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By S. C. Oliphant, R. Floyd Farris

Presented in this paper is a summary of the results of experiments conducted in both the laboratory and the field during the past three years in connection with casing-perfora. tion problems. Included are studies of gun features that influence bullet performance and penetration, and studies of the effect of perforator bullets on casing and the neat cement in the annulus. Discussion and data are also presented relative to the accuracy of depth measurements in deep wells. Introduction It is a common practice in the oil industry to effect the completion of oil wells by setting and cementing casing through the producing horizons and perforating the section of casing opposite the desired interval by means of a gun lowered into the well on a cable or on the tubing. This practice has been followed for some time, and this method of completion has been given considerable study by the companies that render perforating service as well as by the oil companies that utilize their services. Through continued research on this subject, it has been possible to develop guns, bullets, and powder that will permit controlled firing at great depths, and penetration of as many as two strings of casing. It is the object of this paper to present the results of studies made of gun perforating in both the field and the laboratory. These studies were made to determine the factors that affect penetration of the bullet, burring of the casing, accuracy of depth measurements, and other items. It is hoped that by presenting the results of these investigations a better understanding may be obtained of certain of the factors involved in gun perforating and further investigation of the subject will be prompted. Subsurface Tests A well approximately 9000 ft deep, which was being prepared for abandonment, was selected for subsurface tests of gun-perforating experiments, In preparing the well for the experiment, 51/2-in. casing in the hole was pulled and racked in the derrick. A test section of pipe, which consisted of 65 ft of 5-in. 18-lb J-55 casing centered inside 7-in. 28-lb N-80 casing, was placed in the derrick corner and the annulus between the two pipes was cemented from the bottom up with 161/2 lb per gal neat cement, which was mixed and displaced with a cementing truck in the usual manner. After the cement had been allowed to harden for about a week, the test section was lowered into the hole on the 51/2-in. casing to a depth of 6600 ft by casing measurements. The hole was filled with drilling fluid weighing 10 lb per gallon. A perforating company was called to perforate the pipe, but was not advised that an experiment was being conducted. The company was asked to check the total depth (to cross pins in the bottom of the test section), then to raise the gun a given distance and fire a given number of shots with 1/2-in. bullets, pick up another distance and fire a given number of 3/8-in

Jan 1, 1947

By S. C. Oliphant, R. Floyd Farris

Presented in this paper is a summary of the results of experiments conducted in both the laboratory and the field during the past three years in connection with casing-perfora. tion problems. Included are studies of gun features that influence bullet performance and penetration, and studies of the effect of perforator bullets on casing and the neat cement in the annulus. Discussion and data are also presented relative to the accuracy of depth measurements in deep wells. Introduction It is a common practice in the oil industry to effect the completion of oil wells by setting and cementing casing through the producing horizons and perforating the section of casing opposite the desired interval by means of a gun lowered into the well on a cable or on the tubing. This practice has been followed for some time, and this method of completion has been given considerable study by the companies that render perforating service as well as by the oil companies that utilize their services. Through continued research on this subject, it has been possible to develop guns, bullets, and powder that will permit controlled firing at great depths, and penetration of as many as two strings of casing. It is the object of this paper to present the results of studies made of gun perforating in both the field and the laboratory. These studies were made to determine the factors that affect penetration of the bullet, burring of the casing, accuracy of depth measurements, and other items. It is hoped that by presenting the results of these investigations a better understanding may be obtained of certain of the factors involved in gun perforating and further investigation of the subject will be prompted. Subsurface Tests A well approximately 9000 ft deep, which was being prepared for abandonment, was selected for subsurface tests of gun-perforating experiments, In preparing the well for the experiment, 51/2-in. casing in the hole was pulled and racked in the derrick. A test section of pipe, which consisted of 65 ft of 5-in. 18-lb J-55 casing centered inside 7-in. 28-lb N-80 casing, was placed in the derrick corner and the annulus between the two pipes was cemented from the bottom up with 161/2 lb per gal neat cement, which was mixed and displaced with a cementing truck in the usual manner. After the cement had been allowed to harden for about a week, the test section was lowered into the hole on the 51/2-in. casing to a depth of 6600 ft by casing measurements. The hole was filled with drilling fluid weighing 10 lb per gallon. A perforating company was called to perforate the pipe, but was not advised that an experiment was being conducted. The company was asked to check the total depth (to cross pins in the bottom of the test section), then to raise the gun a given distance and fire a given number of shots with 1/2-in. bullets, pick up another distance and fire a given number of 3/8-in

Jan 1, 1947

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday's constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By A. J. Williams

THE province of Saskatchewan, situated in the center of the Great Plains region of Canada, has, like most prairie areas, an essentially agricultural economy. Most of its population of about 860,000 is located in the southern half of the province in the farming and ranching areas. To the north of the prairie is a broad forested belt supporting a considerable timbering industry, and the northern one third of the province is glaciated pre-Cambrian rock formation. This latter area is relatively barren of vegetation, but the presence within it of a considerable variety of radioactive, noble and base metals, and industrial minerals has been shown by prospecting in recent years.&apos; Glacial Geology The Keewatin ice sheet, considered to have accumulated in the country to the west of Hudson Bay in Pleistocene time, covered at its maximum advancement almost all of Saskatchewan and extended south of the international boundary. Only in the Cypress Hills in the southwest and around Wood Mountain in the south central portion of the province did the preglacial formations escape the action for this glacial period. The bedrock of the plains and forest areas therefore is overlain by moraines and modified glacial drift, which vary in thickness from a few feet to 400 or 500 ft.&apos; Glacial action in the pre-Cambrian area of the province was largely erosional, most of the more recent formations and some of the pre-Cambrian rock being transported out of the area to the south and west. It has been estimated that about 13 pct of this area is composed of lakes and rivers not too adaptable to rail or water transportation, so that until the use of aviation for exploration purposes became general, development of the area was slow. To the south, the heavy mantle of glacial drift has to some extent deterred the discovery of industrial minerals in the bedrock underlying the forest and prairie regions3 At the same time, this drift contains numerous deposits of those most elementary and necessary industrial minerals, sand and gravel. Sedimentary Basin The major feature of the sedimentary deposits underlying the plains regions is the basinal structure known as the Moose Jaw syncline, which runs from the southeast corner of the province in a northwesterly direction. To the west of this syncline the formations curve upward, then have been faulted and further upthrust to appear at the surface in the foothills of the Rockies in Alberta; to the east and north they curve upward into Manitoba and northern Saskatchewan, but the surface contacts are covered mostly with glacial drift.238 The axis of the syncline dips to the southeast, so that there is also an upward trend of the formations along the axis to the northwest. In illustration of the regional structure underlying the province, the pre-Cambrian basement has been logged in drillholes at the following depths in several locations: Ogema (south central), 9390 ft; Gronlid (northeast), 2599 ft; Vera (northwest), 4422 ft; Big River (north northwest), 2348 ft. Fig. 1 indicates the general surface geology of the province, ignoring such glacial overburden as may overlie many of the bedrock formations. Also indicated is the approximate location of the axis of the Moose Jaw syncline.&apos; Industrial Minerals Clays: The province is fortunate in possessing a widespread distribution of clays of ceramic value, ranging from those used for heavy structural products to the high grade pottery and china clays. Shales suitable for brick and tile production are found in the Upper Cretaceous and Tertiary formations across the south of the province where the glacial drift is thin or nonexistent. Many deposits of glacial lake clays suitable for such wares are found scattered over the rest of the province south of the pre-Cambrian area. The Whitemud formation of the Upper Cretaceous is a narrow sedimentary band of secondary clays found intermittently at points across the south of the province where glacial action did not disturb or remove them.&apos; In the southwest corner of the province, around Eastend in the Frenchman River valley, the refractory clays of this formation are contaminated somewhat with iron compounds or other alteration products of basaltic rocks. This eliminates the use of those clays in true whitewares, as they fire to creamy buff shades at the lower temperatures and to a blue-specked grey at cone 8 to 12, (2280°F to 2390°F), the range commonly used in firing whiteware. However, for use in the production of colored artware, caneware, stoneware or crockery, and sewerpipe, this type of clay makes an excellent body that requires little or no addition of flint, feldspar, or other fluxing materials such as are required in the higher class of ware.&apos; It is not a grade of clay that can be shipped great distances to the manufacturing centers, but a market for considerable tonnages has developed at nearby Medicine Hat, where cheap natural gas is available for the firing of the ware. Farther east in the south central portion of the province, the clays of the Whitemud formation are generally more refractory and white burning. The formation is divided into three zones, consisting of white clays, brown shale, and white sandy clays.

Jan 1, 1953

By LeRoy Scharon

EACH year it becomes apparent that geophysical activities in the fields of mining and engineering are increasing in the number and variety of applications. Many mining companies are including, as part of their exploration programs, geophysical surveys. The value of geophysics in highway and structural foundation investigations has been realized and is now an important part of subsurface investigations in conjunction with soil and rock borings. United States of America One of the major orebody discoveries of the year is that of the Grace mine near Morgantown in Berks County, Pa. This orebody, now under development by the Bethlehem Steel Co., was discovered by an airborne magnetometer survey carried out by the Aero Service Corp. of Philadelphia. The orebody, the geological occurrence of which is similar to those existing at Cornwall, Pa., was found at a depth of 1500 ft under a cover of Triassic sediments and is reported to have a reserve of well over 100 million tons. Shaft sinking and other construction work has started at the site. Resistivity work was carried out at proposed dam sites in New York and in connection with the search for fluorspar veins in Kentucky. Spontaneous polarization investigations were pursued in the Appalachian region at various localities from North Caro¬lina up into Virginia. This work was done in connection with the search for sulphide-bearing structures. Several indications were proven by subsequent drilling to correspond to unknown sulphide deposits, a few of these occurring in the vicinity of properties long under exploitation. Refraction seismic methods applied to bedrock depth determinations as related to water problems on the Marquette Range and the extension of the. regional gravity survey on the Menominee Range to learn the major structural features of the area have been reported by, Lloyal O. Bacon. A gravity survey has been completed in the vicinity of Tioga, Bradford County, Pa. with a gravity profile being observed from Tioga east to the Delaware basin. The Indiana Geological Survey is concerned with a state-wide gravity survey. Judson Mead, University of Indiana, reports that the bulk of the State Survey&apos;s geophysical work, however, has been "seismic refraction work in connection with drift thickness problems. The survey has made almost 1000 determinations in areas of moderately thick drift. The results of this work are of interest to both the coal mining industry and to the stone industry." In the southeastern Missouri lead belt, magnetic electrical resistivity, and electromagnetic applications for the discovery of new lead deposits have been used with success. A gravity survey of the residual-barite deposits in Washington County, Mo., was made during the summer season with preliminary computations of tonnages checking with tonnages mined. Robert M. Dryer, of the University of Kansas has had considerable success in mapping structural features in southwestern Kansas with the gravity meter and is now engaged in tracing shoestring sands in eastern Kansas by resistivity surveys. Several, foundation sites were investigated in greater St. Louis using electrical resistivity and seismic refraction methods with success. A minimum amount of drilling data was available for checking and interpreting the geophysical results (Fig. 1). It is to be noted that geophysical methods are finding a place in subsurface investigations for highway and foundation problems. Interest has been so keen in this field that the American Society for Testing Materials, at its annual meeting in June of this year, devoted one session of its symposium on surface and subsurface reconnaissance to geophysical papers involving the application of the electrical resistivity and seismic refraction methods to subsurface studies. At least three major mining companies in the United States have entered the field recently in geochemistry. The program of research and development of geochemical techniques by the U. S. Geological Survey continues. Experimental field projects were conducted over lead-silver, cobalt, copper and zinc deposits in Idaho, Oregon, California, Wisconsin and Montana. Similar experiments were carried on by M. P. Nackowski in the Illinois-Kentucky fluorspar district and in the Tri-State Zinc district by R. Maurice Tripp with favorable results. Geophysical activities of the U. S. Geological Survey for 1951 were extensive and varied. About 21,000 miles of airborne magnetic and 10,000 miles of airborne radioactivity traverse were flown in 1951 by the U. S. Geological Survey. A total of 35,000 miles of aeromagnetic traverse were compiled, 57 aeromagnetic maps were published and 14 preliminary maps were placed on open file. Airborne surveys were made in Aroostook County, in the Katahdin and Dead River areas in Maine; in northwest Washington; over the Mother Lode district in California; in northeastern and northwestern Minnesota; and in the New York-New Jersey highlands. Of special interest were the surveys in Washington, where highly magnetic Eocene lavas gave information on structures in the overlying Miocene sedimentary rocks and in northeastern Minnesota over the Duluth gabbro. The latter survey was made following the discovery of nickel-copper mineralization in the gabbro near its contact with the Virginia slate. The principal ground geophysical surveys for metalliferous deposits and related purposes were made in the Colorado Plateau region, where electrical surveys assisted in prospecting; in Aroostook County, Maine, where ground magnetic surveys, following aeromagnetic surveys, have permitted tracing

Jan 1, 1952

By C. B. E. Douglas

The following analysis was stimulated by a previous article on evaluation of the water problem at Eureka, Nev., which describes a method using formulas especially devised to calculate flow potential of extensive aquifers characterized by relatively even porosity and permeability throughout. The present discussion submits that the method was unsuitable for solving the kind of problem occurring at Eureka, where the amount of water available, rather than the flow potential, may have been the vital factor. IN an interesting article on evaluation of the water problem at Eureka, Nev.,1 W. T. Stuart describes how a difficult water problem, or one phase of it, may be evaluated by means of a small scale test. Test data are plotted by a method rendering, under certain conditions, a straight-line graph that can be projected to show how much the water table will be lowered by pumping at any specified rate for a given time. A formula is then used to determine the size of opening, or extent of workings, necessary to provide sufficient inflow to enable pumping to be maintained at that rate. At first glance this might seem the answer to a miner&apos;s prayer, but a word of caution is in order. It may not be the whole answer. Moreover, results obtained by the method described are reliable only for conditions approximating those assumed. Even where conditions do not meet this requirement, however, it may be possible to draw helpful inferences from the results, perhaps enough to facilitate another approach to evaluation of a problem. The two formulas Mr. Stuart used, the Theis formula and the one developed from it by Cooper and Jacob, were given field checks a number of years ago in valley alluvials by the Water Supply Div. of the U. S. Geological Survey and found to be reliable when the aquifer is very large in horizontal extent and sufficiently isotropic for the test well and observation wells to be in material of the same average permeability as the saturated part of the aquifer as a whole." Extensive valley alluvials, sands, and gravels can be evaluated in this way, and there are even cases in which the method could apply to porous limestones, such as flat beds of very large areal extent that have been submerged below the water table after extensive weathering. These are sometimes prolific sources of water for towns and industries. It is necessary for them to have been above the water table for some geologically long period of time in a fairly humid climate before submergence because the necessary high porosity and permeability, and large reservoir capacity, are the result of weathering, that is, of solution by the carbonic acid (H,CO3) in rainwater formed by the absorption of CO, from the air by raindrops, and this dissolving action must cease when all the H2CO3 has been consumed by re- action with the carbonate to form the more soluble bicarbonate. Consequently this weathering process is largely restricted to a zone that does not extend much below the water level, and submergence is necessary after the weathering to provide large reservoir capacity and good hydraulic continuity. On the other hand, water courses tend to form along faults and fractures in limestone, and to become enlarged by solution, well below water level when, as often happens, fresh meteoric water is circulated rapidly through them to considerable depth by hydrostatic pressure, as through an inverted syphon. Although the reservoir capacity of such water courses is relatively small they may extend far enough to tap more prolific sources. Cavities, and sometimes caves of considerable size, are found in limestones where the acid formed by the oxidation of sulphides has attacked them. This action can take place as deep below water level as surface water is carried by syphonic or artesian circulation, because the oxygen it carries in solution will not be consumed until it reacts with some reducing agent, such as a sulphide. Moreover, the formation of acid and solution of limestone in this way is not confined to the immediate vicinity of the sulphide. Oxidation of pyrite, for example, results in formation of acid in several successive stages, each taking place as more oxygen becomes available, as by the accession of fresh water into the circulation at some place beyond the sulphides. When the acid thus formed attacks the limestone, CO, is liberated and the ultimate effect of the complete oxidation of one unit of pyrite will be the removal of six times its volume of limestone as the sulphate and bicarbonate, both of which are relatively soluble. The reaction may be continued or renewed along a water course far from the site of the sulphides, where the small electric potential produced by contact with the limestone helped to start the reaction. Mr. Stuart refers2 0 caves in the old mining area in the block of Eldorado limestone southwest of the Ruby Hill fault at Eureka, Nev., and to the cavities encountered in drillholes in the downthrown block on the other side of the fault. Although he interprets these cavities as evidence that this formation was sufficiently isotropic (evenly porous and permeable) to give reliable results by the method he describes, they may, in fact, be entirely local conditions. There is reason to think they were probably formed

Jan 1, 1956

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By J. G. Faller, L. P. Skolnick

The distribution of cobalt and vanadium over non-equivalent crystallographic sites in C14-type Zr(VCo), alloys has been investigated. An anomalous X-ray scattering technique developed by Skolnick, Kondo. and lavine7 by which the separation in the scattering factors of two similar atoms can be enhanced was employed. Six alloys spanning the pseudobinary section ZrV1.6Co0.4-ZrVO.6CO1.4 at 10pct steps showed a nonrandom compositionally dependent distribution. Specifically, at high vanadium content cobalt preferentially occupied sites of type (6h) and vanadium, sites of type (2a; at low vanadium content the reverse was observed. In addition to the distribution fraction the structural parameters x and z were obtained. There was no significant deviation of these parameters from those obtained in the ideal C14 structure. Certain suggestions are made to account for the observed nonrandomness in the distribution of atoms on the two types of sites. INTERMETALLIC compounds of formula AB2 iso-morphous with MgCu2, MgZn2, and MgNi2 are known as Laves phases. Because Laves phases exhibit high symmetry and coordination numbers, the highest possible for an AB2-type compound,1 they are among the most frequently observed compounds in nature. In recent years interest has centered about the purely transition metal Laves phases2-&apos; in efforts to understand the function of atomic size and electronic structure in the formation of these compounds. It has been observed that pseudobinary Laves phase systems often show a variation of structure across the phase diagram. Such a system is the ZrV2-ZrCo2 in which the structure varies from cubic MgCu2 to hexagonal MgZn2 to cubic MgCu2.4 Some understanding about the conditions under which the second modification is stable can perhaps be gained by studying the distribution of cobalt and vanadium atoms on lattice sites in the MgZn2 modification of the system ZrV2-ZrCo2. In both the MgZn2 and MgNi2-types there exist nonequivalent positions open to occupancy by the B element, whereas in the MgCu2 prototype all sites are equivalent. Skolnick, Kondo, and La-vine7 have developed an anomalous scattering technique suitable for this type of investigation. Whereas the influence of size on the formation of a Laves phase is well recognized, no substantial evidence has been put forth in support of the size ratio dependence of a particular prototype. Berry and Raynor8 suggested that RA /RB ratio does indeed affect the type of structure that is chosen, MgZn2 compounds tending to cluster about 1.225 while MgCu2 compounds were found at larger deviations from this ratio. Dwight,3 however, from a study of 164 Laves phases does not believe this generalization to be justified. Electronic effects are certain to play a part in the stability of Laves phases in general and in the choice of a structure type in particular. For example, size along would favor the formation of Laves compounds of Ti, Zr, Hf, Ta, or Nb as the A element with nickel or copper as the B element. The absence of such is attributed to an unfavorable electron : atom ratio by Elliott and rostoker.4 Early experiments of Laves and witte9 with pseudobinary and pseudoternary systems of the three prototypes established the dependence of crystal structure upon electron: atom ratios. They observed that the MgCu2 structure dissolved elements of higher valency until the electron: atom ratio of =1.8 was reached; the MgZn2 likewise dissolved elements of lower valency replacing zinc. witte,6 from calculations of the electron : atom volumes of Brillouin Zones, obtained limits of stability for the prototypes MgCu2 and MgZn2. Elliott and Rostoker4 used these limits with considerable success in the all-transition element Laves phases they investigated. According to witte,6 compounds between the electron :atom ratios of 1.80 and 2.32 were of the MgZn2 type; those above and below exhibited the MgCu2-type structure. On the basis of these limits and an assumed valency of zirconium based upon the near tetra-valence of titanium, Elliott and Rostoker obtained valencies for the first transition series elements. For the Laves phases with which this investigation is concerned, ZrV2 and ZrCo2, the authors calculated electron :atom ratios of 2.54 and 1.56, respectively. These ratios are for the MgCu2-type structure and straddle the stability band of the MgZn2 modification. One could, therefore, predict that a pseudobinary system ZrV2-ZrCo2 should pass through the MgZn2 modification in traversing the composition diagram from one end to the other. Implicit in this assumption is a smooth change of the electron: atom ratio from 2&apos;54 to 1.56. MOSS10 states that his finding the low temperature structure of ZrCr2 to be C15 instead of C14 alters greatly Elliott&apos;s valency of zirconium and hence the assumed valencies of the other metals. Such a quantitative correlation of structure with electron : atom

Jan 1, 1963

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.&apos;-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23&apos;24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300&apos; and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 &apos; RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.&apos; By

Jan 1, 1970

By R. Wang, N. J. Grant, B. C. Giessen

By crystallographic and X-ray methods, the existence and isonzorphism of Ti3Rh5 and Hf3Rhs were confirmed. Both phases are of the orthorhombic Ge3Rh5 type; lattice parameters and refined positional parameters are given. The structure is related both to the filled-up NiAs-B8 and Cu-AI types. An analogous phase with zirconium does not exist; the effect of ternary substitutions for titanium ad hafnium suggests a size factor limit to be active. A recent survey of phase diagrams of the T4 metals titanium, zirconium, and hafnium with the T, noble metals rhodium and iridium indicated the existence of the A3B5 phases Ti3Rhs, ZrsRhs, and HfsRhs. Ti3Rhs and Hf3Rh5 were found to be isostructural, based on the line-rich powder patterns which had not been analyzed. Zr3Rh5 was considered to have a substructure of the NbRu type (orthorhombically distorted B2-CsCl type).&apos; Because, in combinations with other transition metals, hafnium and zirconium are generally more likely to form isostructural phases than hafnium and titanium (with the significant exception of the Ti2Ni-"E93" type phases based on T4 metals2), the reversal of this relation for the A3B5 phases was of interest. As shown in the following, the nonexistence of Zr3Rhs has been established, the structures of Ti3Rh5 and Hf3Rh5 have been worked out, and crystal chemical relationships and stability criteria are reported. EXPERIMENTAL METHODS AND RESULTS Alloy Preparation and Phase Diagram Work. Alloys were prepared from high-purity (99.99+ pct) elements by arc-meltin3,4.Heat-treated alloys were annealed in a vacuum of 3 x X torr for 24 hr at 1300DC. Metal-lographic samples were etched electrolytically in concentrated HCl with 5 v ac for 5 min.3 X-ray diffraction powder patterns were taken on a GE XRD-5 dif-fractometer with Cum radiation at low scanning rates (0.2 deg per min for 28). It was confirmed that Ti3Rhs and Hf3Rh5 have similar diffraction patterns, and that an alloy with the composition Zr3Rhs has a different pattern. Six Zr-Fh alloys with 59 to 69 at. pct Rh were therefore prepared and investigated in the as-cast state by X-ray diffraction and metallography. Alloys at 59 and 61 at. pct Rh were found to be a single phase, with the distorted B2-CsC1 type structure typical for the off-stoichio- metric region of the phase (Zr,-,Rh,)Rh. This phase forms a eutectic with ZrRhs at about 66 at. pct Rh: accordingly, alloys between 61 and 69 pct at. pct Rh consisted of two phases. There is no evidence for the existence of Zr3Rh5. Based on the results in Rafs. 1 and 5, on the present work on Zr-Rh, and on several additional alloys investigated, the portions between the AB and AB3 stoi-chiometry for Ti-Rh, Zr-Rh, and Hf-Rh are as follows: Further, several ternary alloys near Ti3Rhs and Hf,Rhs were prepared in which it was attempted to replace titanium and hafnium partly by zirconium, niobium, tantalum, and germanium. The results will be discussed in a later section. Structure Determination of Ti3Rh5. Since Ti3Rh5 and Hf3Rh5 are isostructural, the following discussion will largely deal with the former. Although the powder pattern of TisRhs is complex, as found previously,1 it could be indexed by comparison with other structures of A3Bs stoichiometry. Ti3Rh5 was found to be isostructural with Ge3Rh5, whose orthorhombic structure had been elucidated by Geller.9 As both the sizes and atomic numbers of germanium and titanium are comparable, the unit cell volume and the peak intensities could be expected to be similar; however, significant differences exist in the atomic positions, as will be shown. All lines in the powder patterns of Ti3Rh5 and Hf3Rhj could be indexed with primitive orthorhombic unit cells with the lattice constants: The fractional errors are 10 The low-angle portion of the indexed powder pattern of Ti3Rh with sin2 8 < 0.30 is listed in Table I. The extinction laws Okl only with k = 2n and hOl only with h - 2n are compatible with the space group Pbo2 and the more symmetrical space group Phnm of Ge3Rh5. Finally, the positional parameters of Ti3Rh5 and HfsRhs were refined under the assumption that titanium and hafnium occupy the germanium positions in Ge3Rh5. Integrated intensities were obtained from the diffraction patterns by planimetry. Intensities of overlapping reflections were separated by an iteration process incorporated into the least-squares positional refinement program according to a method described previously. The intensities of Ge3Rh5 were used in the first separation cycle, while the atomic parameters of Ge3Rh5 were used as starting values in the first refinement cycle. Absorption due to specimen

Jan 1, 1970

By S. Jana, C. M. Wayman

The reverse transformation of bcc martensite to the fcc phase was studied in an Fe-33.95 wl pct Ni alloy by nzeans oj dilatometry, melallography, and electron microscopy. Upon "slozc" heating (-1°C per min) length cJmnge us temperature plots showed u gradual contracLion over the temperature range 200" to 280"C ,followed by a more abrupt contraction beginning a1 -280°C. Howet,ev, zchen the heating rate was increased -4°C per tnin, no gradual contraction was observed and only the abrupt contraction starting at -2BO"C was found. Thus on slower heating- the AS "temperature" for the subject alloy, unlike the MS temperature, is better defined as a range of temperatures. Both optical and transmissiorl electron microscope observations showed that some of the martensite plates exizibited a partial loss of transformation twins during reversal. The midvib region of the martensite plates disappeaved relatively early duirng the reversal. Metallographic observations slowed that the earliest detectable stage of the rezlerse tvansforrvration begins (axd Moues inulardly) at The Martensens i te - parent interface. At higher temperatirres, the. formation of martensitically reversed jcc plates within the bcc martensite plales was observed. It is concluded that the reverse transformation consists of a diffusion less process (martensitic); but this is ps-obably aided by a prior or simultaneous dijjusiorz-comltvolled process, at leasl in the case of slower heat-ing&apos; experiments. ALTHOUGH numerous investigations have dealt with the parent-to-martensite ("forward") transformation (fcc — bcc) in Fe-Ni alloys, comparatively little is reported on the ("reverse7&apos;) martensite-to-parent transformation.&apos;-4 Even though such reverse transformations have been studied in detail in some nonferrous systems, one of the difficulties of studying the reverse transformation in most ferrous mar-tensites is that the martensite decomposes by tempering during heating. However, carbonless Fe-Ni alloys do not exhibit this difficulty since the transformation in these alloys is completely reversible. The present investigation represents an attempt to shed more light on the nature and mechanism of the martensite-to-parent transformation. 1) EXPERIMENTAL PROCEDURE 1.1) Alloy Prepatation. Fe-Ni alloys of compositions near 34 wt pct Ni were prepared from zone-refined iron (99.994 wt pct Fe) and high-purity nickel (99.999 wt pct Ni) by induction melting in recrystallized alumina crucibles in an argon atmosphere, with prior vacuum evacuation to 10"3 mm Hg. The alloys were homogenized by induction stirring in the molten state for 5 min. After solidification, the alloys were further homogenized in evacuated quartz capsules for 96 hr at 1230°C. 1.2) Dilatometry. Slices of the ingot were hot-forged (750°C in air) into approximate rod form and these specimens were then hot-swaged (750°C in air) into long cylindrical rods 0.55 mm diam. From the rods, specimens about 1 in. long were cut. These were then vacuum-annealed for 24 hr at 1200°C, cooled to room temperature, and subsequently transformed to martensite in liquid nitrogen (whereby about 40 pct transformation was obtained). Dilatation measurements were made by observing length changes in a vacuum dilatometer with an externally mounted LVDT sensing element. 1. 3) Preparation of Electron Microscope Specimens. Slices of the ingots were cold-rolled (with intermediate vacuum anneals) to -0.020 in. Out of these rolled sheets, specimens (about 1 by 1 in.) were cut. These were then vacuum-annealed, transformed to martensite by cooling in liquid nitrogen, and subsequently heated from room temperature to various temperatures to effect either partial or complete reverse transformation. These specimens were then chemically polished to 0.002 in. in l:l HsOz (30 pct) and &PO4 (85 pct) solution, and thinned to electron transparency in an electrolyte consisting of 150 g CraOs, 750 ml glacial acetic acid, and 30 ml ~~0.~ Observations were made with a 100-kv Hitachi HU-11 electron microscope equipped with an HK-2A tilting device. 1.4) Optical Microscopy. Metallographic observations were made with a Leitz MM5 metallograph on the same 0.020-in. sheet specimens as were used for electron microscopy and on bulk specimens which were 0.2 in. or more on a side. The chemical thinning solution when cooled below 20°C also served as an etchant for this alloy. Observations of surface relief were made with a Zeiss interference microscope employing a Thallium light source of wavelength 0.54 p. Specimens for interference studies were prepared by two-stage polishing on Buehler vibromet polishers using 0.3 and 0.05 p alumina abrasives. 2) EXPERIMENTAL RESULTS 2.1) Comparison of the MS,AS, and Af Tempera-tures wTth Previous Re sults. The AS aLd Af tempera -tures of several Fe-Ni alloys were determined dila-tometrically. The MS temperatures of the same alloys were determined by continuously lowering the temperature using a mixture of isopentane and liquid nitrogen and observing the highest temperature at which a prepolished specimen showed surface upheavals. For the present the As temperature is defined as the temperature at which an abrupt decrease in length occurs in the dilatation plot. The Ms,As7 and A determinations in the present investigation and those of Kaufman

Jan 1, 1968

By Mark J. Klein

The creep of 043 was studied over the temperature range 1650" to 3200°F and over the stress range 3000 to 44,000 psi. The steady-state creep rate over this range of stress and temperature can be expressed by the equation where A is a constant, is the stress, and is -0.8 x 103 psi-&apos;. Over a narrow range of stress variations c0 a and for this proportionality n varies from 3 to 30 in accordance with the relation n = aB. Above about 2400° F, H, the apparent activation energy for creep, is 110,000 cal per mole, a value about equal to that estimated for self-diffusion in this alloy. Below 2400°F, H increases with decreasing temperature reaching a value of -125,000 cal per mole at 1700° F. In this temperature region, H appears to be a function of the interstitial concentration of the alloy. MOST of the detailed creep studies of dispersion strengthened metals have been concerned with metals having fcc structures. However, there are a number of important refractory alloys with bcc structures that derive part of their high temperature strength from an interstitial phase and whose creep behavior has not been well defined. This paper describes the creep behavior of the bcc alloy, D43, over the temperature range 1650" to 3200°F (0.4 to 0.7 Thm) and over the stress range 3000 to 44,000 psi. In addition to colum-bium, this alloy contains 10 pct W. 1 pct Zr, and sufficient carbon (-0.1 pct) to form a carbide dispersion throughout the matrix of the alloy. The effects of variations in temperature and stress on the steady-state creep rate of this alloy are presented in this paper. EXPERIMENTAL PROCEDURES Creep tests were made in a vacuum of 106 torr under constant tensile stress conditions using a Full-man-type lever arm.&apos; Creep specimens were machined from 0.020-in. D43 sheet (grain size -5 x l0-4 in.) processed in a duplex condition (solution annealed -2900°F, 40 pct reduction in area, aged 2600°F). The specimens were tested in this condition without further heat treatment. Specimen extensions over 1-in. gage lengths were continuously recorded using a high temperature strain gage extensometer. Differential temperature and stress measurements were used to determine temperature and stress dependencies of the creep rate. Activation energies were calculated from the changes in strain rate induced by abrupt shifts in the temperature during constant stress creep tests. The 100°F temperature shifts used in most of the activation energy determinations required 15 to 90 sec depending upon the temperature at which the shift was made. The dependence of strain rate on stress was determined by measuring the change in strain rate for incremental stress reductions during constant temperature tests. It has been shown that columbium-base alloys such as D43 are susceptible to contamination by gaseous interstitial elements during vacuum heat treatments.&apos; In this regard, it is unlikely that these alloys can be heat treated without some loss or gain of interstitial elements despite the precautions taken to control the heat treating environment. However, several factors suggest that changes in interstitial concentrations of the specimens during testing did not affect the results presented in this paper. First, the dependence of the creep rate on the stress or temperature determined during the course of a single creep test showed no variations with the duration of the test. A variation would be expected if a loss or gain in interstitial concentration during the course of the test affected results. In addition, precautions taken during this investigation to minimize interstitial contamination by wrapping the gage lengths of the specimens with various foils2 (Mo, Ta, W) did not produce a detectable change in the stress and temperature dependencies relative to the unwrapped specimens. The averages of duplicate analyses for carbon and oxygen in several specimens determined before and after creep testing are listed in Table I. The combined nitrogen and hydrogen concentrations which were ordinarily less than 50 ppm did not change in a detectable way with creep testing. The analyses show that only minor changes in carbon concentration occurred during creep testing except for specimen 4. This specimen which was tested at 3100°F lost a significant amount of its carbon concentration to the vacuum environment. Specimen 1 gained 100 ppm of O, while specimens 2, 3, and 4, which were tested at progressively higher temperatures, lost increasing portions of their initial oxygen concentrations during testing. RESULTS AND DISCUSSION The Temperature Dependence of the Creep Rate. The apparent activation energy for creep, H, was de-rived from creep curves similar to that shown in Fig. 1. Steady-state creep was rapidly attained at the beginning of the test and with each change in temperature. This behavior suggests that the alloy rapidly attains a stable structure with each shift in temperature or that the structure is constant throughout the test. Since the dispersion will tend to stabilize the structure, the latter is probably the case. The activation energy was found to be independent of the direction of the temperature shift and the magnitude of the shift (50" or 100°F). Although H was approximately independent of the strain, there was a tendency for it

Jan 1, 1970

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan&apos;s theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4&apos;5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.&apos; reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do&apos;s or the H&apos;S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.&apos; In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,&apos; the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.&apos; Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.&apos; The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.&apos;&apos; Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967