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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 H. R. Brannon, R. J. Robinson, G. W. Kattawar

Accurate prediction of storm wave characteristics are needed for design of offshore structures. Statistical methods of random noise analysis provide techniques for predicting required wave properties. These techniques have been used to analyze and characterize storm wave profiles from Gulf of Mexico recording installations in 34, 65 and .98 ft of water. Correlations based on the results can be used to predict wave crest probabilities and wave shapes for a range of Gulf water depths and storm conditions. Example predictions of wave crest probability as a function of water depth for a particular set of storm conditions are given. INTRODUCTION Accurate predictions of wave crests and wave shapes are needed for design of offshore structures. With predictions of wave crests, platform deck elevations giving adequate protection from exposure to storm waves can be selected. Use of hydro-dynamic wave theories with the wave crest and wave shape predictions permits an estimate of the wave forces an offshore structure must withstand. Observation of ocean waves suggests use of statistical analysis for studying wave characteristics for water depths beyond the breaking wave zone; recent wave generation theories lend support to this approach. l-3 One of the most powerful methods of statistically analyzing wave profiles was introduced by Cartwright and Longuet-Higgins; most of the basic relations used were developed by Rice5.6 in studies of random noise theory. This method predicts wave crest elevation probabilities from two parameters characterizing a wave profile. The statistical approach also provides a means for predicting wave shapes. In the random noise model of a wave profile, surface elevation is represented as an infinite sum of sine waves with closely spaced frequencies and random phase angles. Power density is proportional to the sum of the squares of the amplitudes of sine waves having frequencies within a narrow band, and the distribution of power density as a function of frequency is called the power density spectrum, or power spectrum. The power spectrum characterizes an irregular sea, and hence finds use in motion studies of ships, barges and semisubmersible drilling platforms. From the power spectrum, a wave profile of any duration of time can, in principle, be calculated; this long wave profile depicts the many wave shapes to which a structure may be exposed. Thus, the statistical methods of wave analysis provide an approach to selecting wave shapes as well as wave crest elevations needed for design of offshore structures. For practical application of these techniques, power spectra and related quantities must be predicted from storm properties. Barber and Tucker 7 have reviewed correlations of wave properties and storm conditions. Their review summarizes work of Darbyshire,8 among others, in which a correlation of power spectra with wind intensity of the North Atlantic was developed. These results, plus more recent work by Pierson and Moskowitz and Kitaigorodskii,10 establish feasibility of correlation, but there is no theoretical basis for modifications extending the relations to other areas as remote as the Gulf of Mexico. Hence, to predict characteristics of Gulf of Mexico waves, a study of local observations is needed. This paper presents (1) a practical approach to computing wave profiles hat depict shapes of waves for use in force calculations, (2) a summary of relations for predicting probabilities of wave crest elevations, (3) correlations of parameters needed to apply these methods in the Gulf of Mexico and (4) examples of application of the techniques. THEORETICAL BACKGROUND The following sections summarize relations needed to calculate wave profiles and to estimate wave crest probabilities. These relations also identify quantities that must be related to storm

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By G. G. Priest, B. E. Morgan

The production of oil and gas from wells is often seriously hindered by the compaction of solids in the perforations during the perforating process. To realize the full productive capacity of a well, it is necessary either to remove the plugging material from the perforations or to perforate in a manner which does not cause plugging of the perforations. The latter method can be accomplished by having a non-plugging fluid in the casing at the time the well is perforated. This paper describes the results of laboratory tests, perforating tests, and experimental field tests which demonstrate that certain emulsions serve effectively as non-plugging perforating fluids. The principal components of these emulsions are two liquids: an aqueous phase consisting of a solution of either sodium chloride or calcium chloride, and an oil phase consisting of diesel oil, tetrachloroethylene, or a combination of both. Small amounts of other agents which serve to stubilize the emulsions, to reduce the fluid loss, and to inhibit corrosion are also present. The density of the emulsions is controllable within the range of 7.5 to 12.5 lb/gal; no insoluble solids are present, the filtration rate is low, and the thermal stability is satisfactory at temperatures as high as 200°F. The corrosion of steel by these emulsions is negligible. Tests conducted under conditions which simulate the temperature and the pressure in an actual well demonstrate that these emulsions fulfill the requirements of a non-plugging perforating fluid. In addition, lirnited field experience furnishes evidence that these emulsions remain in position after they are spotted, that they are retained in the casing after the perforations are made, and that they are easily removed from the perforations when the well is opened for production. When the pressure in the borehole is greater than the formation pressure at the time a well is perforated, plugging of the perforations can be avoided by spotting an emulsion adjacent the interval to be perforated. This procedure should eliminate low well productivity caused by plugging the perforations. INTRODUCTION Nature of Problem The most widely used method for the completion of oil and gas wells is to set and cement casing through productive horizons, and then to obtain production by gun-perforating the section of casing opposite the desired interval. This method is gen- erally successful and it was thought at one time that those failures which did occur were due to insufficient penetration by the perforator. Despite recent improvements in perforators which assure ample penetration, unsatisfactory fluid production continues to be a problem. Evidently, the trouble comes from some other source. Recent results obtained by Allen and Worzel1 demonstrated that low fluid productivity may be caused by the perforating process and/or by the fluid in the wellbore at the time of shooting. They found that perforations are often completely plugged by debris from the perforator, pulverized sand from the formation, and compacted solids from the drilling mud when the pressure in the wellbore is greater than the pressure in the formation at the time of perforation. In some cases a differential pressure in excess of 400 psi was required to initiate flow into the well through these plugged perforations. The plugging of perforations by solids not only causes low productivity from wells, but it creates simultaneously other problems in the production of oil and gas. For example, when most of the perforations are plugged, high rates of flow must occur through the few perforations that are open. The resulting high pressure drop may cause production

Jan 1, 1958

By Sam N. Dewitt, Albert S. Trube

This paper presents a discussion of the pressure maintenance operations which were begun in the New Hope Field. Franklin County. Texas. in 1944. The project has required the injection of extraneous waters at depths from 7.300 to 8.000 ft with intake well-head pressures up to 4.000 psi in three different reservoirs — the Bacon. Hill. and Pittsburg. Records of oil and water production. water injection and the GOR have been kept for each reservoir and reservoir pressures were taken at regular intervals. These data indicate that the Bacon Reservoir had no apparent water encroachment up to the time of water injection. However. the Pittsburg and Hill reservoirs had some natural water influx hut not sufficient to prevent pressures from declining below the bubble point. The Bacon and Hill reservoirs responded almost immediately to water injection. while the Pittsburg which is the least permeable. has shown good pressure response only since .August, 1948. The principle objective of the project has been to increase ultimate recovery. Success of the project to date also has resulted in reduced lifting costs. Esti- mates based on the initial water breakthrough patterns indicate that the primary objective of substantial additional recovery will he accomplished, and there is a possibility that the original estimates elf oil recovery with pres-sure maintenance will he exceeded. INTRODUCTION This pressure maintenance project was one of the earliest primary pressure maintenance programs to he attempted on a multiple zone field. There are three producing reservoirs into which water is being injected for the purpose of maintaining pressure and increasing the ultimate recovery- from each. This paper is limited in scope to al1 account of the development of the project. the pressure production relationship prior to the injection of water and the effect of water injection on the producing reservoirs. Also discussed are the nature of the injection system and the indicated results on initial water break-through in the Bacon Reservoir. FIELD CONDITIONS The New Hope Field, which is located about 12 miles northeast of Winusboro, Franklin County, Texas, is an elongated symmetrical anticline containing four known oil reservoirs. The reservoirs are of the Trinity group of the Comanchean or Lower Cretaceous period and are found in Table I. The oil productive portion of each reservoir is not present in all of the producing wells because their areas and positions vary with respect to one another. Fig. 1 shows the relative position of the four reservoirs and illusIrate? how some wells could penetrate all four, while others are restricted to three. two. or perhaps one. depending on structural location. The first three reservoirs contain undersaturated oil. The deepest. the Elledge, has a primary gas cap. Although this reservoir covers a considerable area of the field. it has a very thin section and a low order of permeability. Elledge producing wells have generally been characterized by an early increase in GOR, making it necessary to recomplete them in other reservoirs. (At present. one well is completed in the Elledge. which is still producing.) Because of the difficulties en-countered in producing oil from this reservoir. and the small quantity of oil actually present. future attempts at producing it will probably be on a salvage basis during the later life of the program. For this reason, the remainder of this report will be confined to a discussion of the Bacon, Hill and pius-burg reservoirs.

Jan 1, 1950

By John Hower, Frank J. Markewicz, William Lodding

Greensand, greensand marl, and green earth are names given to sediments rich in the bluish green to greenish black mineral known as glauconite by the mineralogist. The word glauconite is from the Greek word glaukos, meaning bluish green. The term "greensand" as a rock name for a glauconite-bearing sediment is more appropriate than "greensand marl," a term that has been doggedly perpetuated in the literature. Because of its potash and phosphate content, greensand was dug and marketed as a fertilizer and soil conditioner for more than 100 years. The advent of prepared fertilizers with adjustable nutrient ratios led to the decline of greensand for agricultural application. The material has since been recognized for use in water treatment. Unfortunately, in spite of large reserves and worldwide distribution, the mineral has not been utilized to any significant commercial extent because no major application has been found for a substance with its chemical composition and properties. This lack is probably due to a paucity of research on its potential commercial application. Extraction of potash received considerable attention during and just after World War I. Because of relatively high extraction costs and generally low potash content (up to 8% ), glauconite lost its appeal as a source of this commodity. Historical Background Greensand was used as a fertilizer in New Jersey in the latter part of the 1700s. During the early 1800s its use became more common; applications of up to 100 tons per acre were sometimes made, although recommendations for agricultural use suggested 20 to 50 tons per acre (Tedrow, 1957). Many crops, especially the forage type, were said to improve with greensand application; however, because of, slow release of potash, large quantities were required. Certain greensands that contain sulfur and sulfide minerals are harmful to plant growth, and these were classified as "poison," "burning," or "black marls." The availability of higher-grade potash salts from other mineral sources, and the manufacture of prepared fertilizers, displaced the agricultural use of greensand during the later 1800s. During the mid-1800s the domestic greensand industry, centered in a small section of the eastern United States, grossed more than $500,000 per year. Toward the end of the century, annual production had dwindled to less than $100,000. By 1910 there were only six or eight greensand producers, grossing less than $5000 (Tyler, 1934). There was a small revival in the industry during World War I because of the curtailment of foreign potash, especially from Germany. During the later 1940s and early 1950s greensand was again recommended as a food nutrient for plants and farm crops. Agronomic studies discussed its potential as a soil additive that gradually releases potash and many trace-element nutrients essential for plant growth (Tedrow, 1957). Greensand was sold with the idea that it would condition soil and absorb and hold water while its base-exchange properties would release trace elements. For a short time glauconite was utilized in certain parts of New Jersey as a binding additive in the brick industry, and in the 1800s for making green glass (Cook, 1868). In the early 1900s the base-exchange property of glauconite was recognized for water treatment, and the mineral gained acceptance as a water softener. Mansfield (1922) does not mention base-exchange; however, the base ex-

Jan 1, 1983

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.' Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,' and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.' Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,' and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct Cr region were carefully resolved. Phase relationships in the 50 to 100 atomic pct region were outlined. A single intermediate phase, ZrCr,, was established in the system. A eutectic and a eutectoid were found in the zirconium-rich region of the system, while a eutectic was located in the chromium-rich region. Limited solubility of chromium in both a and a zirconium was observed. THIS is another in a series of papers on zirconium-base binary phase diagrams based on a program sponsored by the Atomic Energy Commission. The Zr-Sn,' Zr-Si,' and Zr-Mo and Zr-W" systems have already been published. Previous work on the Zr-Cr system includes a partial diagram by Hayes, Roberson, and Davies' and a complete diagram by McQuillan." The phase relationships reported by these authors were determined with magnesium-reduced zirconium, whereas those reported herein are based on iodide metal. Some X-ray work on the intermediate phase in this system was also reported by Hayes et al., as well as by Wallbaum.' Comparisons with these data are made in the appropriate sections. Thermal analysis, metallographic and incipient melting techniques were employed to accurately resolve phase relationships in the 0 to 50 atomic pct Cr region, while the remainder of the diagram is outlined on a basis of cast structures and thermal analysis. A description and analyses of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar (Westinghouse "Grade 3") was used. This material was produced by the decomposition of a volatile iodide onto a hot zirconium filament. The as-received crystal bar was coated with corrosion product from a standard autoclave test by which its grade designation is determined. A sand-blasting and subsequent HF-HNO, pickling treatment was employed to remove this contamination. The bars were cold-rolled to approximately 1/32-in. sheet, pickled again, sheared to 1/4-in. squares, washed with acetone, and stored for use. Ingot chromium metal from National Research Corp. and electrolytic chromium flakes from Johnson, Matthey and Co., Ltd., were available as alloy additions. The ingot chromium was received in granular form. The large granules were sized by crushing, treated for iron removal, rinsed with acetone, and stored. The flakes were broken to approximately 1/8 in. with mortar and pestle, cleaned with acetone, and stored for charging. Experimental Procedure A nonconsumable electrode arc furnace identical to that described by Hansen, Kessler, and McPher-son,' was used in this work. A 400 amp dc welding generator was the source of power. To insure homogeneity, ingots were melted in a water-cooled spun copper crucible, a total of four times without opening the furnace. No difficulties were encountered in the preparation of these binary alloys. Analyzed chromium contents were found to agree very well with the intended content. Melts of pure zirconium were interspersed in the course of preparing the alloys and their hardness was measured to keep a constant check on the melting technique. Vycor and quartz bulbs were used to contain the samples for isothermal annealing treatments. Vycor bulbs were employed for temperatures up to 110O°C, while quartz was used above this temperature. For treatments up to 950°C the bulbs were evacuated before sealing, but for higher temperatures a partial pressure of argon was admitted to the

Jan 1, 1954

By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.' Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.'-' At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,' but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By C. W. Phillips, D. N. Frey

A commercial Ti-Fe-Cr alloy, Ti-150, exhibits a martensitic transformation on cooling and two nucleation and growth reactions, one above and one below the Mg-Mf region, on isothermal holding below the single-phase ß temperature range. The reactions were followed by metallographic, X-ray diffraction, and microhardness methods. THE rapidly expanding engineering application of titanium and its alloys makes increasingly urgent an adequate knowledge of the effect of heat treatment on this material. The work herein reported is an attempt to determine certain aspects of the behavior of a commercially available alloy, Ti-150, during heat treatment. The alloy, with a nominal composition of 2.7 pct Cr, 1.3 pct Fe, 0.25 pct 0, 0.02 pct N, and 0.02 pct C, was received in the as-rolled condition as a 3/4 in. round. Slugs 0.11 to 0.12 in. thick were cut under a coolant using a silicon carbide wheel. Preliminary work established that the alloy consists of two phases, a (hexagonal close-packed) and /3 (body-centered cubic), at temperatures below 1750" to 1775"F, and of only /3 phase at higher temperatures. The slugs were heated for 1 hr in air at 1800°F to form a single-phase /3 matrix, then transferred to molten tin (1250° to 1650°F) or lead (1150°F and below) for isothermal holding. Holding temperatures ranged from 700° to 1650°F, times from 0.001 to 23 hr. The treated slugs were then sectioned, one part for metallographic examination and diamond pyramid hardness, the other, after deep etching to remove the high oxygen surface,' for comparative lattice parameter determination and X-ray phase identification. Hardness measurements were taken on the lightly etched surfaces of the metallographic specimens; a 1000 g load on a 136° diamond pyramid was used. Five impressions on each sample were made and the average of the hardness calculated. The use of microhardness measurements to follow the course of an isothermal transformation reaction is undesirable because of the possibility of wide differences in microconstituent hardness.' They were used in this case, however, because of the small amount of material available. At the higher transformation temperatures, where the above-mentioned objection was apparent, the readings were proportioned to correspond to the estimated ratio of transformed and untransformed constituents present. At lower temperatures, resulting in much finer microconstituents, the microhardness measurements were more uniform. The standard deviation of the mean of five impressions calculated from these latter values was 4.2 DPH. Employing 2a limits (probability 0.95) the experimental error of the hardness measurements averages was 8.4 DPH. The etchant used was composed of one part glyc-erol and one part 48 pct hydrofluoric acid." Of a number of etches tried, this one appeared most satisfactory. All micrographs were taken at 500X magnification and with oblique lighting to permit easier identification of the acicular structure resulting from rapid cooling. No advantage was gained by using polarized light for metallographic examination. Phase identification and lattice parameter measurements were made with a North American Philips high angle spectrometer in conjunction with a recording potentiometer. Considerable difficulty was encountered with some of the lattice parameter measurements because of the extreme broadness of the few diffraction lines obtained from samples consisting mainly of strained, untempered, quenched structures.

Jan 1, 1953

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

By Oscar M. Wicken

The mineral magnesite (MgCO3) if pure would consist of 47.7 pct MgO and 52.3 pct CO2. It is one of the calcite group of rhombohedral carbonates which includes calcite (CaCO3), siderite (FeCO3), rhodocrosite (MnCO3), and smithsonite (ZnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions, whose range is still imperfectly known.* MgCO3 and FeCO3 appear to form a complete series of which breunnerite (ferroan magnesite) is a well known variety. Because of the considerable difference in size of the Ca and Mg ions, there is only a limited range in substitution in the MgCO3-CaCO3 series. (Dolomite, not strictly a member of the calcite group, may be regarded as an ordered structure developed when Ca: Mg is approximately 1:1.) The practical consequence of these relationships is that the lime carbonates (calcite and dolomite) are commonly present in magnesite deposits chiefly as mechanical mixtures. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black through shades of yellow, blue, red or gray. It is rarely found pure but generally contains variable amounts of iron, lime, and silicate minerals. Color cannot be used as an index of purity except under specific local conditions in a single quarry. In a given quarry an experienced man may be able roughly to grade magnesite by intuitively assessing such features as crystallinity and color. Crystalline magnesite occurs in larger deposits, but the cryptocrystalline variety is more common. The latter is fine-grained and compact and shows no cleavage; often it is descriptively called "bone magnesite." The fracture is usually conchoidal, and hardness is 3.5 to 5.0. It is normally white, but sometimes it is light yellow to orange or buff because of included impurities. In addition to lime and iron, which may be present in small amounts, silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. In general, commercial deposits of "amorphous" magnesite have lesser amounts of accessory minerals than does crystalline magnesite. The specific gravity of "amorphous" magnesite is 2.90 to 3.0. Pure, crystalline magnesite has a specific gravity of 3.02, but iron carbonate, commonly present, raises the specific gravity to somewhat higher values. Magnesite dissociates, when sufficiently heated, into magnesia (MgO) and carbon dioxide. Either simultaneously or upon further heating the magnesia develops a crystalline structure identical with that of the natural mineral, periclase, which occurs sparingly in nature but not normally in workable deposits. Brucite is another magnesium mineral capable of being directly reduced to magnesia by heat alone. Brucite (Mg(OH)2) has been mined for the production of various grades of magnesia. It theoretically contains 69.1 pct MgO and 30.9 pct H2O. It may be white, but is generally blue or green with a gray cast. It has a translucent appearance. The mineral is soft (hardness, 2.5), and has a specific gravity of about 2.4. Nomenclature of Products The word "magnesite" literally refers to the natural mineral, but common usage has applied it plus a prefatory word to two other

Jan 1, 1960

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,'who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

By S. A. Spachner

An analysis of the powder patterns of the omega transition phase in three binary titanium alloys containing 8 pct Cr, 13 pet Mo, and 15 pet V, respectively, showed that all could be indexed on an orthorhombic unit cell. The unit-cell dimensions were all quite similar. There is evidence for the occurrence of more than one transition phase in Ti-Cr and Ti-V alloys. FOLLOWING the discovery of a new brittle phase in certain titanium-chromium alloys by Frost, Parris, Hirsch, Doig, and Schwartz,' named ? by these investigators, much interest has developed concerning the identification of alloy systems in which this phase exists, kinetics of the transformation in such systems, and the crystal structure of the ? phases appearing. Omega has been found in alloys of titanium-manganese, titanium-molybdenum, titanium-iron,' and titanium-vanadium.' In the present work, a study was made of the powder patterns of the ? phase occurring in alloys of Ti-8Cr, Ti-13Mo and Ti-15V in an effort to obtain a basis of comparison for ? phases appearing in these different alloys. Comparison of Alloys for ?-Phases Two hundred mesh powders of Ti-8Cr, Ti-13Mo and Ti-15V were prepared. A portion of powder sufficient for three x-ray powder specimens was placed in a Vycor tube, evacuated to less than 0.1 µ pressure, filled with argon, and sealed. The tubes were then heated to 900°C, held at this temperature for 30 min, and water-quenched. Following this transformation to the ß phase, the specimens were quenched in lead or solder pots, held at the desired temperature for varying lengths of time and water-quenched. The heat-treatments used and the phases identified are listed in Table I. The intermediate water quench was used in lieu of direct downquenching from 900°C to the bath temperature desired to circumvent the possibility of transformation of the powder specimen from ß to (ß + a) while it was being moved from the homog-enization furnace to the lead bath. To check the possibility that upquenching to the bath temperature might bring into play a different mechanism than downquenching to this temperature, resistivity measurements were compared on Ti-8Cr rod specimens which were transformed isothermally at 400°C by downquenching from the solution-treatment temperature and those which were transformed at 400" C by upquenching ß specimens from room temperature. The results are shown in Fig. 1. No difference in transformation mechanism was noted. It soon became apparent that sufficiently detailed Debye-Scherrer photograms of the ? phase in the alloys which were to be used could not be obtained by the use of copper radiation. Although satisfactory photograms of ß and ß + a phases were obtained with this radiation, the ? phase appeared to exhibit mild fluorescence, making interplanar spacing computation virtually impossible. Molybdenum radiation appeared to offer promise in cutting down this fluorescent effect, the mass absorption of titanium for molybdenum radiation being 23.7 in contrast to 204 for copper radiation. The reduction in the accuracy in determining the location of the photo-gram lines caused by the shorter wave length of molybdenum characteristic radiation did not appear to be a significant factor. Utilizing a camera of 57.3 mm radius, best results were obtained for exposure times ranging between 30 and 40 hr. Tube potential

Jan 1, 1959

By A. R. Gregory, M. R. J. Wyllie

The literature reveals that scant attention has been paid to the systematic experimental determination of the formation factors of unconsolidated porous media. No experiments appear to have been made on the effect of increasing cementation on the formation factor of an initially unconsolidated porous medium. Measurements have accordingly been made of formation factors as a function of porosity for aggregates of spheres in the porobity range 12-56 per cent and of cubes, cylinders, discs and triangular prisms in the porosity range 30-45 per cent. The results are examined in the light of the theoretical equations of Clerk Maxwell. Fricke and Slawinski. Aggregates of unconsolidated spheres and beach sands have been artificially cemented with silica and the formation factor-porosity relationships determined. A theory is outlined which seeks to explain the results obtained and which postulates that formation factor and porosity data for consolidated sandatones may be used to determine the original porosity of the unconsolidated sands from which the consolidated sandstones were derived. It follows also that for consolidated sandstones F' = C where F is formation factor, fractional porosity and C and k are constants. INTRODUCTION All schemes of electric log interpretation implicitly or explicitly require the use of formation resistivity factors or? as they are now generally called. formation factors. 'The originator both of the concept of formation factor and of the use of formation factor data in electric log interpretation was Archie.' More recently it has been suggested that formation factors are of value in describing fluid flow in porous media. A full discussion of this problem together with adequate reference.: has been given by Wyllie and Spangler.' In spite of the theoretical and practical importance of the subject, there appear to be remarkably few basic formation factor data in the petroleum literature. A wider search reveals that this situation is nut confined to the literature of the to industry. at various times over the last century, attempts have been made to compute the theoretical relationship between the formation factor and porosity of simple systems of unconsolidated particle.. However. the formulae derived are not all identical and the experimental evidence adduced in support of each i; not wholly convincitng. Most of the experimental work has been carried out on system. of unconsolidated spheres, although some attention has been given to systems of spheroids and cylinder. Other simple shapes have received neither theoretical nor experimental investigation. The writers feel that a better understanding of the formation factors of complex systems of practical importance requires a firm foundation of reliable experimental data applicable to simple systems. Accordingly, they have reviewed the relevant literature and have determined experimentally the relationship between the formation factor and porosity of unconsolidated aggregates of particles of regular geometrical shapes. Some experiments have also been carried out to investigate the effect of cementation on the formation factor-porosity relationship. PREVIOUS WORK Although the term formation factor was not used. the relationship between the resistivity of a solution containing dielectric solids and the resistivity of a similar solution not containing solids is an old and important problem. The formation factor of a system of dispersed spheres as a function of porosity was considered by Clerk Maxwell. Maxwell arrived theoretically at the following expression: where F is formation factor and fractional porosity. Lord Rayleigh' also examined the problem of the formation factor of systems of spheres and cylinders and concluded that for spheres Clerk Maxwell'.; expression gave a value of F whirl]. at low porosities particularly, was too small. However,

Jan 1, 1953

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 V. Koump, T. F. Perzak, R. G. Olsson

The vate of dissolutioz of carbon in molten Fe-C alloys urns studied by votating- cylindrical g-vaphite sairlples in a stationary crucible containing the melt. The rate of dissolltion was determdined from the change in the bnth co)npositiorz. Alccss-tvansfev coeffi'cients, calcilated with the assurlption that the inte)yacial liquid ulas saturated with carbon, were found to be in agreement with an existing Correlation fov mass transfer jroni votating cylinders. It is corzcllrded tlat, itz the wnge of- Reynolds' numbers itzvestigated (790 to 18,000), the vate of dissolutio of carborz in Fe-C alloys is controlled by tile rate of carbon difirsion from the interface. The dissolution of carbon in molten Fe-C alloys has been the subject of a number of investigations. Most of these investigations have been inconclusive because of poorly defined experimental variables. Two of the more sophisticated studies are summarized below. Dahlke and Knacke' studied the phenomenon by, in part, immersing graphite rods into 0.5 pct carbon-steel for different lengths of time. Since the experiments were conducted in air or in CO atmospheres, the melt was strongly agitated by gas evolution. It was concluded that the change in bath composition as a function of immersion time was in agreement with the assumption that the dissolution process was transport-controlled. The hydrodynamic conditions in these experiments, however, were not well-defined and gave no indication of the nature of the dissolution process at higher fluid velocities. In a recent study Shurygin and ruk investigated the dissolution of carbon in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Small graphite disks were rotated in a crucible containing molten alloys under such conditions that only the lower face of the disk was exposed to the melt. The results of this investigation indicate that, over the range of velocities (100 to 1000 rpm) and bulk liquid concentrations (0.7 to 4.5 wt pct C) considered, the dissolution of carbon in the iron alloys is limited by the diffusion of carbon from the interface to the bulk liquid (a transport mechanism). For the particular geometry used by these authors, exact analytical solutions of hydrodynamic and diffusion problems are aailable. Hence the experimental results obtained by Shurygin and Kryuk permit the evaluation of diffusion coefficients of carbon in the four systems investigated. In the present investigation a series of experiments were conducted in which the rate of dissolution of carbon in Fe-C alloys was measured under conditions which permitted wide variation of the fluid velocity and the carbon concentration of the bulk liquid. Graphite cylinders were rotated at different speeds in a stationary concentric crucible containing various molten Fe-C alloys. THEORETICAL DEVELOPMENT In general, the resistance to mass transfer from a solid interface to a turbulent liquid is assumed to reside in a laminar boundary layer adjacent to the interface. If it is also assumed that the diffusion coefficient is independent of concentration, the steady-state rate of dissolution for the case of arbitrary liquid and solid densities can be obtained from the integration of the equations of continuity. The derivation is similar to that used by Lommel and chalmers4 for the case of pl = ps. The solution, expressed in terms where N = rate of diffusion of the solute from the interface. Exact analytical solutions of the hydrodynamic equation for the boundary layer thickness are available for only a limited number of geometries. Consequently, a mass-transfer coefficient, k, is usually

Jan 1, 1967