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By I. Fatt

The chromalographic effect refers to the separation of constituents in a moving fluid phase which occurs when the phase is passed over a stationary phase, either solid or liquid, or large areal extent. In performing chemical analyses, the large surface contact areal is provided in the case of gas-solid chromatography by-passing the gas over a porous solid and for gas-liquid chronla tog rap hy by-passing the gas over a porous solid which has been coated with a nonvolatile liquid. The porous medium is usually placed in a cylindrical tube, although it may be a relatively flat sheet as in paper chroma-tography. According to one theory,' the separation results from the difference in time spent by various components in the stationary phahe. A gaseous component which is conlpletely insoluble in the stationary phase, or is not adsorbed on the solid, proceeds unimpeded through the column. The versatility and power of the various types of chromatogruphy for the analysis of complex mixtures are evident from their widespread use in performing chemical analyses and from the large number of symposia, books, and papers devoted to the subject in recent years. Associated developments are the application of chromatography to the determination of heats of solution, heats of adsorption, solubilities orK-values, etc. Gas-liquicl chromatography analyses may be characterized by the manner in which the samples are introduced and displaced from the column'. The three techniques used are known as (1) frontal analysis, (3) displacement analysis, and (3) elution analysis. The frontal analysis is performed by displacing an inert gas from the column by a continuous stream of the sample. As indicated in Fig. l(A), all but the first fraction leaving the column represent mixtures rather than pure components. The displacement analysis is conducted by filling the column with a sample, then displacing it with a more strongly adsorbed or absorbed vapor. The resulting chro-matogram is illustrated by Fig. 1(B). Finally, in the elution analysis a small sample of the mixture to be analyzed is introduced as a "plug" into a Rowing stream of carrier gas to give an elution-type chromato-gram. Fig. l(C). The three techniques may be used to provide models to which Row patterns in other physical situations may be compared. PURPOSE OF THE INVESTIGATION The purpose of this investigation was to determine whether natural reservoir rocks, when coated with crude oil, provided sufficient surface areas to give rise to a chromato-graphic separation of light hydrocarbon constituents. The tests were conducted with the light hydrocar-bons in the gaseous state. SANDS TESTED Two sands of widely different permeabilities have been studied: (1) Ventura core (16 md), and (2) Torpedo sandstone core (578 md).Table 1 gives a description of the cores that were tested. With the exception of one frontal-type flow arrangement which was performed on Core 3, the tests were of theelution-type in which a methane-propane mixture was eluted through the core by means of helium. The Ventura core, when impregnated with a weathered crude from the same field, became so impermeable to gas flow that it was necessary to conduct the tests on the granulated cores (Cores 2 and 3).

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By Lane Mitchell

A ceramic product or processed material is a solid composed of materials which have been subjected to heat above 468.3°C (875°F). The raw materials, which are blended together (or in some cases used singly), are selected and utilized for various reasons such as ease of fabrication, aid to processing, to yield desired properties after processing, lack or controllable degree of toxicity or hazard, availability, cost, and perhaps other considerations. Almost all solid inorganic, some organic, and some liquid and gaseous materials have the potential to be used individually in some ceramic product. There are several fundamental functions to be fulfilled in every ceramic product and a number of secondary functions are desirable in specified products. These functions are generally met by the most widely occurring minerals and rocks of the earth and their debris. This fact characterizes ceramics as a field utilizing the raw materials most available to man. Of course, specified products utilize synthetics, organics, and rare inorganics to produce desired results. Any solid nonmetallic product processed by subjection to temperature above a red heat may be called a ceramic product. Widely used construction materials and units, domestic utensils and units, industrial parts to facilitate manufacture, technical components, and aesthetic creations are very often of a ceramic nature because of their durability, inertness, hardness, ease of fabrication, cost, and availability of the ingredients. Often, organics or metals cannot meet desired specifications for some of these products. The rocks and minerals and mineral debris of the earth are largely siliceous. Oxygen and silicon comprise roughly 75% of the earth's crust with aluminum, iron, calcium, and the alkalies following in abundance. Silica (SiO2) and silicates can be melted to form glasses. Alumina (A1203), present in a mineral compound, gives greater durability, hardness, and strength, but lessens the glass-forming property. Iron, calcium, and the other alkalies flux silica and reduce melting points. Thus sand, which is generally almost pure SiO2, and clay, which is generally hydrated alumina silicate, are the most widely used of all ceramic raw materials-principally because of the glass-forming propensities of silicates. In ceramic formulations, clay is generally a refractory filler or skeletal material, having in the raw state a plasticity derived from its colloidal grain size and its water-loving nature. On the other hand, silica sand is a glass former or nonplastic filler. Clay and silica sand in pure forms are quite refractory, i.e., not easily melted. Clay, although siliceous, is less of a glass former than pure silica and is more refractory. Natural contaminants, such as iron oxide or limestone, adulterate many clays and some sands. These contaminants act as fluxes and reduce the fusion points of the mineral or blends. Glass is made from silica sand by fluxing the sand with strong bases, usually soda ash and limestone. Red building bricks are hard and durable because the sand and clay have been partially fused with help of natural iron oxide serving as a flux. The iron oxide performs a dual function, serving as a pigment as well as a flux. In a blend of clay and sand and iron oxide, the sand is more susceptible to fusion than is the clay. Although silica sand and clay are the most widely used raw materials in most ceramic products, many other minerals, and some nonminerals are utilized in products where these materials can produce or aid in achieving desired results. Limestone and dolomite, feldspars, pigmentary minerals, refractory oxides or carbides, and special property producers can

Jan 1, 1983

By J. A. Hafford, J. K. Kerver, J. G. Richardson, P. M. Blair, J. S. Osoba

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By Ralph V. Higgins

This paper concerns the magnitude of the amount of supersaturation that occurs in an underground reservoir during the flow of oil and gas to wells and to the amount of undersaturation that occurs during repres-suring of an oil reservoir where some effective permeability to gas exists. The study is based on earlier laboratory findings of other investigators on the rate of diffusion of gas in oil as a function of the depth of oil. Utilizing these relationships and the principles of reservoir mechanics, a quantitative estimate of undersaturation and super-saturation was calculated. The results showed that the diffusion of the gas is rapid enough that for all practical purposes no supersaturation exists during the flow of oil to wells or undersaturation during repressuring in reservoir sands having some effective permeability to gas. The reason diffusion of the gas virtually keeps the oil saturated is the long time required in radial flow for oil to reach the well and the slow rate at which pressure in reservoirs is increased during repressuring. INTRODUCTION Knowledge of the phase relationships during flow of gas and oil in an underground reservoir is essential to operating the reservoir in the most efficient manner. In material-balance calculations and in fluid-flow studies, the oil is assumed to contain all the gas that it will dissolve at given temperature and pressure. Pressure-volume-temperature relationships are normally obtained in the laboratory using "bottom-hole" or combined samples of the reservoir fluids. In such laboratory determinations equilibrium is obtained between the oil and gas in the pressure cells by mechanical agitation. During the flow of oil and gas in reservoirs, however, no comparable agitation occurs to mix thoroughly these fluids to aid in effecting equilibrium between the two phases. During repressuring of a partly depleted underground reservoir, the gas is usually injected into the reservoir faster than the oil can absorb it; consequently, the oil is undersaturated. On the other hand, as the oil flows through the reservoir to the wells during producing operations the pressure decreases faster than the gas in solution can diffuse through the oil to the gas phase. The oil therefore is supersaturated with gas. Where the oil is undersaturated, gas diffuses away from the gas-oil interface, and where it is supersaturated the gas diffuses toward the interface. In either case the gas moves from a higher to a lower saturation. This report contains the results of a study of the factors influencing the degree of nonequilibrium of the phase relations of oil and gas in porous mediums during the flow of oil through reservoirs to wells and also during the injection of gas into partially depleted sands. Data from an underground reservoir are presented and the degree of supersaturation during the flow of the oil through the reservoir to the well is approximated. Also data from another reservoir are used and the degree of undersaturation during the repressuring operation is calculated. In addition, the flow rates of oil in laboratory experiments and in underground reservoirs are compared, as data from the laboratory are often used to interpret events in the reservoir, and the rates of flow influence appreciably the degree of nonequilibrium. Much of the contents of this report was prepared in 1943; but, because of other activities during and since the war, the manuscript was left untouched until 1952, when it was decided to include an estimate of the amount of undersaturation during repressuring as well as supersaturation during flow.

Jan 1, 1955

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By J. K. Kerver, J. S. Osoba, J. G. Richardson, P. M. Blair, J. A. Hafford

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By D. Mills, G. B. Craig

The defortnaliotz of zirconicltt single crystals conlaining osygen in the range 740 to 6800 atom parts per nilllion was esanined oc7er the range 77" to 950°K. An anctlsis of the dqfarmaliotz parameters leads to the cotcllsiotr that the rale -cotzfrolling thermally activated dqivr,irrtion process oe-r /he range 77" to 560°K is oc.crco,ling osvgen alotns. A thermally actitaled defor,ilntion process is not found between 600" and 800", but does occur aboz%e 800°K. THE present investigation was undertaken to measure the effects of controlled amounts of oxygen on the deformation parameters of a zirconium single crystals over the temperature range 77" to 950°K and to determine the rate-controlling mechanisms. Although there is no doubt that the mechanical properties of the group IV metals, titanium, zirconium, and hafnium, are strongly influenced by the interstitial impurities oxygen, nitrogen, carbon, and hydrogen, there are many conflicting theories as to the role played by the interstitials during the deformation proess.'- There is general agreement that the mechanisms which control plastic flow in a metal impose characteristic values on such parameters as the flow stress and its temperature dependence, the activation volume, and the activation energies. These parameters will be used to analyze the deformation mechanisms. eltham,' Sargent,16 and ibbs' have shown that the stress relaxation technique allows the activation volume characteristic of the deformation process to be found during the course of a simple tension test. In many cases it is found that the relaxation of stress is logarithmic with time and obeys a relationship of the following form: T-T = AT =S logl0(qt + C) [I] where t, is the shear stress at the start of the relaxation test, t is the shear stress at time t, and S. q, and C are experimental constants, and S is the strain rate sensitivity of the stress t as shown in the appendix. The slope found from a semilogarithmic plot of At vs time is approximately equal to S. The activation volume u, association with the deformation process, is found from the following relationship: The theoretical treatment of thermally activated plastic flow due to schoeck18 shows that the activation volume when combined with the temperature dependence of the flow stress gives the activation energy for the process according to equations: seegerZ3 considers that the flow stress at lower temperatures ld is composed of two parts such that Tapplied = tinternal + Teffective , where Teffective 3 ff , is the stress necessary to overcome the local obstacles to deformation and Tinternal, ri, is the stress necessary to overcome the long-range elastic stress field of dislocations on other planes. ri is considered to be largely elastic in origin and can be estimated from the stress value at the temperature independent portion of the flow stress-temperature curve. EXPERIMENTAL The crystal bar zirconium used in this investigation was supplied by Wah Chang Corp. whose certified analysis gave the following impurity contents in parts per million by weight: oxygen, 150; nitrogen, 10; iron, 180. All others were less than 100 ppm. The oxygen and iron contents were confirmed by neutron activation and chemical analyses, respectively. Single crystals were grown in an electron beam furnace according to the method of Wilson and Pickle-simer'' and ills.'' The orientation of the crystals was such that the specimen axes were located in the lower third of the standard section of the basal plane stereographic projection for zirconium. This orienta-

Jan 1, 1969

By K. R. Janowski, A. B. Chase, E. J. Stofel

Ruby crystals of exceptional optical quality have been grown from fluxes composed of Bi2O3 + PbF2 or Bi2O3 + BiF3. Careful control of growth conditions was required to minimize the number of growth defects consisting primarily of dislocations, occluded flux, and growth twins. Slow growth rates coupled with the addition of small amounts of La2O3 as a flux dopant were helpful in producing nearly perfect crystals. Chromium concentrations up to 1 pet were incorporated into these crystals without adversely affecting their perfection. Crystals up to 10 mm in diameter having as few as one to ten dislocations per crystal were typical of those produced under optimum growth conditions. Under these same conditions the occlusions were eliminated, and growth twins were either eliminated or reduced to one to three twin boundaries per crystal. INTEREST in the nature of lattice imperfections produced during the growth of ruby crystals (Al2O3-corundum structure) has been stimulated recently by the need for ruby lasers of good optical uniformity. As a result, ruby crystals grown by the flame-fusion (Verneuil) process have been studied in detail and have been found to contain high densities of dislocations (106 to 107 dislocations per sq cm) and mosaic structures that impair their optical quality.'-3 Attempts to improve the quality of Verneuil-grown crystals by controlling the growth variables have not been entirely successful. On the other hand, rubies grown by the flux process have received little attention even though their more nearly equilibrium growth conditions suggest that they would have fewer growth defects. Nelson and Remeika have shown recently that small flux-grown rubies can indeed be made into very low-loss lasers. However, they did not report information on crystalline imperfections in these crystals.4 Stephens and Alford have reported briefly on defects found in a flux-grown corundum crystal but they neither described these defects in detail nor related them to the method of growth.5 The present investigation was undertaken to establish the relationship between growth conditions and crystalline perfection of flux-grown rubies, sapphires, and other crystals of the corundum family. EXPERIMENTAL PROCEDURE The corundum crystals used in this study were grown by slowly cooling solutions of A12O3 in molten-salt solvents of PbO + PbF2, Bi2O3 + PbF2 or Bi2O3 + BiF3. The materials employed were Linde A (a Al2O3 powder) with reagent-grade chemicals as solvents. Some of the solutions also contained small additions (1 pet or less) of one or more of the transition metal elements chromium, manganese, iron, and titanium as crystal dopants. La2O3 was added to some of the solutions to alter the growth habit of the crystals. The La2O3 promoted the occurrence of growth facets parallel to (0112) and {1011} planes, where the indexing system is the morphological system described in detail by Kron-berg6 and used throughout this paper. The melts from which the crystals were grown were prepared by mechanically mixing the various constituents and placing them in platinum crucibles. The covered 50- and 100-ml platinum crucibles were heated in muffle furnaces at 1250°C for short periods of time (1 to 4 hr) and then program-cooled at either 2° or 4°C per hr to 1000°C. At this lower

Jan 1, 1965

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By Ralph H. Sweetser

C. H. Herty, Jr.,* Pittsburgh, Pa.—The procedure of the Open-hearth Committee in studying pig iron and its effects in the open hearth has been influenced by the discussions at a number of meetings of the Committee. Those discussions have brought out very clearly that, as far as the pig iron affects the quality, interference with quality should be studied for three definite types of pig iron: (1) low-silicon pig iron; (2) very high-silicon pig iron, and (3) pig iron in which the silicon varies over a wide range in short periods, such as 1 to 3 casts. If a blast furnace is running steadily at 1 per cent. silicon iron, practically no trouble, apparently, can be traced to the pig iron, but if the furnace is running from 0.60 up to 1.50 and then down to 0.60 per cent., trouble in the finished steel is liable to occur, which apparently cannot be corrected by open-hearth practice. The open-hearth discussions have shown fairly definitely that with low-silicon iron, one type of trouble arises on the finished product and with the high-silicon iron, another. Our experience with the high-silicon is that any non-metallic matter that may form, does so when the pig iron is put into the furnace; that is, silicates immediately form which are more liable to be high in silica than would happen with low-silicon iron. I think Mr. Sweetser will agree with mc that if a blast furnace is very irregular, different points in the furnace may be working irregularly, in other words, the temperature gradient all over the furnace is not uniform. We have made many determinations on that point which indicate that a varying blast furnace causes hot spots and cold spots around the periphery. If some of those spots are hot and others are cold, although the analysis of the iron may be constant, then unreduced oxide, going through on one side, and good iron, going through on the other, may mix and the average temperature of the iron is not high enough to get completely rid of the oxides. So our method of attack is directly on that point; it is our first objective. Our procedure is to make a number of consecutive tests at a blast furnace, making a detailed study of the blast-furnace operation. We follow the iron through the open-hearth heat, being sure that we know just how much of each kind of iron gets into the open hearth, and take out specified samples at certain times during the process, working on steel where no finishing additions are made in the furnace. We are following one type of iron through the billet mills and into the finished product and are obtaining complete data on open-hearth operation. Besides the ordinary chemical analyses on the samples of slag and metal, we are running samples of the plg iron, the steel in the open hearth and the finished steel, for oxygen and silicates. We are going to find out whether or not oxygen, as silicates or oxides, has some connection with this trouble. If not, we may be able to locate some other factor. I am inclined to think that the silicates are responsible, judging from the indications in some other work that the Bureau of Mines is doing in Pittsburgh. We have laid out a very definite method of testing to which we will adhere at the different plants where we are now working and at others in the future. Our aim is to

Jan 1, 1927

By Roshan B. Bhappu, Raul A. Deju

A method is proposed by which the chemical reactions between water and a silicate bed can be related to equations of flow. First the reaction mechanism is studied both theoretically and experimentally. Once the reaction mechanism is established, the equations of flow are solved, and a solution (under physically reasonable side conditions) is obtained. Experiments to substantiate the solution are also presented. The knowledge of surface reactions at the water-solid interface is of critical importance in extractive metallurgy. This is especially true in regard to the froth-flotation process of mineral concentration and all phases of hydro metallurgical recovery of metals. Similarly, the problem of ground-water contamination is one of growing concern, not only because of the increasing demands on our sources of supply but also because of the increasing necessity to find vehicles of waste disposal. The hydrochemistry of waste waters must be understood to exploit and develop such resources properly. To understand these problems, it is necessary to obtain a better insight into the reactions that take place between water and a solid packed bed. To do this, we will develop here in a theoretical model that predicts the fate of a chemical species in solution as it reacts with a silicate bed through which the liquid percolates. The treatment will be one-dimensional in nature and will not include dispersion. Experiments will also be presented to substantiate the theoretical model, using the silicate minerals listed in Table 1. This paper is preliminary in nature and is part of a larger study of the surface chemistry of the silicate-water interface. Mechanism of Surface Reactions In a previous paper,' the authors discussed the properties of various silicate minerals from a mineralogical standpoint. Now efforts will be made to study the reactions that occur when these minerals are put in contact with water. The reactions occur almost entirely in the surface layer of the mineralsa and are termed sorp-tion reactions. In this study sorption denotes the composite of all physical adsorption and chemical adsorption occurring between the silicate surface and the water in contact with it. A model of sorption as seen from a chemical-bond standpoint is presented below. On the basis of this model, the surface reactions between deionized water and a silicate mineral can be studied. Sorption Model: It is known that as the oxygen-silicon ratio increases from quartz to the olivines, a greater percentage of the oxygen bonding power is available for bonding to cations other than silicon. Hence, with an increasing oxygen-silicon ratio, the oxygen-to-metal bonding increases. Upon the fracturing of a silicate-mineral crystal, the oxygen-metal bond breaks more easily than the stronger oxygen-silicon bond, resulting in a negatively charged surface. Then, if the mineral is immersed in a liquid containing hydrogen ions, the negatively charged surface should tend to be neutralized by hydrogen ions from solution, resulting in a change of the solution pH. Thus, an increase in the degree of sorption of hydrogen ions must occur as the oxygen-silicon ratio in the crystal structure increases. Also in a previous paper,' the authors found that for a given silicate mineral the change of pH with time is given by

Jan 1, 1971

By D. M. Boulin, E. S. Greiner

Single crystals of vanadium were bent at 293" and 77°K to a maximum fiber strain of about 1 pct. Analysis of slip line and etch markings of- crystals deformed at either temperature show the slip planes are {112}. The slip directions at 298° and 77°K, deterwined from the asterism axes of rotation of crystals compressed in a {110} direclion, were (111). Etch pits, associated with dislocations, were observed in the plastically deformed vanadium. There was no evidence of mechanical twinning. THIS paper presents results on single crystals of vanadium plastically deformed by bending and compressing at 298° and 77°K. Bcc metals have been observed to slip on {110}, (1121, and (123) planes while the slip direction has invariably been found to be ( 111) 1 Lindley and smallman2 have studied the deformation intension of polycrystalline vanadium between 298° and 20°K and reported that at and above 77°K the deformation is predominantly by slip, but at 20°K the deformation is associated with twinning. Later, Edington and smallman3 found that single crystals of vanadium compressed in a (111) direction at 77°K deformed by twinning on { 112}( 111) systems. Clough and pavlovic4 have reported that mechanical twins were observed in vanadium loaded by impact at 77°, 173°, and 195°K, respectively. PREPARATION OF SINGLE CRYSTALS The vanadium single crystals were made from commercial vanadium reported to contain 0.03 pct C, 0.03 pct 0, 0.02 pct N, 0.0X* pct Ca, 0.0X pct Si, proximately 0.8 cm diam, 4 cm long and were grown in (100) and (110) directions. A crystal for studies of etch pits was gound to have a face parallel to a {l00} plane by the Bond crystal-orienting technique.7 In order to avoid straining, the crystals were placed on the steel mount with a low-melting organic compound (glycol phthalate) before grinding. Crystals for the bending experiments were ground to have the four side faces parallel to ( 100) planes. The crystals were electropolished8 in 10 pct H2So4 using a current density of about 3 amp per sq cm to remove the strained surface material. The crystals were bent slowly by three-point loading in a stainless-steel jig designed by Sylwestrowicz.9 The end rollers of the jig were 3.8 cm apart. DEFORMATION AT 298°K The bent vanadium crystal, after removal from the jig, had a radius of curvature of 20.4 cm over the 2-cm length close to the center loading roller, where the maximum bending moment occurred. This radius of curvature corresponded to a maximum fiber strain of 0.9 pet. The side faces contained slip bands as shown in Fig. 1. These bands are straight where the strain is high, top and bottom of micrograph, but are curved on either side of the neutral axis in the center. This curvature of the slip bands in the low-stress area may be due to cross slip. The plastically deformed crystal was subsequently electropolished and then electroetched in 10 pct H2SO4 solution, using a current density of 0.25 amp per sq cm. The structure is shown in Fig. 2. The directions of the traces on two adjoining faces were plotted stereo graphically, Fig. 3.* Since there were two sets of

Jan 1, 1968

By Edwin S. Smith

Current research in the phenomenon of liquefaction has indicated some of the in situ material properties which should be considered in the planning of waste deposits. Practical experience in tailings disposal, however, must be combined with the results of theoretical and laboratory studies to develop the most economical and safe techniques against liquefaction failure. One of the many responsibilities of mining engineers and mill superintendents is providing for the safe and economic disposal of wastes (or tailings) that remain after a mineral has been extracted from an ore. The cost of disposal of these tailings exerts a considerable influence on the minimum grade of ore extracted from the mine. It varies to a great extent with each project and is dependent on many diverse factors, such as the local topographical, meteorological and seismological conditions together with the applicable water pollution laws of the area. The process used to extract a mineral from an ore determines the physical characteristics of the tailings and, thus, is one of the more important factors to be considered in the planning of disposal facilities. Today's trends in ore-processing operations complicate the problems of waste disposal: recently developed extraction methods result in the production of finer tailings, the use of lower grade ores produces greater volumes of wastes, and the enhanced land values in the vicinity of industrial plants preclude the former practice of spreading wastes laterally and force the expansion of waste deposits upwards to greater heights. The frequent occurrence of stability problems in waste deposits indicates that many mining organizations may not be employing current soil mechanics concepts and practices. One of the most spectacular, and often most disastrous, types of tailings dike failure is that resulting from liquefaction of the fine particles combined with a breach of the main retaining dike. TAILINGS DISPOSAL Since the many variations in site conditions, ore bodies and extraction processes dictate the general disposal procedures and mill superintendents incorporate special facilities to provide the most economical disposal method consistent with accepted safety standards, it is only natural that there are almost as many different disposal techniques as there are disposal areas. Methods used in the construction of retaining dikes include: (1) transporting granular material from an adjacent borrow pit and (2) mechanically segregating the total effluent and allowing the coarse fraction to form a retaining dike by hydraulic deposition. The location of a plant and the surrounding topography exert the greatest influence on the layout of tailings disposal facilities. Most of the above-ground waste deposits can be classified as side-hill, (Fig. 1,) cross-valley, (Fig. 2,) or stockpile deposits. Side-hill disposal areas are probably the most common type of layout because of the natural advantage of gravity flow, without the disadvantage of river diversion usually needed for tailings ponds formed behind cross-valley dikes. Stockpiles, which are placed on relatively level ground, require four retaining dikes and the effluent generally has to be pumped up into the disposal area. Changing production techniques or developments adjacent to disposal areas have produced variations or partial combinations of these three categories. In a series of articles, Lenhart describes many of the problems encountered in the disposal of tailings and certain innovations used to overcome them. He discusses weaknesses in design and layout and shows that disposal techniques are often learned the

Jan 1, 1970

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.' Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.' The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt's observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt's earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.'-' While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962