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By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.'-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By E. S. Wheeler

The rapid increase in the use of monel metal and malleable nickel in the form of sheet, rod and tube has resulted in a similar increase in the demand for these metals in the form of castings. These castings range in size from small valves and pipe fittings weighing a few ounces to large centrifugal pumps, gate valves and marine propellers, some of the last weighing as much as 24,000 lb. A group of such castings is shown in Fig. 1. A large nickel agitator is shown in Fig. 2. Monel metal castings are widely used in accessories for steam power plants and in a variety of chemical plant equipment where the corrosion resistance, high strength and toughness characteristic of this metal render it particularly valuable. Nickel castings find extensive use in the construction of corrosion-resistant apparatus, and are often used in conjunction with wrought nickel sheet and tube in the fabrication of equipment for handling a variety of chemical and food products, particularly dairy products. In response to this demand for castings, numerous foundries have undertaken the production of castings of these metals and have met with varying degrees of success. The successful production of castings of monel metal and nickel requires careful attention to molding practice, proper melting equipment

Jan 1, 1930

By H. T. Kennedy, S. G. Dardaganian, J. L. Clanton

This paper presents equilibrium ratios measured on oil and gas samples taken from the Kelly-Snyder field at the reservoir temperature of 128°F. From these data smoothed curves were constructed for the reservoir fluid up to the bubble-point, 1,874 psia. A material balance calculation, based on the use of equilibrium ratios instead of the usual solubility and shrinkage meayr~rements is made on the field and compared to the con\.entional method. DETERMINATION OF EQUILIBRIUM RATIOS The equilibrium ratios, or K values were obtained by recombining separator samples of oil and gas taken when the reservoir was above its bubble point, and thus represented the reservoir fluid before any change had occurred due to the evolution of gas. The well sampled had a gas-oil ratio of 617 cu ft of high pressure sepalator gas per barrel of separator oil. and a bottom-hole temperature of 128°F. Samples were brought to equilibrium by agitating for 24 hours in a thermostat, maintained at the proper temperature within 0.2ºF, mercury being added when necessary to maintain the pressure constant. Samples of oil and gas were then taken by constant pressure displacement, and analyzed by low temperature frac-tionation. Equilibrium ratios were determined at 128°F and 500, 800, 1,000 and 1,400 psig. At the latter pressure, there were indications that the gas samples were contaminated with small quantities of oil, and only data taken at the first three pressures were included in Fig. I. This figure has been extended to higher and lower pressures by the use of the Fluor charts for 3,000 psi convergence pressure, on which the experimental points fit well. MATERIAL BALANCE EQUATIONS The possible errors involved in conventional material balance equations have been analyzed by Muskat1. Where the errors occur in field measurements, or in obtaining effective averages from variables such as gas-oil ratio and pressure, they will evidently be involved in any attempt to estimate the content of the reservoir. On the other hand, substantial errors may be introduced in conventional material balance calculations by: (1) the neglect of the amount of oil dissolved in gas at high pressures and temperatures in the reservoir, but which condenses under separator conditions; (2) the assumption that the separation of oil and gas in the reservoir may be duplicated by a differential liberation in the

By Rodney L. Stone, David S. Cahn

As part of an over-all laboratory and plant test program to determine mixing ad other techniques for a more economic use of bentonite as an iron ore pellet binder, a settling test for measuring the bentonite content within a pellet or a batch of pellets has been developed. Through this test, it has been shown that dry fracture load is directly proportional to bentonite content in batches of pellets, but inversely propor tional to bentonite content in individual pellets of the same batch. This apparent paradox is explained by a negative correlation between a pellet's size and its bentonite content and the fact that large pellets can withstand a higher fracture load than small pellets. In past attempts to characterize green and dry iron ore pellets, the authors found large variations in the results of strength tests on closely sized pellets from the same batch.' Reasons advanced for such variations in the quality of pellets in which the binder is bentonite were the presence of internal flaws and the nonuniform distribution of the binder. Even when resulting pellet strength is good, there is still the question of whether the same strength could have been attained through a more effective use of a smaller amount of bentonite. The authors' own and other studies 2-3 have pointed out the strong dependence of pellet strength on the degree of "mixedness" of the iron ore concentrate and the bentonite binder. However, before such a relationship could serve as a guide for the development of better mixing techniques and the associated economy of

Jan 1, 1969

By H. Rush Spedden

R. T. Hukki has extended his study of ball mill grinding at supercritical speeds with an excellent mathematical analysis of tumbling mill grinding. When he speaks of supercritical speeds he is referring to the original Fahrenwald critical-speed formula. He said that, as an example of the use of supercritical speeds, if a fine grinding mill of any type is wet-grinding ore of 3.5 sp gr with steel balls at a certain conventional subcritical speed, the same power input and capacity should be obtainable with autogenous medium of 3.5 sp gr at a speed 100 to 120 pct of the critical in a grate- type mill of the same effective size. In addition, he introduced what he calls the base mill concept which, he stated, makes it possible to compare performances of mills of different sizes grinding with a metallic medium or with an autogenous medium of any specific gravity and at any speed. He showed the use of this concept and explained how it makes possible the evaluation of mill sizes and motors for any grinding purpose at any accuracy well within the conventional standards of design in milling practice. He further stated that the maximum capacity in pilot plant mills with various media, either metallic or autogenous, has always been found to be within the supercritical speed range. In his discussion of this paper he substantiated these findings with statements showing the increased capacity obtained in a milling plant in Finland which followed his principles.

Jan 7, 1960

Victor G. Hills, Cripple Creek, Colo. (communication to the Secretary): In continuation of the subject of the perform ance of "baby machine-drills," presented by Mr. Thane, I sub mit the following records of work done with these drills in the Cripple Creek district of Colorado. Two years ago, the Anchoria-Leland mine began to use baby drills ; and, to make the experiment more complete, began by purchasing two machines, of the same size, but of different make. The little drills were first used for stoping and up raising, in which they achieved at once an unqualified success. Soon after, they began to be used for the smaller branch-drifts and prospecting cross-cuts, while the large two-man drills were still used for the main drifts. Now they have almost entirely superseded the large drills, since it has been found that they will do any ordinary work in the mine at less cost, both for labor and for powder, per ton of rock broken. The large drills, of course, make more rapid progress; but it is only where time is a specially important factor that they are now used. The Portland mine, where, until within a year, only the large machines were used, is now using some small drills for stoping, and also for drifting. Mr. Thane speaks of having two men to operate a baby-drill; but in this district the baby-machine is always worked by one man without help. Again, in Prof. Christy's postscript, the quoted extract from a letter of Mr. L. T. Seymour, the South African engineer, mentions a " 2 1/2-inch Little Giant," as though that were the smallest machine used in that region. These statements leave some doubt as to just what Mr. Thane means by a " baby-drill." To avoid any such uncertainty as to the present communication, I will say that the large or two-man drill in common use at Cripple Creek has a 3 1/8-inch cylinder; while a few mines employ a 3-inch, and a few, in running large tunnels, a 3 1/2-inch drill. What we call a baby-drill here has a

Jan 1, 1900

By J. M. Uys, T. B. King

WalSH, Chipman, King, and rant' have measured the water content (as hydrogen) of actual steel-making slags. An average water content of 290 ppm was found for basic open-hearth tapping slags and 114 ppm for acid open-hearth slags. Upon equilibration of these slags at 1550°C with a 25 pct H20-75 pct Nz atmosphere, the water content increased to about 410 and 300 ppm for the basic and acid slags, respectively. Walsh et al. concluded that an acid slag was thus relatively far removed from equilibrium, and that basic slags showed a closer approach to equilibrium, with the water vapor in the furnace atmosphere. Herasymenko2 contended that these conclusions were unjustified, as the oxygen pressure used in the equilibration experiments, ;bout 5 x X atm, was quite different from that found in the furnace. Consequently, during the experiments the slag composition would have changed due to oxidation of ferrous iron. As an extension of Walsh's work and to attempt to clarify this matter, the solubility of water in a basic open-hearth slag was measured as a function of oxygen pressure. Similar measurements were also made on synthetic silicates in the "Fe0"-Fe203-SiO, system. The experimental technique has been described previously by Walsh et a1.l and Uys and King.3 Samples of the basic open-hearth finishing slag, contained in 10-cc platinum crucibles, were equilibrated at 1550°C with atmospheres of different oxygen pressure but constant water-vapor pressure, Ph~o = 0.192 atm. Calculations, as well as measurements, indicate that this figure approximates the water pressure of the combustion gases in a steam-atomized, oil-fired open hearth. Oxygen pressures in the open hearth can vary from 10"2 atm in the combustion gases to between l0-' and 10" atm in the steel bath. The former figure depends on the combustion practice and the latter on the carbon content and temperature of the bath. The oxygen pressure of the slag should lie somewhere between these extremes and is expected to be closer to that of the steel bath than that of the combustion gases. Oxygen pressures were therefore varied between 10" and 6 x l0 atm. At the lowest pressure the slag "puffed up" when quenched (indicating possible loss of water) so experiments were not conducted at lower oxygen pressures. The results are shown in Fig. 1, which includes the water content of the slag "as sampled". The results show that the water content of the slag increased appreciably on equilibration with water vapor at 0.192 atm pressure and that the water solubility apparently decreases with increased oxygen pressure. The solubilities found are comparable to those of the Li20-Ca0-Si02 system.3 Work with synthetic slags in the "Fe0"-Fe203-SiOz system was performed at 1500" C, with Ph20 = 0.192 atrn and for oxygen pressures varying between 10"2 and 10-lo atm. Samples for chemical analysis were prepared as described by Larson.4 The results are shown in Fig. 2. Some low-silica melts tested at low oxygen pressures "puffed up" when quenched and analyzed less than 100 ppm water; these results are not included in Fig. 2. The melts containing 40 mol pct silica also showed a tendency to "puff up" during the quench, when they were tested at the lowest oxygen pressure. These results indicate that, at constant silica content, the solubility of water decreases somewhat with increased oxygen pressure. The effect is, however, small considering the wide range of oxygen pressures studied. Also, at constant oxygen pressure (above about lom5 atm) the solubility increases

Jan 1, 1963

By A. W. Asman

The problem of balanced design in a belt conveyor has been under constant study. Increased use of this method of transport in recent years has stimulated investigations. Conveyor belt, power transmission and other machinery should be adequate to perform the required service. All components of the belt conveyor should work as an efficient unit moving its load continuously between terminals. As part of a long term research project on belt conveyors, Hewitt-Robins established in 1954 a 2-year grant at Pennsylvania State University. Under terms of the grant, certain fundamental phenomena were to be studied. This work evolved a new concept in belt conveyor power determination based on the principle of belt tension. The Penn State contract furnished the foundation for later more detailed studies. From these most recent investigations, more specific factors were defined. In the final analysis, all of the data collected has been worthwhile in belt conveyor design. Units now operate over long distances at speeds of over 800 fpm. Long high lifts are commonplace. Where vertical or inclined shafts were the rule, belt conveyors receive first consideration. Although belt conveyors have moved forward rapidly, the future will see a tremendous gain in their use. The ideal test belt conveyor would be several thousand feet in length and have a maximum tension of at least 70,000 lb., Also, this conveyor should be horizontai and have a variable feed rate of more than one material. Data from such a field belt conveyor combined with laboratory information would permit accurate analysis. Since this type of conveyor was not available, many field locations were visited: An alternate would have been to erect a closed circuit system in the laboratory. Either method had limitations and the first was selected as having the best possibilities. Manufacturers of conveyor belting and machinery basically have been using the same horsepower formula. As more information became available from field installations, factors in the basic formula were modified. Practically all conveyors are designed today by adding together the horsepowers required to move the empty belt, move the load horizontally, and elevate the load. In selecting size of drive motor, the first two elements are relatively unimportant if the last is large. However, it is the combination of

Jan 1, 1961

By John F. Abel

In the debate between miners and ecologists, our industry has at last begun to get some of its story told. I have been told many times that it is hopeless to even try to get our side across. Some are sure that no one will believe us even when our cause is just. My reply would be that we have to tell the truth; again, again, and again. We will never convert a fanatic, but we must try to reach the reasonable and thinking people. I am encouraged because more of us are trying. Various mining companies here in Arizona have bought newspaper space to set forth some of the facts around our local environmental problems. The Arizona Mining Association co-sponsored a symposium in March: Mining and Ecology in the Arid Environment. The symposium program included tours arranged with local mining companies. The participants saw an acid plant, an acid leaching operation, an alluvial tailings dike, a tailings pond, a smelter, and a couple of open pit mines. This wouldn't phase you until you realized that half the visitors were ecologists, watershed and wild- life managers, and other assorted conservationists. It took a lot of guts. I am proud that we had that much confidence. As Pogo said, "We have met the enemy and they is us!" Actually, we met the enemy and they were just like us-concerned.

Jan 1, 1970

By H. E. Biber

DURING the production of tin plate a thin layer of FeSn2, is formed at the interface between the steel sheet and the protective tin coating. Because excessive amounts of this alloy layer are undesirable, the kinetics of its formation is a subject of interest in the tin-plate industry. A recent study of this subject at our laboratory uncovered a relationship which should be of general interest to anyone studying kinetics of reactions in metallic systems. It had been previously concluded that, at any given temperature in the range 175" to 330°C, the Fe-Sn alloy layer would have a parabolic growth rate.1,2 However, our studies showed that this rule apparently holds only when the tin plate is heated very slowly to the "reaction" temperature; when the tin plate is rapidly heated, considerably different growth rates occur. An example of this effect of heating rate on growth behavior is contained in the accompanying results of alloy-layer growth measurements at 240°C in oil baths stirred at 10,500, 1800, and 0 rpm. The heating curves for these three conditions are given in Fig. 1, and the growth data are presented in Fig. 2. With the rapid heating rate, provided by the stirring at 10,500 rpm, the alloy layer had three distinct stages of growth. In the initial stage, which persisted well beyond the time required to heat the tin plate to bath temperature, the alloy layer formed very rapidly. The growth followed a rate law of the form w = ktn where n > 1. This initial stage was followed by a growth-retardation stage of about 50-sec duration in which little additional alloy was formed. In the third stage the growth again followed a rate law of the form w = ktn, but here « =0.3. With the intermediate heating rate provided by stirring at 1800 rpm, the three-stage nature was less pronounced and the slope of the third stage increased (i.e., n > 0.3). With the slow heating rate provided by the unstirred oil bath, the alloy layer grew in two stages. The initial rapid-growth stage persisted only until the specimen was heated to bath temperature, no growth retardation was observed, and the slope of the main portion of the plotted data was greater than in the stirred baths, having a value of almost 0.5. Similar results were obtained for other bath temperatures in the range 200" to 300°C. This effect of heating rate on growth behavior may be due to changes in the rate of nucleation of FeSn, crystallites. The iron and tin are in contact from the onset of heating. Thus the initial formation of FeSn, occurs not at the "reaction" temperature but rather while the tin plate is being heated to that temperature. Because nucleation is in general temperature-dependent, different heating rates could cause different over-all nucleation rates, which in turn could cause different growth behaviors. A more detailed discussion of the growth of Fe-Sn alloy layer and the effect of heating rate will be published shortly.

Jan 1, 1965

By Jasper L. Stuckey

PYROPHYLLITE, first identified as soapstone,1 later as agalmatolite,2 and finally as pyrophyllite,3 has been known to occur in North Carolina for more than 130 years and has been produced intermittently in commercial amounts for the past 100 years. Pyrophyllite mining, however, has become a major industry in North Carolina only during the past 25 years. North Carolina and California are the chief producing states. Current annual production averages 125,000 tons, of which slightly more than 90 pct comes from North Carolina. Distribution and Geologic Setting: All known pyrophyllite deposits in North Carolina are associated with rocks of the Carolina Slate Belt,4 which is composed of a vast series of metamorphosed volcanic and sedimentary materials, occurring as two zones extending in a northeast-southwest direction across the state. The larger of these zones, lying in the central Piedmont region, varies from 8 to 50 miles wide. The smaller zone lies along the eastern edge of the Piedmont region and is partly covered by coastal plain sediments.

Jan 1, 1958

By Byron W. Cheever

In working up the process which I described at the Chicago Meeting, May, 1884 (p. 163 of the present volume), for the estimation of phosphorus in iron and steel, I employed samples of steel obtained from one works only, and of a given brand. Since then I have had frequent occasion to test the process on other steels, and find that it works equally well. But some steels present certain colors which may mislead the operator; and I therefore propose a slight change in the directions formerly given. On the second page of my paper, in the second paragraph, I would substitute the following modified directions: Place the flask under the hydrant, till the solution is perfectly cold ; then add, gradually, strong ammonia, with constant stirring, till the solution is changed into a pasty mass and the ammonia is in slight excess; then add cautiously HNO3 (1.40 specific gravity)

Jan 1, 1885

By Howard R. Pratt, Jimmie L. Bratton

The Air Force Weapons Laboratory (AFWL) has been carrying out a series of experiments whose principal purpose is to measure the dynamic response of rock media to large pressure pulses. Coupled with the field experiments have been theoretical calculations simulating this response. These two approaches allow an appraisal of the current ability to measure in-situ rock response under extreme conditions and also give a fair estimate of the current state-of-the-art in the area of computer calculation of the response of "real" geologic media to a large load. The area chosen for the test series is composed of a sequence of sedimentary units (shale, sandstone, and limestone) located in the Estancia Valley 45 miles east of Albuquerque, N.M. (Fig. 1). The units, which dip gently off the uplifted Manzano Mountains to the west, are essentially horizontal at the test site. An extensive geologic and geophysical investigation of the area was carried out in the form of surface mapping and seismic exploration. Numerous holes were cored and material properties were determined from tests of the cores. In-situ geophysical measure¬ments were also carried out. The experiment consisted of loading a 60X40 ft test area with a 4000-psi transient exponentially decaying pressure pulse. The pulse was initiated at one end and traveled the 60-ft length of the test bed. The test area was instrumented with acceleration, velocity, and strain measuring devices placed in drill holes to depths of 30 ft. Theoretical computer calculations of the response of the layered geologic media have been carried out on the AFWL CDC 6600 using one and

Jan 1, 1972

By Frederic Benard

PRIOR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow-gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of transferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 1 ¼ miles. Although common in steel practice, the transportation of blister copper in this form had not previously been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended on the design and combination used for the particular experiment. The vessel was filled with approximately 2 ½ tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack on refractories. From the information derived, and in consultation with the engineering staff of the supplying company, an order was placed for the first

Jan 1, 1938

By M. J. Mullikin, J. B. Conway

Equations capable of representing combined first -and second-stage creep behavior include the Andrade, Cottrell-Aytekin, Garofalo, and de Lacombe equations along with a third-degree polynomial in t1/3. Employing some recent high- temperature creep data for arc-cast tungsten the effectiveness of these expressions was evaluated. It was found that, in this instance, the most accurate representations were afforded by the third-degree polynomial in t1/3 and the de Lacombe equation. Also noted was the fact that the Andrade equation gave results just slightly inferior to those obtained with the third-degree polynomial, definitely better than those due to the Cottrell-Aytekin equation, and slightly superior to those furnished by the Garofalo equation. EXPRESSIONS designed to describe combined first -and second-stage creep behavior must possess certain specific characteristics. At time zero the equation must reduce to a strain value corresponding to the instantaneous deformation on loading. Then in the early moments following load application transient-creep behavior must be described to reflect a creep rate which constantly decreases with time. And finally at larger time values linear (or at least nearly linear) strain-time behavior must be accounted for to yield the steady state or minimum creep rate. Some equations, such as the one based on the parabolic creep law, yield fairly satisfactory results in transient analyses but are not effective at all when combined first- and second-stage data are to be analyzed. Other equations give equally accurate results in both instances although in general the complexity of the equation is slightly increased. For example the Andrade1 equation: has found fairly general application in expressing first-stage creep behavior. Furthermore the contribution of the exponential term becomes more and more prominent as the time increases and causes this equation to exhibit a point of inflection at large values of time. With a proper selection of equation constants the curve can be made fairly flat in the region of the inflection point indicating a desirable equation form for combined first- and second-stage creep analysis. Another equation form with the proper characteristic is that of Cottrell and Aytekin:2 e =a +bt1/3 +ct [2] Obviously as time increases the first derivative of this expression approaches a constant value to suggest application to combined first- and second-stage creep analysis. Similarly a third-degree polynomial in t1/3: e -a + bt1/3 + ct2/3 +dt [3] has the same characteristics. Expressions of this type have been shown3 to be very effective in the analysis of transient-creep behavior and the fact that the first derivative has the same characteristic as Eq. [2] suggests use in the combined analysis.

Jan 1, 1967

By J. B. Clark

In 1933, R. paris1 published a phase diagram for the entire Mg-Ca-Zn system. He reported the existence of a ternary intermetallic phase, Mg5Zn5Ca2, which formed a quasi-binary with the magnesium solid solution. Since then, no extensive work has been reported on the system. Recently however, indications of the existence of a second ternary in-termetallic phase in equilibrium with the magnesium solid solution led to a reinvestigation of the solid phase equilibria involving the magnesium solid solution. The 335°C (635°F) isothermal section was chosen for study. Metallography and powder X-ray diffraction were selected as the best mutually corroborating methods for determining the solid phase constitution. Seventy-six alloys were prepared from singly sublimed (99.95 pct) magnesium, electrolytic (99.95 pct) zinc and USP calcium. The analyses of some of the alloys are shown in Fig. 1. The alloys were melted in a graphite crucible under a chloride flu and chill cast in a split graphite mold. Dif-fusion couples (see Fig. 2) were prepared by casting molten Mg-20 wt pct Zn alloy around a cylinder of Mg-30 wt pct Ca alloy. The alloy samples and the diffusion couples were sealed under argon in Pyrex vials and annealed in a furnace capable of controlling within 1/2°C of 335°C. At the conclusion of the anneal, the alloy samples were quenched in ice water and the diffusion couples were air cooled. Procedures standard for magnesium alloys were used for metallographic examination. Powder X-ray diffraction patterns were taken on a G. E. camera with a 14.32 cm dim using nickel-filtered copper radiation. The redetermined 335°C (635°) section of the Mg-Ca-Zn phase diagram is shown in Fig. 1. TWO ternary intermetallic phases, designated w and

Jan 1, 1962

By F. A. Olson, S. L. Pohlman

A unique method of measuring weight loss as a function 3 of time, with a sensitivity of 10-5 grams, while leaching copper minerals with a flowing acid leach solution has been developed. Kinetic results obtained coupled with visual and microprobe analyses show topochemical reaction for the leaching of chrysocolla with sulfuric acid. The kinetics follow a shrinking core model and show ion diffusion through a product layer, chemical reaction at the unreacted core interface and mass transfer through the boundary layer as being important.

Jan 1, 1974

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By H. E. Hawkes, D. A. Barr

Time variations in the copper content of the sediments of streams draining mineralized areas were studied in two areas of contrasting climatic environment, one in northern and one in southern British Columbia. In each area, samples were collected and observations made of rainfall, stream discharge and air and water temperature at intervals throughout the summer season. Samples were analyzed for total and cold-extractable copper. Results showed a weak inverse relation between cold-extractable copper and discharge in two out of the three test sites in the southern area, and a decrease in ratio of COld-extractable to total copper over the duration of the test period at a highly anomalous site in the northern area. In suspended rock flour resulting from glacial erosion of mineralized rock in the northern area, virtually all the copper was found to be soluble in cold, dilute hydrochloric acid. None of the variations observed is sufficient to cause serious problems in geochemical sediment surveys. Systematic collection and trace analysis of stream sediments has seen wide application in recent years as a method of primary prospecting in primitive areas. Common practice is to collect fine-grained samples of sediment either from the active channel or from the flood plain near the channel. Samples are dried, sieved and the -80-mesh fraction analyzed after breakdown of the sample by a relatively strong attack, such as by fusion or by treatment with hot perchloric acid. Drying, sieving and rigorous chemical attack requires established facilities, either in a well equipped central laboratory or in base camp. Thus analysis for total metal involves a substantial delay from the time the samples are collected until the analytical data can be reported. An alternative system uses a cold aqueous extrac-tant in place of the hot acid or flux.4 Advantages of the cold-extraction techniques are that kits can be prepared for use directly at the sample site and that, in some problems, the patterns in cold-extractable metal, usually abbreviated cxMe, are more useful as ore guides than the patterns in total metal.' In the course of operational geochemical sediment surveys, a problem that has come up repeatedly is failure to reproduce anomalous values or patterns by resampling the same areas. The mystery of the vanishing anomaly has led to speculation as to whether there is a significant variation in the metal content of sediment samples with the weather or with the time of year. Review of the published literature shows that a number of experiments have been carried out on time variations in the metal content of stream water.1,2,5,7-9 The only published report on time variations in stream sediments that has come to the authors' attention, however, is by Govett,3 working in Northern Rhodesia.

Jan 1, 1963

By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967