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By H. L. Bilhartz, H. F. Dunlap, C. R. Bailey, Ellis Shuler

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent 'saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge's paper.' In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01' the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949

By C. R. Bailey, H. F. Dunlap, Ellis Shuler, H. L. Bilhartz

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent 'saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge's paper.' In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01' the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949

By K. G. Kreider, J. H. Brophy, J. Wulff

The technology of nickel-activated sintering of tungsten powder has been successfully applied to the densification of plasma-sprayed tungsten. Nickel was added by infiltration in a zinc solution followed by evaporation of the solvent. After sintering one hour at 1300°C density 95 pct of theoretical and transverse rupture strength of 74,000 psi were obtained. Shrinkage was found to be anisotropic and the mechanism of densification was comparable to that found in the nickel-activated sintering of tungsten powder. 1 HE use of a plasma spray gun for the fabrication of massive tungsten parts has become increasingly interesting. Applications now exist where a deposit in the as-sprayed condition is satisfactory. However, these deposits are generally characterized by a lamellar anisotropic microstructure containing 15 pct porosity of which, typically, two-thirds is open to the surface. Mechanically, the as-sprayed deposits fail at relatively low stress levels with a biscuit-like fracture. As a result of these problems the possibility of improving structure and strength by sintering treatments subsequent to spraying is particularly attractive. Preferably this sintering treatment should be adaptable to large bodies of sprayed metal. The similarity between the as-sprayed tungsten structure and that of a powder compact suggests that the relatively low-temperature activated sintering technique1 might be profitably employed in the densification of plasma-sprayed tungsten. It was the purpose of the present investigation to develop a technique for introducing the nickel-activating agent into the sprayed structure, to evaluate the amount and mechanism of densification obtained as a function of time and temperature, and to obtain an indication of the relative strength before and after sintering. EXPERIMENTAL PROCEDURE Powder used for spraying was purchased from the Wah Chang Corp. in several size fractions ranging from an average size of 4 to 150 . These powders were sized further for an explicit study of the influence of average feed size on densification. All powders were dried at 200°C before use. Spraying was accomplished with a Plasma Flame unit manufactured by Thermal Dynamics Corp. Several modifications of the unit were helpful in conducting the investigation. A variable speed auger feed mechanism coupled with the carrier gas mecha nism facilitated the use of fine particle sizes. A coil of ten turns of copper tubing in series with the arc power and concentrically would around the nozzle improved nozzle life and extended the range of operating currents available. The function of the auxiliary coil was to cause the arc to spin and to prevent impingement at only one point in the nozzle. Normally air sprayed deposits were made with an arc maintained at 400 amp at 50 to 70 v. The arc was blown by a gas mixture containing from 5 pct H, 95 pct N for the finest powder feed sizes ranging to 20 pct H, 80 pct N for the coarsest size. The flow rate was maintained at 100 cu ft per hr NTP through a nozzle of 0.25 in. ID. When apraying in air, the powder stream was directed toward an aluminum substrate for ease of mechanical removal of the deposit. The substrate was cooled by diverting the plasma flame with an air jet, and a second jet was directed on the deposit surface. In this configuration a gun-to-work distance of 2 to 3 in. was found to be satisfactory. Fig. 1 represents a typical as-sprayed deposit micro-structure. Laboratory studies of protective atmosphere spraying were carried out in cylindrical chamber 8 in. in diam by 18 in. in length. In operating the nozzle attached to such a chamber, particular care was required to avoid nozzle burn out due to reduced gas flow. The structure and density of the chamber sprayed deposits varied over wide ranges depending on substrate temperature. For the purposes of this investigation, flat deposits were made approximately 2 in. sq by 3/8 in. thick. From these deposits individual samples were cut an ground to a rectangular shape typically 1 1/2 in. by 1/8 in. sq such that the long dimension was perpendicular to the spraying direction. For the study of shrinkage anisotropy deposits up to one inch thick were produced. From these, rectangular samples were cut having a longer dimension parallel to the spraying axis. Prior to the addition of activating agent, the samples were deoxidized in hydrogen at 800°C for 20 min. No detectable dimensional or microstructural change was observed after this treatment. The addition of nickel was accomplished by infil-

Jan 1, 1963

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By Eckhard Nembach

The phase diagram of the system Pb-In has been investigated between -27° and + 40°C, using nzainly X-ray dijfraction. In accordance with t her mo dynamic measurements by Heumann and Predel, a segregation occurs at low temperatures, though not in the form of a nziscibility gap. THE phase diagram of the system Pb-In has been the subject of extensive investigations,1&apos;1 but recently Heumann and prede13 concluded from their thermodynamic data that a new feature should occur below room temperature. These authors observed that the maximum values for the enthalpy and entropy of mixing, which occurred at a composition of 50 at. pct Pb, were +400 and —1.7 cal per g-atom deg, respectively. From this the authors estimated that a miscibility gap should occur below 30°C, centered at 50 at. pct Pb. Resistivity measurements seemed to support this view. These authors proposed the phase diagram outlined in Fig. 1. Three phases exist at 30°C: the tetragonal indium phase with c/a > 1, the tetragonal intermediate phase a, with c/a < 1, and the fcc lead phase. During an investigation of the superconducting properties of Pb-In alloys. it has been observed4 that aging a specimen with 50 at. pct Pb for 14 days at -18°C decreased the superconducting transition temperature about 0.13"K and tripled the transition width. In this paper, the results of an investigation of the Pb-In phase diagram in the temperature range from — 2T to +40°C are reported. Superconductivity and X-ray methods have been used. 1) SPECIMEN PREPARATION The materials were provided by the American Smelting and Refining Co. According to the manufacturer their purity was 99.999 pct. The weighed amounts of the constituents were sealed in quartz tubes under an atmosphere of 10 torr helium, mixed for 24 hr in a rocking furnace at 380°C, quenched in ice water, and homogenized at 20" to 30°C below the solidus line, established by Heumann and Predel. The annealing times were 144 hr for specimens containing Less than 30 at. pct Pb and 36 hr for the remainder. 2) SUPERCONDUCTIVITY EXPERIMENTS The specimens were quenched from the homogeniza-tion treatment into ice water and their superconducting transition temperatures T, measured. The procedure used has been described in Ref. 4. The transition was detected by the change of the mutual induc- tance of two coaxial coils containing the sample. T, was defined as the temperature at which 50 pct of the total change in inductance had occurred. The repro-ducibility with which T, could be measured was i0.002"K. Then the specimens with lead contents between 38 and 75 at. pct were aged for 7 days at temperatures between -30" and 40°C. If this treatment caused T, to change by more than 0.005"K or the width of the transition to increase by more than 0.002"K, it was concluded that the specimen had undergone a phase change and no longer consisted only of the fcc lead phase: as it did immediately after homogenizing. The result is shown in Fig. 2. From this one can estimate at what temperatures and concentrations phase changes occur. The X-ray measurements were based on these preliminary results. 3) X-RAY EXPERIMENTS Because of the softness of the material, relatively coarse powders. 75 p, had to be used, which were filed in a helium atmosphere from homogenized specimens. The powders were annealed at least 30 min at temperatures between 120" and 16OJC, depending on their concentration, and quenched in ice water. Then their X-ray patterns were taken at -178°C with a Picker diffractometer, model 3488K, and a cold stage. on which the specimen was in thermal contact with a liquid-nitrogen reservoir. In this way the following relation was established for the fcc lead phase: a = 4.697 + 0.00247C for 40 5 C 5 75 11 where n is the lattice constant (A) and C is the at. pct of lead. The coarseness of the powder made it impossible to use lines with 0 > 75 deg; therefore n was averaged from lines with 45 deg 5 0 5 75 deg. The results were reproducible to within i0.05 pct. Relation [I] is very similar to the one found by Heumann and Predel at room temperature. Following this, homogenized specimens with compositions between 15 and 56 at. pct Pb were aged for at least 10 days at temperatures between -27" and

Jan 1, 1970

By Robert Glass Cleland

WALTER DOUGLAS succeeded his father, Dr. James Douglas, as president of Phelps Dodge in 1916. Before assuming office, the new president had been assayer at Bisbee, superintendent of the Copper Queen, general manager of all the Phelps Dodge mining interests, and altogether had spent a full quarter of a century in various phases of the company&apos;s business. Energetic and imaginative, experienced and courageous, he had need of all these qualities before he surrendered the direction of affairs into younger hands, fourteen years later. For the period of his administration was one of sudden ebb apd flow, flush production, drastic curtailment, quick recovery, and near-disaster. In 1917, soon after Walter Douglas became president, Phelps, Dodge & Co., Inc., which had been formed in 1908 as a holding company, went through an internal reorganization for the purpose of simplifying the structure and changing it from a holding company to an operating company. The Copper Queen Consolidated Mining Company, which had the necessary charter power and authority to carry on the business of any and all the subsidiary com-

Jan 1, 1952

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By N. B. Aughenbaugh, W. C. Patrick

The availability of a thorough, simple-to-use roof fall classification system is desirable for several reasons. First, such a system would expedite the reporting of falls for the purposes of estimating material removal costs, analyzing damage levels, and complying with federal regulations to report falls in certain areas of the mine. Second, the classification system would allow the mining engineer to record falls routinely with little time and effort expended. This would encourage him to make observations concerning what type of roof support would work best in a given situation. Third, and probably most important, an

Jan 1, 1980

By L. C. Noakes

Despite a long history of mining. Australia had no Commonwealth organization dealing specifically with the mineral industry until 1946, when the Australian Bureau of Mineral Resources, Geology and Geophysics was established. Once formed, this new organization quickly expanded to include a Mineral Economics Section, which was established in 1947. Australia&apos;s slowness to develop a Federal bureau for the mineral industry can best be explained in the light of her political history. From a group of British crown colonies, Australia evolved into six sovereign states which had no unified federal government until they formed the present Commonwealth in 1901.

Jan 1, 1970

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By G. R. Heckman, H. J. Murphy, C. T. Sims

An incestigation has been made of the effects of heat treatment and alloy composition on the long-time stress-rupture properties and structural stability of the similar nickel-base alloys Udimet-500, Lrdimet-520, and Udimet-700. Rupture test data are presented at stresses ranging from 4 to 50 ksi at temperatures from 1450° to 1900°F for times up to 14,000 hr. Ductility response is emphasized. Optical and electron tnicroscopy were complemented by X-ray diffraction analyses of extracted phases to relate microstructural stability to the observed rupture properties. Particular attention is paid to Udimet-520 since structural characteristics of this alloy appear to vary somewhat from its sister alloys. Both cast and wrought performance of Lrdimet-500 are discussed. The computerized PHACOMP calculational technique, based on electron-vacuncy theory, is discussed and related to structural stability where appropriate. Electron microscopy and microprobe techniques were used to conduct evaluation of the oxidation characteristics of Udimet-500 exposed in air for 16,100 hr. The steady advance in strength and reliability of nickel-base superalloys continues to be one of the high points of modern metallurgy. The stress capability of these materials has increased steadily, allowing higher and higher operating temperatures in the highly sophisticated aircraft and industrial gas turbines now on the market. The attendant increase in efficiency, of course, means greatly improved power output. Gas turbines for industrial and marine use have long been designed with these objectives paramount the usual design requirements in terms of time of service being 100,000 hr. High-efficiency, long-life aircraft such as the supersonic transport require superalloy engine materials with high-strength and long-time structural stability. Thus, materials studied for and operating experience from industrial gas turbines provide a good reservoir from which technology of high value to the SST program can be drawn. This study is one such case. Three prominent nickel-base super alloys—Udimet 500, Udimet 520, and Udimet 700 were extensively evaluated for industrial gas turbine bucket use. Particular attention was directed toward structural stability as a requisite property. Within the present context, structural stability is defined as freedom from the propensity to form strength-robbing or embrittling phases such as u,p,x,or Laves, and the ability to maintain useful rupture strength and ductility throughout design life. MATERIALS The three alloys, cast Udimet 500 (U-500C), Udimet 520, and Udimet 700, were chosen for detailed evaluation based on preliminary studies which indicated that U-500C and U-520 possessed comparable rupture strength capabilities, and that U -700 had a greater strength capability but somewhat poorer ductility than wrought U-500. The nominal compositions of the three alloys, along with the compositions of the heats investigated, are presented in Table I. PROCEDURE Dimensionally rejected U-520 buckets from Special Metals Corp. heat 63370 were heat-treated using the four cycles delineated in Table 11. Cycle A was investigated to determine the effects of a shortened 1700°F primary age. Cycle B was considered a "standard" treatment. Cycle C investigated a higher solution temperature in combination with a shortened primary age, while cycle D assessed the effect of the higher solution temperature alone. These heat treatments were designed to produce optimum combinations of rupture strength and ductility through maximum y&apos; development, the development of a y&apos; grain boundary cushion, promotion of MC carbide degeneration reactions, and agglomeration of resultant M23CB. Since one of the premises of the evaluation of U-520 was that rupture strength would be equivalent to U-500, forged U-500 buckets from Special Metals Corp. heat 62916 were heat-treated with cycles A, B, and C to provide comparison. The heat-treated structures of U-520 and U-500 are illustrated in the 8700 times electron micrographs of Fig. l. The U-700 tested was all from 3-in.-diam hot-rolled and centerless-ground rod from Special Metals Corp. heat 2-1426. Two heat-treatment cycles were employed, E and F of Table 11. Cycle E is a standard four-step, triple-age treatment intended to provide an optimum match of strength and ductility through well-developed matrix and grain boundary y&apos;, as recommended by U-700 vendors. Treatment F is a shortened , single-age cycle which could provide a significant processing cost reduction should adequate strength and ductility be maintained. Following heat treatment, rupture specimens of U-500 and U-520 were machined from the buckets and tested. Standard rupture bars of U -700 were machined from the heat-treated rod and rupture-tested. Failed and withdrawn rupture bars were prepared and examined by optical and electron microscopy. Select specimens were electrolytically digested, and the residues analyzed for carbide and topologically close-packed phases using CrKa or CoKo radiation. Of the six different U-500C heats evaluated, five were cast by Misco Precision Casting Co. and one was cast by Haynes Stellite Co. Cast-to-size rupture bars

Jan 1, 1968

By ME ME

IT just so happens that we do our best thinking while painting wood- work and last Saturday while finishing up the screens (the bugs come late where we live) the paint very nearly ran out. By adding turpentine, it just stretched. It was pretty thin for the job though, which made us think that that is just about what the situation is going to be in the mining industry if something isn&apos;t done to increase the number of enrollments in engineering curricula. Engineers are going to be spread too thin for the job at hand.

Jan 8, 1951

CORPORAL SHEPPARD B. GORDY Sheppard B. Gordy, a brief biography of whom was printed inn the January Bulletin, entered the employ of the Braden Copper Co. immediately on his graduation from the Sheffield Scientific School in 1912. He remained with this company four years, working up through the various grades to assistant foreman and foreman to one of the individual mines. The last year he was in its employ, he acted as general mine foreman. He was for a short time with the Chile Exploration Co. and then went with the Andes Exploration Co. (Anaconda) and remained with CORPORAL SHEPPARD B. GORDY. the latter, doing mine exploration and development work, until he sailed for home in June, 1918, to give a more personal and active service to his country in her need. He declined a tender of induction into an officers&apos; training camp, at the urgent request of Professor McClelland supplemented by Mr. Potter, because they demonstrated to his satisfaction that he could give more valuable service to his country in helping out with the aircraft production. Being within the draft age, in order to carry out this plan, it was necessary for him to be called by his Local Board and sent to camp. This call came Aug. 26. Two weeks before that time lie had gone to Dayton, Ohio; to begin the study of aircraft production, and was sent by the Dayton Board to Camp Sherman, Chillicothe, Ohio, where he died of pneumonia on Oct. 9.

Jan 3, 1919

By Raymond Ward

IN the past few years several papers have appeared dealing with different aspects of the oxidation of dilute alloys, especially with respect to the formation of internal oxides or subscales. Subscale has been defined1 as that layer or zone of oxide particles precipitated in a matrix of metallic metal in which the oxide particles are dispersed uniformly and occur by diffusion of the oxygen inward from the metal surface. Alloys composed of a solvent metal more noble than the alloying elements are subject to subscaling or internal oxidation. In these alloys the solute must be present in such quantities that if the alloy is exposed to an oxidizing atmosphere at elevated temperatures, the rate of diffusion of the oxygen into the metal will be greater than the rate of diffusion of the solute outward. There is a composition range of the iron-silicon system that falls into this classification. Knowledge of the nature and rates of oxidation of iron-silicon alloys is of great commercial importance, but very little information of this nature is available. Darken2 recently has made calculations to show the limits of concentration of silicon for which subscales are produced in iron-silicon alloys; however, the main thesis of his paper was to analyze and to explain the already existing data. The purpose of this paper is to present the effect of com position, temperature, time, and atmosphere on the type of scale-metal layer obtained and to give some qualitative indication of the effect of these variables on the rates of oxidation. Since this paper is a study of silicon steels that are available commercially, extremely low-silicon and high-silicon alloys are not included. EXPERIMENTAL PROCEDURE The alloys used in the experiment were taken from heats of silicon steel that ranged in analysis from 0.70 to 5.8 per cent silicon. This composition range takes in most of the commercial silicon steels. In Table I are listed the compositions of alloys used. Other than iron and silicon, the alloys normally contained approximately the following impurities: carbon, 0.03 per cent; manganese, 0.07; phosphorus, 0.008; sulphur, 0.02; copper, 0.07; tin, 0.01, and from nil to a trace of chromium, nickel and copper. All of the alloys used were melted in open-hearth furnaces, except where otherwise noted, and were hot-rolled to 0.100-in. plate. Samples approximately 1/2 in. square were then cut from these materials. So that the surface conditions of the samples used for oxidation would be standardized, each sample was ground through 000 emery paper immediately before oxidation. Two different techniques were employed in carrying out the oxidizing treatments. One consisted simply of heating the samples with free access to air. In this treatment the samples were set on edge on a refrac-

Jan 1, 1945

Upon the recommendation of its Technical Committee, The Com-pressed Air Society has adopted the following definitions of, certain terms. Displacement.-The displacement of an air compressor is the volume displaced by the net area of the compressor piston. Capacity.-The capacity should be expressed in cubic feet per minute, and is the actual amount of air compressed and delivered, expressed in terms of free air at intake temperature and at the pressure of dry air at the suction. Volumetric Efficiency.-Volumetric efficiency is the ratio of the capacity to the displacement of the compressor, all as defined above. Compression Efficiency.-Compression efficiency is the ratio of the work required to compress isothermally all the air delivered by an air compressor to the work actually clone within the compressor cylinder, as shown by indicator cards, and may he expressed is the product of the volumetric efficiency (the intake pressure and the hyperbolic logarithm of the ratio of compression), all divided by the indicated mean effective pressure within the air cylinder or cylinders.

Jan 8, 1918

By Robert M. Dreyer

AGGREGATE With an annual domestic production of over 1.6 billion tons at a value of over $2 billion (see Table 15.1.1), the production of aggregate (crushed rock, sand, and gravel) is a basic industry of utmost economic importance. Because of the role of aggregate materials as essential ingredients of concrete, asphalt surfacing, and plaster, their delivered prices are major factors in determining the cost of construction. The annual domestic production comes from nearly 10,000 plants. About 15% of these plants account for over one-half the production. In a rapidly inflating economy, the average mine sales price of aggregate has remained relatively stable. The actual mine sales prices, however, vary greatly depending on quarrying costs in various parts of the country. Of much more importance in construction costs, however, is the delivered price of aggregate. This varies for each job, depending on the distance from the quarry and resulting transportation costs, as well as the initial cost at the mine. Because of a proliferation of regulations limiting new quarries in the vicinity of the encroaching urban sprawl, the average distance which aggregate must be transported has been increasing rapidly. Although it is impossible to derive an average delivered cost for aggregate, it should be noted that even an increase of only $1 per ton in average delivered cost over the last decade (probably a minimal assumption) would mean an annual cost $1.5 billion higher than ten years ago. In recent years, structural engineering considerations, as well as an increasing use of lightweight concrete blocks, have resulted in a rapidly increasing demand for lightweight concrete and plaster, the essential ingredient of which is lightweight aggregate. Principal lightweight aggregates are: pumice, slag, perlite (thermally expanded hydrous volcanic glass), vermiculite, and expanded shale, formed by the thermal expansion of shale and slate. The United States now has the capacity to expand, annually, over 13 million tons of shale and slate and to expand over 600,000 tons of perlite. In locating a site for aggregate production. the following factors must be considered: (1) tonnage available; (2) quality of aggregate (including local variations); (3) distance from major use areas; (4) transportation costs, including those resulting from present and possible future haulage restrictions; (5) zoning regulations; (6) operating costs, including the cost effects of compliance with local regulations governing blasting, air pollution, water pollution and drainage, noise levels, and operating periods. At one time, locating a suitable site for the production of crushed rock, sand, or gravel, in most areas, was regarded as an extremely simple task. In the past few years, however, finding a site for profitable production of aggregate has assumed ever-increasing com-

Jan 1, 1976

By Frederick O?Neil

SCOPE OF THIS REPORT THE object of this paper is to describe the present status and possibilities of liquid oxygen as an explosive based upon the investigations, research and practical work of the Ingersoll-Rand Co., and of the Air Reduction Co., from early in 1922 to date. The following work was done. 1. A study of the history and physical theory of L. 0. X. as an explosive. (No attempt will be made in this paper to give the history or theory, as this has already been covered by the literature on the subject.) 2. An investigation of the use and the practice with L. 0. X. in the iron mines of Lorraine where L. 0. X. has its largest application in Europe. Although L. 0. X. is extensively employed in the; iron mines of Lorraine, many of the mines using it exclusively, and blasting with it a total of approximately three million tons of iron ore per year, the fact that the mining practice in Lorraine1 is to drill comparatively shallow holes and blast only a few holes at a time, renders the data obtained there of very little value in estimating the possibility of replacing dynamite with L. 0. X. in American mining methods. In fact, in the iron mines in Lorraine, L. 0. X. replaced black powder, or its equivalent. 3. Laboratory research work on properties of absorbent materials. 4. Work in the Bureau of Mines explosive laboratory at Pittsburgh, Pa., on the properties of L. 0. X. cartridges. 5. Practical work underground with L. 0. X. cartridges in the Witherbee-Sherman iron mines at Mineville, N. Y. 6. Practical work in the quarries of the Calcite Quarry Co., Myers-town, Pa. 7. Practical blasting in several quarries and open-pit mines.

Jan 2, 1926

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10&apos;1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.&apos; only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

By George M. Enos, Robert J. Anderson

An impoRtant factor affecting the rate and nature of corrosion of metals and alloys is the film, or coating, formed on the surface; and this may accelerate or retard corrosive action once started. The formation of films and coatings is intimately associated with the chemical composition and physical constitution of both the metal and the corroding medium. A film or coating may be either the corrosion product resulting from oxidation; that is, an oxide or salt, or a deposition of suspended matter from the corroding media upon the surface of the metal, or a mixture of both. The coating may adhere tightly or loosely to the surface of the corroded metal. In short, a film or coating is the reaction product of the corroding medium and the metal, which adheres to the surface of the metal and with which may be intermingled material from the attacking media not concerned in the chemical reactions. As the terms film and coating are used by different writers for very different things, distinction is made between the two, by the present writers, on the basis of thickness. Thus, a film is defined as a corrosion product or deposition, on the surface of a corroded metal, that is of such thickness that it cannot be measured by the metallurgical microscope. A coating, on the other hand, is of such thickness that it can be measured. If the resolving power of the 2-mm. (equivalent focal length) apochro-matic oil immersion objective (N.A. 1.4) is taken as the limit of the microscope, the limiting resolution is two lines that are 0.0002 to 0.0004 mm. apart. It is thus possible to measure coatings that are greater than 0.0002 to 0.0004 mm. thick. This thickness is equivalent to 50,000-

Jan 1, 1925

By W. C. Snow

The plant of the Electrolytic Zinc Company of Australasia Limited, situated at Risdon on the estuary of the River Derwent, near Hobart, was designed and erected primarily to produce high-grade zinc from zinc concentrates produced by the mines of Broken Hill, N. S. W. Consequently the metallurgy of the process has been influenced in its development by the peculiar characteristics of the Broken Hill concentrate, which on treatment gives into solution relatively large amounts of cobalt, manganese and silica. The Risdon works (Fig. 1) produces high-grade electrolytic zinc, leaded electrolytic zinc, zinc dust, cadmium, sulphuric acid and superphosphate. This paper, however, is concerned only with the zinc plant and process. Roasting The roasting of raw concentrate is not a major feature of Risdon&apos;s process, and in this respect practice is unlike that of most zinc plants. The roasting is mostly done on the Australian mainland at centers where the sulphuric acid made from the roaster gases can be used for superphosphate manufacture. A small amount, approximately 40 tons per day, is roasted at Risdon, acid being manufactured from the gases. The amount that can be roasted there is limited by the acid requirements of the zinc plant and of the superphosphate plant. Roasting is not carried to completion at the mainland plants, and the product, known as preroast calcine, largely constitutes the raw material for the Risdon zinc plant. It contains about 6 per cent of sulphur as sulphide. Roasting is completed at Risdon for reasons that are set out later in this paper. The zinc plant proper is divided into four main divisions: (1) final roasting division, (2) leaching and purification division, (3) electrolytic division, (4) melting and casting division. There are two subsidiary divisions—the cadmium division and the preroast, acid and superphosphate division.

Jan 1, 1937