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By T. B. Crowe

MucH has been written upon the precipitation of metals from cyanide Solution by zinc. We often read of the many factors that influence precipitation, such as zinc surface, purity of zinc, percentage of lead, temperature of solutions, strength of solutions in cyanide or alkali, etc. -Little do, we hear, however, of the part that oxygen plays in precipitation. Caldecottl says: "As the dissolving of gold is essentially an oxidation process, so its precipitation is one of reduction." All who have studied or worked with cyanide solutions will agree that Caldecott's statement is true.' . In the cyanide work in the mills of the Portland Gold Mining Co., we have always found oxygen to be the greatest enemy to precipitation. Oxygen Antagonistic to Good Precipitation A few years ago, while making some experiments on the effect of pressure upon the dissolving rate of gold from our ores, to prove a point, I made some bottle tests under vacuum. The results were surprising, and showed that under vacuum practically no gold dissolved, which confirmed my belief that Elsner's equation was true and also led me to investigate the amount of dissolved air carried by solutions at atmospheric pressure. The experiment consisted in partly filling an acid-bottle with mill-solution and connecting it by a rubber hose to a vacuum pump. When the vacuum was suddenly applied, a cloud composed of thousands of small air bubbles rose out of the solution, showing qualitatvcily' the amount of dissolved air that was contained in the solution, and also proving that the relief of atmospheric pressure on the solution permitted this dissolved air to escape. In studying literature on the subject, we find Henry's law—"The amount of gas dissolved by a liquid is proportional to the pressure to which the gas is subjected."

Jan 1, 1919

By PHILIP N. MOORE

PHILIP NORTH MOORE was born on July 8, 1849, at Connersville, Ind. His father, a civil engineer, was descended from Henry Moore who came from Ireland in 1773 to live in Washington, Pa. Through his mother, Philip Moore was descended from John North, who came to America in 1635 and settled in Connecticut. The story of Mr. Moore's life as told by himself is given on pages 373-386 of T. A. Rickard's "Interviews with Mining Engineers." He studied at Miami University, where he gained the degree of A.B. in 1870, and A.M. in 1873. In 1920 his alma muter conferred on him the honorary degree of LL.D. He, as a special student, was a member of the class of 1872 at the School of Mines of Columbia University.

Jan 1, 1930

By Oliver Bowles

DISCUSSIONS of trade and commerce are generally more comprehensive today than in the past; the problems are approached with a vision unrestricted by national boundaries, and broad enough to comprise the entire world. The extent to which the limited viewpoint that has characterized past ages is yielding to an economy of world-wide scope is exemplified by the Atlantic Charter which blazes a trail in the direction of trade principles that aim to preserve the interest of each individual country in the commonwealth of nations. Its fourth article promulgated the principle that all nations should have access on equal terms to the trade and to the raw materials of the world which may be needed for their economic prosperity. Future developments in reciprocal international trade may have some effect upon the flow of nonmetallic minerals but such effects are not likely to be great because tariffs and trade policies have not affected that flow profoundly in the past. Nevertheless conditions may change and new problems may arise demanding important decisions. Sudden changes are not to be expected, but rather an orderly evolution in which national interests will merit due consideration in establishing broader policies.

Jan 1, 1945

By N. C. Nissen, J. A. Thomas, A. Illis, K. N. Subramanian

Successful miniplant and laboratory testwork has indicated that high purity selenium can be produced from copper refinery slimes. The recovery technique fits into existing unit operations, and the selenium recovery in the new process was close to 99%. This recovery virtually eliminated any selenium being processed through the smelting stage. In addition, miniplant tests conducted at Inco Metals Co.'s J. Roy Gordon Research Laboratory in Mississauga, Ontario, have demonstrated the reliability of the process with respect to extractions, product quality, filtration characteristics, and effluent disposal. Inco's copper refinery at Copper Cliff, Ontario, produces about 500 t/d of copper with the anode slimes fall typically averaging 0.5% of the throughput. Investigations relating to the treatment of slimes within Inco's R&D have been conducted on several occasions since 1959, when the available alternatives such as acid or alkaline pressure leaching, aqueous or high temperature chlorination, roasting, smelting, etc., were considered. Interest in slimes processing was revived recently to meet increasingly stringent environmental standards and to replace equipment of a relatively old plant.

Jan 11, 1978

By L. T. Sanchez, W. T. Rogers

This paper presents the results of a production experiment evaluating the effect of the use of oxygen in the bessemer converter with respect to its relation to blowing time, amount of steel scrap or cold pig iron which can be melted and teeming temperatures of the molten steel. THE simplest and probably the most efficient and economical means for producing steel from molten pig iron is the bessemer converter. This process is essentially a mechanism for bringing oxygen into contact with the molten metal thereby oxidizing the elements silicon, manganese, and carbon. The source of oxygen is that contained in the air and is limited by that amount. In theory, there is an intermediate chemical reaction due to the mass action of iron and air which is represented by the equation: 2Fe + O2- = 2Fe0 The FeO then becomes the oxidizing agent and reacts with the silicon, manganese, and carbon to produce silicon dioxide (SiO,), manganese oxide (MnO), and carbon monoxide (CO), in the order mentioned. The balancing of the various chemical reactions shows that in the ordinary bessemer process more than sufficient oxygen is delivered to satisfy these reactions, which indicates that a further increase in the oxygen content of the air would serve no useful purpose. In spite of this reasoning, however, it will be demonstrated that when melting stelel scrap, commercially pure industrial oxygen introduced into the normal air blast will permit the melting of a larger proportion of steel scrap than is possible with air alone and also will increase the production rate by a substantial reduction in blowing time. It will also be shown that when melting cold pig iron, it is possible to melt up to twice as much pig iron with the use of oxygen as can be melted without added oxygen with a nominal increase in blowing time. At the plant where this study was made, oxygen is purchased from a nearby supplier and piped directly into the plant. It is supplied to the bessemer converter by being introduced directly into the blast line through an automatic control system which may be adjusted by the bessemer operator or "blower." Normally, iron is supplied by five blast furnaces to an open hearth shop containing twelve 165-ton capacity stationary furnaces and a bessemer converting shop having three 30-ton converters. The molten metal from the blast furnaces is allocated to one shop or the other in a manner to best provide for maximum production. At various times, it is desirable to direct the maximum amount of available blast furnace production to the open hearth shop. This has the effect of reducing the production of the bessemer shop. When this condition exists, it is desirable to supplement the reduced iron charge at the bessemer with steel scrap or cold pig iron to the maximum possible extent in order to maintain high total ingot production. This condition becomes aggravated when one of the blast furnaces is taken out of production for any repair job and particularly for extended periods such as when relining is necessary. The purpose of the investigation and experimentation with oxygen was to determine whether or not it would contribute to increased flexibility in the use of the raw materials, molten iron, steel scrap, and cold pig iron. In addition to the effect of oxygen on flexibility of operation, it was also necessary to determine the relation of its use to production rate or "blowing time," final finishing temperature of the steel or "teeming temperature," and steel quality.

Jan 1, 1953

By Carl Lee

OXYGEN-FREE high-conductivity copper (OFHC brand) that is now being commercially offered for the first time represents a notable achievement in electro-metallurgy and is the outcome of endeavors that have extended over a long period. Its manufacture is novel in that electrolytically refined copper is melted in electric furnaces and cast into vertical water-cooled molds. The ingots show the "pipe" characteristic of sound gas-free metal and microscopic examination even at high magnification reveals no cuprous oxide in the copper. Owing to the patent situation, the United States Metals Refining Co., the producers, cannot at this time divulge the details of manufacture, but the operations are under precise control so that the castings are of great uniformity and the copper contains no residual deoxidant. Figs. 1 and 2 show photographs of cross-sections of a wirebar and a billet, both vertically cast.

Jan 1, 1933

"The Tooele plant is situated at the mouth of Pine Canyon, five miles northeast of Tooele City. The site forms one terminus of the Tooele Valley railway, which runs southwest through Tooele City to Warner, a station on the Los Angeles and Salt Lake Railroad, thirty-five miles southwest of Salt Lake City.An aerial tramway, four miles in length, crosses the Oquirrh Mountains and connects the plant with the Bingham district.The plant consists of a lead-zinc flotation concentrator, lead smelter and copper smelter.SAMPLING MILL The mill is a standard Taylor and Brunton sampling mill, built in two sections, each with a capacity of 100 tons per hour. The building is of steel and concrete, 40x84 feet. A well-equipped pulping, sampling and drying room is attached.All ore is sampled here and then distributed by conveyors to cencentrator, lead smelter and copper smelter bins.CONCENTRATOR This flotation mill is arranged in two units of 500 tons capacity each, one equipped with Callow pneumatic flotation cells, the other with Mineral Separation sub-aeration machines.The feed is maintained as uniform as possible by bedding, after coarse crushing at the sampling mill. Standard practice of ball mill grinding and classification is followed."

Jan 1, 1925

By Carl Lee

WITH the modern trend toward motor drive in coal mines, more careful forethought should be given to future layouts than has usually been done in the past. Both top and bottom equipment of future new mines is likely to differ radically from those of a decade ago. No one is able to predict very far ahead, but provisions can be made to allow for uncertainty. One thing stands out: the mine of the future will be laid out for long life compared to that of the small mine of the past, where an inexpensive top plant, simple equipment, a small timbered shaft, small cars, light rail, hand loading and mule haulage all contributed to a short economical life.

Jan 1, 1933

W. E., RUDER, Schenectady, N. Y. (written discussion *).-Professor Howe, with characteristic thoroughness, has demonstrated that Professor Jeffries' "Reversed Inheritance" explanation of the case in question is contrary to fact, as shown by many previous observers. Since the photographs were my own, I feel it my duty to say a few words in discussion. In the first place, it is to be noted that these photographs were of pressed powders, and although many of Professor Jeffries' original experiments were made from this kind of material, the nature of such a specimen must of necessity be different from that of the fused metal, although the same basic laws of grain growth may apply in both cases, certain factors, such as the rate of change, for example, are undoubtedly different in each case. That the 1000° C. grain is a natal grain is evident from its appearance contrasted with the more perfectly formed, though smaller, grains in the 1300° C. photograph. I am not sure that Professor Howe's explanation of the formation of this grain is necessarily the correct one, although it agrees with. Stead and Carpenter's results. I am inclined to think that this grain may have been formed on heating, because I have been able to produce grains of the shape and magnitude of Stead and Carpenter's grains by heating to 850° C. pure electrolytic iron, which has been subjected to a strain gradient. On reheating to 1300° C., the mobility being so much greater, the individual crystals had time for unhampered re-arrangement and growth after their second refinement on passing Ac3, so that we have in this case a true fused metal condition in which the individual crystals are arranged in true equiaxed grains of a size consistent with their high temperature anneal. In this case the grains are equiaxed, inheriting none of the columnar tendencies of the previous grain, because they were not affected by any strain gradient, except possibly some accidental local gradients. It seems to me that the introduction of pressed powders into the discussion of grain growth, where allotropic changes take place, unnecessarily complicates an already complicated problem.

Jan 1, 1918

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961

By M. J. Pool, J. R. Guadagno

THE relative partial molar heats of solution in liquid tin have been determined for phosphorous, arsenic, and antimony at 750°K. This work was carried out as part of an over-all program to determine the heats of formation of the III-V semiconducting compounds. A differential twin-type liquid tin solution calorimeter was used in the investigation. All three elements are endothermic upon solution in tin. The relative partial molar heats of solution go through a minimum value at arsenic. No concentration dependence of the heat of solution was found in the dilute (0 to 2 at. pct solute) solution range investigated. The measured heat effects and the calculated relative partial molar heats of solution at infinite dilution are listed in Table I along with the relative heat contents of the solutes calculated from the data of kelley.1 All of the values are referred to 750°K even though the calorimeter temperature fluctuated by *1°K during the course of the experiments. In this range of temperature change no variations were found which were outside the experimental error. This would be expected since the partial molar heat of solution is in general a very insensitive function of temperature. The limits of error given in Table I represent the standard deviation from the mean. The reported error estimates only apply to the estimated precision of the data and not the accuracy. Systematic errors could be present which would affect the absolute values given. This is especially true in the case of phosphorous and arsenic where vaporization could occur. If this were true, the experimental values reported here would be too high and the true partial molar heat of solution would be less than that given in Table I. Moreover, the heat-content data could be in error and this would also affect the calculated values. The relative partial molar heat of solution of phosphorous at infinite dilution in liquid tin is given in Table I. This value is based on eight drops at

Jan 1, 1965

By Herbert J. French

ALLOY steels have become essential to industry in meeting the rigid requirements on materials imposed by our, advanced technology. In comparison with the total ingot capacity of the steel industry, the volume of alloy steels is relatively small although for many years annual alloy-ingot tonnage has, been in seven figures. However, the monetary value of the alloy-steel production is exceedingly high and the benefits derived from the products are relatively great. The trend in total ingot production since 1932 has been generally upward with only two major interruptions. That of the year 1938 was due to a decrease in general business activity whereas that of 1946 resulted largely from work stoppages. Traditionally, the tonnage of alloy-steel ingots produced was in the neighborhood of 5 to

Jan 1, 1948

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By J. S. Marsh

TUESDAY, Feb. 16, was no day for strolling along the cold sidewalks of New York, and a large number of metallurgists sat down with pleasure to the warming task of wiping a few soldered joints. Presented by a joint-wiper of the modern school, G. M. Bouton, of the well-known team of Schumacher, Bouton, and Phipps, the initial paper brought into focus the theme of conservation of strategic metals and described the technique of making the fillet-type joint now employed by the Bell System. Using an over-all average of only 40 per cent of the solder formerly used by the conventional method. this important development bids fair to stick when the war is over. D. L. Martin and E. R. Parker then described the embrittling effect of hydrogen on silver previously heated in oxygen and the less serious but troublesome result obtained under the converse conditions. An interesting example of grain growth restriction created additional material for the lively discussion that ensued among those who have encountered one or another of these phenomena in silver and copper.

Jan 1, 1943

By P. D. I. Honeyman

IN THE Southwestern copper region the event of greatest interest was the starting up of the new Hurley, N. Mex., smelter of the Chino Mines division of the Nevada Consolidated Copper Corp., which occurred in May. This plant, built as a wet-charge smelter for treating largely an all-concentrate charge, embodies in its de- sign the latest in materials-handling equipment. Noticeable around this smelter is the absence of tram cars and trackage for the handling of charge, dust and other materials. Concentrate from the mills is received in bottom- dump cars which are unloaded into a series of concentrate bins. Concentrate is then reclaimed through the bottom of the bins and discharged through a feeder on to a conveyor belt. Flux for the charge is fed on to the conveyor ahead of the concentrate charge. The belt-mixed charge is conveyed to the furnace building and discharged into the furnace charge bin ready for feeding to the reverberatory furnace. As in the McGill plant, the furnace is fed by vibrating conveyors, one down each side of the furnace.

Jan 1, 1940

ANNUAL meeting of the Woman's Auxiliary of the American Institute of Mining and Metal-lurgical Engineers convened on Tuesday morn-ing, Feb. 20, the president, Mrs. H. W. Hardinge, presiding. President Hardinge, in opening the meet-ing, said: "I have the honor and great pleasure to welcome you to our seventh annual meeting. It has been a happy year, though I started in fear and trembling. My fear is partly gone and my trembling becomes less as time goes on. Never has a chairman had such splendid cooperation and harmony in her work; no. matter how much was asked nor what the task, I have always received the same answer, `We are with you, of course we can do it.' Often the road has been untried and the way full of snares, but we have all pulled together. Is it any wonder we have had a prosperous year? I cannot thank the governing -board and officers enough for their help." Mrs. Hardinge described her trip through the West last summer, during which she visited many of the local sections of the Auxiliary. She also spoke of the work of the Rossiter Raymond memorial library which has been started as an activity of the Woman's Auxiliary. Mrs. Reynders read the minutes of the last annual meeting, and Mrs. Kemp read the treasurer's report. The latter showed that on Feb. 1, 1922, there was a bank balance of $683.61 and on Feb. 10, 1923, the bal-ance was $947.93. Mrs. Westervelt expressed the sorrow of the Auxiliary for the death -of Mrs. Florence Howe Hall and of Mrs. Levi P. Holbrook.

Jan 4, 1923

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By G. D. Boozer, W. H. Somerton

RESEARCH CORP., LA HABRA, CALIF. Thermal diffusivities of some typical sedimentary rocks have been measured by a rapid unsteady-state technique. Thermal data including diffusivity and conductivity are presented for the temperature range of 200" to 1,800°F. Diffusivities calculated from steady-state conductivity rneasurernents compared favorably with unsteady-state data at the lower temperatures. Unsteady-state data are less reliable at higher temperatures; reported values may be as much as 20 per cent high at temperatures in excess of 1,500°F. This is caused partly by the simplified method used in calculating diffusivity from experimental data and partly by the many thermal reactions which occur at the higher temperatures. The marked decrease in thermal diffusivity and conductivity at elevated temperatures indicates the importance of considering the temperature dependence of thermal properties in subsurface heat-transfer calculntions. Knowledge of the effects of liquid saturation, overburden and pore pressures, and heats of reaction of reservoir materials will be required before complete subsurface thermal analyses may be made. INTRODUCTION Heat-transfer calculations are becoming increasingly important in the analysis of in situ combustion and underground nuclear explosions. Thermal data for natural rock materials at elevated temperatures are generally unavailable. Calculations at high temperatures may be grossly inaccurate if temperature-dependent thermal properties of rocks are not considered. It is known that the heat capacities of rocks increase with temperature. Heat capacities may be calculated from chemical or mineralogica1 analyses of the rock system. Thermal bulk expansion of rocks is believed to be small, although few data are available. Thermal conductivities of most natural rock materials decrease with increased temperature. Thermal diffusivity, defined as the thermal conductivity divided by the product of the heat capacity and the bulk density of the material, is used in unsteadv-state heat-transfer calculations. It is apparent that thermal diffusivity decreases markedly with increased temperature. A new method, which gives a nearly continuous record of thermal diffusivity within the temperature range of 200° to 1,800°F and requires less than 1.5 hours for the run,' was used to measure the diffusivity of several sedimentary rocks. Thermal conductivities were calculated from measured bulk densities, heat capacities calculated from chemical analysis and the measured diffusivity values. Thermal conductivities were measured at lower temperatures by a steady-state technique1 to test the agreement of data obtained by the two methods.

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969