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By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By H. Habenicht, J. J. Scott

An experimental method is described to compare strain data for rock and rock bolts when exposed to shock waves released by blastings. Static and dynamic strains were measured. Bolt gage response indicated a static decay of the bolt anchorage coupled with a reaction due to blasting vibrations. A distinct loss of bolt tension was indicated during vibrations and this was accompanied by a smaller but steady loss of tension due to static loading. The strain losses were found to relate to the shock source distance and the vibrational amplitude in the rock and bolts. Millions of roof bolts are used each year to stabilize mine openings and prevent their failure. Frequently, bolts become loose and lose their effectiveness as reinforcement to the mine structure. Many attempts have been made to determine the cause of loosening, including observation of the bolt tension or bolt torque through the use of torque wrenches, compression pads, and load cells. Pull tests have been used extensively to determine anchorage characteristics.102 These investigations have shown that even when bolts are loaded below the nominal anchorage capacity of the rock under 'static' conditions they exhibit a decay of load through adjustments and slippage at the bolt anchor. Since bolts are quite often found with the plate hanging loose from the rock surface, this condition suggests that some additional mechanism may have played a part in loosening the anchorage. Vibration from blasting or shock loading have been suggested as one cause in this type of anchorage deterioration. This paper gives the results of an investigation carried on at the University of Missouri at Rolla to determine the influence of shock waves on rock-bolt anchorage stability. ROCK BOLT ANCHORAGE UNDER DYNAMIC LOADING CONDITIONS In this report dynamic loading conditions are defined as conditions under which rock and bolts are exposed to vibrations occurring as a consequence of blasting, machine vibrations, earthquakes, rock bursts, etc. Whatever the location of the shock source, the waves created suffer extensive alterations along their travel paths, depending upon the vibrational properties and geometric parameters of the transmitting media. Together with reflection, refraction and diffraction at material boundaries, waves suffer changes in their nature to form tensile, compressive and shear waves. They become polarized, retracted, accelerated, dispersed, so that the waves incident at a point in the material can be the result of either one or a combination of this wide range of processes. A certain fraction of the wave energy will be lost due to friction, deformation, and material failure at the anchor-rock contact. Thus, the physical nature of wave propagation is such that it inhibits an exact analytical solution. For this reason this investigation should be considered qualitative rather than quantitative even though numerical data have been used as a base. CONCEPT OF THE INVESTIGATION Experiments were designed to find, from a series of rock bolts installed in natural mine rock, whether or not, and to what extent, bolt tensions would be influenced when bolts were exposed repeatedly to shock waves such as those produced by blasting. Electronic instrumentation available in the rock mechanics laboratory of the University of Missouri at Rolla was used to observe wave development in the rock and vibrational reactions in the bolts. EXPERIMENTAL PROCEDURE Fig. 1 illustrates schematically the experimental equipment. Electric resistance wire strain gages were used as sensors for the strain response of the rock and the bolts. Bolts were 5 ft long and 5/8 in. in diam, equipped with two-leaf type expansion shells for 1 3/8 in. boreholes. The bolt gages were mounted by use of Du Pont Household Cement, covered with an epoxy insulation and then enclosed in a copper foil for electronic shielding. For details of placement and the wiring diagram see Fig. 2 and 3. The output of both the rock gages and the bolt gages was fed into cathode ray oscilloscopes from which the vibrational traces could be photographed. A static strain indicator was also used to read the output of all gages.

Jan 1, 1968

By L. R. Plitt, E. O. Lilge

Tests carried out with both kaolin and silica slurries show that flocculants of the polyacrylamide type can be used to improve the thickening performance of hydrocyclones. This thickening improvement demonstrates that contrary to previously held theories, flocs can be formed which are capable of resisting the shear forces in a hydrocyclone. For the 1.25-in.-diam cyclone used, optimum thickening occurs when the flocculant solution is injected into the slurry stream at or near the feed inlet. Hydrocyclones offer many distinct advantages over gravity thickeners. These advantages include simplicity, low initial and operating costs, small space requirements, and flexibility of operation. In spite of these advantages hydrocyclones have not been widely used as thickeners. The main reason for their lack of application is that hydrocyclones are unable to efficiently remove semicolloidal particles (less than 5 microns) from the suspending solution. In gravity thickeners, the fine particles can be induced to form particle aggregates, or flocs, which have the settling characteristics of large particles. In the hydrocyclone, however, it was always assumed that the existence of shear would prevent the formation of flocs.1-3 Thus, if no floc structure is retained, the thickening hydrocyclone must be designed so that its separation size is below the size of the smallest particle to be recovered. To obtain a very small separation size requires the formation of very high centrifugal forces, which necessitates the use of small-diameter cyclones. Small hydrocyclones have, in turn, very low throughput capacities which render them impractical for many industrial thickening applications. Thus, if the effects of flocculation cannot be utilized, the usefulness of hydrocyclones as thickeners remains limited to pulps which contain no very fine particles. It is well established that most substances acquire a surface electric charge when brought into contact with an aqueous medium. The repulsive interactions between similarly charged particles act to prevent flocculation. One method of flocculating a dispersion is to neutralize the repulsive surface charges by the addition of an electrolyte. The reduction of the electrostatic surface charge (Zeta potential) then permits the universal van der Waals attractive forces to operate between the atoms of the various particles and form particle aggregates. The lime additions used by thickener operators promotes flocculation by this mechanism. A second method of flocculating a dispersion is by the addition of long-chain macromolecules. In this case flocculation is brought about by a bridging mechanism in which the molecules are adsorbed with part of their length on two or more particles, thus forming a molecular bridge between the particles.4,5 The molecules also form bridges between themselves when a single particle is bonded to several polymer molecules. The type of bonding between the flocculant molecule and the particle may be hydrogen bonding, chemical bonding, or electrolytic attraction.6 The flour and glue which are used as thickener additives are believed to promote flocculation in this manner. In the past decade synthetic long-chain polymers with extremely high flocculating capabilities have been developed. The flocs formed by these new polymeric flocculants are larger and more shear-resistant than those formed by the presence of electrolytes.7 The advent of these flocculants raises the question: Are the flocs formed by these synthetic polymers stable enough to resist the liquid shearing forces in a hydrocyclone? The investigations reported in this paper were carried out in order to provide some answers to this question. EXPERIMENTAL WORK For the bulk of the test work a 5% slurry of commercially available kaolin with an average particle size of 5 microns was used. An initial evaluation of the available flocculants was carried out to determine which flocculant formed the most shear-resistant flocs. A combination of the techniques used by Healy7 and Booth8 was used for this purpose. This initial study revealed that the neutral high-molecular weight polyacrylamides produced the most shear-resistant flocs. One of these flocculants, Separan MGL*, was selected and then used for all the hydrocyclone tests. The flocculant was dissolved in water and added to the hydrocyclone as a dilute solution.

Jan 1, 1968

By D. C. Seidel, E. F. Fitzhugh

The cementation of nickel from acidic solutions by metallic iron is discussed. The cementation is carried out in pressure vessels at temperatures above 100°C. The results from bench scale studies on variables such as retention time, temperature, and solution pH are presented. A continuous processing flowsheet is proposed. Cementation is one of the oldest known hydrometal-lurgical reactions. The cementation of copper on iron was recorded by 'Paracelsus the Great' in about 1500,1 and by 1600 the technique was being used to recover copper at the Rio Tinto operations in Spain.2 At least one early author felt that cementation may have been one of the primary reasons for the alchemists' belief in the transmutation of metals.' The early writings state that when iron was placed in the clear waters from some mountain springs, the iron disappears and copper is found in its place. To the alchemists this may well have been one of the most convincing proofs that transmutation could and did occur. Since these early times the recovery of copper from acidic solutions by cementation has been practiced in plants throughout the world. Probably the cementation technique in some form has been common to more copper mining and milling operations than any other single recovery process. During current hydrometallurgical extraction studies, which were sponsored by the Republic Steel Corp. at the Colorado School of Mines Research Foundation, Inc., it was found that under the proper conditions, metallic nickel could be cemented from acidic solutions by powdered iron. The reactions are apparently similar to those that occur during the cementation of copper, but the nickel cementation had not been anticipated because iron and nickel are nearly adjacent in the electromotive series. The potential difference between iron and copper is approximately 0.78 v, while the potential difference between iron and nickel is less than 0.21 v. The cementation of nickel with iron at room temperature is almost negligible, but when the reaction is carried out in a closed vessel at temperatures in excess of 100°C, the nickel can be cemented almost quantitatively. The part played by this discovery in a practical method of nickel recovery is set forth in a separate paper.3 The following paragraphs are a discussion of experimental studies that were made to investigate this cementation reaction. The technique has been designated the HTC or High Temperature Cementation procedure. The cementation work was part of a study on hydrometallurgical techniques for the extraction of nickel from the garnierite or silicate type nickel ores. A hydrothermal extraction procedure had been developed, and this technique produced an acidic pulp or solution that contained both nickel and appreciable amounts of magnesium.3 Small quantities of ferric and ferrous iron were also present along with cobalt, manganese, and chromium. The potential for recovering the nickel from these acidic solutions by ion exchange or solvent extraction did not appear to be promising because of the relatively high magnesium content. The Ni ++ and Mg++ have nearly identical ionic dimensions and tend to be co-absorbed or extracted during ion exchange or solvent extraction treatments. Preliminary tests indicated that the nickel could be precipitated as a sulfide when using the high pressure H2S precipitation technique developed for the Moa Bay operations of the Freeport Nickel CO.4 This technique gave good recoveries, but the nickel sulfide product requires considerable additional processing before a marketable form of nickel is realized. The process also requires clarified feed solutions, and the solids-liquid separations on the garnierite residues are difficult. A program was initiated to investigate alternate procedures that might shorten the route to a marketable nickel product, and hopefully also permit bypassing the difficult solids-liquid separation steps required for the H2S precipitation technique. It was during these studies that the nickel cementation reaction with iron was encountered. EXPERIMENTAL EQUIPMENT AND PROCEDURES The bench scale precipitation tests which were conducted during this experimental program were made in 2-liter stirred autoclaves.* A photograph showing the form and arrangement of the autoclave

Jan 1, 1968

By R. E. Reed-Hill

A simple accurate graphical method for orienting fcc crystals using (111) slip traces on a single surface is described. Solutions placing the pole of the surface in a unit stereographic triangle are obtained using a Wulffnet, a (111) standard projection showing the four (111) planes, and a (111) standard projection ruled into unit stereogmphic triangles. The multiplicity of solutions is described in relation to this method. AN accurate, rapid single-surface technique for orienting fcc crystals, using (111) slip or twin traces, has been a matter of continuing interest, as evidenced by the periodic appearance of papers on this subject.'-4 This note presents a new method possessing some advantages over those previously reported. It is an analog to the technique for hcp metals5 where the solution is based upon a stereographic rotation of the specimen surface on a (0002) standard projection that contains the planes of the possible features that might account for the observed traces. In the hexagonal solution, the axis of rotation is the basal-plane trace in the surface. In the fcc case, the axis of rotation is one of the observed ( 111) slip or twin traces. It has been observed that the solution is greatly facilitated if the indicated movements of the (111) traces during the rotation of the surface are plotted directly on a paper copy of a Wulff net as shown schematically in Fig. 1. The trace selected to represent the axis of rotation is assumed to fall at the north-south poles of the Wulff net. The directions of the other traces are then plotted as points at the proper angles around one-half of the basic circle of the net. The loci of points corresponding to the movements of these traces (directions) during a 90-deg rotation of the surface, about the polar axis of the net, are then easily and accurately drawn by following the appropriate small circles on the Wulff net. The solutions to the problem are obtained with the aid of a (111) standard projection of the (111) planes, see Fig. 2. This is normally a Xerox copy of a carefully drawn master made on high-quality tracing paper. The (111) standard projection is superimposed over the Wulff net and rotated about its center until the points of intersection of the loci of surface traces, drawn on the Wulff net, and the great circles representing the (111) traces, all lie along a common meridian of the Wulff net as demonstrated in Fig. 3. This latter great circle represents a possible position of the surface. The pole of this plane is then plotted on the (111) standard projection. Its location in a unit stereographic triangle may be readily obtained by superimposing (over the standard projection) another tracing paper (111) standard projection subdivided into unit stereographic triangles. The result of this last operation is shown in Fig. 4. MULTIPLICITY OF THE SOLUTIONS The maximum possible number of (111) traces on a single grain surface is four. Any one may be selected as the axis about which the surface is rotated. Corresponding to each such choice are three possible surface-pole orientations, related to each other by a simple 120-deg rotation about the pole of the (111) basic circle. This is a direct result of the threefold symmetry of the (111) standard projection. Since each of the four rotations will normally give a different set of three-pole positions, there are, accordingly, twelve possible solutions. Each of these twelve solutions places the surface pole in the same relative position in a stereographic triangle so that all are crystallo-graphically equivalent. Accordingly, only a single solution is required to obtain a basic orientation of the crystal. It should be noted, however, that the orientations obtained by reflecting* any of these twelve orien- *The reflected orientations may be obtained by a 90-deg rotation of the opposite sense to that shown in Fig. 1. This rotation places the correspond-ing trace loci in the lower hemisphere of the Wulff net rather than in the upper hemisphere. tations through the surface are also possible orientations that could account for the surface traces. Thus, a given set of four traces always corresponds to a pair of basic orientations related by reflection through the specimen surface. This ambiguity can only be re-

Jan 1, 1967

By R. W. Snyder, H. J. Ramey

This paper presents the results of applying the Buckley-Leverett' displacement theory to petroleum reservoirs consisting of a finite number of layers. The layers are assumed to communicate only in the wellbores, and the reservoir may be represented as a linear system. Most previous investigations of this nature were limited by assumptions and by inconsistent calculation techniques. This study improves on previous work by applying the Buckley-Lev-erett displacement theory to a noncommunicating layered system where permeability, porosity, initial saturation, residual saturation and relative permeability vary from layer to layer in a logical and consistent manner. Gravity and capillary-pressure effects are neglected. A modification of the Higgins-Leighton calculation method was used in this study. Waterflood predictions were made with all properties varying, and then with only permeability varying using several inability ratios. These results were compared with the Stiles and Dykstra-Parsons predictions. It is shown that the latter methods generally give poor values for the breakthrough recovery and pessimistic predictions for the performance after breakthrough. Similar results were obtained for a gas-displacement case. lNTRODUCTION Field experience with immiscible displacement usually shows constant producing conditions until breakthrough of the displacing fluid. Then oil production continues at increasing displacing-to-displaced fluid ratios until the economic limit is reached. Three different ideal mechanisms are known that will produce this behavior: (1) relative permeability effects as described by Buckley-Leverett frontal advance theory,' (2) vertical stratification as considered by Stiles,2 Dykstra and Parsons5 and others and (3) different path lengths involved in areal (two-dimensional) flow between wells as described by Dyes et al.4 Without question, a combination of these factors modified by formation heterogeneity and other known and unknown factors actually does control the behavior of real systems. This paper presents results of an investigation of certain factors that should affect performance but which have received little attention to date. In 1944, Law5 demonstrated that porosity and perme- ability are often found to have normal and logarithmic-normal distributions, respectively. throughout cored intervals in natural formations. This led to the concept of the noncommunicating, multilayered reservoir model for immiscible displacement. This model assumes that the reservoir is composed of a number of layers that communicate only at the wellbores. Each layer is individually homogeneous, but may be different from every other layer. Stiles' presented one of the earliest applications of this model to waterflood performance. In addition, Stiles assumed that the initial saturations and relative permeabilities were the same for each layer, porosity was the same. displacement was piston-like, fluids were incompressible and injection into each layer was proportional to that layer's permeability capacity (permeability-thickness product). The last assumption would be true if the mobility ratio for the displacement were unity.21 Dykstra and Parsons" used the same model as Stiles, but rigorously included mobility ratios other than unity for piston-like displacement. Dykstra and Parsons used their general result to produce charts for log-normal permeability distributions between layers. Similarly, Muskat6 Pub1ished analytical solutions for linear and exponential permeability distributions. In 1959, Roberts' described a scheme for calculating water-drive performance for the noncommunicating, layered reservoir model which considered two-phase flow in the displaced region. Roberts used the same model and assumed that the injection rate into a layer was proportional to that layer's permeability capacity, but that flood front locations could be evaluated from the Dykstra-Parsons results. These assumptions are inconsistent, and a material balance cannot be maintained except for a mobility ratio of unity. At the same time, Kufus and Lynch8 coupled Buckley-Leverett displacement theory with the layered model to provide an improvement of the Dykstra-Parsons method that was consistent. In 1960, Higgins and Leighton9 resented a numerical method for calculating waterflood performance also considering two-phase flow in the displaced region. The result was used to investigate variation in absolute permeability and oil viscosity. An excellent, detailed history of using the noncomrnunicating, layered reservoir model was presented by Nielsen.'" The preceding techniques (and many related ones) were similar in that differences in initial saturations, residual saturations and relative permeabilities from layer to layer were neglected. It is well known that the irreducible water saturation is an important function of absolute permeability. Calhoun11 showed that the irreducible water saturation

By John E. O’Rourke, Kevin M. O’Connor, Pamela H. Rey

INTRODUCTION The resurgence of coal mining activity in the United States, brought on by the spiraling costs of fossil fw1 energy in the Seventies, has come at a time of intense public concern for the quality of the environment. Notwithstanding pressure on our economy to develop alternate sources of fue1 energy to the import of oil, the legislatures of several states have reacted to public concern over the environment by passing strict regulations aimed at con- trolling the subsidence effect s of underground mining. Agencies of the federal government charged with assistance to the mining industry, including the Department of Energy and the Bureau of Mines, have sponsored a number of instrumentation and field measurement projects aimed at the development of subsidence prediction models that can aid the mine operator's task of subsidence control. There are good empirical models developed in Europe for subsidence prediction, but they were made possible by a large body of mining-induced subsidence data collected there over a long period of time. No com- parable subsidence data base exists in the United States, and consequently empirical modeling of subsidence is not a realistic approach for our near term needs. Moreover, the geologic and topographic diversity of the several coal regions in the United States is expected to necessitate the development of several empirical models, each one expected to be relevant to its own region. Because of the time and costs that are likely to be involved in an empirical modeling approach, it is considered more expedient and cost effective to develop a general, mechanistic model for subsidence prediction purposes. In order to develop such a model, it is necessary to investigate and quantify the mechanics of the subsidence process from the mine level up to the ground surface. The series of projects discussed in this paper are designed to achieve this objective and include the following work: (1) the identification of geotechnical instrumentation that will pro- vide mine level overburden and surface subsidence data. (2) a field demonstration of selected instruments, and (3) documentation of case histories for complete subsidence mechanics, using the demonstrated and preferred instruments. An identification of feasible instrumentation and monitoring techniques was completed by Woodward-Clyde Consultants (WCC) in 1977 (O'Rourke and others). This paper discusses a demonstration of those instruments at a mine in Utah, and at two subsequent projects, currently underway at longwall mines in Colorado and West Virginia. 'he latter two projects when complete will provide documented case histories of subsidence mechanics. The process of optimizing subsidence instrumentation and monitoring techniques to the conditions encountered during installation and monitoring for these underground mines is shown to be an evolving one, and one which has had some notable successes to date. INITIAL DEMONSTRATION The initial design and demonstration of selected monitoring systems was carried out at the SUFCO No. 1 mine, near Salina, Utah. The instrumented panel was approximately 152 m wide. 640 m long. and was 290 m to 320 m deep. The mined height of coal. seam averaged 2.4 m. The mining method was room and pillar using continuous mining machines. This method allowed some monitoring of the supported condition during development, and eventually allowed monitoring of a caved system when both chain pillars and room pillars were extracted on retreat. The two instrument systems shown on Table 1 were selected from the earlier feasibility report for demonstration at SUFCO No. 1. Collectively, the two systems, one for a fully-supported mining method and the other for a fully-caved method, incorporate most of the instrumentation to be found within all five systems listed in the earlier feasibility report. The instrumentation includes surface, subsurface and mine monitoring installations. All of the SUFCO instruments selected to meet the specifications of the general instrument types listed on Table 1 were manually operated. That is, data from the installed system could only be obtained while a person was there to physically observe or operate the system readout. Automatic data recording equipment was available for some installations, but the objectives were to keep the systems as simple as possible for the demonstration project. A complete description of the surface, sub- surface and mine level instruments, and the demonstration project results are given in WCC (1982), and selected features are discussed in this paper.

Jan 1, 1982

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,' and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By R. W. Hertzberg, F. D. Lemkey, J. A. Ford

The effect oj unidirectional solidification upon the microstructural, crystallographic and mechanical characteristics of high -purity A1-A13Ni eutectic a1loy specimens has been investigated. varying the growth rate caused the morphology of the Al3Ni phase to gradually change from platelets to rods. In addition, the effect of increasing the rate of planar liquid-solid interlace movement is to decrease the Al3Ni rod diameter and inter-rod spacing. The platelets and rods grow approxinlately parallel to each other and are aligned in a faulted substructure. A single unique crystallographic relationship hetween the A1 and ASNi phases was found and may he descrihed as : interface {001} Al3Ni {331} Al and growth direction <010>Al3Ni || <110> Al The platelet interlace and the aligned rows of rods are both uniquely defined by the above statements. Alignment of the Al3Ni phase by unidirectional solidification has given rise to a threefold increase in strength over that exhibited by specimens with an as-cast microstructure. These results illustrate the possible use of this eutectic alloy as a zohisker -reinforced structure. It has been demonstrated by Winegard et al.,1 Kraft and Albrighht,2 Chilton and winegard,3 Chad-wick,4 Yue,5 Tiller,6 and others that a planar liquid-solid interface may be established in binary eutectic alloys by proper control of heat flow during the solidification process. The unidirectional movement of such an interface results in a eutectic mi-crostructure consisting of an essentially parallel array of the two phases over an entire ingot. Two dominant phase micromorphologies have been produced using this technique: that of substantially parallel alternating lamellae of each phase or long thin parallel rods of one phase imbedded in a continuous matrix of the other phase. While not all eutectics can be controlled in this manner, it has been shown that a "normal" eutectic may, under properly controlled conditions of purity, liquid and solid thermal gradients, and solidification rate, be forced to solidify with essentially parallel phase particles. Kraft and Albright2 have demonstrated that, when the growth rate is too rapid or when the thermal gradient in the liquid at the growing interface is too low, a layer of constitutionally supercooled liquid, formed by impurity build-up, will stabilize a cellular rather than a planar interface. The unidirectional movement of the cellular interface forms the macrostructure of eutectic colonies.7 Chilton,3 Chadwick,4 and Tiller,&apos; studying eutectics of zone-refined Pb-Sn, A1-CuAl2, Zn-Sn, and Cd-Zn systems, noted that in the absence of impurities a planar interface is stabilized even when rapidly solidified. Although it is generally agreed that impurities break down a planar interface to form the eutectic-colony macrostructure, at present the origin of the varying micromorphologies (i.c., plates or rods) in a given normal eutectic alloy is not completely understood. Tiller8 has predicted that the micromor-phology produced may be dependent on solidification rate (i.e., at fast rates a rodlike structure is preferred whereas at slow rates a lamellar structure should form), and also suggested that rod formation may be favored at large phase-volume ratios. yue5 has experimentally verified Tiller&apos;s prediction in the eutectic Mg-Mg17Al12 by observing a lamellae-to-rod transition with increasing growth rate where the phase-volume ratio was approximately 2.3:1. However, Hunt and chilton9 more recently unidirec-tionally solidified over a wide range of growth velocities six different eutectic systems with phase-volume ratios between 12:l and 2.7:1 and observed no lamellae-to-rod transition. chadwickl0 has proposed that the change in micromorphology in some eutectic alloys is due entirely to the presence of impurities and further states that the lamellar structure is the characteristic structure of pure eutectic alloys even when the phase-volume ratio is as great as 12:l. Kraft11,12 has shown that the parallel lamellae in certain eutectic alloys assume a unique crystallographic relationship during unidirectional growth. This preferred crystallography may be developed

Jan 1, 1965

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett&apos; reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y&apos;, respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By C. D. Allman

Specifications for coal at the Grand Lake thermal electric station read in part: "Coal will be Rom Minto Bituminous (strip operation). Maximum lump 3x3x4 ft. Very corrosive, abrasive and when damp, sticky. Coal may consist of frozen lumps of coal, snow and ice." To maintain quality control it was necessary to develop an automatic sampling system capable of: 1) sampling from one 10-ton truckload every 1½ min; 2) permitting an operator to automatically take a sample from each truckload; 3) depositing the sample in a pre-selected container, one of a possible 10; and 4) performing the sampling operations in accordance with latest ASTM specifications for sampling coal with an ash content of 35%. This paper tells how these and other problems were resolved and describes the equipment used. The New Brunswick Electric Power Commission issued detailed specification No. 5351-5009 outlining the scope of work and general requirements for a mechanical coal handling system to be installed at the Commissions Grand Lake Generating Station. The thermal station is located at Newcastle Creek, some 40 miles east of Fredericton, N.B. Canada, on the shore of Grand Lake. This particular location is immediately adjacent to the Minto strip mining coal area of New Brunswick. Contained in the specifications, but not detailed specifically was an automatic coal sampling system. The system outlined, was to be designed and specified by the individual equipment tenderers. In conjunction with the Hardinge Co., the Barber-Greene Co. designed a sampling system which was contained in the general contract proposal. The system as designed originally, however, presented certain limitations to a continuous coal handling system and was ultimately changed. However, it was only through preliminary study and design that problems created by the specifications were determined, and these problems discussed and finally negotiated with the NBEPC engineering staff created the subsequent sampling system now being installed by Barber-Greene. It must be considered that where the original specifications did not detail the mechanical equipment, it was necessary to present a system which would correspond to the intent of specification and for which Barber-Greene would be responsible as to function, but remain in a competitive position with regard to the tender considered primarily on a price basis. The system now being installed, contains basically all the components which were detailed originally, with the exception of the holding bin arrangement, which was changed to allow a continuous operation of the entire coal handling system. SPECIFICATIONS The specifications covering the sampling system follow. 4.5 Sampler: An automatic sampling system shall be installed capable of sampling one-truck load of coal every 1½ min. When the coal is dumped into the receiving hopper, the operator shall push a button and the sampler shall automatically take a sample of that particular coal when it reaches the sampler. Then the sample taken shall be crushed and reduced in quantity to a workable sample and deposited in a pre-selected container, one of a possible ten. All samples and sampling operations shall be in accordance with the latest edition of ASTM designation 492 for sampling coal with an ash content of 35%. The coal for the initial sample shall have maximum sized lumps of about 3/4 in. and the final sample shall be adjustable from 2 to 5 lb per sample and capable of passing through a sieve with 1/8-in. diam openings. It should be noted that, because of the time delay between the time the sample is requested and when it is actually taken, the operator may call for one or two additional samples from different coal before the first sample is completely refined and in the final sample can. Coal is received from a number of different suppliers on the same day, therefore, the system shall be designed so that there is no possibility of mixing or contaminating the coal from the different suppliers. All coal rejected from the sample shall be returned to the main conveyor. All chutes, hoppers, etc. shall be designed in accordance with Section 4.6 of these specifications. 4.6 Chutes, Hoppers, etc. All chutes and hoppers

Jan 1, 1963

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.&apos; These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:&apos; , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.&apos; The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,&apos; but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Robert E. Green, Robert A. Swanson

Ultrasonic attenuation and stress were measured simultaneously as a function of strain for aluminum single crystals tested in compression. The propagation mode and polarization of the ultrasonic waves were chosen with reference to the theoretical analysis presented in Part I. Good experimental agreement was found with this theory and with earlier experimental work in tensile tests. Support is given to the contention that ultrasonic -attenuation measurements are much more sensitive to the early stages of plastic deformation than are conventional stress -strain measurements. Dislocation meclzanisms are suggested which are compatible with both the present and the earlier experimental observations. A brief historical introduction of previous work concerned with the study of dislocation motion by ultrasonic-attenuation measurements has been given in Part I. The purpose of the present experimental investigation was to make use of the theoretical considerations from Part I in order to gain further knowledge concerning dislocation motions during plastic deformation. Emphasis was placed on the choice of propagation modes and polarization of the waves, such that interactions between these waves and dislocation movement on a specific slip system could be investigated. EXPERIMENTAL PROCEDURE Since the primary concern of this investigation was dislocation damping, other sources of damping were eliminated as much as possible. The test specimens were 0.5-in.-diam single crystals of 99.99+ pct pure aluminum grown from the melt by a modified Bridgman technique. Ultrasonic-attenuation measurements were made at a frequency of 10 megacycles per sec using a Style 56A001 Ultrasonic Attenuation Comparator manufactured by Sperry Products Inc. after a design by Chick, An- derson, and Truell.1 At this frequency the particle vibrations are essentially adiabatic and thermo-elastic damping should be absent. This frequency was selected since it was one of the frequencies used by Hikata et al.2 n conjunction with tensile tests on aluminum crystals, thus allowing direct comparison with this work. The use of quartz-crystal transducers insures that the amplitude of vibration is not sufficient to cause the break away of the dislocation loops from weak pinning points. The quartz-crystal transducers used all possessed a resonance frequency of 10 megacycles per sec and were thin circular discs 0.375 in. in diameter. X-cut crystals were used to generate the longitudinal waves and AC-cut crystals to generate the transverse waves. Aluminum was chosen as the basic material because it is a typical fcc metal whose deformation behavior is well-known and because the most recent work at the time the present research was initiated was that by Hikata et al. who used aluminum. The present tests were run in compression to see if such tests could be satisfactorily run in compression without being severely masked by grip effects.. A second reason was to compare the results in compression with those of the tension experiments of Hikata et at. Finally, shorter specimens could be run in compression with less over-all damping than in tension. All of the aluminum-crystal test specimens used were oriented for plastic deformation by single slip; i.e., they possessed the orientation having a maximum Schmid factor of 0.5. Because of the well-known time dependence 3 of plastic strain at constant stress, the test specimens were subjected to a quasi-static loading. Previous investigations4-&apos; have indicated that attenuation after plastic deformation is also time-dependent, so any continuous loading of the specimen would show that changes in attenuation were also a function of strain rate. By loading the specimen to a given stress level and holding it constant until the recovery process was essentially complete, the time dependence was eliminated. The quartz transducer was permanently bonded to the aluminum crystal using Eastman 910 cement. Excess cement was removed from around the quartz with DMF (dimethyl formamide). Eastman 910 was found to be far superior for bonding, especially with regard to the shear-wave transducer, since it formed a solid bond which readily supports shear-wave propagation. The solid bond formed by the Eastman 910 cement also insured that the quartz

Jan 1, 1964

By Elmars Ence, Harold Margolin

The Ti-Fe and Ti-Fe-0 systems were re-examined because of the controversy regarding the existence of Ti2Fe, and to consider all available data points to the existence of Ti,Fe. The Ti-Fe-0 system contains two ternary compounds: E, corresponding to Ti2Fe; and y. SEVERAL authors have investigated the constitution of titanium-rich alloys of the Ti-Fe system. The most extensive study of titanium-rich portions of the Ti-Fe system was by Van Thyne, Kessler, and Hansen,&apos; who investigated this system up to 50 pet Fe and used the highest purity materials available for their alloy preparation (iodide titanium was used for alloys up to 20 pet Fe). According to Van Thyne et al., phase relationships in the region of investigation are governed by phases a,ß, and TiFe. No evidence of an intermetallic compound Ti,Fe was found. although earlier. works by Laves and Wallbaum,&apos; and Duwez and Taylor&apos; reported its existence. Rostoker&apos;s study on the occurrence of TilX phases" confirmed the findings of Van Thyne et al. Rostoker proposed that the compound Ti Fe found by Duwez does not exist but is actually a ternary compound, Ti1Fe3O, originated by inadvertent oxygen contamination. The partial isothermal section of the ternary Ti-Fe-0 system as reported by Rostoker&apos; seems to confirm this explanation. In the course of phase diagram work conducted at New York University, however, certain irregularities were observed to be associated with ternary systems of the type Ti-Fe-X. The ternary phase 6, observed in the systems Ti-Fe-Mo&apos; and Ti-Fe-V." was found to be structurally identical to the com-pound Ti2Fe as reported by Duwez and Taylor, and to Rostoker&apos;s compound Ti1,Fe2O. Since the amount of oxygen possibly present in the Ti-Fe-Mo and Ti-Fe-V systems could not account for the observed amounts of the compound, it appears that the d phase in these systems is not Ti,Fe,O. On the other hand, considering the amounts of the 6 phase, particularly in the Ti-Fe-Mo system, the location of the phase was uncertain. It was felt that the introduction of the Ti2Fe phase would alleviate some of the inconsistencies of the two systems. Because of the uncertainties relating to the phase Ti2Fe, or Ti1Fe2O, it appeared worthwhile to re-examine the Ti-Fe and Ti-Fe-O systems in the vicinity of these compounds with highly sensitive metallographic techniques and with X-ray methods. Experimental Procedure Alloy Preparation—For the study of the binary system four alloys were prepared, containing 26.9 (30 wt pct), 34.0 (37.5 wt pet), 41.2 (45 wt pet), and 56.3 (60 wt pet) atomic pet Fe, and for the ternary Ti-Fe-O system 18 alloys were prepared in the composition range of 1.6 to 16.9 atomic pet 0 and 24.3 to 55.7 atomic pet Fe. The materials used for the Ti-Fe alloys were iodide titanium (99.98 pet Ti, 0.002 pet 0) and Ferro-vac-E iron (99.95 pet Fe, 0.0052 to 0.0072 pet 0). For the Ti-Fe-O study the materials used were sponge titanium containing less than 0.06 pet 0, Ferrovnc-E iron, and Baker&apos;s analyzed TiO2. The nominal weight and atomic percentages of the ternary alloys prepared are shown in Table I. Melting—Charges of 10 to 15 g were melted in a nonconsumable arc furnace in argon atmosphere according to the technique described elsewhere.&apos;" Since there was practically no weight loss through the various stages of melting and oxygen losses have not been observed previously, it appeared justifiable to use nominal composition for interpretation of data. Iodide titanium control buttons, of the same mass as the Ti-Fe charges, and melted under the same conditions, were used to check hardness pickup during melting. A hardness increase of 2 to 3 Vhn was found. Heat Treatment—The specimens were annealed in quartz capsules under argon. To avoid contact between the specimen and capsule material all specimens were wrapped in titanium sheet. The annealing times are given in Table 11. The attain-

Jan 1, 1957

By J. A. Putnam, A. D. K. Laird

In laboratory research on the behavior of oil, gas and water in porous materials, no direct method has been devised to measure saturation without disturbing the flow. Indirect methods involving various forms of radiation have been developed for measuring one or two components. The X-ray absorption method for two components has been described previously1-3. The possibility of three component measurement has also been mentioned1. Since two component measurement still requires considerable care to insure accuracy, the fact that three components can be measured satisfactorily is not generally appreciated. The fraction of the energy of an X-ray beam of one wavelength transmitted through a material is given by the transmission factor. in which 1 is the beam&apos;s path length through the fluid. p is the fluid density, and 1,. is its mass absorption coefficient. Eq. 1 implies that all parts of the beam pass through equal amounts of the fluid. Practical applications are, therefore, limited to systems in which the fluid is distributed so that I varies negligibly over the cross-section of the beam. Typical variations of the transmission factor with X-ray tube potential arc shown in Fig. 2 from which experimental points have been omitted for clarity. The X-ray absorption of low pressure gases in a core is practically zero so it cannot he distinguished from that a vacuum by instruments that will differentiate between liquids. The transmission factor of a gas in a core is. therefore, unity. Consequently, the saturation of only one gaseous component can be found. If two fluids completely fill a core, their two saturations add to unity and, therefore, only one value of the transmission factor, T, is needed to determine both of them. When two liquids do not completely fill the core, their saturations do not add to unity and transmission factors at two wavelengths must be measured. At one of these wavelengths, 7 for one liquid must be different from T or the other liquid. The change of T for one liquid us the wavelength is changed between the two values must be different from the corresponding change of T in the other liquid. The two values of fluid saturation will also give that of the gas because the three saturations must add to unity. In Fig. 2 it can be seen that there are many large differences of T between various oil solutions and water solutions at any one potential, and between potentials for any one solution. Consequently, conditions for optimum accuracy of measurement of the saturations of a gas and two liquids can be chosen. Once the operating potentials have been selected, however. it is more convenient to cross plot the data from Fig. 2 on transmission factor-solution concentration coordinates for the chosen potentials, as shown in Fig. 3. Fig. 3 was used to plan the experimental procedure for Core N-38-1. Since the voltage control at 45 kv was good, the slopes of the curves in Fig. 2 at this potential would cause little error. At low potentials, however, the voltage control was not good, so 33 kv was chosen because the small slopes of the curves made voltage control less critical. The lowest strength beam that could be measured reasonably at 33 kv corresponded to a minimum T factor of 0.385. Fig. 3 shows that both 4.80 weight per cent of cadmium chloride in water and 24.0 per cent of iodobenzene in crystal oil had this T value, and, consequently, were indistinguishable to the X-rays at 33 kv. Thus, at 33 kv, the liquid saturation was given by the same curve regardless of the relative amounts of oil and water solutions present. This simple calibration curve from which the gas and liquid saturation can be read, is shown in Fig. 4. Fig. 3 also shows that at 45 kv, T for the aqueous solution is 0.610. and that T for the oil solution is 0.220. These values were transferred to Fig. 4 to give the triangular calibration plot from which the brine and oil saturations can be found, after the gas saturation has been determined at 33 kv.

By K. K. Clark

Excessive injection pressures in water injection wells may create deeply penetrating fractures, or may open up existing reservoir fractures. If these fractures are oriented toward offset producing wells, oil recovery at injected water breakthrough and ultimate recovery will be impaired. A method of calculating fracture lengths from pressure fall-off test data is presented. The method is based on a linear flow model that simulates conditions present during the early-time period after shutting in an injection well. Fracture lengths can be calculated directly if formation permeability is known. A graphical technique is presented that provides fracture lengths based on permeabilities calculated from normal fall-off tests, where those permeabilities are adjusted for flow geometry. Test data from four injection wells and results obtained from applying the method to these wells are discussed. Introduction Rates of water injection into nonstimulated wells in low permeability reservoirs frequently fall below economically desirable levels. Therefore, some form of stimulation such as hydraulic fracturing often is performed on these wells. Usually these fractures penetrate a short distance from the well — short as compared with interwell spacing — and therefore should not create problems of water channeling to offset producing wells. In the past, some operators have been tempted to increase injection pressures continually to maintain a specified injection rate. But pressures cannot be increased indefinitely. Field data indicate that continued injection above fracture opening pressure can cause excessively long fractures to approach between well distances. If these long fractures intersect or closely approach offset producing wells, premature water breakthrough can result. It is difficult to seal effectively these fractures by various workover procedures after premature water breakthrough has occurred. This paper describes testing procedures that are potentially capable of detecting premature water breakthrough before it occurs. Knowledge of fracture lengths and fracture opening pressures can assist field engineers in selecting optimum operating conditions for water injection wells. Fracture lengths should be calculated from pressure fall-off tests on injection wells, and maximum permissible iniection pressures should be determined from step-rate injectivity tests. Equipped with this information, the field engineer is in a better position to recommend for a particular injection well the optimum operating conditions that will lessen the chances of channeling to offset producers. Historically, pressure transient tests have been conducted primarily on producing wells and analysis procedures have been based on radial flow concepts. Several authors have suggested that these same procedures be applied to tests conducted on water injection wells. This application is justified for wells that are not connected to extensive fracture systems. However, if the formation is severely fractured, the interpretation methods must be modified. Several authors have presented the pressure response of various systems that are intended to simulate reservoir conditions. A paper by Russell and Truitt* on vertically fractured svstems is probablv the most useful from the standpoint bf the fieid engineer. Russell and Truitt presented the pressure-vs-time behavior of a well connected to vertical fractures with various fixed lengths. Their permeability adjustment technique is used in this paper to refine methods of calculating fracture length and interwell permeability. Theory and Definitions Three flow-system geometries are considered in analyzing injection well test data. These various geometries are applicable during specific time intervals of transient pressure tests. Schematic drawings of the flow models, and the time intervals over which they are applicable, are shown in Fig. 1 in the chronological order that they are applied to the pressure response of water injection wells in fractured formations. The very early response is simulated by an infinite linear system as shown in Fig. 1A. This representation permits the calculation of matrix surface area exposed to the fracture. The model shown in Fig. 1B is identical with the one studied by Russell and Truitt. They evaluated the transient pressure response of this vertically fractured system by finite difference techniques. The results were presented as tabulations of dimensionless pressure drop functions for a range of fracture lengths. A semilog plot of these data shows that the apparent matrix permeability can be related to the true matrix permeability by a simple exponential function. Their adjustment factor is used in this paper to improve the accuracy of matrix-permeability and fracture-length calculations.

Jan 1, 1969

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of&apos; carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,&apos;-&apos; it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;&apos; the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970