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By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By J. O. Brittain, E. Lautenschlager

An investigation was conducted on fine grained airon wire to measure the influence of the temperature of deformation on strain aging near room temperature. Specimens were deformed various amounts at 77°, 195°, or 273°K and aged. The strain aging was followed by either internal friction or return of the yield-point measurements. The results show that strain aging occurs in three stages. During the first stage there is small, almost immediate return of the yield point. The solute carbon concentration, as mesured by internal friction, remains constant in stage I but is lower than the concentration in the unstrained condition. In the second stage, the solute concentration decreases while the magnitude of the yield point increases. In the third stage, the solute atoms continue to drain from the solution, the yield point approaches a maximum, and the strain-hardening coefficient and flow curve increase. The kinetics of the strain aging reaction are not the same for the two sets of measurements since the internal friction results lag behind the yield-point measurements. However, the strain-aging kinetics measured at 44° and 64°C showed no effect due to the difference in initial deformation temperature; nor were the strain aging kinetics influenced by low-temperature anneals at 77°, 195°, and 273°K. 1 HE object of this investigation was to measure the effect of initial deformation temperature on the strain aging of a-iron by tensile tests (i.e., return of the yield point) and internal friction methods, to correlate the results of the two measuring methods, and to measure the effect of low-temperature annealing (<273°K) after low-temperature deformation upon strain aging. The experiments were performed on fine-grained a-iron wire containing 0.02 wt pct c.l According to Thomas and Leak,&apos; return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solid solution, while the return of the yield point as a function of the aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,3 during aging the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point on subsequent testing. It has been shown that after low-temperature neutron bombardment, a-iron goes through a stage of recovery at low temperatures which can be attributed to the annealing of iron interstitials&apos; and/or vacancies.4 If, after low-temperature deformation, there is an interaction during a low-temperature anneal between mobile point defects and the solute atoms (i.e., carbon atom interaction with vacancy or iron interstitial), it is possible that some solute atoms will be found at defect sites other than dislocations. Such changes in the sinks for the carbon atoms might be expected to alter the strain-aging kinetics sufficiently to be detected by either inter-

Jan 1, 1962

By P. Hudock

Thin films of PbS and CdS have been deposited on insulutiug- sapphire substrates by euzploying a subliwzation technique rising near-equilibriurum conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have mobilities approachitzg values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. By performing the depositiotz of a compound within a small chamber heated to a UNiform temperature within a Vacuum systerrz, it is possible to approach equiilibrium cod-tions r.~litl~irs the chamber. In this way; the sublimation and condensation proceed under near equilibrium co?zditions, and it was found that the properties of dePosited corrzpounds were similar to those of the source material. Oriented PbS films on sapphire have a roor?l- temperature unobility of 700 sq cm per v sec and a T-5/2 temperature dependence characteristic of bulk crrystnls. CdS layers on sapphive Izazse a resistivity ~uhich is corrlpamble to the resistivity of the souvce crystals over a range of four ordem of rrlagnitude. Irz contrast, Ihe resistivity of CdS films prepared by conventional evaporation depends largely upon the substrate terrzperat~ire and postheating treatrrletlt, vather than upon the properties of&apos; the solirce rrraterial. In the case oj the CdS films the achievment of high carrier mobility required the cargful exclusion of cont~~~~ii~unts from the films. The steps taken to accomplish this included presublimation of the source material, performance of the deposition at a backg-m~ozd pressure less than 10-8 Torr, and a solvent extraction with liquid cadminum, similar to that described by Aven and woodbury. The deposition of ,films under near-equilibrium conditions is being op-plied to other classes oj COmpounds. II should he of 1:allce ,tor llle deposition of nny matevial that decomposes in the vapor state. THIN films of PbS and CdS have been deposited on insulating sapphire substrates by employing a sublimation technique using near-equilibrium conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have Hall mobilities approaching values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. Depositions were performed in a small quartz sublimation cell shown in Fig. 1 that contained the compound and the single-crystal sapphire substrate. The substrates were etched in tapered solutions of hot phosphoric acid, rinsed in deionized water, dried, and transferred to the cell under dry nitrogen. Graphite crucibles and substrates were used in experiments where it was necessary to provide an inert test vehicle for the analytical determination of impurities in the source crystals and deposited films. The crucibles and substrates were machined out of spectrographic-grade graphite having less than 1 ppm of impurities. A quartz mask was sometimes used to define a pattern which could be used for Hall and resistivity measurements. Close spacing between the compound and substrate was maintained to insure better transport of each component from the source material.

Jan 1, 1968

By J. Gurland

The wmk is concerned with the estimate of the degee of continuity of a particulate phase dispersed in a matrix. The first section is a verieu: of the parameters nzeasurable by quantitative rnetallogvaphy, namely the contact area and, under certain conditions, the number of contacts between particles of one phase. In the second section, the frequency of particle contacts is related to the degee of continuity of a randomly embedded phase orz the basis of the lattice-percolation model of Hamrnersley and others. THE extent of continuity of the constituent phases may greatly influence the structure-sensitive properties of phase mixtures, particularly if the phase properties differ significantly. An example from the literature1 is shown in Fig. 1. The marked decrease of the electrical resistivity of sintered silver-alumina bodies near 25 pct by volume of silver presumably occurs because the more conductive phase changes from a discontinuous to a continuous structure. Other example of electrical- and thermal-conductivity transitions are cited by kingery In view of these observations, a knowledge and understanding of the connectivity of the microstructure may be of considerable practical importance. This study is concerned with one aspect of the genera1 problem, namely the estimate of the degree of continuity of a particulate phase dispersed in an opaque matrix. The first section reviews the parameters measurable on a polished cross section by auantitative metallography, such as the contact area and under certain conditions, the number of contacts between particles of one phase. In the second section, an attempt is made to relate the frequency of particle contacts to the degree of continuity of a randomly embedded phase. For the purpose of this discussion, the aggregate has two constituents: the particulate phase and the matrix. The latter is considered to be homogeneous. The term "particle" is used with the meaning of "grain", i.e., a minute unit of matter which is usually a single crystal of a readily distinguishable substance within the confines of a simply connected boundary. While many of the concepts which are used here to describe the structural variables characterizing the microstructure of phase mixtures are qualitative and ill-defined, they are presented with the intent of stimulating further work of a more general and rigorous nature. I) PARTICLE CONTACT, CONTIGUITY, AND MEAN FREE PATH 1) Measurement of Contiguity. The fraction of the total internal surface of a phase a shared with particles of that same phase in a two-phase mixture of and $ is indicated by the contiguity ratio:3 whereis the area of the interface between o particles, and Sap is the area of the interface between a particles and matrix P, per unit volume of mixture. The contiguity ratio ranges from 0 to 1 as the distribution of the a phase changes from a completely dispersed to a completely agglomerated structure. The interfacial areas may be obtained from simple intercept measurements on a random plane, after Smith and Guttman where and N are the numbers of intercepts between a random line of unit length on a plane of polish and the interparticle and interphase interfaces, respectively. The equations are valid for any distribution of particle sizes and shapes.

Jan 1, 1967

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,&apos;" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By S. K. Sarkar, B. Dr. Singh

INTRODUCTION India like USA has traditionally relied on bord and pillars as dominant underground method. Coal has generally been mined at shallow depth from relatively thick and horizontally bedded coal seams. These&apos; factors contributed towards large scale adoption of bard and pillar. After nationalisation of coal industry in two stages in 1971 and 1973, large scale mechanisation and modernisation programmes were undertaken. Longwall mining was identified as one of the major that area for increasing underground coal production. The idea to introduce longwall mining was mooted to increase productivity and to promote conservation and safety. The nationalised coal industry has already worked about twenty longwall faces with different types of support. The tempo of introducing longwall is catching up and a number of longwall programmes with, Self advancing supports of different types and Capacity are in active stage of implementation. The country has not yet started producing mechanised Supports and therefore supports and machineries are being imported from U.K. and other countries of the continent. The of the major problem faced in the longwall projects is to choose suitable type and capacity of supports. The suppliers and manufacturers of these supports are not competent enough to choose and offer the right type and capacity of supports as their knowledge and information about Indian strata conditions are extremely limited. The Central Wining Research Station (Q.!RS), has undertaken a research programme for evaluating the rock mechanical conditions obtaining in the proposed longwall locales and has worked out a method for selection of proper type and capacity of supports on the basis of projected strata behaviour at the proposed locale. STRATA CCNTROL FAILURES Indian coal industry had made some attempts to introduce longwall caving in the early fifties after a working group set up by the Government of India had recommended its adoption to increase productivity and to modernise mines. Approximately 20 longwall faces were tried in the major Indian coalfields of Jharia, Ranigunj and Karanpurr between 1951 and 1968. The supports used consisted of 20T hydraulic props or 35140~ friction props. A number of these faces had suffered total strata control failures and a large number of support elements were lost. The Central Mining Research Station initiated a research programme to analyse these failures in the general background of behaviour of Indian coal measure strata at longwall faces. All the available data regarding the cases of failures were collected and physico-mechanical properties of overlying roof rocks were determined in the laboratory. Simultaneously, observations were continued to establish the behviour pattern of Indian coal measure strata at longwall faces. These studies were helpful in analysing the occurrences of collapse. BEHAVIOUR OF INDIAN COAL MEASURE STRATA The coal measure strata encountered in the principal Indian coalfields of Jharia, Ranigunj and Karanpura are in general strong in nature however, the immediate roof (mostly up to 1.5 to 2 m) in most of the cases is weak and false bedded shale. MI idea about the strength properties of immediate and overlying roofs may be obtained from the following table.

Jan 1, 1982

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7&apos;8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By J. C. Uy, A. A. Burr

IN the primary solid solutions of zirconium-base alloys, there is a striking regularity of the effect of solute valence on the stabilization of the allotropic phases.1 The valences derived by pauling2 are for elements as they are bonded in the solid metallic state. Effects of variations in isotopes, alloying elements, and allotropes on their valences are difficult to determine and such data are presently unavailable. Pauling&apos;s values are somewhat empirical and approximate, but if some definite correlations can be found between those values and experimental observations, this will lend support to the tacit assumption that the possible variations in valence mentioned above are small. Pauling has amassed a large amount of evidence of such correlations. It is the purpose of this technical note to show another application of the Pauling valences and to offer a possible explanation for this observation. The relationship between the Pauling metallic valence of the solute and the stabilization of allotropic phases in zirconium is shown in Table I, which has been compiled from available data in the literature3 plus the results of work done at Rens-selaer Polvtechnic Institute.&apos; The chemical valences are included for comparison. It can be seen that a solute whose metallic valence is lower than that of the solvent tends to stabilize the a phase while one whose metallic valence is higher than that of the solvent tends to stabilize the 0 phase. It should be noted that, inasmuch as the Pauling valences are periodic with atomic number, this is tantamount to saying that the elements in groups I-A, 11-A, III-A, III-B, IV-B, V-B, and VI-B are a stabilizers while those in groups IV-A, V-A, VI-A, VII-A, VIII-A, I-B, and 11-B are ß stabilizers. The chemical valences do not show such consistency. Although the zirconium-rich end of the Zr-Au diagram is not available, it call be expected that gold, having a metallic valence of 5.56, would stabilize the ß phase. At absolute zero, the Fermi energy level is the criterion of equilibrium, i.e., the structure having the lower Fermi level will be more stable. Conse- quently, allotropic transformation occurs in a metal when thermal excitation raises the Fermi level to a point at which the atoms can be better accomodated by a different structure which yields a lower Fermi level.4-6 Thus in allotropic transformation, a change in structure occurs as a result of the change in the energies of the bonding electrons. Since the Pauling valence is the number of bonding electrons per atom, and these are the only electrons whose energies are affected by thermal excitation,* it can be inferred that the introduction of a solute which has a higher Pauling valence than that of the solvent raises the initial Fermi level; consequently, the transformation temperature is lowered. The converse is also true. The fact that at the transformation temperatures this statement is still fairly valid implies that the contribution due to the difference in specific heat terms of the two allotropes is comparatively small.

Jan 1, 1962

By J. M. Oblak, R. F. Hehemann, R. H. Goodenow

STUDIES of surface relief and growth kinetics have lead to the concept that widmanstatten ferrite along with upper and lower bainite constitute a continuous series of decomposition products.1-4 Current models4 propose that these products form as plates with a coherent or semicoherent leading edge which propagates at a rate controlled by diffusion of carbon into the surrounding austenite. There are, however, important crystallographic and morphological differences between these products—particularly between upper and lower bainite. For example, upper bainite appears to exhibit a (11lIy orientation habit, whereas lower bainite develops with a more irrational habit near {2251y.5-7 Many of the morphological features of these decomposition products are not yet well-documented. Recent studiess have demonstrated that low-carbon martensites form as sheets of closely spaced needles on {lllly planes while higher-carbon martensites form as plates with {225}? or other orientation habits. The similarity in the crystallography of these two modifications of martensite with upper and lower bainite is striking. Therefore, a study of the morphology of bainite in a series of hypoeutec-toid alloy steels has been initiated to explore these relationships further. The question of immediate interest is whether upper and lower bainite form as plates or needles. A two-surface (approximately perpendicular) metallographic method was employed to study the morphology of bainite in a variety of low and medium alloy steels. Compositions of these steels have been reported elewhere. The behavior of 4340 and 4370 was typical and will be described here. Austenitizing treatments involved 20 min at 2350°F for 4340 and at 2000°F for 4370. Isothermal transformation was conducted in molten-salt baths. Upper bainite was produced at 925°F in the 4340 steel and lower bainite at 575°F in 4370 with transformation times adjusted to produce 10 to 15 pct of the decomposition product. Many of the morphological features of upper bainite have been catalogued in the recent literature.&apos;&apos; The two principal variants observed in the present investigation are illustrated in Fig. l(a). One form appears as long, thin plates or needles and the other as small, frequently irregularly shaped particles. Both variants may occur as isolated forms but more frequently appear in groups as demonstrated in Fig. l(a). Two-surface analysis reveals that these two variants constitute different sections through a single morphological form. To demonstrate this, a number of sections perpendicular to the plane of Fig. l(a) were prepared at various positions along the length of the elongated particles. A section taken at position 1 in Fig. l(a) is presented in Fig. l(b). Here, the dark line represents the edge of the sample and the left-hand portion of this photomicrograph is that from the surface perpendicular to the original plane of polish. Since it was necessary to repolish the original surface after each sectioning, the shape of the bainite particles on this surface, right hand side of Fig. l(b), changes with each sectioning. The disappearance of plate A, Fig. l(a), in Fig. l(b) emphasizes the small cross section of these structures. The group of particles in the lower left-hand

Jan 1, 1964

By Roger A. Gregg, Barry J. Piearcey

MANY of the nickel-base superalloys developed recently for use in the as-cast condition exhibit a massive "white-etching" constituent1 in the inter-dendritic regions. Commercial alloys in this category are SM 200,* IN 100, INCO 713, and Nicrotung. The appearance of a similar microconstituent in nickel-rich Ni-A1-B alloys has been reported by Schijbel and Stadelmaier. Their investigation revealed that this constituent was the binary eutectic of the terminal nickel-base solid solution and the inter metallic based on Ni3A1. This binary eutectic is degenerate and NhA1 is the major phase. At lower temperatures the eutectic composition lies within the NkA1 phase field and under equilibrium conditions is single-phase NisAl. Taylor and F&apos;loyd3 have shown that in Ni-Al-Cr alloys containing at least 8 at. pct Cr, liquid compositions which solidify by the eutectic reaction in the nickel-rich portion, precipitate nickel-base solid solution and NiAl rather than nickel-base solid solution and NkA1 in the binary Ni-A1 system. Since the nickel-base alloys contain chromium in excess of 8 at. pct and are further alloyed with one or more of the elements titanium, cobalt, molybdenum, or tungsten, it is possible that the eutectic could contain NiAl rather than NisAl. In addition, Benson4 has reported that in low-nickel austenitic high-temperature alloys, which possess Ni/(Al + Ti) atomic-weight ratios <18.0, the Ni (Al, Ti) phase may precipitate from the melt during solidification. Since SM 200 and similar high-temperature materials were developed from alloys which were designed for solution treatment, the appearance of a eutectic would indicate that the limit of solid solubility has been exceeded. The purpose of this note is to confirm that the massive white constituent in the complex nickel-base alloys investigated is based on the binary eutectic Ni + NbAl and that the limit of solid solubility need not be exceeded to produce it, in common with other observations of cast alloys. Successive polishing of a sample of SM 200 showed that, in agreement with Schobel and Stadelmaier, particles of the constituent were spherulitic and in particular were a) situated between cored dendrite arms, Fig. 1, and b) nucleated at the surface of dendrites, Fig. 2. The Ni/(Al + Ti) atomic-weight ratios for the nickel-base alloys which were observed to contain the massive eutectic constituent in the interdendritic regions are 12.1 (Nicrotung), 9.2 (IN loo), 19.5 (INCO 713), and 14.5 (SM 200). However, the results of X-ray analysis of these alloys in the as-cast condition failed to reveal the presence of the Ni (Al, Ti) phase. An electron microanalyzer was therefore employed to analyze the composition of this constituent in SM 200. The results of analyses of representative particles are as follows5: 8.4 at. pct Ti, 8.8 at. pct Co, 5.5 at. pct Cr, 0.9 at. pct W, 12.8 at. pct Al, and 63.6 at. pct Ni. Assuming that

Jan 1, 1964

By S. A. Herres, A. R. Elsea

Temper brittleness refers to the loss in the notched-bar impact resistance encountered in most medium- or low-alloy steels when they are tempered within the temperature range of 700 to ll00°F or slowly cooled from a higher tempering temperature. Temper brittleness is important because it impairs the service properties of otherwise suitable steels over the range of hardnesses obtained at medium tempering temperatures and because it is impractical to cool pieces of large section rapidly enough from higher tempering temperatures to prevent temper brittleness. The problem of temper brittleness has always been closely associated with ordnance manufacture because armor plate and gun steels require good shock resistance and are often heat treated in heavy section. However, it is now realized that many brittle failures in structural alloy steel parts are attributable to temper brittleness, and there is little question that it contributes to the low impact resistance of alloy steels used in the hot-rolled or normalized condition which are slowly cooled from the hot-rolling or normalizing temperature. Recently Hollomonl has presented a comprehensive summary of the literature on the subject and an excellent description of the manner in which temper brittleness affects the notched-bar impact resistance and other mechanical properties of steel. Carpenter and Robertson2 have given a good analysis of the probable mechanism of temper brittleness, which is similar in many respects to the precipitation-hardening phenomenon. Fig 1 is their diagram illustrating the response to tempering of a susceptible steel. Three changes are recognized as the temperature of tempering a previously quenched steel is raised: (1) pre- cipitation occurs more rapidly and to a greater extent and the notched-bar impact value falls to a minimum; (2) coalescence of the precipitated particles begins to be effective and the impact values for both rapidly cooled and slowly cooled specimens increase; (3) the precipitate goes back into solution at higher tempering temperatures and the impact values of specimens cooled rapidly enough to retain the solution increase, while reprecipitation occurs in slowly cooled specimens and their impact values decrease again. No change must proceed to completion before the following one begins and there is overlapping in temperature ranges. Although there have been a large number of experimental investigations of temper brittleness, insufficient evidence has been accumulated to permit definite identification of the precipitate wnich causes temper brittleness nor have the specific effects on it of various alloy elements and impurities in steel been definitely established. This lack of evidence is largely a result of the lack of a suitable measure for temper brittleness. Temper brittleness is evidenced by an increase in the temperature of brittle failure of notched-bar impact specimens, but most of the data are in the form of an arbitrary susceptibility ratio of the room-temperature impact value for specimens quenched from a high tempering temper to that of similar specimens furnace cooled from the temper. It is obvious that this numerical ratio is dependent upon the type of specimen used and the specific conditions of testing rather than the characteristics of the steel. In general, manganese, chromium, and nickel alloy steels are most susceptible to temper brittleness and molybdenum has heen used to decrease

Jan 1, 1950

By H. E. Stamm, H. H. Spain, R. C. Rumble

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By H. H. Spain, R. C. Rumble, H. E. Stamm

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By L. B. Schmitt, N. H. Polakowski

Square bars of cold-dvawn copper, mild steel and a 2024 aluminum alloy were forced through an adjulstable gap between two hardened steel rollers by pulling or pushing. The rollers were either free to rotate or were locked in position so that conditions comparable with drawing, rolling, ad containerless extrusion could be created at will. Push or pull forces as well as roll separatirg forces were measured. Forming efficiency and coefficients of friction were determined. For- slow-rate deformation the values ot µ wrere between 0.09 and 0.14. Possibilities for further investigation are indicated. THIS work was undertaken with the aim of a) determining the principal parameters of cold drawing under simplified conditions directly, without recourse to speculative assumptions and b) comparing drawing with rolling and extrusion from the viewpoint of forces involved and deformation efficiency. Data of type a) relating forces in axially-symmet-rical drawing to die geometry. drafting schedules, material properties and lubrication conditions are abundant. Their intrinsic value is. however. limited as long as the radial die forces are unknown. On the other hand. the difficulties associated with measurement of these forces are serious as witnessed by the extreme paucity of such information."" Comparative investigations of type b) were also remarkably few and they all employed ring-shaped dies through which round bars were either drawn or pushed.2-4 Only in one case were the applied and the die splitting forces measured simultaneously.2 In order to simplify the problem, deformation under approximately biaxial conditions was adopted in the present work;. This enables both the drawing (rolling, extruding) efforts and the separating forces to be measured with reasonable ease by conventional methods. Since drawing, extrusion, and rolling can be carried out under virtually identical conditions only in a roller die. an adjustable tool of this type was constructed. The circular die profile involved a difficulty with interpreting the drawing and extrusion data. This was obviated by arbitrarily defining the angle between a contact chord and the drawing plane as the -.equivalent" die semiangle. The simplification was considered permissible since the effect of die angle was not specifically investigated. An additional conlplication was caused by the square cross section of the processed bars. This shape was selected as a compromise between the desire to have as massive as possible specimens and the capacity of the roller die. The metal was only partially restrained from spreading laterally. the flow conditions being therefore intermediate between plane stress and plane strain. On the Huber-Mises yield criterion the constrained and uni-axial yield strengths differ by up to 16 pct but the actual error due to the ignorance of the constraint factor was presumably much smaller than the maximum. In spite of these reservations it was felt that the method employed and results obtained have some merit. With certain further refinements to be indicated later, this technique can yield data perhaps more useful for checking metal forming theories than other, mostly indirect, methods. EXPERIMENTAL Materials—The metals used together with their principal mechanical properties are listed in Table I.

Jan 1, 1961

By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans&apos; calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,&apos; the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275&apos;C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By M. P. Tixier, K. S. Kunz

A method for the interpretation of temperature curves recorded in gas producing wells is described. One essen-tial feature of the method is a simple graphical construction which conveniently reflects the amount of gas flowing from a given producing formation. This method, applied in conjunction with the Induction Log and radioactivity logs, is valuable to determine the points of entry of gas and to estimate the over-all thickness of the producing zones and their respective contributions to the total production. The method in particular is helpful in evaluating the effect of fracturing operations. An outstanding result of the application of the method is to bring to the light the relative importance of sand-shale interfaces in the production of gas. The paper is illustrated with field examp1es. INTRODUCTION The electrical logging tools involving conventional systems are not applied in wells which do not contain water base mud (empty holes, or wells filled with oil base mud), because of the absence of electrical connection between the electrodes and the surrounding formations. It is, therefore, common practice in this case to use other methods which do not require the presence of a conductive fluid in the borehole: resistivity log with scratcher electrodes, Induction Log, radioactivity logs, temperature log. . . . Such conditions are encountered in some regions, as the San Juan Basin, N. Mex., where a technique of drilling gas wells, using gas as a drilling fluid, has been introduced in the last two years. By the middle of 1953, an appropriate method for the logging of these wells was devised on the basis of field tests and of theoretical studies. It is the purpose of the present paper to give a description of this method. In these wells the logging operations are performed during the process of gas production, so that the temperatures in the boreholes are strongly affected by the cooling due to the expansion of the gas. On the other hand, a special thermometer, with a high sensivity and a short time constant, has been recently made available, which has enabled much more detailed and accurate recordings of the borehole temperatures than with the conventional instruments. As a result of these two circumstances, the temperature log constitutes the essential element of the method, in making possible the detection of the gas producing zones, the definition of their boundaries, and the estimation of the respective contributions of each separate zone to the total production. The method also involves the radioactivity and Induction Logs, as auxiliary documents. These logs in the present instance are helpful in the determination of the reservoirs. However, the information they give in this respect is limited. This comes from the fact that, due to the absence of the MicroLog and/or MicroLaterolog and of the SP log, the estimation of formation factors and connate water salinities is somewhat conjectural. Furthermore, little help is obtained from the Neutron log for the evaluation of porosity and of formation factor because the variations of gas saturation affect the Neutron log in a way similar to the variations of porosity. It should be said also that even an exact knowledge of the gas saturation of the reservoir beds would not

Jan 1, 1956

By A. C. Stoddard

Early in the present century, prospect-ing was active in the area of the present Miami district. There were plenty of blue and green copper outcroppings, but very little ore of a grade that would stand shipping costs had been uncovered. Late in the first decade of the century, tunnels were driven into the north and south slopes of the Inspiration ridge, and two of them exposed disseminated copper sulphide ore. This was the original discovery of such ore on the ground of what eventually became the Inspiration Division of the consolidated company. By 1910 exploration of the ground area was well along and by 1911 underground development had been started. In the next few years a large tonnage of disseminated copper ore had been proven— sufficient to justify the expenditure of several million dollars in mine development and for mine equipment plus large sums for treatment plants. The mine and treatment plants were placed in production July 1, 1915. To Jan. I, 1945, there had been produced from the mines of the Inspiration Consoli-dated Copper Co., more than 106,000,000 tons of ore. Nearly all of this tonnage had been recovered by block caving. GeologIcal and EconomIc FActors Block caving is a mining system based on the fact that if a mass of rock has a sufficient number of fractures and planes of weakness the mass will disintegrate if the support of an area of sufficient size is taken away—that is, "undercut." If the material that caves away from the bottom of a block is drawn off the spalling is progressive. There is a limit to the speed of this spalling or caving action, which varies with the structure of the rock being caved. If the rock is drawn at a rate faster than the caving rate, and if this drawing is continued too long, a void may be created that could make a very dangerous condition if the area should drop as a block and force the air below the uncaved rock out through the raises and drifts. This can be a very destructive force. On the other hand, if the broken material is not drawn fast enough the swell of the material in place to broken material would pack the mass until it was almost solid again and could not be drawn without much blasting, or perhaps even partially undercutting again. Geologically therefore it would seem that any rock with seams and fractures would cave; but for block caving there should be enough seams and fractures in a limited area so that such an area will cave and produce a product that can be drawn safely, rapidly enough and at a cost justified by the value of the product being drawn. At the Inspiration the disseminated ores occur in two formations, the Pinal schist and the Schultze granite. There is no material difference in the grade of the ore formed in the schist and in the granite. The chief copper minerals are chalcocite, malachite, azurite and chrysocolla. Other copper minerals occur in limited quantity.

Jan 1, 1946