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By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By Y. C. Kim, C. B. Manula

This paper is concerned with the details of the derivation of an operations research model, specifically linear programming, to solve production scheduling problems. While some results are presented for an actual study, the calculation of cases of a more general nature have not yet been completed. Production managers from those segments of the mining industry that experience a seasonal or highly variable sales demand find it rather difficult to develop overall producing plans for their organizations. In an attempt to solve this technical problem, demands are usually met by keeping production corresponding exactly to sales. This results in a fluctuating production schedule which is costly to maintain because of overtime premiums in periods of high requirements and because of costs associated with an idle mine plant during slack periods. An alternate solution may be to produce part of the desired amount and make up any deficiencies by using overproduction in previous time periods. This tends to smooth the production pattern through the use of a stockpile. However, because of associated storage costs, the solution may again be undesirable if it yields comparatively large surpluses. In general, this type of scheduling problem has an infinite number of solutions which satisfy the requirements. These are largely dependent on the extent to which an operation is geared to changes in production and on the size of its stockpiling facility. The determination of an efficient schedule is implied, therefore, as one lying between two extreme solutions, i.e., one that minimizes surpluses and one that minimizes output fluctuations. These conflicting objectives result in an economic balance problem between the costs of carrying surpluses forward from slack periods versus the cost of high production levels during peak demands. Various methods of operations research have been developed to handle problems whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. Those who are familiar with mining operations know that most managers have not progressed satisfactorily in this area. Production planning systems which most mines employ today are often no more than rough records of management's mental planning. For small mines these means are normally sufficient; but as operations grow larger and become more complex, this type of planning ability is no longer adequate. Managers may find themselves losing control of cost relationships, taking longer to outline production sequences, and becoming forgetful of certain resource availabilities. ORIGIN AND SCOPE OF A SCHEDULING PROBLEM The more fundamental aspects of the production scheduling problem can be brought into focus by demonstrating how it exists in a bituminous coal mine* located in southwestern Pennsylvania. This mine, operating in the Pittsburgh seam, uses a definite room-and-pillar block system of mining, which is planned and carried out with only slight variations to meet local conditions. The coal seam, which is firm and varying in thickness from 8 to 9 ft with the bottom 6% ft being extracted, is under 500 ft of cover and opened by a shaft. The bulk of the coal (60%) is obtained from the pillaring activity with the mains and sections, which are considered primarily as development activities, contributing the balance of 12% and 28%, respectively. All coal is won by a ripper-type continuous miner in conjunction with shuttle-cars directly behind a loading machine. Track haulage is employed to move coal from these machine centers to the shaft bottom. The coal, thus mined, is shipped to one destination as part of a mixture of coals to be used in the making of steel. A material flow diagram of this distribution scheme is illustrated in Fig. 1. PROBLEM STATEMENT From the above types of shipments and mining limitations, the basic problem is to determine an economic means of producing and stockpiling a single coal product produced in three different machine centers (main, section, and pillar). Fig. 2 shows total demand for coal as a function of time. Because of the extremely high peak demands, slack period production must be stored and then distributed

Jan 1, 1969

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.''4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6'" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2'11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By E. A. Farrell

A comprehensive survey is made of the status of the asbestos industry as it relates to marketing the product. Included are descriptions of the various types of asbestos and the grading and classification systems used. The uses of asbestos, distribution practices, and types of ore bodies are all related to marketing. World production, the producers and their capacities and world consumption for 1966-67 are summarized and statistical data are included. Asbestos is a general term describing a family of fibrous minerals of the serpentine and amphibole mineral groups. Asbestos has a long history going back to the time of the Egyptians, when it was used as a lamp wick. The commercial mining of asbestos started in Canada, Russia, and Africa in the 1800's, and the first asbestos products were made in Italy and Russia. The five main types of asbestos are: chrysotile, accounting for 95% of the total mined, amosite, crocido-lite, anthophyllite, and tremolite. Canada, Russia, and Africa are the major producers of asbestos. The commercial utility of asbestos was at first based on the heat resistance of the fibrous mineral in the form of packing, at the start of the industrial revolution. Its current utility is based more on its ability to reinforce binders such as portland cement, rubber, and plastics. Its inertness to the chemical nature of most binders is unique. Most important is its ability to maintain its reinforcing utility when the product is exposed to weather and soil conditions as in asbestos cement boards and pipe, and heat, pressure, and chemical exposure as in brake linings and gaskets and packings. The mineral asbestos is also unique because its fibrous form permits it to be spun and woven to cloth or formed into paper. Many asbestos applications are critical to national defense and at the present time, there are no satisfactory substitutes. Grading and Classification Canadian chrysotile asbestos fiber is graded and priced by length since basically the longer the fiber the higher the utility. The Canadian asbestos industry does not, however, classify the fiber by direct length measurement, but by a dry screening test. The method is called the Quebec Standard Screen (QS) test. One pound of fiber is mechanically shaken in four vertically stacked sieve boxes. The relative proportions remaining on the sieves defines the grade. The longer the fiber, the larger is the amount that stays on the top coarse screens and the less on the lower, finer mesh screens. Other tests can be used to further define the length distribution of fiber such as the wet screen Bauer McNett and the Suter Webb Comb (3 group only). The Canadian grading system divides the milled fibers into 5 main groups: group 3, 4, 5, 6, and 7, with 3 group being the longest, and 7 the shortest. Each group is further divided to subgrades, identified in each group by the letters A to Z, with "A" the longest and "Z" the shortest. See Appendix 1 for the Canadian QS classification system. The Russians also use the QS test on chrysotile. The Africans classify their chrysotile into grades similar to Canadian. The African crocidolite and amosite, however, are classified into actual length groups such as l to 2 in. and 2 to 3 in. Amosite and crocidolite are generally longer than chrysotile but also more brittle. Milled asbestos is not composed of staple length fibers like fiber glass or cotton, but of a mixture or blend of fibers ranging from long to short. Milled asbestos has a fiber length distribution similar to the particle size distribution of a powder. For example, the longest group 3 chrysotile grades have a high percentage of the longest fibers (1/2 to 3/4 in.) and low percentage of short fibers (0.003 in.). The figures in Table 1 give the approximate length distribution of the longest, middle, and shortest groups. A second and further method of classifying fiber is the degree to which the fiber bundles are separated to form a larger number of smaller diameter bundles. This property is normally described as the degree of fiberization, openness or surface area. Air permeability tests are used to measure surface area. Asbestos pro-

Jan 1, 1971

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By C. B. Sclar and

A graphical solution is presented for the equation v =v &-cU where vb is the volume of liquid b of density 6 that must be added to liquid a of volume va and density d, in order to obtain a heavy-liquid solution of preferred density dm for mineral fractionation. The equation is valid only for pairs of liquids whose volumes are additive, but empirical density-composi-tion data show that this condition is met over wide compositional ranges by all of the heavy solutions that are commonly used for mineralogical analysis. The chart is a nomograph which consists of two horizontal volume scales ad a vertical density scale arranged so that one volume scale occurs on each side of the density scale. All the scales are linear. For two liquids of density d, and &, respectively, each volume scale has an independent level on the density scale, ad the graphical solution for vb on the nomograph is obtained by construction of one straight line. The chart can be prepared easily to cover any density range with any desired accuracy by proper selection of the scales. Heavy-liquid separation of particulate samples is an indispensable analytical procedure in the mineralogical and mineral-process ing laboratory. Heavy liquids may be used 1) to isolate specific minerals in the form of high purity products or to fractionate samples into several products with density limits for petrographic, chemical, spectrographic, and X-ray diffraction analysis,'-' 2) to determine the density of minerals,'-l4 3) to facilitate the recognition and identification of optically similar associated minerals,15 and 4) to determine quantitatively the degree of liberation of ore minerals in ores and mill products at various limiting sizes." The preparation and recovery of heavy liquids suitable for mineralogical analysis are discussed fully in the literature and operational procedures and special equipment for heavy-liquid separation are described in numerous references.'747837' 13,18,25-42 Useful tabulations of heavy liquids for mineralogical analysis are given by Tickell, Mil-ner,' Twenhofel and Tyler,' and Lange and a very complete up-to-date list of minerals arranged according to increasing density is given by Mursky and Thompson. USEFULNESS OF THE DENSITY CHART For any particulate sample, the limiting densities selected for its fractionation by means of heavy- liquid separation depend on the respective densities of the constituent minerals and the specific objectives of the separation. In many instances, the densities of readily available and practicable heavy liquids do not coincide with those that are required, and suitable liquids of the proper density are obtained by dilution with miscible liquids. In the general case, one may wish to mix either a pure liquid (A) or a solution of two miscible liquids (AP,,) of known density with either a pure liquid (B) or a different solution of the two miscible liquids (A,B,) of higher or lower density in order to obtain a final liquid of the preferred density. In conventional practice, the latter is reached empirically by trial-and-error addition of increments of one liquid to the other. The density of the final solution may be determined either by accurately weighing a known volume of the final liquid,'' 532;4;40, or by means of I)a Westphal balance, 2)a hydrometer, a refractometer in the case of binary liquid systems for which density-refractive index data are available,15 4) natural or synthetic .indicators of known density, a pycno-meter. Like all trial-and-error methods, these procedures are time consuming and many require special equipment which may not be available, The purpose of this paper is to show that the volume of a liquid of known density which is to be added to another liquid of known volume and density in order to obtain a solution with an intermediate preferred density may be determined rapidly and accurately by a graphical method provided that the two liquids form ideal or quasi-ideal solutions whose volumes are additive. Empirical data47'8~'8~4B'49 show that solutions prepared from pairs of miscible

Jan 1, 1961

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By J. L. Walter

Extra-low carbon iron sheet, when deformed and annealed, undergoes exaggerated or abnormal grain growth in the critically deformed regions of the sheet. This exaggerated pmth occurs, for low strains (3 to 6 pct), only in sheet which has a fine dispersion of precipitates in the subsurface region of the sheet and fewer and coarser precipitates in the sheet interior. These particles have been identified as manganese sulfides. Wing the anneal, grains near the surface are gvowth-inhibited by the fine particles but the grains in the interior are free to grow normally. With the additional driving force provided by the strain energy, the interior grains first grow into the small subsurface pains. Eventually, these growing grains grow completely through the sheet. Calculations of limiting grain sizes at various values of strain indicate that a volume fraction of precipitates in excess of 10-' would be required to eliminate exaggerated growth in material strained to 10 pct. OPEN-COIL annealing has made decarburization of sheet steel both efficient and economically practical. Use of such material for porcelain-enameling stock is one of many possible applications of low-carbon iron since carbon in steel is deleterious to porcelain-enameling properties.' However, the extra-low carbon iron presently available presents another problem, that of exaggerated grain growth in regions where the sheet has been deformed as by bending or stretching. In exaggerated grain growth a few grains start to absorb their neighbors and these may become very much larger than the average grains of the sheet. Other names for exaggerated grain growth are coarsening, critical grain growth, secondary recrystallization, abnormal grain growth, or discontinuous grain growth. While this grain growth does not affect the enameling qualities of the low-carbon iron sheet, their presence results in a marked reduction of tensile-yield strength in the region of the sheet containing the large grains. The loss of tensile yield strength may render the material unsuitable for many applications . This report describes the results of a study undertaken to determine the cause of the exaggerated grab growth in extra-1ow carbon iron and, if possi- ble, to prescribe practical procedures for its prevention. GENERAL THEORY The driving force for exaggerated grain growth is the grain boundary free energy. This driving force is proportional to (l/rl + l/r2) where rl and r2 are the mutually perpendicular radii of curvature of the boundary between the growing grain and the grain being consumed. Thus, the greater the difference in size between the growing grain and the matrix grains, the higher the driving force for grain growth. If, however, the matrix grains are free to grow simultaneously, the driving force for exaggerated growth will be diminished. Stability toward growth of the matrix grains may be caused by a) a strong single orientation texture (texture inhibition),' b) a dispersed second phase,3"5 c) the thickness effect,' or d) intergranular segregation.7"9 As exaggerated growth occurs when growth of the matrix grains has been slowed by the stabilizing processes mentioned above, there must be an additional factor acting to promote growth of a few of the grains to the point where they are enough larger than the matrix grains that boundary energy driving forces are sufficient to cause continued growth. For instance, at the annealing temperature, growth-inhibiting inclusions may slowly dissolve and coalesce. Eventually, a grain boundary becomes unlocked and migration occurs at the expense of neighboring grains. Or, an additional driving force may be supplied to some of the grains if the material is strained. Then, since some grains will be strained less than others, the difference in strain energy between adjacent grains may be sufficient to overcome boundary locking and allow growth of the grains with lower strain energies. In the present study, therefore, such factors as the presence or absence of dispersed phases, the nature of the exaggerated growth, and the effect of strain have been considered. EXPERIMENTAL PROCEDURE I) Material and Processing. Three types of low-carbon iron were used in this study; types A and B were commercial grades, each from a different supplier.* The precise details of the processing of

Jan 1, 1963

By W. M. Robertson

The kinetics of grain boundary groove formation on copper surfaces immersed in liquid lead have been studied over the temperature range of 400° to 900°C. The groove widths were Proportional to the cube root of the annealing time, indicating that the diffusion of copper through the saturated liquid-lead solution is the mechanism by which grooves form. The rate constant for the process can be calculated by a theory due to Mullins. Using published data for the solubility of copper in liquid lead, for the interfacial energy of the solid copper-liquid lead interface, and for the diffusion coefficient of copper in liquid lead, the calculated rate constants almost exactly reproduce the measured values over the entire temperature range. The decay of scratches placed on copper surfaces has also been studied. The rate constant for scratch decay agrees with that for grain boundary groove growth, though scratch decay is sensitive to convection currents in the liquid. The interaction of solid and liquid metals has been studied extensively and has been found to be rather complex. Many of the studies have been complicated by a host of competing effects, including temperature gradients, concentration gradients, the formation of one or more intermetallic phases, natural or forced convection, and the presence in both the solid and liquid of considerable amounts of impurities and alloying elements. Recently theories have been developed of changes in surface profiles driven by capillary forces,' which allow the interaction of the solid and liquid to be analyzed quite directly. The present paper reports a study of the formation of grain boundary grooves on pure copper immersed in liquid lead, which allows the theory to be checked quantitatively. The Cu-Pb equilibrium diagram is quite simple: there are no intermetallic compounds, copper is just slightly soluble in liquid lead, and lead is almost completely insoluble in solid copper.2 The Cu-Pb system has been studied extensively,3-9 and all of the quantities—interfacial energy, diffusion coefficients, and equilibrium solubilities-necessary to calculate the rate of groove growth by a volume-diffusion mechanism are known. The kinetics of grain boundary grooving and scratch smoothing have been studied on the noble metals and the iron group metals in a reducing atmosphere or in vacuum.10 The main interest of these studies has been the determination of surface-diffusion coefficients at metal-gas interfaces using the theories developed by Mullins.1 The present paper uses similar methods for the study of diffusion processes at the interface between two condensed phases. There has been one previous study" of the kinetics of groove growth in a solid-liquid system, which, however, was troubled by the fact that neither interface energies nor diffusion coefficients were known in the Ni-S system studied. THEORY The theory of grain boundary groove growth has been developed by Mullins for the cases of volume diffusion," surface diffusion," and a combination of the two processes.14 He has also analyzed the kinetics of the flattening of a scratched surface by these processes.l5,l6 Several assumptions and approximations were used in the derivations of the surface profile shapes. The applicability of these assumptions and approximations to the present system will be considered in the discussion. At the intersection of a grain boundary with an initially flat interface the equilibrium between the interfacial energy and the grain boundary energy establishes an equilibrium groove angle. This induces curvatures in the interface. The chemical potential of material at a curved interface is higher than at a flat interface, so that material moves away from the region of the grain boundary. Mullins' calculations indicated that the groove profile would be similar to that shown schematically in Fig. 1. Small humps form above the level of the original flat surface. For a volume-diffusion mechanism the separation, w, of these humps at a time, t, is given by and where co is the equilibrium concentration of the solid in the liquid, y, the solid-liquid interfacial free energy, O the volume occupied by a solute atom in the liquid, D the diffusion coefficient of the solid in the liquid, and kT has its usual meaning. For a surface-diffusion mechanism the groove width is proportional to the fourth root of the time. For grooves forming by a combined surface and volume-diffusion mechanism the exponent of the

Jan 1, 1965

By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By R. G. Ward, A. E. El-Mehairy

A technique was developed to calculate the density of liquid metals from the profile of a weighed levitated drop obtained by emitted light photography and calibration. The density of liquid copper was determined over the temperature range 1370" to 2100°K and expressed with the equation: The molar volumes and thermal coefficients of expansion are calculated. Copper, upon melting, was found to expand 3.34 pct. A knowledge of the density of liquid metals is essential as it is a parameter appearing in most theories of the liquid state. The liquid density is also necessary for the calculation of the commercially important contraction occurring on solidification. Unfortunately good density values are rarely available and the present work was undertaken to establish a new method of density determination free from the limitations of the existing methods. For liquid metals with high melting points, the variation and the limited number of density values reported in the literature have been caused primarily by difficulties in technique, a matter which has been adequately discussed by Urbain.' In all the methods used for measuring the density of the high-melting liquid metals there are sources of error, and corrections have to be made. For example, in the method of balanced columns, the formation of gas bubbles in one or both arms was a great source of error. In the pyknometer3 and immersed-sinker methods, corrections of certain volumes for thermal expansion to the operating temperature exceed 4 pct. In the maximum-bubble method5 a correction for the thermal expansion of the bubble-tube is used (about 1.6 pct); a second correction takes into account the change in the volume of liquid displaced by the bubble-tube (about 3.5 pct). Another method used is based on the shape of a drop of liquid, at rest on an inert refractory plaque, obtained photographically or radiographi-cally. The volume is calculated from the shape, which is sensitive to the surface tension and supporting material, by some intricate empirical relation. The drop contour changes with 90 deg rotation of the support.7 The application of all methods is limited by reaction between liquid metal and the apparatus. The successful stabilization of a mass of liquid metal during levitation melting8 afforded a technique for measuring the density of liquid metals out of contact with solid materials. The technique was developed by using copper as the density of liquid copper has already been studied extensively, thus allowing comparison with the new method. It consists of calculating the volume from the dimensioned profile of the levitated drop obtained by emitted-light photography and careful calibration. The molten egg-shaped drop spins around the magnetic axis of the coil (lined vertically) at a speed which seems to increase with increasing temperature. The method does not involve corrections and the experimental setup allows the use of vacuum or special atmospheres. The maximum operating temperature is limited by excessive evaporation of metal from the droplet. EXPERIMENTAL Levitating System. A stabilizing ring was used in conjunction with a 3-turn levitating coil energized by a 450-kc per sec, 10-kw Toccotron with a high current-low voltage output stabilized to f 1 pet.' APyrex glass tube with a Pyrex Optical flat window inserted through the coil and ring allowed the use of special atmospheres during levitation melting, as shown in Fig. 1. Optical System. Fig. 1 shows the optical arrangement used to photograph the profiles of the drop, parallel and perpendicular to the vertical spinning axis, simultaneously on the same frame of a high-speed 35-mm film. The optical system was adjusted to avoid any distortion of the profiles and to ensure that both profiles are in focus. The length of path from object to objective was about 30 cm, and a magnification factor close to 1 was obtained with the single-lens reflex-camera system. Temperature Measurement and Control. In operation, the specimen temperature was constant to 5 C for a fixed power input to the levitating coil and fixed rate of gas flow through the tube. The temperature was measured by an automatic two-color pyrometer (Coloratio) checked at the melting

Jan 1, 1963

By W. F. Hower, W. Brown

Large-scale sand consolidation tests were conducted in an effort to determine the reasons for the successes and failures of this method of sand control. Several different consolidating materials were used in treating both clean and bentonitic sands that were packed in a chamber having a capacity of 3.3 cu ft. The results were essentially the same for all of the different consolidating materials, The data show that low-viscosity consolidating materials pumped at a relatively slow rate gave the best results. Where the formation has produced sand, the treating fluids can compress the formation, thus permitting the channeling of fluids to another horizon. Pressure-packing these zones before attempting to consolidate is recommended. Sands containing more than 4 per cent of water-swelling clays are not good candidates for consolidation. It is indicated that loose sand, particularly when it is bentonitic, can be fractured during the placement of the treating fluids. INTRODUCTION Sand production in oil and gas wells has plagued the industry for many years, and numerous cures for this problem have been suggested. Most methods have been successful to a certain degree, but the great variety of well conditions that exist in the different areas has magni- fied the problem and limited the successful use of the various systems. Four review papers1-4 present a wealth of information concerning the degrees of success that have been obtained by the different sand-control methods. The bridging of sand grains by the use of gravel packs and screens has been quite successful. However, these methods do not leave the casing clear for all types of multiple completions, and the cure does not last for the production life of the well in some instance:;. The control of loose sands by sand consolidation with resins has never been as successful as desired. It has always been hoped that such a treatment would eliminate all sand problems for the life of the well, but. initial applications, starting in the middle 1940's, were only moderately successful. Lott, et a1,3 reported a success ratio of approximately 50 per cent and made the following conclusions. The highest percentage of successes were obtained where: a. Consolidation of a zone was made at the time of initial completion or prior to the production of sand. b. The interval treated was less than 12 ft in length. c. Between 30 and 50 gill plastic/ft of producing interval was displaced through the perforations. REASONS FOR SAND CONSOLIDATION FAILURES Our own experiences in the field of sand consolidation point toward the following conditions as the major reasons for the failure of sand consolidation attempts. 1. Mud-plugged perforations and mud invasion of the formation. 2. Sand in the casing covering all or part of the perforations. This sand could be either formation sand or one of the coarser sands used as propping agents in hydraulic fracturing. 3. Holes in the casing. 4. Channels behind the casing. 5. Attempting to treat too long a perforated section. 6. Too high a percentage of water-swelling clays in the formation. 7. Formations that have produced sand. Recent attempts were made to treat perforated sections ranging from 10 to 30 ft, in wells that have produced sand, by using a straddle packer that was raised and lowered through the perforations as the consolidating material was being pumped. In most instances, the pressure required to pump fluid into the formation varied considerably as the tool was raised and lowered. This suggested the possibility that significant differences in permeability were present or that only part of the formation had produced sand. There were times when a sudden break in pressure indicated that a fracture was being formed. Research conducted several years ago concerning the problem of the control of water in air and gas drilling indicated that shale sections could be fractured quite easily. In addition, it was determined that it was easier to pump fluids into shale bodies by fracturing the shale itself, or the interface between the shale and sand, than to pump into a fluid-saturated formation. Formations that produce sand are usually adjacent to shale bodies and frequently have shale streaks of various thicknesses inter-bedded in the sand. Therefore, where shale is exposed to fluid pressure it

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By R. J. Stoehr, F. Howell

Since the ore mined in the Grants-Ambrosia Lake uranium area is taken from a water-saturated sandstone formation, part of the milling operation includes a drying process. The authors discuss the merits and disadvantages of two methods: natural drying and mechanical gas-fired drying; operating and cost data are included. In the Grants-Ambrosia Lake uranium area, approximately 7000 tons of ore are mined each day from a water-saturated sandstone formation. This ore is sampled and treated at four separate milling operations. Prior to the design and initial construction of the milling facilities, very little was known as to the physical properties of the ore which would be handled in the sampling and crushing facilities at the mills. All four mills initially were constructed without ore-drying facilities. As mining proceeded, it was determined that, even after drying the ore in place by use of drainage development underground, the moisture content of the ore as hoisted averaged approximately 18 pct. Actually, some of the mines produced ores which resembled cream-of-wheat in character and had a moisture content in excess of 24 pct. Each of the four mills had a differently designed sampling and crushing plant; therefore, the moisture content of the ores had varying adverse effects upon the operation of the plants. It was determined after some experience that most of the sampling and crushing facilities could not economically handle ore if the moisture content was greater than 10 pct—one operator considers 12 pct moisture as a maximum. In all of the plants, moisture content over 8 pct increases costs to some extent. In addition to the added sampling and crushing costs, some of the mills were located 15 to 20 miles from the mines and the high moisture content of the ores increased the haulage costs from the mine to the mill. It was generally conceded that it was necessary to employ some method to reduce the moisture content of the ore prior to sampling. Several methods were considered: 1) natural drying at the mine site, 2) mechanical gas-fired drying at the mill site, 3) mechanical gas-fired drying at the mine site, 4) radiant heating on concrete clabs, and 5) infrared shed drying. After preliminary investigation all possibilities but natural drying and mechanical gas-fired drying at the mill site were eliminated. NATURAL DRYING A cooperative feasibility study was conducted on the natural drying method. This study indicated the following: 1) During summer months May through September, ore piled 4-ft deep would dry from +20 to +10 pct HzO in 30 days with no mechanical turning. 2) In the first four days after piling a reduction of 5 to 7 pct total moisture content was accomplished by drainage and absorption of the water into the underlying ground on which the ore was piled, providing the ground surface absorption rates approached 10 gal per sq ft per day. After the first four days the decrease of moisture caused by drainage was practically nonexistent. 3) In the summer months drying by evaporation amounted to approximately 0.1 pct decrease in total moisture per day and mechanical turning of the ore could increase this as much as three times. 4) Climatic conditions of the area indicated that: a) Air temperatures averaged 64&apos; May, June, July, August, September; 41" October, November, December, March, April; 31" January, February. b) Average rain fall was 10 in. with 40 pct of this occurring during July and August. c) Only on very rare occasions were there over five consecutive days with below freezing temperatures. d) The annual evaporation rate was approximately 75 in. On the basis of this study, two of the mill operations decided to attempt to meet the moisture specifications by natural drying supplemented by mechanical turning. The other two operations decided upon rotary gas-fired drying at the mill site. The natural drying method has been quite successful in practice. The ore running approximately 18 pct moisture is trucked from the head frame and piled in rows about 6 ft wide, 3 1/2 ft deep, 5 feet apart during the months of May through September. In approximately 30 days this ore will

Jan 1, 1961

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