(Po) = kD(p0)/M(p0)z0(Po).......(1) related to cumulation of condensate in pores of the reservoir as pressure declines. Methods were available for relating mobility to saturation, saturation to liquid-vapor volume ratio, liquid-vapor volume ratio to pressure and, hence, mobility to pressure to obtain W(pD). However, certain assumptions had to be made in advance of program execution concerning movement of the liquid phase and change in radial distribution of liquid saturation as recovery progressed. Because reservoir fluid mobility and related pressure gradients are markedly dependent on liquid saturation, it was desirable to eliminate the necessity for these assumptions and in this respect improve the reliability of a result obtained by integration. Experimental research was begun to determine the relationship of variables that control the reservoir flow of low liquid-vapor ratio fluids. With the porous medium partly saturated, permeability to a two-phase flowing fluid could not be measured because the viscosity was unknown. Viscosity could not be measured without knowing permeability of the liquid-containing medium; but mobility, the ratio of permeability to viscosity, was measurable. This property, and liquid-vapor volume ratio of the flowing phases, have values determined by nature of the fluid and porous medium and, in addition, were found to be pressure, velocity and saturation dependent. A program developed by Kniazeff and Naville 2 for computing multicom-ponent, two-phase flow used polynomials to represent saturation dependence of permeabilities for gas and for liquid phases, and an effluent viscosity constant under reservoir conditions. The authors developed a program based on a partial differential equation of similar mass balance origin but designed to represent distribution of an unlimited number of components between gas and liquid phases utilizing the experimental information available as to variable dependence. Attention was given to liquid-vapor volume ratio of the flowing phases, a property which is essential as a liquid saturation boundary condition. A program for computing implicitly saturation increase at uniform intervals along the drainage radius was combined with an existing program for calculating pressures, and the two were used alternately in an iterative solution for both saturations and pressures. The function W(pD) needed for calculating pressures was replaced by the ratio of mobility to compressibility factor. BASIC EQUATIONS The partial differential equation for calculating

By W. V. Kotlensky, H. E. Martens

In an earlier communication, Ref. 1, the authors presented the tensile properties and the changes in crystal structure and microstructure for pyrolytic graphite tested at 2750°C. It was suggested that changes in the structure may have an effect on the tensile properties of this material. Accordingly, tensile tests were run on a series of specimens, from one block of pyrolytic graphite, some of which were hot-worked by being strained at 2750°C, others of which were tested in the as-deposited condition. According to the manufacturer, General Electric Co., the polycrystalline material was deposited at 2100°C on a substrate of synthetic graphite by decomposition of a dilute natural gas mixture. The as-deposited material had a density of approximately 2.19 g per cc, and as shown in Fig. 1 had a structure of medium size growth cones which were regenera-tively nucleated. All specimens had a gage section 0.75 in. long by 0.06 in. wide by 0.1 in. thick with the thickness direction perpendicular to the basal planes. The testing method and equipment used have been previously described, Ref. 2 and 3. For both the hot-working and the testing the load was applied parallel to the basal planes; a cross-head speed of 1.5 x l04 in, per sec was used. All heating was done in an atmosphere of bottled helium.

Jan 1, 1962